Fuel reprocessing of the fast molten salt reactor: actinides et lanthanides extraction

International Nuclear Information System (INIS)

Jaskierowicz, S.

2012-01-01

The fuel reprocessing of the molten salt reactor (Gen IV concept) is a multi-steps process in which actinides and lanthanides extraction is performed by a reductive extraction technique. The development of an analytic model has showed that the contact between the liquid fuel LiF-ThF 4 and a metallic phase constituted of Bi-Li provide firstly a selective and quantitative extraction of actinides and secondly a quantitative extraction of lanthanides. The control of this process implies the knowledge of saline phase properties. Studies of the physico-chemical properties of fluoride salts lead to develop a technique based on potentiometric measurements to evaluate the fluoro-acidity of the salts. An acidity scale was established in order to classify the different fluoride salts considered. Another electrochemical method was also developed in order to determine the solvation properties of solutes in fluoride F- environment (and particularly ThF 4 by F-) in reductive extraction technique, a metallic phase is also involved. A method to prepare this phase was developed by electro-reduction of lithium on a bismuth liquid cathode in LiCl-LiF melt. This technique allows to accurately control the molar fraction of lithium introduced into the liquid bismuth, which is a main parameter to obtain an efficient extraction. (author)

Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

Energy Technology Data Exchange (ETDEWEB)

Toulemonde, V [CEA Centre d` Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France); [CEA Centre d` Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d` Exploitation du Retraitement et de Demantelement

1995-12-20

The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

Actinides complexes in solvent extraction. The amide type of extractants

International Nuclear Information System (INIS)

Musikas, C.; Condamines, N.; Charbonnel, M.C.; Hubert, H.

1989-01-01

The N,N-dialkylamides and the N,N'-tetraalkyl. 2-alkyl 1,3-diamide propane are two promising classes of extractants which could replace advantageously the organophosphorus molecules for the separations of the actinide. The main advantages of the amides lie in their complete incinerability and the small interference of their radiolytic and hydrolytic degradation products for the processes. The actinide extraction chemistry with various amides is reviewed in this paper

Actinide extractants for the nuclear industry of the future

International Nuclear Information System (INIS)

Musikas, C.; Morisseau, J.C.; Hoel, P.; Guillaume, B.

1987-06-01

Non organo-phosphorus extractants properties regarding the extractions of actinides in nuclear fuels reprocessing are presented. N,N-dialkylamides are proposed as alternatives to TBP.N,N'-tetraalkylamides or pentaalkyl propane diamides properties are reported. They show that those bidentate extractants are alternatives to bidentate organophosphorus extractants for actinides (III) extraction from concentrated nitric acid. 11 figs, 15 refs

Preparation, properties, and some recent studies of the actinide metals

International Nuclear Information System (INIS)

Haire, R.G.

1985-01-01

The actinide elements form a unique series of metals. The variation in their physial properties combined with the varying availability of the different elements offers a challenge to the preparative scientist. This article provides a brief review of selected methods used for preparing μg to kg amounts of the actinide metals and the properties of these metals. In addition, some recent studies on selected actinide metals are discussed. 62 refs

Extracting metals directly from metal oxides

International Nuclear Information System (INIS)

Wai, C.M.; Smart, N.G.; Phelps, C.

1997-01-01

A method of extracting metals directly from metal oxides by exposing the oxide to a supercritical fluid solvent containing a chelating agent is described. Preferably, the metal is an actinide or a lanthanide. More preferably, the metal is uranium, thorium or plutonium. The chelating agent forms chelates that are soluble in the supercritical fluid, thereby allowing direct removal of the metal from the metal oxide. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent is selected from the group consisting of β-diketones, halogenated β-diketones, phosphinic acids, halogenated phosphinic acids, carboxylic acids, halogenated carboxylic acids, and mixtures thereof. In especially preferred embodiments, at least one of the chelating agents is fluorinated. The method provides an environmentally benign process for removing metals from metal oxides without using acids or biologically harmful solvents. The chelate and supercritical fluid can be regenerated, and the metal recovered, to provide an economic, efficient process. 4 figs

Casting of metallic fuel containing minor actinide additions

International Nuclear Information System (INIS)

Trybus, C.L.; Henslee, S.P.; Sanecki, J.E.

1992-01-01

A significant attribute of the Integral Fast Reactor (IFR) concept is the transmutation of long-lived minor actinide fission products. These isotopes require isolation for thousands of years, and if they could be removed from the waste, disposal problems would be reduced. The IFR utilizes pyroprocessing of metallic fuel to separate auranium, plutonium, and the minor actinides from nonfissionable constituents. These materials are reintroduced into the fuel and reirradiated. Spent IFR fuel is expected to contain low levels of americium, neptunium, and curium because the hard neutron spectrum should transmute these isotopes as they are produced. This opens the possibility of using an IFR to trnasmute minor actinide waste from conventional light water reactors (LWRs). A standard IFR fuel is based on the alloy U-20% Pu-10% Zr (in weight percent). A metallic fuel system eases the requirements for reprocessing methods and enables the minor actinide metals to be incorporated into the fuel with simple modifications to the basic fuel casting process. In this paper, the authors report the initial casting experience with minor actinide element addition to an IFR U-Pu-Zr metallic fuel

Synergistic extraction of actinides : Part I. Hexa-and pentavalent actinides

International Nuclear Information System (INIS)

Patil, S.K.; Ramakrishna, V.V.

1980-01-01

A detailed discussion on the reported literature on the synergistic extraction of hexa- and pentavalent actinide ions, by different combinations of extractants and from different aqueous media, is presented. Structural aspects of the various complexes involved in synergism also are reviewed. A short account of the applications based on synergistic extraction is also given. (author)

Crystal structure of actinide metals at high compression

International Nuclear Information System (INIS)

Fast, L.; Soederlind, P.

1995-08-01

The crystal structures of some light actinide metals are studied theoretically as a function of applied pressure. The first principles electronic structure theory is formulated in the framework of density functional theory, with the gradient corrected local density approximation of the exchange-correlation functional. The light actinide metals are shown to be well described as itinerant (metallic) f-electron metals and generally, they display a crystal structure which have, in agreement with previous theoretical suggestions, increasing degree of symmetry and closed-packing upon compression. The theoretical calculations agree well with available experimental data. At very high compression, the theory predicts closed-packed structures such as the fcc or the hcp structures or the nearly closed-packed bcc structure for the light actinide metals. A simple canonical band picture is presented to explain in which particular closed-packed form these metals will crystallize at ultra-high pressure

The removal of actinide metals from solution

International Nuclear Information System (INIS)

Hancock, R.D.; Howell, I.V.

1980-01-01

A process is specified for removing actinide metals (e.g. uranium) from solutions. The solution is contacted with a substrate comprising the product obtained by reacting an inorganic solid containing surface hydroxyl groups (e.g. silica gel) with a compound containing a silane grouping, a nitrogen-containing group (e.g. an amine) and other specified radicals. After treatment, the actinide metal is recovered from the substrate. (U.K.)

Basic research on solvent extraction of actinide cations with diamide compounds

Energy Technology Data Exchange (ETDEWEB)

Sasaki, Yuji [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1998-11-01

Newly synthesized 4 diamide compounds were tested for solvent extraction of actinide cations. It is obvious that N,N`-dimethyl-N,N`-dihexyl-3-oxapentanediamide (DMDHOPDA) can extract Eu(III), Th(IV), U(VI), Np(V), and Am(III) into organic solvent. Other 3 diamides hardly extract actinide ions, which is supposed that the reasons come from the difference of their chemical structures. In the synergistic extraction with a diamide and thenoyltrifluoroacetone (TTA), all diamides work as a extractant. Furthermore, by examining extracted species, it was confirmed that there are 4 kinds of chemical species of actinides with diamide and TTA. Finally, the mutual separation method of actinide (III), (IV), (V) and (VI) ions by solvent extraction using DMDHOPDA and TTA were developed. (author). 147 refs.

Nonaqueous method for dissolving lanthanide and actinide metals

International Nuclear Information System (INIS)

Crisler, L.R.

1975-01-01

Lanthanide and actinide beta-diketonate complex molecular compounds are produced by reacting a beta-diketone compound with a lanthanide or actinide element in the elemental metallic state in a mixture of carbon tetrachloride and methanol

The effect of high pressures on actinide metals

International Nuclear Information System (INIS)

Benedict, U.

1987-01-01

The solid state properties of the actinides are controlled by the dualism of the localized and itinerant (delocalized) configuration of the 5f electrons. This dualism allows to define two main subgroups. At ambient pressures the first subgroup, of elements with atomic number 91 to 94, is characterized by 5f electrons in an itinerant state and the second subgroup, atomic number 95 to 98, by 5f electrons in a localized state. The latter means that these electrons have well defined energy levels and do not contribute to the metallic bond. The other two subgroups consist of thorium, as a subgroup of its own because its 5f levels are practically unoccupied in the ground state configuration, and of the five heaviest elements with atomic number 99 to 103. The most remarkable effect of pressure on the actinide metals is that due to closer contact between the lattice atoms, localized 5f electrons can become itinerant, hybridise with the conduction electrons and participate in the metallic bond. In this chapter the high-pressure structural behaviour of actinide metals is reviewed. Section 3 gives an introduction into the techniques of generating and measuring pressure and of determining various physical properties of the actinides under pressure and describes a few high-pressure devices and methods. Sections 4 to 7 treat the high-pressure results for each subgroup separately. In section 8 the results of the preceding sections are brought together in a graphical representation which consists of interconnecting binary phase diagrams of neighbouring actinide metals. 155 refs.; 14 figs.; 7 tabs. (H.W.)

Experimental and theoretical studies on extraction of actinides and lanthanides by alicyclic H-phosphonates

Energy Technology Data Exchange (ETDEWEB)

Annam, Suresh; Sivaramakrishna, Akella; Vijayakrishna, Kari [VIT Univ., Tamil Nadu (India). Dept. of Chemistry; Gopakumar, Gopinadhanpillai; Rao, C.V.S. Brahmmananda; Sivaraman, N. [Indira Gandhi Centre for Atomic Research (IGCAR), Tamil Nadu (India). Chemistry Group

2017-06-01

Three different alicyclic substituents H-phosphonates, namely, dicyclopentyl H-phosphonate, dicyclohexyl H-phosphonate and dimenthyl H-phosphonate were synthesized and used for liquid-liquid extraction of actinide elements (U, Am and Th) and lanthanide (Gd) in n-dodecane from nitric acid medium. The physicochemical properties of the extractants, such as density, viscosity, solubility were determined. At lower acidities, these H-phosphonates exhibit higher distribution values and the extraction following cation exchange mechanism through P-OH group of tri-coordinated phosphite form. At higher acidities (2N), the extraction is primarily via solvation mechanism through P=O group of penta-coordinated phosphonate form. Amongst the three H-phosphonates, examined dimenthyl H-phosphonate showed the best results for the actinide extraction. Density functional theory (DFT) calculations were applied to understand the electronic structure of the ligands and the metal complexes. The calculated large complexation energy of UO{sub 2}(NO{sub 3}){sub 2}.@2DMnHP is in agreement with the observed trend in experimental distribution ratio data.

Mixer-settler performance evaluation in actinide extraction

International Nuclear Information System (INIS)

Camilo, R.L.; Goncalves, M.A.; Carvalho, E.I.; Nakazone, A.K.; Araujo, B.F. de; Araujo, J.A.

1988-07-01

This paper deals with four conceptions of mixer-settlers used for actinide purification and recovery. By means of the uranium concentration profiles in the organic and aqueous phases, the evaluation of each mixer-settler was made. The main purpose of this work is the data acquisition, for adapting the different contactor types to actinide recovery by liquid-liquid extraction, in the nuclear fuel cycle. (autor) [pt

Ionic liquids used in extraction and separation of metal ions

International Nuclear Information System (INIS)

Shen Xinghai; Xu Chao; Liu Xinqi; Chu Taiwei

2006-01-01

Ionic liquids as green solvents now have become a research hotspot in the field of separation of metal ions by solvent extraction. Experimental results of extraction of various metal ions with ionic liquids as solvents, including that of alkali metals, alkaline earths, transition metals rare earths and actinides are introduced. The extraction of uranium, plutonium and fission products that are involved in spent nuclear fuel reprocessing is also reviewed. The possible extraction mechanisms are discussed. Finally, the prospect of replacement of volatile and/or toxic organic solvents with environmentally benign ionic liquids for solvent extraction and the potency of applications of ionic liquids in solvent extraction are also commented. (authors)

Calix[6]arenes functionalized with malondiamides at the upper rim as possible extractants for lanthanide and actinide cations

International Nuclear Information System (INIS)

Almaraz, M.; Esperanza, S.; Magrans, O.; Mendoza, J. de; Pradus, P.

2001-01-01

Lipophilic malondiamides have been recently employed successfully as extractants for lanthanide and actinide cations from strongly acidic media. Many complexes between malondiamides and lanthanide-actinides cations have been studied by different techniques. For many of these complexes it has been observed that more than one malondiamide ligand participates in the complexation of each metallic cation. Incorporation of two or three malondiamide moieties into a calixarene platform would probably improve both extraction and selectivity with respect to the already tested malondiamides. According to CPK examination, a calix[6]arene substituted at the upper rim with two or three malondiamide moieties should constitute a promising ligand for lanthanide and actinide cations due to co-operative complexation with the malondiamides. Based on these considerations, we synthesised calix[6]arenes functionalized with malonic acid derivatives. (author)

Metal extraction by alkyl substituted diphosphonic acids. Part 1. P,P'-Di(2-ethylhexyl) methanediphosphonic acid

International Nuclear Information System (INIS)

Chiarizia, R.; Horwitz, E.P.; Rickert, P.G.; Herlinger, A.W.

1996-01-01

Two novel extractants, p,p'-di(2-ethylhexyl) methanediphosphonic acid (H 2 DEH[MDP]) and p,p'-dioctyl methanediphosphonic acid (H 2 DO[MDP]) have been synthesized at high purity and yield. H 2 DEH[MDP] was selected for metal extraction studies because of its better physical properties. An investigation of the extraction of alkaline earth cations, Fe(111) and representative tri-, tetra- and hexavalent actinide ions from nitric acid solutions into o-xylene solutions of H 2 DEH[MDP] at different concentrations was performed. With a few exceptions, the acid dependencies of the extraction of the above metal species strongly resembles those measured in the uptake of the same metals by the chelating ion exchange resin Diphonix R , which contains gem-diphosphonic acid groups chemically attached to a polymeric matrix. The almost lack of acid dependency observed with Fe(III) and tetra- and hexavalent actinides indicates that these ions are chelated by H 2 DEH[MDP] mostly through the P=O groups of the extractant. With Fe(111) and the actinides, variable slopes of the extractant dependencies were measured, their values being strongly dependent on the acidity of the aqueous phase. H 2 DEH[MDP] possesses an extraordinary affinity for actinides and Fe(111). 26 refs., 7 figs

Synergistic extraction of tetravalent actinides by mixtures of a β-diketone and a neutral donor : a review [Paper No. : IIIA-2

International Nuclear Information System (INIS)

Patil, S.K.; Ramakrishna, V.V.

1979-01-01

Synergistic extraction of metal ions by mixtures of a β-diketone and a neutral donor has been studied extensively. Due to large synergistic enhancement of extraction both the formulas of the extractable species and the adduct formation constants with various neutral donors have been ascertained. Relatively few such studies have been devoted to the extraction of tetravalent actinides and these are reviewed critically in the present paper. In addition the work on synergistic extraction of tetravelent actinides by HTTA in admixture with several neutral donors carried out at Radiochemistry Division, BARC, is included. Attempts are made to explain the observed trends in the adduct formation constants. (author)

Evaluation of a novel task specific ionic liquid for actinide ion extraction

International Nuclear Information System (INIS)

Paramanik, M.; Ghosh, S.K.; Raut, D.R.; Mohapatra, P.K.

2016-01-01

Separation of U and Pu from nuclear waste is of great relevance for a sustainable closed fuel cycle point of view. Spent fuel reprocessing by the well known PUREX process is done world wide for the recovery of U and Pu using TBP as the extractant. Room temperature ionic liquids (RTILs) have shown significantly higher extraction of metal ions, particularly at lower acidity as compared to the molecular diluents. Functionalization of ionic liquids has resulted in highly efficient task specific ionic liquids (TSILs) with superior extraction properties than the analogous extractants dissolved in ionic liquids. The present paper reports the evaluation of a novel task specific ionic liquid (TSIL) containing >P=O functional group for the extraction of actinides like U(VI) and Pu(IV)

Hydrophilic actinide complexation studied by solvent extraction radiotracer technique

International Nuclear Information System (INIS)

Rydberg, J.

1996-10-01

Actinide migration in the ground water is enhanced by the formation of water soluble complexes. It is essential to the risk analysis of a wet repository to know the concentration of central atoms and the ligands in the ground water, and the stability of complexes formed between them. Because the chemical behavior at trace concentrations often differ from that at macro concentrations, it is important to know the chemical behavior of actinides at trace concentrations in ground water. One method used for such investigations is the solvent extraction radiotracer (SXRT) technique. This report describes the SXRT technique in some detail. A particular reason for this analysis is the claim that complex formation constants obtained by SXRT are less reliable than results obtained by other techniques. It is true that several difficulties are encountered in the application of SXRT technique to actinide solution, such as redox instability, hydrophilic complexation by side reactions and sorption, but it is also shown that a careful application of the SXRT technique yields results as reliable as by any other technique. The report contains a literature survey on solvent extraction studies of actinide complexes formed in aqueous solutions, particularly by using the organic reagent thenoyltrifluoroacetone (TTA) dissolved in benzene or chloroform. Hydrolysis constants obtained by solvent extraction are listed as well as all actinide complexes studied by SX with inorganic and organic ligands. 116 refs, 11 tabs

Hydrophilic actinide complexation studied by solvent extraction radiotracer technique

Energy Technology Data Exchange (ETDEWEB)

Rydberg, J [Chalmers Univ. of Technology, Goeteborg (Sweden). Dept. of Nuclear Chemistry and Radiochemistry Consultant Group, Vaestra Froelunda (Sweden)

1996-10-01

Actinide migration in the ground water is enhanced by the formation of water soluble complexes. It is essential to the risk analysis of a wet repository to know the concentration of central atoms and the ligands in the ground water, and the stability of complexes formed between them. Because the chemical behavior at trace concentrations often differ from that at macro concentrations, it is important to know the chemical behavior of actinides at trace concentrations in ground water. One method used for such investigations is the solvent extraction radiotracer (SXRT) technique. This report describes the SXRT technique in some detail. A particular reason for this analysis is the claim that complex formation constants obtained by SXRT are less reliable than results obtained by other techniques. It is true that several difficulties are encountered in the application of SXRT technique to actinide solution, such as redox instability, hydrophilic complexation by side reactions and sorption, but it is also shown that a careful application of the SXRT technique yields results as reliable as by any other technique. The report contains a literature survey on solvent extraction studies of actinide complexes formed in aqueous solutions, particularly by using the organic reagent thenoyltrifluoroacetone (TTA) dissolved in benzene or chloroform. Hydrolysis constants obtained by solvent extraction are listed as well as all actinide complexes studied by SX with inorganic and organic ligands. 116 refs, 11 tabs.

Selective extraction of actinides from high level liquid wastes. Study of the possibilities offered by the Redox properties of actinides

International Nuclear Information System (INIS)

Adnet, J.M.

1991-07-01

Partitioning of high level liquid wastes coming from nuclear fuel reprocessing by the PUREX process, consists in the elimination of minor actinides (Np, Am, and traces of Pu and U). Among the possible processes, the selective extraction of actinides with oxidation states higher than three is studied. First part of this work deals with a preliminary step; the elimination of the ruthenium from fission products solutions using the electrovolatilization of the RuO4 compound. The second part of this work concerns the complexation and oxidation reactions of the elements U, Np, Pu and Am in presence of a compound belonging to the insaturated polyanions family: the potassium phosphotungstate. For actinide ions with oxidation state (IV) complexed with phosphotungstate anion the extraction mechanism by dioctylamine was studied and the use of a chromatographic extraction technic permitted successful separations between tetravalents actinides and trivalents actinides. Finally, in accordance with the obtained results, the basis of a separation scheme for the management of fission products solutions is proposed

Separation of trivalent actinides and lanthanides with some substituted oligopyridines and triazines in synergy with 2-bromodecanoic acid. (Presented at the International Solvent Extraction Conference, July 1999 in Barcelona)

International Nuclear Information System (INIS)

Enarsson, Aa.; Spjuth, L.; Liljenzin, J.O.; Kaellvenius, G.

2000-01-01

The separation of trivalent actinides and lanthanides with some substituted oligopyridines and triazines in synergy with 2-bromodecanoic acid was studied. All ligands, except the quinolinyl-derivatives, showed high metal extraction and good separation factors for trivalent actinides over lanthanides. The substituted di-pyridyltriazines and the quaterpyridine showed the highest distribution ratios and quater- and quinquepyridine the highest separation factors, at low nitric acid concentration. The basicity of the different ligands were determined by non-aqueous titration in acetonitrile media and was related to the metal extraction. The substituted di-pyridyltriazines, which showed the highest metal extraction also showed the lowest basicity

Extraction of actinides from chloride medium using pentaalkylpropanediamides

International Nuclear Information System (INIS)

Cuillerdier, C.; Musikas, C.

1991-01-01

Pyrometallurgical processes for the purification of plutonium create waste solutions containing actinides, mainly americium, in chloride medium. Studies have been undertaken to study the extraction of actinides in chloride medium (hydrochloric acid mixed with concentrated salts such as LiCl, CaCl 2 , MgCl 2 , KCl) using pentaalkylpropanediamides as extractants. Plutonium (IV) is very easily extracted, Am (III) needs a salting out agent such as LiCl. Back extraction of trivalent cations is easy in HCl <5M. Plutonium(IV) and (VI) can be stripped by reduction either with ascorbic acid or hydroxylammonium salts in weak acid medium. Several diluents can be used (aromatic, chlorinated or even aliphatic) with addition of decanol to prevent third phase formation. In conclusion diamides can be used for various wastes declassification, they are potentially completely incinerable, and, as the synthesis has been optimized, they appear to be promising extractants

Synthesis and Evaluation of new Polyfunctional Molecules for Group Actinide Extraction

International Nuclear Information System (INIS)

Marie, C.

2009-10-01

The aim of this project is to design new extracting molecules for spent nuclear fuel reprocessing. In order to minimize the long-term residual radiotoxicity of the waste, the GANEX process is an option based on homogeneous recycling of actinides. All actinides (U, Np, Pu, Am, Cm), present in a highly acidic aqueous solution, would be extracted together and separated from fission products (especially from lanthanides) using liquid-liquid extraction. In this context, twenty new bi-topic ligands constituted of a nitrogen poly-aromatic unit functionalized by amide groups were synthesized. Liquid-liquid extraction tests with these ligands dissolved alone in the organic phase show that N, N, N', N'-tetra-alkyl-6, 6''(2, 2':6', 2''-terpyridine)-diamides are able to selectively extract actinides at different oxidation states (Np(V et VI), U(VI), Pu(IV), Am(III), Cm(III)) from an aqueous solution 3M HNO 3 . Nevertheless, actinides(III) are poorly extracted. According to crystallographic structures of complexes with Nd(III) and U(VI) determined by X-rays diffraction, these ligands are penta-dentate. In solution (methanol), complexes stoichiometries (1:1) of Nd(III), U(VI) and Pu(IV) were determined by electro-spray ionization mass spectrometry. Stability constants, evaluated by UV-visible spectrophotometry in MeOH/H 2 O solutions, confirm the selectivity of ligands toward actinides(III) with respect to lanthanides(III). Associate to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author)

Actinide separation of high-level waste using solvent extractants on magnetic microparticles

International Nuclear Information System (INIS)

Nunez, L.; Buchholz, B.A.; Kaminski, M.; Aase, S.B.; Brown, N.R.; Vandegrift, G.F.

1994-01-01

Polymeric-coated ferromagnetic particles with an absorbed layer of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) diluted by tributyl phosphate (TBP) are being evaluated for application in the separation and the recovery of low concentrations of americium and plutonium from nuclear waste solutions. Due to their chemical nature, these extractants selectively complex americium and plutonium contaminants onto the particles, which can be recovered from the waste solution using a magnet. The effectiveness of the extractant-absorbed particles at removing transuranics (TRU) from simulated solutions and various nitric acid solutions was measured by gamma and liquid scintillation counting of plutonium and americium. The HNO 3 concentration range was 0.01 M to 6M. The partition coefficients (K d ) for various actinides at 2M HNO 3 were determined to be between 3,000 and 30,000. These values are larger than those projected for TRU recovery by traditional liquid/liquid extraction. Results from transmission electron microscopy indicated a large dependence of K d on relative magnetite location within the polymer and the polymer surface area. Energy disperse spectroscopy demonstrated homogeneous metal complexation on the polymer surface with no metal clustering. The radiolytic stability of the particles was determined by using 60 Co gamma irradiation under various conditions. The results showed that K d more strongly depends on the nitric acid dissolution rate of the magnetite than the gamma irradiation dose. Results of actinide separation from simulated high-level waste representative of that at various DOE sites are also discussed

Extraction of trivalent actinides and lanthanides from nitric acid solutions by ion flotation

International Nuclear Information System (INIS)

Mezhov, E.H.; Samatov, A.V.; Troyanovskiy, L.V.

1992-01-01

To determine whether the deep extraction of trivalent actinides from liquid active waste is feasible, the authors made a detailed investigation into the ion flotation of europium (as a simulator of americium) and americium from nitric acid solutions by using as an SAS precipitant either lauril phosphoric acid (LPA) to reprocess 0.1-0.7 M HNO 3 or diphosphine dioxides (PO) for 1-5 M HNO 3 . In all instances the extent of metal removal increases with floto-reagent expenditure. When the floto-reagent excess required for full precipitation is reached, the extraction of the metals under study is high, viz., 97-98% from 0.1 M HNO 3 with LPA and ∼75% from 3-3.5 M HNO 3 with PO per one flotation operation

Advances in Metallic Fuels for High Burnup and Actinide Transmutation

Energy Technology Data Exchange (ETDEWEB)

Hayes, S. L.; Harp, J. M.; Chichester, H. J. M.; Fielding, R. S.; Mariani, R. D.; Carmack, W. J.

2016-10-01

Research and development activities on metallic fuels in the US are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is a desire to demonstrate a multifold increase in burnup potential. A number of metallic fuel design innovations are under investigation with a view toward significantly increasing the burnup potential of metallic fuels, since higher discharge burnups equate to lower potential actinide losses during recycle. Promising innovations under investigation include: 1) lowering the fuel smeared density in order to accommodate the additional swelling expected as burnups increase, 2) utilizing an annular fuel geometry for better geometrical stability at low smeared densities, as well as the potential to eliminate the need for a sodium bond, and 3) minor alloy additions to immobilize lanthanide fission products inside the metallic fuel matrix and prevent their transport to the cladding resulting in fuel-cladding chemical interaction. This paper presents results from these efforts to advance metallic fuel technology in support of high burnup and actinide transmutation objectives. Highlights include examples of fabrication of low smeared density annular metallic fuels, experiments to identify alloy additions effective in immobilizing lanthanide fission products, and early postirradiation examinations of annular metallic fuels having low smeared densities and palladium additions for fission product immobilization.

Extraction of lanthanides and actinides (III) by DI-2 ethyl dithiophosphoric acid and DI-2 ethyl hexyl monothiophosphoric acid. Structure of the complexes in the organic phase

International Nuclear Information System (INIS)

Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

1986-09-01

To operate a trivalent actinide-lanthanide (III) group chemical separation from low pH nitric solutions we studied the extractive properties of the di-2 ethyl hexyl dithiophosphoric acid (HDEHDTP); this bidentate ligand which possesses a sulfur donor atom is a good extractant of soft acids. We so expect a better selectivity for the actinides (III) extraction. We also have investigated extractive properties of di-2 ethyl hexyl monothiophosphoric acid (HDEHTP) for trivalent actinides and lanthanides; HDEHDTP is a bidentate ligand with one oxygen donor atom and so is a better extractant for hard acids like actinides and lanthanides (III); but its selectivity is weak. The addition of TBP (tri-n butyl phosphate) to HDEHDTP deals to strong synergistic organic complexes with a great selectivity for Am(III). We explicited this phenomenon. When the metal is macroconcentrated the organic complexes aggregate and form inverted micelles

Amines as extracting agents for the quantitative determinations of actinides in biological samples

International Nuclear Information System (INIS)

Singh, N.P.

1987-01-01

The use of amines (primary, secondary and tertiary chains and quaternary ammonium salts) as extracting agents for the quantitative determination of actinides in biological samples is reviewed. Among the primary amines, only Primene JM-T is used to determine Pu in urine and bone. No one has investigated the possibility of using secondary amines to quantitatively extract actinides from biological samples. Among the tertiary amines, tri-n-octylamine, tri-iso-octylamine, tyricaprylamine (Alamine) and trilaurylamine (tridodecylamine) are used extensively to extract and separate the actinides from biological samples. Only one quaternary ammonium salt, methyltricapryl ammonium chloride (Aliquat-336), is used to extract Pu from biological samples. (author) 28 refs

Liquid-solid extraction of metallic cations by cationic amphiphiles

International Nuclear Information System (INIS)

Mueller, Wolfram; Sievers, Torsten K.; Zemb, Thomas; Diat, Olivier; Sievers, Torsten K.; Dejugnat, Christophe

2012-01-01

In the field of selective metal ion separation, liquid-liquid extraction is usually conducted through an emulsion mixing of hydrophobic complexants dispersed in an organic phase and acidic water containing the ionic species. Recently, it has been shown that amphiphilic complexants could influence strongly extraction efficiency by enhancing the interfacial interaction between the metal ion in the aqueous and the complexant in the organic phase. Moreover, these amphiphiles can also substitute the organic phase if an appropriate aliphatic chain is chosen. The dispersion of such amphiphilic complexants in an aqueous solution of salt mixtures is not only attractive for studying specific interactions but also to better the understanding of complex formation in aqueous solution of multivalent metal ions, such as lanthanides and actinides. This understanding is of potential interest for a broad range of industries including purification of rare earth metals and pollute treatment e.g. of fission byproducts. This principle can also be applied to liquid-solid extraction, where the final state of the separation is a solid phase containing the selectively extracted ions. Indeed, a novel solid-liquid extraction method exploits the selective precipitation of metal ions from an aqueous salt mixture using a cationic surfactant, below its Krafft point (temperature below which the long aliphatic chains of surfactant crystallize). This technique has been proven to be highly efficient for the separation of actinides and heavy metal using long chain ammonium or pyridinium amphiphiles. The most important point in this process is the recognition of cationic metal ions by cationic surfactants. By computing the free energy of the polar head group per micelle as a function of the different counter-anions, we have demonstrated for the first time that different interactions exist between the micellar surface and the ions. These interactions depend on the nature of the cation but also on

Development of Metallic Fuels for Actinide Transmutation

Energy Technology Data Exchange (ETDEWEB)

Hayes, Steven Lowe [Idaho National Laboratory; Fielding, Randall Sidney [Idaho National Laboratory; Benson, Michael Timothy [Idaho National Laboratory; Chichester, Heather Jean MacLean [Idaho National Laboratory; Carmack, William Jonathan [Idaho National Laboratory

2015-09-01

Research and development activities on metallic fuels are focused on their potential use for actinide transmutation in future sodium fast reactors. As part of this application, there is also a need for a near zero-loss fabrication process and a desire to demonstrate a multifold increase in burnup potential. The incorporation of Am and Np into the traditional U-20Pu-10Zr metallic fuel alloy was demonstrated in the US during the Integral Fast Reactor Program of the 1980’s and early 1990’s. However, the conventional counter gravity injection casting method performed under vacuum, previously used to fabricate these metallic fuel alloys, was not optimized for mitigating loss of the volatile Am constituent in the casting charge; as a result, approximately 40% of the Am casting charge failed to be incorporated into the as-cast fuel alloys. Fabrication development efforts of the past few years have pursued an optimized bottom-pour casting method to increase utilization of the melted charge to near 100%, and a differential pressure casting approach, performed under an argon overpressure, has been demonstrated to result in essentially no loss of Am due to volatilization during fabrication. In short, a path toward zero-loss fabrication of metallic fuels including minor actinides has been shown to be feasible. Irradiation testing of advanced metallic fuel alloys in the Advanced Test Reactor (ATR) has been underway since 2003. Testing in the ATR is performed inside of cadmium-shrouded positions to remove >99% of the thermal flux incident on the test fuels, resulting in an epi-thermal driven fuel test that is free from gross flux depression and producing an essentially prototypic radial temperature profile inside the fuel rodlets. To date, three irradiation test series (AFC-1,2,3) have been completed. Over 20 different metallic fuel alloys have been tested to burnups as high as 30% with constituent compositions of Pu up to 30%, Am up to 12%, Np up to 10%, and Zr between 10

Demonstration of pyropartitioning process by using genuine high-level liquid waste. Reductive-extraction of actinide elements from chlorination product

International Nuclear Information System (INIS)

Uozumi, Koichi; Iizuka, Masatoshi; Kurata, Masaki; Ougier, Michel; Malmbeck, Rikard; Winckel, Stefaan van

2009-01-01

The pyropartitioning process separates the minor actinide elements (MAs) together with uranium and plutonium from the high-level liquid waste generated at the Purex reprocessing of spent LWR fuel and introduces them to metallic fuel cycle. For the demonstration of this technology, a series experiment using 520g of genuine high-level liquid waste was started and the conversion of actinide elements to their chlorides was already demonstrated by denitration and chlorination. In the present study, a reductive extraction experiment in molten salt/liquid cadmium system to recover actinide elements from the chlorination product of the genuine high-level liquid waste was performed. The results of the experiment are as following; 1) By the addition of the cadmium-lithium alloy reductant, almost all of plutonium and MAs in the initial high-level liquid waste were recovered in the cadmium phase. It means no mass loss during denitration, chlorination, and reductive-extraction. 2) The separation factor values of plutonium, MAs, and rare-earth fission product elements versus uranium agreed with the literature values. Therefore, actinide elements will be separated from fission product elements in the actual system. Hence, the pyropartitioning process was successfully demonstrated. (author)

Extraction of actinide and lanthanide complexonates in two-phase aqueous system potassium carbonate-polyethylene glycol-water

International Nuclear Information System (INIS)

Molochnikova, N.P.; Shkinev, V.M.; Spivakov, B.Ya.; Zolotov, Yu.A.; Myasoedov, B.F.

1988-01-01

Extraction system on the basis of polyethylene glycol for the concentration, isolation and separation of actinides is suggested. Extraction of actinides and lanthanides in two-phase aqueous system: potassium carbonate - polyethylene glycol - water in the presence of different complexones is investigated. Trivalent actinides are extracted quantitatively by polyethylene glycol from potassium carbonate solutions in the system with xylenol orange and alizarin-complexone. Under the conditions uranium (6) and plutonium (4) are extracted into the phase, enriched by polyethylene glycol, quite insignificantly, which permits to separate them from trivalent actinides with the separation factor of 10 2 - 10 3 . For actinide and lanthanide separation two complexones were introduced into the system, one of them being extractant, the other one - camouflaging reactant. The best results are obtained for the mixture of xylenol orange and hydroxyethylenediphosphonic acid. Separation coefficients for americium and europium constitute 4.5 - 5.6

Sequestering agents for the removal of actinides from waste streams

Energy Technology Data Exchange (ETDEWEB)

Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R. [Univ. of California, Berkeley, CA (United States)

1997-10-01

The goal of this project is to take a biomimetic approach toward developing new separation technologies for the removal of radioactive elements from contaminated DOE sites. To achieve this objective, the authors are investigating the fundamental chemistry of naturally occurring, highly specific metal ion sequestering agents and developing them into liquid/liquid and solid supported actinide extraction agents. Nature produces sideophores (e.g., Enterobactin and Desferrioxamine B) to selectivity sequester Lewis acidic metal ions, in particular Fe(III), from its surroundings. These chelating agents typically use multiple catechols or hydroxamic acids to form polydentate ligands that chelate the metal ion forming very stable complexes. The authors are investigating and developing analogous molecules into selective chelators targeting actinide(IV) ions, which display similar properties to Fe(III). By taking advantage of differences in charge, preferred coordination number, and pH stability range, the transition from nature to actinide sequestering agents has been applied to the development of new and highly selective actinide extraction technologies. Additionally, the authors have shown that these chelating ligands are versatile ligands for chelating U(VI). In particular, they have been studying their coordination chemistry and fundamental interactions with the uranyl ion [UO{sub 2}]{sup 2+}, the dominant form of uranium found in aqueous media. With an understanding of this chemistry, and results obtained from in vivo uranium sequestration studies, it should be possible to apply these actinide(IV) extraction technologies to the development of new extraction agents for the removal of uranium from waste streams.

Selective solvent extraction of actinides associated to liquid scintillation measurements

International Nuclear Information System (INIS)

Ardois, C.; Musikas, C.

1997-01-01

The problems associated to radioactive waste disposal have acquired a special attention due, particularly, to the element instability and, consequently, to their lixiviation and to their peculiarities which are essential in the radioactivity penetration in the food chains; the other important parameters are the produced amounts and the noxiousnesses. New commercial liquid scintillation counters allow rapid α/β measurements. Associated with liquid-liquid extraction techniques, rapid and selective actinide analyses are possible. Among various actinide extractants, such as amines or organophosphorus compounds, we were particularly interested in tri-n-octyl-phosphine oxide (TOPO). Uranium, thorium and americium extractions with (TOPO) in toluene have been investigated. A systematic study of the counting parameters of a PACKARD 2550 TR/AB TM liquid scintillation analyzer is under completion

Some new developments in actinide solvent extraction systems

International Nuclear Information System (INIS)

Navratil, J.D.

1988-01-01

Consideration is given to application of neutral and acid organophosphoric compounds, adsorbed on various natural and synthetic carriers, in extraction chromatography for separation and isolation of actinides. It is shown that trioctylphosphine oxide (TOPO) on a solid combustible carrier represents the promising material for plutonium extraction. It was established experimentally that polyurethane foam possessed the maximal capacity with respect to TOPO; extractant losses at that after passing of 50 column volumes of nitric acid don't exceed 2 %

Co-deposition of metallic actinides on a solid cathode

Energy Technology Data Exchange (ETDEWEB)

Limmer, S. J.; Williamson, M. A.; Willit, J. L. [Argonne National Laboratory, Argonne (United States)

2008-08-15

The amount of rare earth contamination that will be found in a co-deposit of actinides is a function of the type of cathode used. A non-alloying solid cathode will result in a significantly lower rare earth contamination in the actinide co-deposit than a liquid cadmium cathode. With proper control of the cathode potential vs. a stable reference electrode, co-deposition of uranium with other more electroactive metals has been demonstrated using a non-alloying solid cathode.

Co-deposition of metallic actinides on a solid cathode

International Nuclear Information System (INIS)

Limmer, S. J.; Williamson, M. A.; Willit, J. L.

2008-01-01

The amount of rare earth contamination that will be found in a co-deposit of actinides is a function of the type of cathode used. A non-alloying solid cathode will result in a significantly lower rare earth contamination in the actinide co-deposit than a liquid cadmium cathode. With proper control of the cathode potential vs. a stable reference electrode, co-deposition of uranium with other more electroactive metals has been demonstrated using a non-alloying solid cathode

Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

International Nuclear Information System (INIS)

Wietzke, Raphael

1999-01-01

This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

Protactinium and the intersection of actinide and transition metal chemistry

Energy Technology Data Exchange (ETDEWEB)

Wilson, Richard E.; De Sio, Stephanie; Vallet, Valérie

2018-02-12

The role of the 5f and 6d orbitals in the chemistry of the actinide elements has been of considerable interest since their discovery and synthesis. Relativistic effects cause the energetics of the 5f and 6d orbitals to change as the actinide series is traversed left to right imparting a rich and complex chemistry. The 5f and 6d atomic states cross in energy at protactinium (Pa), making it a potential intersection between transition metal and actinide chemistries. Herein, we report the synthesis of a Pa-peroxo cluster, A(6)(Pa4O(O-2)(6)F-12) [A = Rb, Cs, (CH3)(4)N], formed in pursuit of an actinide polyoxometalate. Quantum chemical calculations at the density functional theory level demonstrate equal 5f and 6d orbital participation in the chemistry of Pa and increasing 5f orbital participation for the heavier actinides. Periodic changes in orbital character to the bonding in the early actinides highlights the influence of the 5f orbitals in their reactivity and chemical structure.

Separation and preconcentration of actinides from acidic media by extraction chromatography

International Nuclear Information System (INIS)

Horwitz, E. Philip; Chiarizia, Renato; Dietz, Mark L.; Diamond, Herbert; Nelson, Donald M.

1993-01-01

A systematic examination of the effect of nitric and hydrochloric acid concentrations and of macro levels of selected elements on the sorption of actinide ions by a novel extraction chromatographic resin comprised of a solution of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide in tri-n-butyl phosphate supported on an inert polymeric substrate is described. Actinide sorption is demonstrated to be most efficient at high (>1 M) nitric acid concentrations, although tetra- and hexavalent actinides are strongly retained even from dilute (e.g., 0.05 M) nitric acid solutions. Macro concentrations of several common anions (e.g., PO 4 3- and SO 4 2- ) or complexing agents (e.g., oxalic acid) are shown not to adversely affect the sorption of trivalent actinides, while reducing the sorption of tetravalents. Such effects, together with oxidation state adjustments, are shown to provide a basis for the sequential elution of individual actinides and for actinide isolation from environmental and biological matrices

Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

Energy Technology Data Exchange (ETDEWEB)

Akhila Maheswari, M.; Subramanian, M.S. [Department of Chemistry, Indian Institute of Technology, Chennai (India)

2005-02-15

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using {sup 13}C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physico-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg{sup -1} for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO{sub 3} medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t{sub 1/2} values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30{mu}gL{sup -1}. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

Comparative synergistic (technetium-actinide) extraction chemistry by tributylphosphate and some amide extractants

International Nuclear Information System (INIS)

Condamines, N.; Musikas, C.

1993-01-01

In nuclear fuel reprocessing, technetium (TcO 4 - ) leads to bad interferences in the extractions, being synergistically co-extracted with different actinide cations as Uranium (VI), Plutonium (IV) and Zirconium (IV). It destroys the hydrazine in the reductive partition of U and Pu, it decreases the decontamination of U and Pu from fission products. Thus, its extraction behaviour with new extractants as N,N-diakylamides is useful to be known. TcO 4 - extraction in nitric acid media is compared for TBP and different amides. The influence of nitric acidity is related to the amides formula

Investigations on synthesis, coordination behaviour and actinide recovery of unexplored phosphine oxides

International Nuclear Information System (INIS)

Veerashekhar Goud, E.; Pavankumar, B.B.; Das, Dhrubajyothi

2016-01-01

The search for the development of an optimum extractant for effective separation of a particular metal from a mixture is an active field of research in both chemistry and chemical engineering. These extractants find extensive application in extractive metallurgy and in nuclear fuel cycle (for the separation of actinides from other fission products). In the case of the latter, solvent extraction and ion exchange are two widely employed separation techniques. In this connection, the present paper reports synthesis and structural characterization of various new phosphine oxide derivatives. The coordination behavior of these ligands is studied with some selected lanthanides and actinides shows the proposed structures of La(III) and Th(IV) metal complexes. The purity and structural characterization of the ligands and their corresponding metal complexes are analyzed by various analytical and spectroscopic techniques. Additionally, we have applied Density functional theory (DFT) calculations to understand the electronic structure of some metal complexes formed during the extraction process. (author)

Synthesis and evaluation structure/extracting and complexing properties of new bi-topic ligands for group actinides extraction

International Nuclear Information System (INIS)

Bisson, J.

2011-01-01

The aim of this project is to design and study new extractants for spent nuclear fuel reprocessing. To decrease the long-term radiotoxicity of the waste, the GANEX process is an option to homogeneously recycle actinides. All actinides (U, Np, Pu, Am, Cm) would be extracted together from a highly acidic media and separated from fission products (especially from lanthanides). In this context, fourteen new bi-topic ligands constituted of a nitrogen poly-aromatic unit from the dipyridyl-phenanthroline and dipyridyl-1,3,5-triazine families and functionalized by amid groups were synthesized. Extraction studies performed with some of these ligands confirmed their interest to selectively separate actinides at different oxidation states from an aqueous solution 3M HNO 3 . To determine the influence of ligands structure on cation complexation, a study in a homogenous media (MeOH/H 2 O) has been carried out. Electro-spray ionization mass spectrometry have been used to characterize the complexes stoichiometries formed with several cations (Eu 3+ , Nd 3+ , Am 3+ , Pu 4+ and NpO 2 + ). Stability constants, evaluated by UV-Visible spectrophotometry, confirm the selectivity of these ligands toward actinides. Lanthanides and actinides complexes have also been characterized in the solid state by infra-red spectroscopy and X-Ray diffraction. Associated to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author) [fr

Actinides-lanthanides (neodymium) separation by electrolytical extraction in molten fluoride media; Separation actinides-lanthanides (neodyne) par extraction electrolytique en milieux fluorures fondus

Energy Technology Data Exchange (ETDEWEB)

Hamel, C

2005-02-15

The aim of this thesis is to assess the potentialities of pyrochemical processes for futur nuclear fuels and Generation IV reactors (more particularly molten salt reactors). This study concerns the Actinides-Lanthanides and Lanthanides-Solvent separation by electrolytical extraction in molten fluoride media at high temperature. Three elements are selected for this study: neodymium (NdF{sub 3}), uranium (UF{sub 4}) and plutonium (PuF{sub 3}). Firstly, the electrochemical study of these three compounds in molten fluoride media is performed to evaluate the separations. Electrodeposition processes are studied and the values of formal potentials of U(III)/U(0), Pu(III)/Pu(0) and Nd(III)/Nd(0) are obtained in LiF-CaF{sub 2} eutectic mixture. Thermodynamically, the values of potentials differences are enough to separate U-Nd and Pu-Nd with a yield of extraction of 99.99%; this value is just sufficient for the Pu-Nd separation. Concerning the Nd-solvent separation this potential difference is too small. Next, the electrodeposition of solid metals on inert electrodes is performed. This study showed that the uranium and neodymium deposits are unstable in several fluoride media. In addition, the presence of salts in the dendritic metal is observed for the U solid deposits. Finally, a reactive cathode is used to improve these separation results and the shape of the deposits. The experimental results on nickel electrodes showed an improvement of the Pu-Nd separation and the Nd-solvent separation with the depolarisation phenomenon of the metal deposit on the nickel. Moreover, U and Nd metal are stabilized in the alloy which allows the elimination of reactions with the solvent as observed for the solid deposit. The formation of liquids alloys makes also easier the recovery of these three. (author)

Actinides-lanthanides (neodymium) separation by electrolytic extraction in molten fluoride media; Separation actinides-lanthanides (neodyne) par extraction electrolytique en milieux fluorures fondus

Energy Technology Data Exchange (ETDEWEB)

Hamel, C

2005-02-15

The aim of this thesis is to assess the potentialities of pyrochemical processes for future nuclear fuels and Generation IV reactors (more particularly molten salt reactors). This study concerns the Actinides-Lanthanides and Lanthanides-Solvent separation by electrolytic extraction in molten fluoride media at high temperature. Three elements are selected for this study: neodymium (NdF{sub 3}), uranium (UF{sub 4}) and plutonium (PuF{sub 3}). Firstly, the electrochemical study of these three compounds in molten fluoride media is performed to evaluate the separations. Electrodeposition processes are studied and the values of formal potentials of U(III)/U(0), Pu(III)/Pu(0) and Nd(III)/Nd(0) are obtained in LiF-CaF{sub 2} eutectic mixture. Thermodynamically, the values of potentials differences are enough to separate U-Nd and Pu-Nd with a yield of extraction of 99.99%; this value is just sufficient for the Pu-Nd separation. Concerning the Nd-solvent separation this potential difference is too small. Next, the electrodeposition of solid metals on inert electrodes is performed. This study showed that the uranium and neodymium deposits are unstable in several fluoride media. In addition, the presence of salts in the dendritic metal is observed for the U solid deposits. Finally, a reactive cathode is used to improve these separation results and the shape of the deposits. The experimental results on nickel electrodes showed an improvement of the Pu-Nd separation and the Nd-solvent separation with the depolarization phenomenon of the metal deposit on the nickel. Moreover, U and Nd metal are stabilized in the alloy which allows the elimination of reactions with the solvent as observed for the solid deposit. The formation of liquids alloys makes also easier the recovery of these three. (author)

Actinide metals

Energy Technology Data Exchange (ETDEWEB)

Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

2016-07-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO{sub 2}OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH{sup 2+} for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Actinide metals

International Nuclear Information System (INIS)

Brown, Paul L.; Ekberg, Christian

2016-01-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO 2 OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH 2+ for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Room temperature ionic liquids for actinide extraction: a 'green' approach?

International Nuclear Information System (INIS)

Mohapatra, P.K.

2013-01-01

Extraction of actinides is one of the key issues in the remediation of high level radioactive wastes emanating from the back end of the nuclear fuel cycle. Effective actinide extraction makes the waste benign and ready for disposal as vitrified waste blocks in deep geological repositories. However, conventional solvent extraction methods, though being routinely used for actinide separations, have several disadvantages, which include large VOC (volatile organic compounds) inventory and generation of huge volumes of secondary wastes. Growing concern for the environment has led to the increasing interest in room temperature ionic liquids (RTIL) as an alternative to molecular diluents in myriad applications including synthesis, catalysis, separation and electrochemistry. Out of these, application of RTILs to separation science has increased enormously as can be seen from the rapid rise in the number of publications in this area in the last decade, due to their unique characteristics of high thermal stability and low volatility

Extraction of tetravalent and hexavalent actinide ions by tetraheptylammonium nitrate

International Nuclear Information System (INIS)

Swarup, Rajendra; Patil, S.K.

1977-01-01

Extraction of Th(IV), Np(IV), Pu(IV), U(VI), Np(VI), and Pu(VI) by tetraheptylammonium nitrate in Solvesso-100 has been studied from nitric acid medium. Attempts were made to identify the complex species in the organic phase by studying the dependence of the distribution coefficient of the actinide on amine concentration and taking the absorption spectra of the organic phase containing actinide ions. A compound tetraheptylammonium trinitratodioxouranate (VI) has been isolated and characterised. (author)

Calculation of binary phase diagrams between the actinide elements, rare earth elements, and transition metal elements

International Nuclear Information System (INIS)

Selle, J.E.

1992-01-01

Attempts were made to apply the Kaufman method of calculating binary phase diagrams to the calculation of binary phase diagrams between the rare earths, actinides, and the refractory transition metals. Difficulties were encountered in applying the method to the rare earths and actinides, and modifications were necessary to provide accurate representation of known diagrams. To calculate the interaction parameters for rare earth-rare earth diagrams, it was necessary to use the atomic volumes for each of the phases: liquid, body-centered cubic, hexagonal close-packed, and face-centered cubic. Determination of the atomic volumes of each of these phases for each element is discussed in detail. In some cases, empirical means were necessary. Results are presented on the calculation of rare earth-rare earth, rare earth-actinide, and actinide-actinide diagrams. For rare earth-refractory transition metal diagrams and actinide-refractory transition metal diagrams, empirical means were required to develop values for the enthalpy of vaporization for rare earth elements and values for the constant (C) required when intermediate phases are present. Results of using the values determined for each element are presented

Ten years of experience in extraction chromatographic processes for the recovery, separation and purification of actinides elements

International Nuclear Information System (INIS)

Madic, C.; Bourges, J.; Koehly, G.

1984-06-01

Ten years ago the extraction chromatographic technique was developed for preparative purposes and is now applied for all chemicals separations needed for the production of actinides isotopes. That technique appears to be simple and flexible. It can be used for the production of microgram to kilogram amounts of actinide isotopes. This paper focuses on the experience gained and describes some peculiar production of actinide isotopes solved by using extraction chromatographic technique. After a review of extracting molecules and equipment, treatment of irradiated targets (preparation of Pu 238 and removal of neptunium, production of Am 243 and Cm 244), recovery of actinides from alpha aqueous wastes (preparation of Am 241) and recovery of decay products from aged actinide stocks (recovery of Am 241 from Pu stocks, of U 234 from Pu 238 stocks) are described

High-performance separation and supercritical extraction of lanthanides and actinides

International Nuclear Information System (INIS)

Datta, Arpita; Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2010-01-01

Extensive studies were carried out at Chemistry Group, IGCAR for the rapid separation of individual lanthanides and actinides using dynamic ion-exchange chromatographic technique. The atom percent fission was determined from the concentrations of the lanthanide fission products, uranium and plutonium contents of dissolver solution. These advantages were exploited to significantly reduce analysis time, liquid waste generation as well as dose to operator. Supercritical fluid extraction (SFE) of actinides from waste matrices was studied in detail at our laboratory using modified supercritical carbon dioxide (Sc-CO 2 ). Complete extraction and recovery of uranium, plutonium and americium from various matrices was achieved using Sc-CO 2 modified with suitable ligands. The technique was demonstrated for the recovery of plutonium from actual waste received from different laboratories. (author)

Separation of actinide elements by solvent extraction using centrifugal contactors in the NEXT process

International Nuclear Information System (INIS)

Nakahara, Masaumi; Sano, Yuichi; Koma, Yoshikazu; Kamiya, Masayoshi; Shibata, Atsuhiro; Koizumi, Tsutomu; Koyama, Tomozo

2007-01-01

Using the advanced aqueous reprocessing system named NEXT process, actinides recovery was attempted by both a simplified solvent extraction process using TBP as an extractant for U, Pu and Np co-recovery and the SETFICS process for Am and Cm recovery from the raffinate. In U, Pu and Np co-recovery experiments a single cycle flow sheet was used under high nitric acid concentration in the feed solution or scrubbing solution. High nitric acid concentration in the feed solution aided Np oxidation not only in the feed solution, but also at the extraction section. This oxidation reaction accomplished Np extraction by TBP with U and Pu. Most of Np could be recovered into the product solution. In the SETFICS process, a TRUEX solvent of 0.2 mol/dm 3 CMPO and 1.4 mol/dm 3 TBP in n-dodecane was employed instead of 0.2 mol/dm 3 CMPO and 1.0 mol/dm 3 TBP in n-dodecane in order to increase the loading of metals. Instead of sodium nitrate, hydroxylamine nitrate was applied to this experimental flow sheet in accordance with a 'salt-free' concept. The counter current experiment succeeded with the Am and Cm product. On the high-loading flow sheet, compared with the previous flow sheet, the flow of the aqueous effluents and spent solvent were expected to decrease by about one half. Two solvent extraction experiments for actinides recovery demonstrated the utility of the flow sheet of these processes in the NEXT process. (author)

Synthesis of selective extractor for minor actinide elements

Energy Technology Data Exchange (ETDEWEB)

Kim, Jong Seung [Konyang University, Nonsan (Korea); Cho, Moon Hwan [Kangwon National University, Chunchon (Korea)

1998-04-01

To selectively co-separate the lanthanide and actinide elements (MA) such as Am or Cm ion from radioactive waste, synthesis of diamide derivatives has been accomplished. In addition, picoline amide derivatives were also synthesized for selectively separate the minor actinide elements from lanthanide elements. The content of research has don are as follows: (1) synthesis of diamide as co-extractant (2) introduction of n-tetradecyl to increase the lipophilicity (3) Picolyl chloride, intermediate of the final product, was synthesized by improved method rather than reported method. (4) The length of alkyl side chain was adjusted to increase the lipophilicity of free ligand and its derivatives able to selectively separate the actinide metal from lanthanide metal ions was successfully synthesized and determined their purity by analytical instruments. (author). 12 refs., 28 figs.

Evaluation of extractants and chelating resins in polishing actinide-contaminated waste streams

International Nuclear Information System (INIS)

Schreiber, S.B.; Dunn, S.L.; Yarbro, S.L.

1991-06-01

At the Los Alamos National Laboratory Plutonium Facility, anion exchange is used for recovering plutonium from nitric acid solutions. Although this approach recovers >99%, the trace amounts of plutonium and other actinides remaining in the effluent require additional processing. We are doing research to develop a secondary unit operation that can directly polish the effluent so that actinide levels are reduced to below the maximum allowed for facility discharge. We selected solvent extraction, the only unit operation that can meet the stringent process requirements imposed; several carbonyl and phosphoryl extractants were evaluated and their performance characterized. We also investigated various engineering approaches for solvent extraction; the most promising was a chelating resin loaded with extractant. Our research now focuses on the synthesis of malonamides, and our goal is to bond these extractants to a resin matrix. 7 refs., 12 figs., 1 tab

Design, synthesis, and evaluation of polyhydroxamate chelators for selective complexation of actinides

International Nuclear Information System (INIS)

Gopalan, A.; Jacobs, H.; Koshti, N.; Stark, P.; Huber, V.; Dasaradhi, L.; Caswell, W.; Smith, P.; Jarvinen, G.

1995-01-01

Specific chelating polymers targeted for actinides have much relevance to problems involving remediation of nuclear waste. Goal is to develop polymer supported, ion specific extraction systems for removing actinides and other hazardous metal ions from wastewaters. This is part of an effort to develop chelators for removing actinide ions such as Pu from soils and waste streams. Selected ligands are being attached to polymeric backbones to create novel chelating polymers. These polymers and other water soluble and insoluble polymers have been synthesized and are being evaluated for ability to selectively remove target metal ions from process waste streams

Extraction of Trivalent Actinides and Lanthanides from Californium Campaign Rework Solution Using TODGA-based Solvent Extraction System

Energy Technology Data Exchange (ETDEWEB)

Benker, Dennis [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Delmau, Laetitia Helene [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Dryman, Joshua Cory [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2017-07-01

This report presents the studies carried out to demonstrate the possibility of quantitatively extracting trivalent actinides and lanthanides from highly acidic solutions using a neutral ligand-based solvent extraction system. These studies stemmed from the perceived advantage of such systems over cationexchange- based solvent extraction systems that require an extensive feed adjustment to make a low-acid feed. The targeted feed solutions are highly acidic aqueous phases obtained after the dissolution of curium targets during a californium (Cf) campaign. Results obtained with actual Cf campaign solutions, but highly diluted to be manageable in a glove box, are presented, followed by results of tests run in the hot cells with Cf campaign rework solutions. It was demonstrated that a solvent extraction system based on the tetraoctyl diglycolamide molecule is capable of quantitatively extracting trivalent actinides from highly acidic solutions. This system was validated using actual feeds from a Cf campaign.

Removal of actinides from nuclear fuel reprocessing waste solutions with bidentate organophosphorus extractants

International Nuclear Information System (INIS)

Schulz, W.W.; McIsaac, L.D.

1975-08-01

The neutral bidentate organophosphorus reagents DBDECMP (dibutyl-N,N-diethylcarbamylmethylenephosphonate) and its dihexyl analogue DHDECMP are candidate extractants for removal of actinides from certain acidic waste streams produced at the U. S. ERDA Hanford and Idaho Falls sites. Various chemical and physical properties including availability, cost, purification, alpha radiolysis, and aqueous phase solubility of DBDECMP and DHDECMP are reviewed. A conceptual flowsheet employing a 15 percent DBDECMP (or DHDECMP)--CCl 4 extractant for removal (and recovery) of Am and Pu from Hanford's Plutonium Reclamation Facility acid waste stream (CAW solution) was successfully demonstrated in laboratory-scale mixer-settler tests; this extraction scheme can be used to produce an actinide-free waste. A 30 percent DBDECMP-xylene flowsheet is being tested at the Idaho Falls site for removal of U, Np, Pu, and Am from Idaho Chemical Processing Plant first-cycle high-level raffinate to produce an actinide-free (less than 10 nCi alpha activity/gram) waste. (auth)

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides

International Nuclear Information System (INIS)

Condamines, N.

1990-03-01

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO 3 , UO 2 2+ , Pu 4+ , Th 4+ are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO 3 )L 2 , (HNO 3 )L, (HNO 3 ) 2 L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing [fr

Minor actinide transmutation using minor actinide burner reactors

International Nuclear Information System (INIS)

Mukaiyama, T.; Yoshida, H.; Gunji, Y.

1991-01-01

The concept of minor actinide burner reactor is proposed as an efficient way to transmute long-lived minor actinides in order to ease the burden of high-level radioactive waste disposal problem. Conceptual design study of minor actinide burner reactors was performed to obtain a reactor model with very hard neutron spectrum and very high neutron flux in which minor actinides can be fissioned efficiently. Two models of burner reactors were obtained, one with metal fuel core and the other with particle fuel core. Minor actinide transmutation by the actinide burner reactors is compared with that by power reactors from both the reactor physics and fuel cycle facilities view point. (author)

Lanthanides and actinides extraction by calixarenes containing CMPO groups

International Nuclear Information System (INIS)

Garcia Carrera, A.

2001-01-01

In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

Elastic-constant systematics in f.c.c. metals, including lanthanides-actinides

Energy Technology Data Exchange (ETDEWEB)

Ledbetter, Hassel [Mechanical Engineering Department, University of Colorado, Boulder, Colorado 80309 (United States); Migliori, Albert [Los Alamos National Laboratory (E536), Los Alamos, New Mexico 87545 (United States)

2008-01-15

For f.c.c. metals, using Blackman's diagram of dimensionless elastic-constant ratios, we consider the systematics of physical properties and interatomic bonding. We focus especially on the lanthanides-actinides La, Ce, Yb, Th, U, Pu, those for which we know some monocrystal elastic constants. Their behavior differs from the other f.c.c. metals, and all except La show a negative Cauchy pressure, contrary to most f.c.c. metals, which show a positive Cauchy pressure. Among the lanthanides-actinides, {delta}-Pu stands apart, consistent with its many odd physical properties. Based on elastic-constant correlations, we suggest that {delta}-Pu possesses a strong s-electron interatomic-bonding component together with a covalent component. Elastically, {delta}-Pu shows properties similar to Yb. (copyright 2008 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

Lanthanides and actinides extraction by calixarenes containing CMPO groups; Extraction des lanthanides et des actinides au moyen de calixarenes portant des groupements CMPO

Energy Technology Data Exchange (ETDEWEB)

Garcia Carrera, A

2001-07-01

In the framework of the French program SPIN concerning the radioactive waste management, researches are performed to develop processes allowing the separation of long-lived radioisotopes in order to their transmutation or their specific conditioning. These studies deal with the extraction and the separation of trivalent lanthanides and actinides in acid solution. Many systems ''calixarene-diluent-aqueous phase'' are examined by extraction liquid-liquid and membrane transport. The extraction efficiency and the selectivity of the synthesized calixarene-CMPO and of the CMPO are compared with these cations, as the nitric acid extraction by these molecules. (A.L.B.)

A contribution to the study of the extraction of mineral acids and of actinide (IV) and (VI) cations by N,N-dialkylamides; Contribution a l'etude de l'extraction d'acides mineraux et de cations actinides aux degres d'oxydation (IV) et (VI) par des N,N-dialkylamides

Energy Technology Data Exchange (ETDEWEB)

Condamines, N

1990-03-15

N,N-dialkylamides are alternate extractants to tributylphosphate, TBP, for the actinides separation in nuclear fuel reprocessing. N,N-di (2-ethyl hexyl) butyramide and N,N-di (2 ethyl hexyl) isobutyramide are selected for their sufficient extraction and partition ability towards actinides (IV) and (VI) without coextracting fission products. Mechanisms of HNO{sub 3}, UO{sub 2}{sup 2+}, Pu{sup 4+}, Th{sup 4+} are investigated. Nitric acid extraction is due to the competitive formation of the species (HNO{sub 3})L{sub 2}, (HNO{sub 3})L, (HNO{sub 3}){sub 2}L (L: DOBA or DOiBA). An hydrogen bond is the driving force of the transfer. For low acidity media, amides are neutral extractants. Physical interactions, between free ligand and metallic complex, arise for high amide concentrations. Taking into account the non-ideality of the organic medium by a hard spheres mixture model, we estimate that such interactions are far from negligible and very specific to the amide group. Unlike TBP, when increasing acidity, amides behave as anionic extractants. DOBA and DOiBA appear to be satisfactory extractants for fuel reprocessing.

Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides; Separation par extraction liquide-liquide des actinides(III) des lanthanides(III) par de nouvelles molecules: les picolinamides

Energy Technology Data Exchange (ETDEWEB)

Cordier, P Y [CEA Marcoule, Departement de Recherche en Retraitement et en Vitrification, 30 - Bagnols-sur-Ceze (France); [Clermont-Ferrand-2 Univ., 63 - Aubiere (France)

1996-07-01

In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author) 105 refs.

Removal of actinides from high activity wastes by solvent extraction: outline of the research work at Ispra J.R.C. laboratories

International Nuclear Information System (INIS)

Mannone, F.

1976-07-01

The development of an advanced waste management alternative such as the actinide nuclear incineration requires an almost quantitative removal of actinides from waste streams. Within the framework of the Ispra JRC Waste Disposal R and D programme, actinide separation studies were directed towards solvent extraction and precipitation methods. To develop a tentative waste partitioning flow-sheet based on solvent extraction, two conceptual process flow-sheet for actinide removal were evaluated on the basis of the currently used actinide recovery processes, i.e. removal after waste adjustment to low-acidity conditions and direct actinide removal from acidic wastes, as they are generated in actual reprocessing plants. No improvements have been devised for actinide recoveries within the conventional Purex reprocessing operations and a currently agreed value has been assumed for neptunium recovery (90%). According to these basic orientations some organic extractants have been selected for testing as promising candidates for waste partitioning and laboratory studies, designed to develop a satisfactory partitioning flow-sheet, have been proposed and described

The electrodeposition and rare earths reduction in the molten salt actinides recovery systems using liquid metal

International Nuclear Information System (INIS)

Shim, J-B.; Lee, J-H.; Kwon, S-W.; Ahn, B-G.; Woo, M-S.; Lee, B-J.; Kim, E-H.; Park, H-S.; Yoo, J-H.

2005-01-01

A pyrochemical partitioning system uses liquid metals such as cadmium and bismuth in order to recover the actinide metals from a molten salt mixture containing rare earth fission product metals. The liquid metals play roles as a cathode in the electrowinning or an extracting phase in the reductive extraction operation. The product resulting from the above operations is metal-cadmium or-bismuth alloy, which should contain the rare earth element amounts as low as possible for a transmutation purpose. In this study, the electrodeposition behaviours of uranium and lanthanide elements such as La, Ce and Nd were investigated for solid molybdenum and liquid cadmium electrodes in a molten LiCl-KCl eutectic salt. Electrochemical methods used are a cyclic voltammetry (CV) and a chronopotentiometry for monitoring the salt phase and recovering the metals, respectively. The CV graphs for monitoring the oxidizing agent CdCl 2 in the salt phase were obtained. These show a time dependently disappearance of the oxidizing agent corresponding to the formation of UCl 3 by inserting the uranium metal into the salt. Also, a sequential oxidation technique which is added at a controlled amount of the oxidizing agents into the salt phase was applied. It was found that this method is feasible for the selective reduction of the rare earths content in liquid metal alloys. (author)

Diglycolamide based dendrimers for sequestration of trivalent actinides: solvent extraction and liquid membrane studies

International Nuclear Information System (INIS)

Ansari, S.A.; Mohapatra, P.K.; Leoncini, A.; Verboom, W.

2017-01-01

Three diglycolamide-functionalized (poly(propylene imine)) diaminobutane dendrimers, viz. zero generation (L_I), first generation (L_I_I), and second generation (L_I_I_I), were synthesized and evaluated for their extraction ability towards trivalent actinides. The distribution ratio (D) of Am"3"+ with 1.0 mmol/L ligand at 3 M HNO_3 followed the order: 0.1 (L_I) < 42 (L_I_I) < 110 (L_I_I_I). The D values of Am(_I_I_I) at lower acidity (0.01 M HNO_3) were significantly low, giving good stripping option with the dilute acid solution. Extraction of other metal ions from 3 M HNO_3 indicated good selectivity of Am(III) over U(VI), Sr(II) and Cs(I). Supported liquid membrane (SLM) studies were explored for the transport of Am(III) from acidic feed solution, where ligand inventory is extremely low. (author)

Some aspects of the extraction separation of actinides by macrocyclic crown compounds

International Nuclear Information System (INIS)

Kumar, Anil; Singh, R.K.; Bajpai, D.D.; Shukla, J.P.

1994-01-01

Selective and effective extraction-separation of U(VI) and Pu(IV) from aqueous nitric acid media by several crown ethers have been investigated in detail. The critical study of various parameters namely aqueous phase acidity, reagent concentration, diluent, period of equilibration, aqueous to organic phase ratio, strippant and diverse ions, have established the conditions for their optimum extraction. Influence of the introduction of sulfur into a crown ether ring forming a mixed sulfur-oxygen containing macrohetrocycle for improved extraction of actinides is also studied. The species extracted appear to be of ion-pair type, UO 2 (CE) 2+ .2NO 3- and Pu(CE) 2 4+ .4NO 3- formed with U(VI) and Pu(IV), respectively. The apparent extraction equilibrium constant, log Kex, into toluene by DC18C6 with U(VI) is 0.44 and 4.44 for Pu(IV). Recovery of actinides from loaded macrocycles is easily accomplished using dilute oxalic acid, perchloric acid, sulphuric acid or sodium carbonate as the strippants. The lack of interference from even appreciable amounts of possible fission product contaminants is a notable feature of this separation procedure. (author). 20 refs., 6 figs., 6 tabs

Use of fast reactors for actinide transmutation

International Nuclear Information System (INIS)

1993-03-01

The management of radioactive waste is one of the key issues in today's discussions on nuclear energy, especially the long term disposal of high level radioactive wastes. The recycling of plutonium in liquid metal fast breeder reactors (LMFBRs) would allow 'burning' of the associated extremely long life transuranic waste, particularly actinides, thus reducing the required isolation time for high level waste from tens of thousands of years to hundreds of years for fission products only. The International Working Group on Fast Reactors (IWGFR) decided to include the topic of actinide transmutation in liquid metal fast breeder reactors in its programme. The IAEA organized the Specialists Meeting on Use of Fast Breeder Reactors for Actinide Transmutation in Obninsk, Russian Federation, from 22 to 24 September 1992. The specialists agree that future progress in solving transmutation problems could be achieved by improvements in: Radiochemical partitioning and extraction of the actinides from the spent fuel (at least 98% for Np and Cm and 99.9% for Pu and Am isotopes); technological research and development on the design, fabrication and irradiation of the minor actinides (MAs) containing fuels; nuclear constants measurement and evaluation (selective cross-sections, fission fragments yields, delayed neutron parameters) especially for MA burners; demonstration of the feasibility of the safe and economic MA burner cores; knowledge of the impact of maximum tolerable amount of rare earths in americium containing fuels. Refs, figs and tabs

Development and testing of metallic fuels with high minor actinide content

International Nuclear Information System (INIS)

Meyer, M.K.; Hayes, S.L.; Kennedy, J.R.; Keiser, D.D.; Hilton, B.A.; Frank, S.M.; Kim, Y.-S.; Chang, G.; Ambrosek, R.G.

2003-01-01

Metallic alloys are promising candidates for use as fuels for transmutation and in advanced closed nuclear cycles. Metallic alloys have high heavy metal atom density, relatively high thermal conductivity, favorable gas release behavior, and lend themselves to remote recycle processes. Both non-fertile and uranium-bearing metal fuels containing minor actinide are under consideration for use as transmutation fuels by the U.S. Advanced Fuel Cycle (AFC) program, however, little irradiation performance data exists for fuel forms containing significant fractions of minor actinides. The first irradiation tests of non-fertile high-actinide-content fuels are scheduled to begin in early 2003 in the Advanced Test Reactor (ATR). The irradiation test matrix was designed to provide basic information on the irradiation behavior of binary Pu-Zr alloy fuel and the effect of the minor actinides americium and neptunium on alloy fuel behavior, together and separately. Five variants of transuranic containing zirconium-based alloy fuels are included in the AFC-1 irradiation test matrix. These are (in wt.%) Pu-40Zr, Pu-60Zr, Pu-12Am-40Zr, Pu-10Np-40Zr and Pu-10Np-10Am-40Zr. PuN-ZrN based fuels containing Am and Np are also included. All five of the fuel alloys have been fabricated in the form of cylindrical fuel slugs by arc-casting. Short melt times, on the order or 5-20 seconds, prevent the volatilization of significant quantities of americium metal, despite the high melt temperatures characteristic of the arc-melting process. Alloy microstructure have been characterized by x-ray diffraction and scanning electron microscopy. Thermal analysis has also been performed. The AFC-1 irradiation experiment configuration consists of twenty-four sodium bonded fuel specimens sealed in helium filled secondary capsules. The first capsule has a design burnup to 7 at.% 239 Pu; goal peak burnup of the second capsule is ∼18 at%. Capsule assemblies are placed within an aluminum flow-through basket

Benzene-centred tripodal diglycolamides for the sequestration of trivalent actinides : Metal ion extraction and luminescence spectroscopic investigations in a room temperature ionic liquid

NARCIS (Netherlands)

Ansari, Seraj Ahmad; Mohapatra, Prasanta Kumar; Leoncini, Andrea; Huskens, Jurriaan; Verboom, Willem

2017-01-01

Three benzene-centred tripodal diglycolamide (Bz-T-DGA) ligands, where the diglycolamide (DGA) moieties are attached to a central benzene ring through ethylene spacers (LI), amide groups (LII) or ether linkages (LIII), were evaluated for their extraction behaviour towards trivalent actinide and

Partitioning of actinides from high active waste solution of Purex origin counter-current extraction studies using TBP and CMPO

International Nuclear Information System (INIS)

Chitnis, R.R.; Dhami, P.S.; Gopalkrishnan, V.; Wattal, P.K.; Ramanujam, A.; Murali, M.S.; Mathur, J.N.; Bauri, A.K.; Chattopadhyay, S.

2000-10-01

A solvent extraction scheme has been formulated for the partitioning of actinides from Purex high level waste (HLW). The scheme is based on the results of earlier studies carried out with simulated waste solutions. In the present studies, the scheme was tested with high active waste (HAW) solution generated during the reprocessing of spent fuel from research reactors using laboratory scale mixer-settlers. The proposed process involved two-step extraction using tri-n-butyl phosphate (TBP) and octyl (phenyl)-N,N-diisobutylcarbamolylmethylphosphine oxide (CMPO). In the first step, uranium, neptunium and plutonium were removed from the waste using TBP as extractant. The minor actinides left in the raffinate were extracted using a mixture of CMPO and TBP in the second step. The results showed complete extraction of actinides from the waste solution. Plutonium and neptunium extracted in TBP, were stripped together using a mixture of hydrogen peroxide and ascorbic acid in 2 M nitric acid medium, leaving uranium in the organic phase. Uranium can later be stripped using dilute nitric acid. Actinides extracted in CMPO-TBP phase were stripped using a mixture of formic acid, hydrazine, hydrate and citric acid. The stripping was quantitative in both the stripping runs. An additional extraction step for the preferential recovery of uranium, neptunium and plutonium from the waste solution using TBP is a modification over the conventional Truex process. Selective stripping of neptunium and plutonium from large quantities of uranium. The extraction of uranium using TBP eliminates the possibility of third phase and undesired loading of CMPO-TBP in the following step. Use of citrate-containing strippant allows the recovery of actinides from loaded CMPO-TBP mixture without causing any reflux of the actinides during stripping. The process has been developed with due consideration to minimising the generation of secondary wastes. The proposed strippants are effective even in presence of

Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

Science.gov (United States)

Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

2016-05-27

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

DISSOLUTION OF METAL OXIDES AND SEPARATION OF URANIUM FROM LANTHANIDES AND ACTINIDES IN SUPERCRITICAL CARBON DIOXIDE

Energy Technology Data Exchange (ETDEWEB)

Donna L. Quach; Bruce J. Mincher; Chien M. Wai

2013-10-01

This paper investigates the feasibility of extracting and separating uranium from lanthanides and other actinides by using supercritical fluid carbon dioxide (sc-CO2) as a solvent modified with tri-n-butylphosphate (TBP) for the development of a counter current stripping technique, which would be a more efficient and environmentally benign technology for spent nuclear fuel reprocessing compared to traditional solvent extraction. Several actinides (U, Pu, and Np) and europium were extracted in sc-CO2 modified with TBP over a range of nitric acid concentrations and then the actinides were exposed to reducing and complexing agents to suppress their extractability. According to this study, uranium/europium and uranium/plutonium extraction and separation in sc-CO2 modified with TBP is successful at nitric acid concentrations of less than 6 M and at nitric acid concentrations of less than 3 M with acetohydroxamic acid or oxalic acid, respectively. A scheme for recycling uranium from spent nuclear fuel by using sc-CO2 and counter current stripping columns is presented.

Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides

International Nuclear Information System (INIS)

Cordier, P.Y.

1996-07-01

In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author)

The neutronics design and analysis of a liquid metal reactor for burning minor actinides

International Nuclear Information System (INIS)

Choi, H.B.; Downar, T.J.

1992-01-01

A liquid metal reactor was designed for the primary purpose of burning the minor actinide waste from commercial light water reactors (LWR). The design was constrained to maintain acceptable safety performance as measured by the burnup reactivity swing, the Doppler coefficient, and the sodium void worth. One of the principal innovations was the use of two core regions, with a fissile plutonium outer core and an inner core consisting only of minor actinides. The physics studies performed here indicate that a 1200 MWth core is able to transmute the annual minor actinide inventory of about 26 LWRs and still exhibit reasonable safety characteristics. Sensitivity analysis of the final core design indicates deficiencies in the minor actinide nuclear data can introduce large uncertainties in the prediction of the core safety performance parameters

Actinide partitioning from HLW in a continuous DIDPA extraction process by means of centrifugal extractors

International Nuclear Information System (INIS)

Morita, Y.; Kubota, M.; Glatz, J.P.; Koch, L.; Pagliosa, G.; Roemer, K.; Nicholl, A.

1996-01-01

An experiment on actinide partitioning from real high level waste (HLW) was performed in a continuous process by extraction with diisodecylphosphoric acid (DIDPA) using a battery of 12 centrifugal extractors installed in a hot cell. The HNO 3 concentration of the HLW was adjusted to 0.5 M by dilution. The extraction section had 8 stages, and H 2 O 2 was added to extract Np effectively. After extraction, Am and Cm were back-extracted with 4 M HNO 3 in 4 stages and Np and Pu were stripped with 0.8 M H 2 C 2 O 4 in 8 stages. The actinides, expect Np, were extracted from HLW with a very high yield. Although only 84% of the Np were recovered in the present experiment, the recovery would be improved to 99.7 % by increasing the temperature to 45 degree C, the number of stages from 8 to 16 and the H 2 O 2 concentration from 1 M to 2 M. Long-lived Tc and the main heat and radiation emitters Cs and Sr were not extracted and were thus separated from the actinides with high decontamination factors. About 98% of Am and Cm were recovered from the loaded solvent in the first stripping step with 4M HNO 3 . About 86% of Np and about 92% of Pu were back-extracted with 0.8 M H 2 C 2 O 4 . These incomplete recoveries would be improved by increasing the number of stages and by optimizing the other process parameters. 18 refs., 5 figs., 3 tabs

Development of Separation Process for Minor Actinides Using TDdDGA and New Extractants

International Nuclear Information System (INIS)

Matsumura, T.; Tsubata, Y.

2015-01-01

Full text of publication follows: Separation process for minor actinides (MA = Am, Cm and Np) has been developed at Japan Atomic Energy Agency using new innovative extractants to improve the partitioning process from the viewpoints of the economy and the reduction of secondary wastes. Phosphorus-free compounds consisting of carbon, hydrogen, oxygen and nitrogen (CHON principle) were applied to the separation steps for MA. At the first step, MA and lanthanide elements (Ln) are recovered from high-level liquid waste by solvent extraction with N,N,N',N'-tetra-dodecyl-diglycolamide (TDdDGA). Trivalent actinides Am and Cm, are separated from RE at the next step by solvent extraction using podand type soft-donor extractant such as N,N,N',N'- tetrakis(pyridin-2-ylmethyl)- decane-1,2-diamine (TPDN) or hybrid type extractant such as N-octyl-N-(ptolyl)- 1,10-phenanthroline-2-carboxamide (OctTolPTA). This paper presents the current status of the research and development programme. This study is carried out under the Innovative Nuclear Research and Development Programme by the Ministry of Education, Culture, Sports, Science and Technology of Japan. (authors)

PREPARATION OF ACTINIDE-ALUMINUM ALLOYS

Science.gov (United States)

Moore, R.H.

1962-09-01

BS>A process is given for preparing alloys of aluminum with plutonium, uranium, and/or thorium by chlorinating actinide oxide dissolved in molten alkali metal chloride with hydrochloric acid, chlorine, and/or phosgene, adding aluminum metal, and passing air and/or water vapor through the mass. Actinide metal is formed and alloyed with the aluminum. After cooling to solidification, the alloy is separated from the salt. (AEC)

Study of kinetics of extraction of actinides in processes of reprocessing of nuclear fuels

International Nuclear Information System (INIS)

Lamotte, Claude

1978-01-01

This research thesis reports a bibliographical study on extraction kinetics. After some generalities on solvent-based extraction, and on the chemistry of actinides in solution, on the methods of kinetics study which are generally used and their mathematical treatments, the author compares the published results for the extraction kinetics of nitric acid, uranium VI, uranium IV, neptunium IV and plutonium IV [fr

End point control of an actinide precipitation reactor

International Nuclear Information System (INIS)

Muske, K.R.

1997-01-01

The actinide precipitation reactors in the nuclear materials processing facility at Los Alamos National Laboratory are used to remove actinides and other heavy metals from the effluent streams generated during the purification of plutonium. These effluent streams consist of hydrochloric acid solutions, ranging from one to five molar in concentration, in which actinides and other metals are dissolved. The actinides present are plutonium and americium. Typical actinide loadings range from one to five grams per liter. The most prevalent heavy metals are iron, chromium, and nickel that are due to stainless steel. Removal of these metals from solution is accomplished by hydroxide precipitation during the neutralization of the effluent. An end point control algorithm for the semi-batch actinide precipitation reactors at Los Alamos National Laboratory is described. The algorithm is based on an equilibrium solubility model of the chemical species in solution. This model is used to predict the amount of base hydroxide necessary to reach the end point of the actinide precipitation reaction. The model parameters are updated by on-line pH measurements

Partnew - New solvent extraction processes for minor actinides - final report; Partnew - Nouveaux procedes d'extraction par solvant pour les actinides mineurs - rapport final

Energy Technology Data Exchange (ETDEWEB)

Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

2004-07-01

The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

Combined Extraction of Cesium, Strontium, and Actinides from Alkaline Media: An Extension of the Caustic-Side Solvent Extraction (CSSX) Process Technology

International Nuclear Information System (INIS)

Kenneth Raymond

2004-01-01

The wastes present at DOE long-term storage sites are usually highly alkaline, and because of this, much of the actinides in these wastes are in the sludge phase. Enough actinide materials still remain in the supernatant liquid that they require separation followed by long-term storage in a geological repository. The removal of these metals from the liquid waste stream would permit their disposal as low-level waste and dramatically reduce the volume of high-level wastes

Standard entropy for borides of non-transition metals, rare-earth metals and actinides

International Nuclear Information System (INIS)

Borovikova, M.S.

1986-01-01

Using as initial data the most reliable values of standard entropy for 10 compounds, the entropies for 40 compounds of non-transition metals, rare-earth metals and actinides have been evaluated by the method of comparative calculation. Taking into account the features of boride structures, two methods, i.e. additive and proportional, have been selected for the entropy calculations. For the range of borides the entropies were calculated from the linear relation of the latter to the number of boron atoms in the boride. For borides of rare-earth metals allowance has been made for magnetic contributions in conformity with the multiplicity of the corresponding ions. Insignificant differences in the electronic contributions to the entropy for borides and metals have been neglected. For dodecaborides only the additive method has been used. This is specified by the most rigid network that provides the same contribution to compound entropy. (orig.)

Partnew - New solvent extraction processes for minor actinides - final report

International Nuclear Information System (INIS)

Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

2004-01-01

The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

Selective chelation-supercritical fluid extraction of metal ions from waste materials

International Nuclear Information System (INIS)

Wai, C.N.; Laintz, K.E.; Yonker, C.R.

1993-01-01

The removal of toxic organics, metals, and radioisotopes from solids or liquids is a major concern in the treatment of industrial and nuclear wastes. For this reason, developing methods for selective separation of toxic metals and radioactive materials from solutions of complex matrix is an important problem in environmental research. Recent developments indicate supercritical fluids are good solvents for organic compounds. Many gases become supercritical fluids under moderate temperatures and pressures. For example, the critical temperature and pressure of carbon dioxide are 31 degrees C and 73 atm, respectively. The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties of supercritical fluid extraction (SFE). Since CO 2 offers the additional benefits of stability and non-toxicity, the SFE technique avoids generation of organic liquid waste and exposure of personnel to toxic solvents. While direct extraction of metal ions by supercritical fluids is highly inefficient, these ions when complexed with organic ligands become quite soluble in supercritical fluids. Specific ligands can be used to achieve selective extraction of metal ions in this process. After SFE, the fluid phase can be depressurized for precipitation of the metal chelates and recycled. The ligand can also be regenerated for repeated use. The success of this selective chelation-supercritical fluid extraction (SC-SFE) process depends on a number of factors including the efficiencies of the selective chelating agents, solubilities of metal chelates in supercritical fluids, rate of extraction, ease of regeneration of the ligands, etc. In this report, the authors present recent results on the studies of the solubilities of metal chelates in supercritical CO 2 , experimental ions from aqueous solution, and the development of selective chelating agents (ionizable crown ethers) for the extraction of lanthanides and actinides

Separation of gallium and actinides in plutonium nuclear materials by extraction chromatography

International Nuclear Information System (INIS)

Eitrheim, E.S.; Knight, A.W.

2015-01-01

Analysis of stable gallium in nuclear materials has applications in nuclear fuel characterization and nuclear forensics. The use of positron-emitting gallium isotope 68 Ga as a tracer for Ga recoveries for analyses in materials containing actinides was explored. A radiochemical method for the separation of Ga, Pu, U, Th, and Am using commercially-available extraction chromatography resins was developed and evaluated. The method effectively allows precise determination of Ga yield (97 ± 3 %) in the analysis of stable Ga (spike recovery 101 ± 1 %) and radioactive Pu (radiochemical yield, 82 ± 10 %; spike recovery, 96 ± 3 %), while also providing pure elemental fractions of other actinides relevant to materials encountered in the analysis Pu-containing materials. (author)

Extraction of trivalent lanthanides and actinides by a synergistic mixture of thenoyltrifluoroacetone and a linear polyether

International Nuclear Information System (INIS)

Ensor, D.D.; Shah, A.H.

1984-01-01

Mixtures of a two component system, a linear polyether, 1,13-bis[8-quinolyl]-1,4,7,10,13-pentaoxatridecane, K-5, and thenoyltrifluoroacetone, HTTA, have been shown to exhibit synergistic character in the extraction of trivalent lanthanides and actinides. The effect of the addition of K-5 to the organic phase on the extractions of Ce(III), Eu(III), Tm(III), Am(III), Cm(III), Bk(III), and Cf(III) by HTTA in chloroform from 0.5M NaNO 3 at 25 0 C has been measured. These results indicate the extraction is enhanced by the formation of M(TTA) 3 K-5 adduct in the organic phase. The organic phase stability constants for the formation of these synergistic species have been calculated for all the metals studied. The magnitude of these organic phase stability constants for K-5 are similar to other common neutral donors. The order of stability does not follow the normal trend based on charge-to-radius ratio, but follows a pattern based on size, with Am(III) being the most stable

CMPO, a new extractant for actinides: A review of the currently available literature

Energy Technology Data Exchange (ETDEWEB)

Liansheng, Wei [Institute of Atomic Energy of Beijing (China); Gasparini, G M [ENEA - Dipartimento Ciclo del Combustibile, Centro Ricerche Energia, Casaccia (Italy)

1989-05-15

The extractive properties of dialkyl-N,N-dialkyl carbamoyl methyl phosphinoxides, a series of extractants for liquid-liquid extraction techniques, suitable for actinides separation in any valence state, are described. These extractants have been especially studied to treat effluents contaminated with alpha emitters. The technical reasons because n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO) and its best experimental conditions have been chosen are examined. CMPO is the extractant utilized to treat the alpha contaminated effluents of the CRE Casaccia Plutonium Laboratory by means of the TESEO Process, studied and verified in our laboratories. (author)

CMPO, a new extractant for actinides: A review of the currently available literature

International Nuclear Information System (INIS)

Wei Liansheng; Gasparini, G.M.

1989-05-01

The extractive properties of dialkyl-N,N-dialkyl carbamoyl methyl phosphinoxides, a series of extractants for liquid-liquid extraction techniques, suitable for actinides separation in any valence state, are described. These extractants have been especially studied to treat effluents contaminated with alpha emitters. The technical reasons because n-octyl(phenyl)-N,N-diisobutyl carbamoyl methyl phosphinoxide (CMPO) and its best experimental conditions have been chosen are examined. CMPO is the extractant utilized to treat the alpha contaminated effluents of the CRE Casaccia Plutonium Laboratory by means of the TESEO Process, studied and verified in our laboratories. (author)

Counter current extraction for the partitioning of actinides from PFBR-SHLW using TODGA

International Nuclear Information System (INIS)

Ansari, S.A.; Gujar, R.B.; Kumar, Mithilesh; Seshagiri, T.K.; Godbole, S.V.; Manchanda, V.K.; Rajeswari, S.; Antony, M.P.; Srinivasan, T.G.

2009-01-01

Counter current extraction for the partitioning of actinides from simulated HLW of PFBR origin was demonstrated with 0.1M TODGA + 0.5M DHOA dissolved in NPH using a 16 stage mixer-settler unit. Results demonstrated that all lanthanides could be quantitatively extracted from the feed solution and quantitatively stripped from the loaded organic phase with 0.2M HNO 3 . The extracted lanthanides are not scrubbed with 0.2M oxalic acid at 5M HNO 3 in the scrubbing cycle. Elements such as Ba, Cd and Sn were not extracted. However, Pd was partially extracted but was scrubbed quantitatively. (author)

Inherent safe fast breeder reactors and actinide burners, metallic fuel

International Nuclear Information System (INIS)

Dorner, S.; Schumacher, G.

1991-04-01

Nuclear power without breeder strategy uses the possibilities for the energy supply only to a small extend compared to the possibilities of fast breeder reactors, which offer an energy supply for thousands of years. Moreover, a fast neutron device offers the opportunity to run an actinide-burner that could improve the situation of waste management. Within this concept metallic fuel could play a key role. The present report shows some important aspects of the concept like the pyrometallic reprocessing, the behaviour of metallic fuel during a core meltdown accident and others. The report should contribute to the discussion of these problems and initialize further work

Partitioning of Minor Actinides from High Active Raffinates using Bis-Diglycol-amides (BisDGA) as new efficient Extractants

Energy Technology Data Exchange (ETDEWEB)

Modolo, G.; Vijgen, H. [Forschungszentrum Juelich GmbH, Institute for Energy Research, Safety Research and Reactor Technology, 52425 Juelich (Germany); Espartero, A.G. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, 28040-Madrid (Spain); Prados, P. [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Mendoza, J. de [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Institut Catala d' Investigacio Quimica (ICIQ) Av. Paisos Catalans 16, 43007-Tarragona (Spain)

2008-07-01

Two new polyamide extractants has been selected, namely UAM-069 and UAM-081, both synthesized at the University of Madrid (UAM), to develop a new separation process. These two ligands are bis-diglycol-amides, consisting of two diglycol-amides moieties grafted on an aromatic platform (UAM-069) or on an aliphatic linker (UAM-081), respectively. The extraction of actinides and fission products was studied from synthetic PUREX raffinate. Actinides(III) and lanthanides(III) are highly extracted from acidities > 1 mol/L HNO{sub 3}. The extraction of Zr, Mo and Pd could be suppressed with complexing agents such as oxalic acid and HEDTA. In the present paper the results of the batch extraction results are presented which serve for the development of a new continuous counter current process to be tested in centrifugal contactors. (authors)

TUCS/phosphate mineralization of actinides

Energy Technology Data Exchange (ETDEWEB)

Nash, K.L. [Argonne National Lab., IL (United States)

1997-10-01

This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

Liquid-liquid extraction of actinides by means of dibutil-N, N-diethylcarbamylphosphanate (DBDECP)

International Nuclear Information System (INIS)

Spezzano, P.; Giacomelli, R.; Sarzanini, C.; Volpe, P.; Benzi, P.

1988-01-01

The extraction of Th(IV), U(VI), Pu(IV), Am(III) and Cm(III) by dibutyl-N, N-diethilcarbamoylphosphonate (DBDECP) from notric, hydrochloric and perchloric acid solutions has been studies as a function of a number of parameters. The effect of size and structure of the extractant molecules has been investigated for lower homologues of carbamoyphosphonate. After evaluating the effect of the diluent, the extraction of inorganic acid HNO 3 , HCl and HClO 4 and the dipendence of the distribution ratios of the actinides from organic extractant concentration and aqueous acid concentration has been studied for the DBDECP-xilene system

A liquid-metal reactor for burning minor actinides of spent light water reactor fuel. 1: Neutronics design study

International Nuclear Information System (INIS)

Choi, H.; Downar, T.J.

1999-01-01

A liquid-metal reactor was designed for the primary purpose of burning the minor actinide waste from commercial light water reactors (LWRs). The design was constrained to maintain acceptable safety performance as measured by the burnup reactivity swing, the Doppler constant, and the sodium void worth. Sensitivity studies were performed for homogeneous and decoupled core designs, and a minor actinide burner design was determined to maximize actinide consumption and satisfy safety constraints. One of the principal innovations was the use of two core regions, with a fissile plutonium outer core and an inner core consisting only of minor actinides. The physics studies performed here indicate that a 1200-MW(thermal) core is able to consume the annual minor actinide inventory of about 16 LWRs and still exhibit reasonable safety characteristics

The effect of actinides on the microstructural development in a metallic high-level nuclear waste form

Energy Technology Data Exchange (ETDEWEB)

Keiser, D. D., Jr.; Sinkler, W.; Abraham, D. P.; Richardson, J. W., Jr.; McDeavitt, S. M.

1999-10-25

Waste forms to contain material residual from an electrometallurgical treatment of spent nuclear fuel have been developed by Argonne National Laboratory. One of these waste forms contains waste stainless steel (SS), fission products that are noble to the process (e.g., Tc, Ru, Pd, Rh), Zr, and actinides. The baseline composition of this metallic waste form is SS-15wt.% Zr. The metallurgy of this baseline alloy has been well characterized. On the other hand, the effects of actinides on the alloy microstructure are not well understood. As a result, SS-Zr alloys with added U, Pu, and/or Np have been cast and then characterized, using scanning electron microscopy, transmission electron microscopy, and neutron diffraction, to investigate the microstructural development in SS-Zr alloys that contain actinides. Actinides were found to congregate non-uniformally in a Zr(Fe,Cr,Ni){sub 2+x} phase. Apparently, the actinides were contained in varying amounts in the different polytypes (C14, C15, and C36) of the Zr(Fe,Cr,Ni){sub 2+x} phase. Heat treatment of an actinide-containing SS-15 wt.% Zr alloy showed the observed microstructure to be stable.

Numerical simulation of minor actinide recovery behaviour in batch processing of spent metallic fuel by electrorefining

Energy Technology Data Exchange (ETDEWEB)

Nawada, H P; Bhat, N P [Metallurgy Division, Indira Gandhi Centre for Atomic Research, Kalpakkam (India); Balasubramanian, G R [Atomic Energy Commission, Mumbai (India)

1994-06-01

Numerical simulation of electro-transport of fuel actinides (FAs), minor actinides (MAs) and rare earths (REs) in the electro-refiner (ER) for pyrochemical reprocessing of a typical spent IFR metallic fuel has been attempted based on improved thermo-chemical model developed for application to multi-component system in the ER. Optimization of MA recovery and decontamination factors (DFs) for MAs and REs in batch processing is presented. (author). 7 refs., 4 figs., 1 tab.

Synthesis and characterization of templated ion exchange resins for the selective complexation of actinide ions. 1998 annual progress report

International Nuclear Information System (INIS)

Murray, G.M.; Uy, O.M.

1998-01-01

'The purpose of this research is to develop polymeric extractants for the selective complexation of uranyl ions (and subsequently other actinyl and actinide ions) from aqueous solutions (lakes, streams, waste tanks and body fluids). Selectivity for a specific actinide ion is obtained by providing polymers with cavities lined with complexing ligands so arranged as to match the charge, coordination number, coordination geometry, and size of the actinide metal ion. These cavity-containing polymers will be produced using a specific actinide ion (or surrogate) as a template around which monomeric complexing ligands will be polymerized. The polymers will provide useful sequestering agents for removing actinide ions from wastes and will form the basis for a variety of analytical techniques for actinide determinations.'

Organometallic compounds of the lanthanides, actinides and early transition metals

Energy Technology Data Exchange (ETDEWEB)

Cardin, D J [Trinity Coll., Dublin (Ireland); Cotton, S A [Stanground School, Peterborough (UK); Green, M [Bristol Univ. (UK); Labinger, J A [Atlantic Richfield Co., Los Angeles, CA (USA); eds.

1985-01-01

This book provides a reference compilation of physical and biographical data on over 1500 of the most important and useful organometallic compounds of the lanthanides, actinides and early transition metals representing 38 different elements. The compounds are listed in molecular formula order in a series of entries in dictionary format. Details of structure, physical and chemical properties, reactions and key references are clearly set out. All the data is fully indexed and a structural index is provided.

Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

Energy Technology Data Exchange (ETDEWEB)

Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-09-30

noncomplexing aqueous solution and submission of this scientific breakthrough as a paper in Science; The first-ever co-crystallization of Am(VI) with UO₂(NO₃)₂ ∙ 6H₂O, opening the door to a new approach for separating hexavalent actinides as a group; Results showing that three potentially problematic metals will not present risk in ALSEP; Improvement in ALSEP contactor stripping kinetics to acceptable performance; A comparison of centrifugal contactors vs mixer-settlers showing the former performs better in ALSEP stripping; Synthesis of new mixed N,O-donor extractants with enhanced solubility and strength for selective trivalent actinide extraction; Development of computational methods showing promise in prediction of the selectivity of new extractants for trivalent actinides vs lanthanides; An order-of-magnitude improvement in aqueous Am/Eu complexation selectivity of an alternative macrocyclic stripping agent for ALSEP, potentially enabling an option for an Am product stream free from both Ln and Cm. An alternative aqueous combination of dipicolinate complexant and malonate buffer that may present options for ALSEP and TALSPEAK (Trivalent Actinide-Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Komplexes) type separations. The ALSEP concept is advancing toward a benchtop flowsheet demonstration planned for FY 2016, and a bench-scale test bed at Idaho National Laboratory (INL) will be employed to demonstrate at least one tandem Am oxidation and separation concept. This report outlines the goals of the STAAR, significance of achieving these goals, STAAR organization around the above aims and questions, recent highlights, and future directions. The report also includes a listing of publications, reports, patents, and dissertations.

Analysis of evidence for an irreproducible martensite-like behavior in actinide metals and alloys below room temperature

International Nuclear Information System (INIS)

Sandenaw, T.A.

1976-05-01

Evidence is presented which suggests that a low-temperature, martensite-like behavior may be quite general in actinide metals and their alloys and compounds. There may be no metastable martensitic embryos in an α-phase structure of high-purity U, Np, and Pu formed by a diffusion-controlled β → α transformation, and thus no evidence for low-temperature phases. The effect of impurity content on observed low-temperature physical properties of these actinides is noted. It is proposed that impurities may be playing several roles. They may permit an electron redistribution in dilute alloys dependent upon the length of holding time. Experimentally determined values for the electronic contribution to heat capacity and the density of states of U, Np, and Pu should thus vary over a considerable range, as has been observed. Variations in interstitial ordering of impurity atoms with processing may yield stacking variants of each basic close-packed actinide metal structure and thus determine the number and structure of low-temperature phase. 46 references

Preparation of thin actinide metal disks using a multiple disk casting technique

International Nuclear Information System (INIS)

Conner, W.V.

1975-01-01

A casting technique has been developed for preparing multiple actinide metal disks which have a minimum thickness of 0.006 inch. This technique was based on an injection casting procedure which utilizes the weight of a tantalum metal rod to force the molten metal into the mold cavity. Using the proper mold design and casting parameters, it has been possible to prepare ten 1/2 inch diameter neptunium or plutonium metal disks in a single casting, This casting technique is capable of producing disks which are very uniform. The average thickness of the disks from a typical casting will vary no more than 0.001 inch and the variation in the thickness of the individual disks will range from 0.0001 to 0.0005 inch. (Auth.)

Preparation of thin actinide metal disks using a multiple disk casting technique

International Nuclear Information System (INIS)

Conner, W.V.

1976-01-01

A casting technique has been developed for preparing multiple actinide metal disks which have a minimum thickness of 0.006 inch. This technique was based on an injection casting procedure which utilizes the weight of a tantalum metal rod to force the molten metal into the mold cavity. Using the proper mold design and casting parameters, it has been possible to prepare ten 1/2 inch diameter neptunium or plutonium metal disks in a single casting. This casting technique is capable of producing disks which are very uniform. The average thickness of the disks from a typical casting will vary no more than 0.001 inch and the variation in the thickness of the individual disks will range from 0.0001 to 0.0005 inch. (author)

New strategies for the chemical separation of actinides and lanthanides

International Nuclear Information System (INIS)

Hudson, M.J.; Iveson, P.B.

2002-01-01

A general model is proposed for the effective design of ligands for partitioning. There is no doubt that the correct design of a molecule is required for the effective separation by separation of metal ions such as lanthanides(III) and actinides(III). Heterocyclic ligands with aromatic rings systems have a rich chemistry, which is only now becoming sufficiently well understood, in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with metal ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazol-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. Primary Coordination Sphere. One of the most critical features concerning whether a molecule is a suitable extraction reagent is the nature of the binding and co-ordination in the primary co-ordination sphere. This effect will be considered in depth for the selected heterocylic molecules. It will be shown how the bonding of the heterocyclic and nitrate ligands changes as the complete lanthanide series is traversed from lanthanum to lutetium. For effective solvent extraction, the ligand(s) should be able completely to occupy the primary co-ordination sphere of the metal ion to be extracted. Interactions in the secondary co-ordination sphere are of less importance. Inter-complex Hydrogen Bonding Interactions. Another feature that will be considered is the intermolecular binding between ligands when bound to the metal ion. Thus the intermolecular structures between complex molecules will be considered

Actinide recycle potential in the Integral Fast Reactor (IFR) fuel cycle

International Nuclear Information System (INIS)

Chang, Y.I.; Till, C.E.

1990-01-01

In the Integral Fast Reactor (IFR) development program, the entire reactor system -- reactor, fuel cycle, and waste process is being developed and optimized at the same time as a single integral entity. The use of metallic fuel in the IFR allows a radically improved fuel cycle technology. Pyroprocessing, which utilizes high temperatures and molten salt and molten metal solvents, can be advantageously utilized for processing metal fuels because the product is metal suitable for fabrication into new fuel elements. The key step in the IFR process is electrorefining, which provides for recovery of the valuable fuel constituents, uranium and plutonium, and for removal of fission products. In the electrorefining operation, uranium and plutonium are selectively transported from an anode to a cathode, leaving impurity elements, mainly fission products, either in the anode compartment or in a molten salt electrolyte. A notable feature of the IFR process is that the actinide elements accompany plutonium through the process. This results in a major advantage in the high-level waste management, because these actinides are automatically recycled back into the reactor for in-situ burning. Based on the recent IFR process development, a preliminary assessment has also been made to investigate the feasibility of further adapting the pyrochemical processes to directly extract actinides from LWR spent fuel. The results of this assessment indicate very promising potential and two most promising flowsheet options have been identified for further research and development. This paper also summarizes current thinking on the rationale for actinide recycle, its ramifications on the geologic repository and the current high-level waste management plans, and the necessary development programs. 5 refs., 4 figs., 4 tabs

Supercritical Carbon Dioxide-Soluble Ligands for Extracting Actinide Metal Ions from Porous Solids

International Nuclear Information System (INIS)

Joan Brennecke; Mark Dietz; Richard Barrans; Alabert Herlinger

2003-01-01

Numerous types of actinide-bearing waste materials are found throughout the DOE complex. Most of these wastes consist of large volumes of non-hazardous materials contaminated with relatively small quantities of actinide elements. Separation of these wastes into their inert and radioactive components would dramatically reduce the costs of stabilization and disposal. For example, the DOE is responsible for decontaminating concrete within 7000 surplus contaminated buildings. The best technology now available for removing surface contamination from concrete involves removing the surface layer by grit blasting, which produces a large volume of blasting residue containing a small amount of radioactive material. Disposal of this residue is expensive because of its large volume and fine particulate nature. Considerable cost savings would result from separation of the radioactive constituents and stabilization of the concrete dust. Similarly, gas diffusion plants for uranium enrichment contain valuable high-purity nickel in the form of diffusion barriers. Decontamination is complicated by the extremely fine pores in these barriers, which are not readily accessible by most cleaning techniques. A cost-effect method for the removal of radioactive contaminants would release this valuable material for salvage

The uncertainty analysis of a liquid metal reactor for burning minor actinides from light water reactors

Energy Technology Data Exchange (ETDEWEB)

Choi, Hang Bok [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1999-12-31

The neutronics analysis of a liquid metal reactor for burning minor actinides has shown that uncertainties in the nuclear data of several key minor actinide isotopes can introduce large uncertainties in the predicted performance of the core. A comprehensive sensitivity and uncertainty analysis was performed on a 1200 MWth actinide burner designed for a low burnup reactivity swing, negative doppler coefficient, and low sodium void worth. Sensitivities were generated using depletion perturbation methods for the equilibrium cycle of the reactor and covariance data was taken ENDF-B/V and other published sources. The relative uncertainties in the burnup swing, doppler coefficient, and void worth were conservatively estimated to be 180%, 97%, and 46%, respectively. 5 refs., 1 fig., 3 tabs. (Author)

The uncertainty analysis of a liquid metal reactor for burning minor actinides from light water reactors

Energy Technology Data Exchange (ETDEWEB)

Choi, Hang Bok [Korea Atomic Energy Research Institute, Taejon (Korea, Republic of)

1998-12-31

The neutronics analysis of a liquid metal reactor for burning minor actinides has shown that uncertainties in the nuclear data of several key minor actinide isotopes can introduce large uncertainties in the predicted performance of the core. A comprehensive sensitivity and uncertainty analysis was performed on a 1200 MWth actinide burner designed for a low burnup reactivity swing, negative doppler coefficient, and low sodium void worth. Sensitivities were generated using depletion perturbation methods for the equilibrium cycle of the reactor and covariance data was taken ENDF-B/V and other published sources. The relative uncertainties in the burnup swing, doppler coefficient, and void worth were conservatively estimated to be 180%, 97%, and 46%, respectively. 5 refs., 1 fig., 3 tabs. (Author)

Development of quantitative analytical methods for the control of actinides in a pyrochemical partitioning process

International Nuclear Information System (INIS)

Abousahl, S.; Belle, P. van; Eberle, H.; Ottmar, H.; Lynch, B.; Vallet, P.; Mayer, K.; Ougier, M.

2005-01-01

Advanced nuclear fuel cycles are being developed in order to reduce the long-term radiotoxicity of highly radioactive waste. Pyrochemical partitioning techniques appear particularly attractive for advanced fuel cycles in which the minor actinides are recycled. The electrochemical processes of practical importance are the electrorefining process and the liquid-liquid extraction of transuranic (TRU) elements from fission products using either non-miscible molten metal or molten salt-metal phases. Analytical methods for the accurate assay of actinide elements in these matrices needed to be developed. A quantitative assay is required in order to establish a material balance for process development and - at a later stage - for accountancy and control purposes. To this end radiometric techniques such as energy-dispersive X-ray fluorescence analysis (XRF), neutron coincidence counting (NCC) and high-resolution gamma spectrometry (HRGS) were extensively employed for the quantitative determination of actinides (U, Np, Pu, Am, Cm) in process samples. Comparative analyses were performed using inductively coupled plasma mass spectrometry (ICP-MS). The respective samples were available in small quantities (≅ 100 mg) either in the form of eutectic salt or in metallic form with Cd, Zr or Bi as major metallic matrix constituents. (orig.)

Actinide separative chemistry

International Nuclear Information System (INIS)

Boullis, B.

2004-01-01

Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

Advancing Understanding of the +4 Metal Extractant Thenoyltrifluoroacetonate (TTA-); Synthesis and Structure of MIVTTA4 (MIV = Zr, Hf, Ce, Th, U, Np, Pu) and MIII(TTA)4- (MIII = Ce, Nd, Sm, Yb).

Science.gov (United States)

Cary, Samantha K; Livshits, Maksim; Cross, Justin N; Ferrier, Maryline G; Mocko, Veronika; Stein, Benjamin W; Kozimor, Stosh A; Scott, Brian L; Rack, Jeffrey J

2018-04-02

Thenoyltrifluoroacetone (HTTA)-based extractions represent popular methods for separating microscopic amounts of transuranic actinides (i.e., Np and Pu) from macroscopic actinide matrixes (e.g. bulk uranium). It is well-established that this procedure enables +4 actinides to be selectively removed from +3, + 5, and +6 f-elements. However, even highly skilled and well-trained researchers find this process complicated and (at times) unpredictable. It is difficult to improve the HTTA extraction-or find alternatives-because little is understood about why this separation works. Even the identities of the extracted species are unknown. In addressing this knowledge gap, we report here advances in fundamental understanding of the HTTA-based extraction. This effort included comparatively evaluating HTTA complexation with +4 and +3 metals (M IV = Zr, Hf, Ce, Th, U, Np, and Pu vs M III = Ce, Nd, Sm, and Yb). We observed +4 metals formed neutral complexes of the general formula M IV (TTA) 4 . Meanwhile, +3 metals formed anionic M III (TTA) 4 - species. Characterization of these M(TTA) 4 x- ( x = 0, 1) compounds by UV-vis-NIR, IR, 1 H and 19 F NMR, single-crystal X-ray diffraction, and X-ray absorption spectroscopy (both near-edge and extended fine structure) was critical for determining that Np IV (TTA) 4 and Pu IV (TTA) 4 were the primary species extracted by HTTA. Furthermore, this information lays the foundation to begin developing and understanding of why the HTTA extraction works so well. The data suggest that the solubility differences between M IV (TTA) 4 and M III (TTA) 4 - are likely a major contributor to the selectivity of HTTA extractions for +4 cations over +3 metals. Moreover, these results will enable future studies focused on explaining HTTA extractions preference for +4 cations, which increases from Np IV to Pu IV , Hf IV , and Zr IV .

Presence and Character of the 5f Electrons in the Actinide Metals

DEFF Research Database (Denmark)

Johansson, B.; Skriver, Hans Lomholt; Mårtensson, N.

1980-01-01

The sensitivity of the Image level binding energy to the occupation of the 5f orbital is pointed out and used to demonstrate the presence of 5f electrons in the uranium metal. It is suggested that the valence band spectrum of uranium might contain satellites originating from excitations...... to localized 5f-electron configurations. Different kinds of core-hole screenings are discussed for the actinide metals as well as the difference between inner and outer core electron ionizations. Finally, the question of itinerant versus localized 5f behaviour is treated by means of a total energy comparison...

Actinide recovery techniques utilizing electromechanical processes

International Nuclear Information System (INIS)

Westphal, B.R.; Benedict, R.W.

1994-01-01

Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

Spin and orbital moments in actinide compounds

DEFF Research Database (Denmark)

Lebech, B.; Wulff, M.; Lander, G.H.

1991-01-01

The extended spatial distribution of both the transition-metal 3d electrons and the actinide 5f electrons results in a strong interaction between these electron states when the relevant elements are alloyed. A particular interesting feature of this hybridization, which is predicted by single...... experiments designed to determine the magnetic moments at the actinide and transition-metal sublattice sites in compounds such as UFe2, NpCo2, and PuFe2 and to separate the spin and orbital components at the actinide sites. The results show, indeed, that the ratio of the orbital to spin moment is reduced...

Debye-Waller factors of the light actinide metals

International Nuclear Information System (INIS)

Lawson, A.C.; Goldstone, J.A.; Cort, B.; Sheldon, R.I.; Foltyn, E.M.

1994-01-01

The authors have been using time-of-flight neutron powder diffraction to determine the Debye-Waller factors of the light actinide metals. The Debye-Waller factor is a measure of the mean-square atomic displacement that arises from the thermal motion of the atoms in any solid. Its temperature dependence determines a Debye-Waller temperature, Θ DW , that is characteristic of the elastic properties of the solid. The data are obtained by Rietveld analysis of neutron diffraction powder patterns obtained at several temperatures. The authors will present results for α-U, α-Np, α-Pu and σ-Pu 0.95 Al 0.05 . The Θ DW 's are temperature dependent, and anharmonic interatomic forces seem to be required to explain the results

Actinide extraction from ICPP sodium bearing waste with 0.75 M DHDECMP/TBP in Isopar L reg-sign

International Nuclear Information System (INIS)

Herbst, R.S.; Brewer, K.N.; Garn, T.G.; Law, J.D.; Rodriguez, A.M.; Tillotson, R.T.

1996-01-01

Recent process development efforts at the Idaho Chemical Processing Plant include examination of solvent extraction technologies for actinide partitioning from sodium bearing waste (SBW) solutions. The use of 0.75 M dihexyl-N, N-diethylcarbamoylmethylphosphonate (DHDECMP or simply CMP) and 1.0 M tri-n-butyl phosphate (TBP) diluted in Isopar L reg-sign was explored for actinide removal from simulated SBW solutions. Experimental evaluations included batch contacts in radiotracer tests with simulated sodium bearing waste solution to measure the extraction and recovery efficiency of the organic solvent. The radioactive isotopes utilized for this study included Pu-238, Pu-239, Am-241, U-233, Np-239, Zr-95, Tc-99m, and Hg-203. Extraction contacts of the organic solvent with the traced SBW stimulant, strip (back-extraction) contacts of the loaded organic solvent with either a 1-hydroxyethane-1, 1-diphosphonic acid (HEDPA) in nitric acid solution or an oxalic acid in nitric acid solution, and solvent wash contacts with sodium carbonate were performed

Actinide recovery techniques utilizing electromechanical processes

International Nuclear Information System (INIS)

Westphal, B.R.; Benedict, R.W.

1994-01-01

Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

Selective extraction of actinides by calixarenes: application to bioassay analysis; Extraction selective des actinides par les calixarenes: application a l'analyse radiotoxicologique

Energy Technology Data Exchange (ETDEWEB)

Boulet, B

2006-01-15

In the context of nuclear workers monitoring, the aim of this PhD was to selectively isolate U, Pu, and Am from urine to propose a new analytical procedure to the Medical and Biology Analysis Laboratories. The 1,3,5-OCH{sub 3}-2,4,6-OCH{sub 2}CONHOH-p-tert-butyl-calix[6]arene molecule has been selected as a promising extractant for U, Pu, and Am. Its physico-chemical properties and its affinity for UO{sub 2}{sup 2+} have been studied through two approaches, one theoretical (molecular modelling at DFT level), and one experimental. The extractions of the three actinides by the hydroxamic calix[6]arene were quantitative in liquid-liquid and solid-liquid systems. Their separation has also been shown possible and efficient. After optimization, the proposed procedure should allow the laboratories to carry out the chemical treatment of urine, before the measurement, in one day instead of the three days needed nowadays. (author)

Advances in computational actinide chemistry in China

Energy Technology Data Exchange (ETDEWEB)

Wang, Dongqi; Wu, Jingyi; Chai, Zhifang [Chinese Academy of Sciences, Beijing (China). Multidisciplinary Initiative Center; Su, Jing [Chinese Academy of Sciences, Shanghai (China). Div. of Nuclear Materials Science and Engineering; Li, Jun [Tsinghua Univ., Beijing (China). Dept. of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering

2014-04-01

The advances in computational actinide chemistry made in China are reviewed. Several areas relevant to chemistry of actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems with metal-metal bonding in their isolated forms (U{sub 2}, Pu{sub 2}) and in fullerene (U{sub 2} rate at C{sub 60}), and the excited states of actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF{sub 6}, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO{sub 2}/CS{sub 2} functionalization promoted by trivalent uranium complex; and (3) migration of actinides in the environment. A future outlook is discussed. (orig.)

Room temperature electrodeposition of actinides from ionic solutions

Science.gov (United States)

Hatchett, David W.; Czerwinski, Kenneth R.; Droessler, Janelle; Kinyanjui, John

2017-04-25

Uranic and transuranic metals and metal oxides are first dissolved in ozone compositions. The resulting solution in ozone can be further dissolved in ionic liquids to form a second solution. The metals in the second solution are then electrochemically deposited from the second solutions as room temperature ionic liquid (RTIL), tri-methyl-n-butyl ammonium n-bis(trifluoromethansulfonylimide) [Me.sub.3N.sup.nBu][TFSI] providing an alternative non-aqueous system for the extraction and reclamation of actinides from reprocessed fuel materials. Deposition of U metal is achieved using TFSI complexes of U(III) and U(IV) containing the anion common to the RTIL. TFSI complexes of uranium were produced to ensure solubility of the species in the ionic liquid. The methods provide a first measure of the thermodynamic properties of U metal deposition using Uranium complexes with different oxidation states from RTIL solution at room temperature.

Electrorecovery of actinides at room temperature

Energy Technology Data Exchange (ETDEWEB)

Stoll, Michael E [Los Alamos National Laboratory; Oldham, Warren J [Los Alamos National Laboratory; Costa, David A [Los Alamos National Laboratory

2008-01-01

There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

ALMR potential for actinide consumption

International Nuclear Information System (INIS)

Cockey, C.L.; Thompson, M.L.

1992-01-01

The Advanced Liquid Metal Reactor (ALMR) is a US Department of Energy (DOE) sponsored fast reactor design based on the Power Reactor, Innovative Small Module (PRISM) concept originated by General Electric. This reactor combines a high degree of passive safety characteristics with a high level of modularity and factory fabrication to achieve attractive economics. The current reference design is a 471 MWt modular reactor fueled with ternary metal fuel. This paper discusses actinide transmutation core designs that fit the design envelope of the ALMR and utilize spent LWR fuel as startup material and for makeup. Actinide transmutation may be accomplished in the ALMR core by using either a breeding or burning configuration. Lifetime actinide mass consumption is calculated as well as changes in consumption behavior throughout the lifetime of the reactor. Impacts on system operational and safety performance are evaluated in a preliminary fashion. Waste disposal impacts are discussed. (author)

Simultaneous separation and detection of actinides in acidic solutions using an extractive scintillating resin.

Science.gov (United States)

Roane, J E; DeVol, T A

2002-11-01

An extractive scintillating resin was evaluated for the simultaneous separation and detection of actinides in acidic solutions. The transuranic extractive scintillating (TRU-ES) resin is composed of an inert macroporous polystyrene core impregnated with organic fluors (diphenyloxazole and 1,4-bis-(4-methyl-5-phenyl-2-oxazolyl)benzene) and an extractant (octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide in tributyl phosphate). The TRU-ES resin was packed into FEP Teflon tubing to produce a flow cell (0.2-mL free column volume), which is placed into a scintillation detection system to obtain pulse height spectra and time series data during loading and elution of actinides onto/from the resin. The alpha-particle absolute detection efficiencies ranged from 77% to 96.5%, depending on the alpha energy and quench. In addition to the on-line analyses, off-line analyses of the effluent can be conducted using conventional detection methods. The TRU-ES resin was applied to the quantification of a mixed radionuclide solution and two actual waste samples. The on-line characterization of the mixed radionuclide solution was within 10% of the reported activities whereas the agreement with the waste samples was not as good due to sorption onto the sample container walls and the oxidation state of plutonium. Agreement between the on-line and off-line analyses was within 35% of one another for both waste samples.

Electrochemical separation of actinides and fission products in molten salt electrolyte

Energy Technology Data Exchange (ETDEWEB)

Gay, R.L.; Grantham, L.F.; Fusselman, S.P. [Rockwell International/Rocketdyne Division, Canoga Park, CA (United States)] [and others

1995-10-01

Molten salt electrochemical separation may be applied to accelerator-based conversion (ABC) and transmutation systems by dissolving the fluoride transport salt in LiCl-KCl eutectic solvent. The resulting fluoride-chloride mixture will contain small concentrations of fission product rare earths (La, Nd, Gd, Pr, Ce, Eu, Sm, and Y) and actinides (U, Np, Pu, Am, and Cm). The Gibbs free energies of formation of the metal chlorides are grouped advantageously such that the actinides can be deposited on a solid cathode with the majority of the rare earths remaining in the electrolyte. Thus, the actinides are recycled for further transmutation. Rockwell and its partners have measured the thermodynamic properties of the metal chlorides of interest (rare earths and actinides) and demonstrated separation of actinides from rare earths in laboratory studies. A model is being developed to predict the performance of a commercial electrochemical cell for separations starting with PUREX compositions. This model predicts excellent separation of plutonium and other actinides from the rare earths in metal-salt systems.

Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding.

Science.gov (United States)

Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

2011-06-01

Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented.

Recovery of actinides from TBP-Na2Co3 scrub-waste solutions: the ARALEX process

International Nuclear Information System (INIS)

Horwitz, E.P.; Bloomquist, C.A.A.; Mason, G.W.; Leonard, R.A.; Ziegler, A.A.

1979-08-01

A flowsheet for the recovery of actinides from TBP-Na 2 CO 3 scrub-waste solutions has been developed, based on batch extraction data, and tested, using laboratory-scale countercurrent extraction techniques. The process, called the ARALEX process, uses 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H 2 MBP) from acidified Na 2 CO 3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds, which also diminish the ability of the HDBP and H 2 MBP to complex actinides. Thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds (e.g., detergents) that interfere with conventional actinide ion exchange and liquid-liquid extraction procedures. 20 figures, 6 tables

Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

International Nuclear Information System (INIS)

Wai, C.M.; Smart, N.G.; Lin, Y.

1998-01-01

A method is described for extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process. 7 figs

Extraction of metals and/or metalloids from acidic media using supercritical fluids and salts

Science.gov (United States)

Wai, Chien M.; Smart, Neil G.; Lin, Yuehe

1998-01-01

A method of extracting metalloid and metal species from a solid or liquid material by exposing the material to a fluid solvent, particularly supercritical carbon dioxide, containing a chelating agent is described. The chelating agent forms chelates that are soluble in the fluid to allow removal of the species from the material. In preferred embodiments, the extraction solvent is supercritical carbon dioxide and the chelating agent comprises a trialkyl phosphate, a triaryl phosphate, a trialkylphosphine oxide, a triarylphosphine oxide, or mixtures thereof. The method provides an environmentally benign process for removing contaminants from industrial waste. The method is particularly useful for extracting actinides from acidic solutions, and the process can be aided by the addition of nitrate salts. The chelate and supercritical fluid can be regenerated, and the contaminant species recovered, to provide an economic, efficient process.

Mercury extraction by the TRUEX process solvent. II. Selective partitioning of mercury from co-extracted actinides in a simulated acidic ICPP waste stream

International Nuclear Information System (INIS)

Brewer, K.N.; Herbst, R.S.; Tranter, T.J.; Todd, T.A.

1995-01-01

The TRUEX process is being evaluated at the Idaho Chemical Processing Plant (ICPP) as a means to partition the actinides from acidic sodium-bearing waste (SBW). The mercury content of this waste averages 1 g/l. Because the chemistry of mercury has not been extensively evaluated in the TRUEX process, mercury was singled out as an element of interest. Radioactive mercury, 203 Hg, was spiked into a simulated solution of SBW containing 1 g/l mercury. Successive extraction batch contacts with the mercury spiked waste and successive scrubbing and stripping batch contacts of the mercury loaded TRUEX solvent (0.2 M CMPO-1.4 M TBP in dodecane) show that mercury will extract into and strip from the solvent. The extraction distribution coefficient for mercury, as HgCl 2 , from SBW having a nitric acid concentration of 1.4 M and a chloride concentration of 0.035 M was found to be 3. The stripping distribution coefficient was found to be 0.5 with 5 M HNO 3 and 0.077 with 0.25 M Na 2 CO 3 . Because experiments described here show that mercury can be extracted from SBW and stripped from the solvent, a process has been developed to partition mercury from the actinides in SBW. 10 refs., 3 figs., 10 tabs

Liquid-liquid extraction of actinides, lanthanides, and fission products by use of ionic liquids: from discovery to understanding

International Nuclear Information System (INIS)

Billard, Isabelle; Ouadi, Ali; Gaillard, Clotilde

2011-01-01

Liquid-liquid extraction of actinides and lanthanides by use of ionic liquids is reviewed, considering, first, phenomenological aspects, then looking more deeply at the various mechanisms. Future trends in this developing field are presented. (orig.)

Superconductivity in the actinides

International Nuclear Information System (INIS)

Smith, J.L.; Lawson, A.C.

1985-01-01

The trends in the occurrence of superconductivity in actinide materials are discussed. Most of them seem to show simple transition metal behavior. However, the superconductivity of americium proves that the f electrons are localized in that element and that ''actinides'' is the correct name for this row of elements. Recently the superconductivity of UBe 13 and UPt 3 has been shown to be extremely unusual, and these compounds fall in the new class of compounds now known as heavy fermion materials

Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides.

Science.gov (United States)

Allred, Benjamin E; Rupert, Peter B; Gauny, Stacey S; An, Dahlia D; Ralston, Corie Y; Sturzbecher-Hoehne, Manuel; Strong, Roland K; Abergel, Rebecca J

2015-08-18

Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications.

Lanthanide and actinide extractions with cobalt bis(dicarbollide) ion derivatives covalently bonded to diglycolyl diamide platform

Czech Academy of Sciences Publication Activity Database

Lučaníková, M.; Selucký, P.; Rais, J.; Grüner, Bohumír; Kvíčalová, Magdalena

2011-01-01

Roč. 1, č. 1 (2011), s. 89-95 ISSN 2193-2875 R&D Projects: GA ČR GA104/09/0668; GA MŠk LC523 Institutional research plan: CEZ:AV0Z40320502 Keywords : Dicarbollides derivatives * TODGA * Liquid-liquid extraction * Lanthanides * Actinides Subject RIV: CA - Inorganic Chemistry

Selective extraction of actinides by calixarenes: application to bioassay analysis

International Nuclear Information System (INIS)

Boulet, B.

2006-01-01

In the context of nuclear workers monitoring, the aim of this PhD was to selectively isolate U, Pu, and Am from urine to propose a new analytical procedure to the Medical and Biology Analysis Laboratories. The 1,3,5-OCH 3 -2,4,6-OCH 2 CONHOH-p-tert-butyl-calix[6]arene molecule has been selected as a promising extractant for U, Pu, and Am. Its physico-chemical properties and its affinity for UO 2 2+ have been studied through two approaches, one theoretical (molecular modelling at DFT level), and one experimental. The extractions of the three actinides by the hydroxamic calix[6]arene were quantitative in liquid-liquid and solid-liquid systems. Their separation has also been shown possible and efficient. After optimization, the proposed procedure should allow the laboratories to carry out the chemical treatment of urine, before the measurement, in one day instead of the three days needed nowadays. (author)

Highly efficient separation materials created by computational approach. For the separation of lanthanides and actinides

International Nuclear Information System (INIS)

Goto, Masahiro; Uezu, Kazuya; Aoshima, Atsushi; Koma, Yoshikazu

2002-05-01

In this study, efficient separation materials have been created by the computational approach. Based on the computational calculation, novel organophosphorus extractants, which have two functional moieties in the molecular structure, were developed for the recycle system of transuranium elements using liquid-liquid extraction. Furthermore, molecularly imprinted resins were prepared by the surface-imprint polymerization technique. Thorough this research project, we obtained two principal results: 1) design of novel extractants by computational approach, and 2) preparation of highly selective resins by the molecular imprinting technique. The synthesized extractants showed extremely high extractability to rare earth metals compared to those of commercially available extractants. The results of extraction equilibrium suggested that the structural effect of extractants is one of the key factors to enhance the selectivity and extractability in rare earth extractions. Furthermore, a computational analysis was carried out to evaluate the extraction properties for the extraction of rare earth metals by the synthesized extractants. The computer simulation was shown to be very useful for designing new extractants. The new concept to connect some functional moieties with a spacer is very useful and is a promising method to develop novel extractants for the treatment of nuclear fuel. In the second part, we proposed a novel molecular imprinting technique (surface template polymerization) for the separation of lanthanides and actinides. A surface-templated resin is prepared by an emulsion polymerization using an ion-binding (host) monomer, a resin matrix-forming monomer and the target Nd(III) metal ion. A host monomer which has amphiphilic nature forms a complex with a metal ion at the interface, and the complex remains as it is. After the matrix is polymerized, the coordination structure is 'imprinted' at the resin interface. Adsorption of Nd(III) and La(III) ions onto the

Bidentate organophosphorus extractants: purification, properties and applications to removal of actinides from acidic waste solutions

International Nuclear Information System (INIS)

Schulz, W.W.; McIsaac, L.D.

1977-05-01

At both Hanford and Idaho, DHDECMP (dihexyl-N, N-diethylcarbamylmethylene phosphonate) continuous counter-current solvent extraction processes are being developed for removal of americium, plutonium, and, in some cases, other actinides from acidic wastes generated at these locations. Bench and, eventually, pilot and plant-scale testing and application of these processes have been substantially enhanced by the discovery of suitable chemical and physical methods of removing deleterious impurities from technical-grade DHDECMP. Flowsheet details, as well as various properties of purified DHDECMP extractants, are enumerated

Selective extraction of trivalent actinides with hard-soft mixed donor ligands: role of intra-ligand synergism

International Nuclear Information System (INIS)

Ghanty, Tapan K.

2016-01-01

In recent years, considerable attention has been given to understand the coordination chemistry of trivalent lanthanide (Ln) and actinide (An) with various ligands because of its close link with the nuclear waste management processes. It is well known that lanthanide-actinide separation is a challenging and difficult task because of very similar chemical properties of these two series of ions, which are associated with similar ionic radii and coordination numbers. Recently, we have introduced a new concept, 'intra-ligand synergism', where hard donor atom, such as, oxygen preferentially binds to trivalent actinides (An(III)) as compared to the valence iso-electronic trivalent lanthanides (Ln(III)) in presence of another soft donor centre. In the present work, the conventional concept of selective complexation of actinides with soft donor ligands (either S or N donor) has been modified through exploiting this concept, and thereby the higher selectivity of 1,10-phenanthroline-2,9-dicarboxylamide (PDAM) based ligands, namely PDAM and its isobutyl and decyl derivatives towards Am(III) ion has been predicted theoretically through density functional calculations. Subsequently, several such amide derivatives have been synthesized to optimize the solubility of the ligands in organic phase. Finally, solvent extraction experiments have been carried out to validate the theoretical prediction on the selectivity of oxygen donor ligands towards Am(III) as compared to Eu(III), and a maximum separation factor of about 51 has been achieved experimentally using 2,9-bis(N-decylaminocarbonyl)-1,10-phenanthroline ligand. The separation factor is increased with the decrease in pH, which is very interesting since extraction of the Am 3+ ion is considered to be important under highly acidic conditions from the nuclear waste management point of view. (author)

Removal of actinide elements from high level radioactive waste by trialkylphosphine oxide (TRPO)

International Nuclear Information System (INIS)

Song Chongli; Yang Dazhu; He Longhai; Xu Jingming; Zhu Yongjun

1992-03-01

The modified TRPO process for removing actinide elements from synthetic solution, which was taken from reprocessing of power reactor nuclear fuel, was verified by cascade experiment. Neptunium valence was adjusted in the process for improving neptunium removing efficiency. At 1 mol/L concentration of HNO 3 of feed solution and after a few stages of extraction with 30% t=TRPO kerosene, over 99.9% of Am, Pu, Np and U could be removed from HAW (high level radioactive waste) solution. The stripping of actinides loaded in TRPO are accomplished by high concentration nitric acid, oxalic acid and sodium carbonate instead of amino carboxylic complexing agents used in previous process. The actinides stripped were divided into three groups, which are Am + RE, Np + Pu, and U, and the cross contamination between them is small. Behaviours of F.P. elements are divided into three types which are not extracted, little extracted and extracted elements. The extracted elements are rare earth and Pd, Zr and Mo which are co-extracted with actinides. The separation factor between actinides and other two types of F.P.elements will increase if more scrubbing sections are added in the process. The relative concentration profile of actinide elements and Tc in various stages as well as the distribution of actinides and F.P. elements in the process stream solutions are also presented

Recovery actinide values

International Nuclear Information System (INIS)

Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

1979-01-01

A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of di-hexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid. (author)

Rare earths and actinides

International Nuclear Information System (INIS)

Coqblin, B.

1982-01-01

This paper reviews the different properties of rare-earths and actinides, either as pure metals or as in alloys or compounds. Three different cases are considered: (i) First, in the case of 'normal' rare-earths which are characterized by a valence of 3, we discuss essentially the magnetic ordering, the coexistence between superconductivity and magnetism and the properties of amorphous rare-earth systems. (ii) Second, in the case of 'anomalous' rare-earths, we distinguish between either 'intermediate-valence' systems or 'Kondo' systems. Special emphasis is given to the problems of the 'Kondo lattice' (for compounds such as CeAl 2 ,CeAl 3 or CeB 6 ) or the 'Anderson lattice' (for compounds such as TmSe). The problem of neutron diffraction in these systems is also discussed. (iii) Third, in the case of actinides, we can separate between the d-f hybridized and almost magnetic metals at the beginning of the series and the rare-earth like the metals after americium. (orig.)

Actinide recycle potential in the integral fast reactor (IFR) fuel cycle

International Nuclear Information System (INIS)

Chang, Y.I.; Till, C.E.

1991-01-01

In the Integral Fast Reactor (IFR) development program, the entire reactor system -- reactor, fuel cycle, and waste process is being developed and optimized at the same time as a single integral entity. The use of metallic fuel in the IFR allows a radically improved fuel cycle technology. Based on the recent IFR process development, a preliminary assessment has been made to investigate the feasibility of further adapting pyrochemical processes to directly extract actinides from LWR spent fuel. The results of this assessment indicate very promising potential and two most promising flowsheet options have been identified for further research and development. This paper also summarizes current thinking on the rationale for actinide recycle, its ramifications on the geologic repository and the current high-level waste management plans, and the necessary development programs

Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

Energy Technology Data Exchange (ETDEWEB)

Krishnan Balasubramanian

2009-07-18

This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

Electronic Structure of Transition Metal Clusters, Actinide Complexes and Their Reactivities

International Nuclear Information System (INIS)

Balasubramanian, Krishnan

2009-01-01

This is a continuing DOE-BES funded project on transition metal and actinide containing species, aimed at the electronic structure and spectroscopy of transition metal and actinide containing species. While a long term connection of these species is to catalysis and environmental management of high-level nuclear wastes, the immediate relevance is directly to other DOE-BES funded experimental projects at DOE-National labs and universities. There are a number of ongoing gas-phase spectroscopic studies of these species at various places, and our computational work has been inspired by these experimental studies and we have also inspired other experimental and theoretical studies. Thus our studies have varied from spectroscopy of diatomic transition metal carbides to large complexes containing transition metals, and actinide complexes that are critical to the environment. In addition, we are continuing to make code enhancements and modernization of ALCHEMY II set of codes and its interface with relativistic configuration interaction (RCI). At present these codes can carry out multi-reference computations that included up to 60 million configurations and multiple states from each such CI expansion. ALCHEMY II codes have been modernized and converted to a variety of platforms such as Windows XP, and Linux. We have revamped the symbolic CI code to automate the MRSDCI technique so that the references are automatically chosen with a given cutoff from the CASSCF and thus we are doing accurate MRSDCI computations with 10,000 or larger reference space of configurations. The RCI code can also handle a large number of reference configurations, which include up to 10,000 reference configurations. Another major progress is in routinely including larger basis sets up to 5g functions in thee computations. Of course higher angular momenta functions can also be handled using Gaussian and other codes with other methods such as DFT, MP2, CCSD(T), etc. We have also calibrated our RECP

Rapid column extraction method for actinides and strontium in fish and other animal tissue samples

International Nuclear Information System (INIS)

Maxwell III, S.L.; Faison, D.M.

2008-01-01

The analysis of actinides and radiostrontium in animal tissue samples is very important for environmental monitoring. There is a need to measure actinide isotopes and strontium with very low detection limits in animal tissue samples, including fish, deer, hogs, beef and shellfish. A new, rapid separation method has been developed that allows the measurement of plutonium, neptunium, uranium, americium, curium and strontium isotopes in large animal tissue samples (100-200 g) with high chemical recoveries and effective removal of matrix interferences. This method uses stacked TEVA Resin R , TRU Resin R and DGA Resin R cartridges from Eichrom Technologies (Darien, IL, USA) that allows the rapid separation of plutonium (Pu), neptunium (Np), uranium (U), americium (Am), and curium (Cm) using a single multi-stage column combined with alphaspectrometry. Strontium is collected on Sr Resin R from Eichrom Technologies (Darien, IL, USA). After acid digestion and furnace heating of the animal tissue samples, the actinides and 89/90 Sr are separated using column extraction chromatography. This method has been shown to be effective over a wide range of animal tissue matrices. Vacuum box cartridge technology with rapid flow rates is used to minimize sample preparation time. (author)

Liquid-solid extraction of cationic metals by cationic amphiphiles

International Nuclear Information System (INIS)

Muller, W.

2010-01-01

In the field of selective separation for recycling of spent nuclear fuel, liquid-liquid extraction processes are widely used (PUREX, DIAMEX..) in industrial scale. In order to guarantee a sustainable nuclear energy for the forthcoming generations, alternative reprocessing techniques are under development. One of them bases on the studies from Heckmann et al in the 80's and consists in selectively precipitating actinides from aqueous waste solutions by cationic surfactants (liquid-solid extraction). This technique has some interesting advantages over liquid-liquid extraction techniques, because several steps are omitted like stripping or solvent washing. Moreover, the amount of waste is decreased considerably, since no contaminated organic solvent is produced. In this thesis, we have carried out a physico-chemical study to understand the specific interactions between the metallic cations with the cationic surfactant. First, we have analysed the specific effect of the different counter-ions (Cl - , NO 3 - , C 2 O 4 2- ) and then the effect of alkaline cations on the structural properties of the surfactant aggregation in varying thermodynamical conditions. Finally, different multivalent cations (Cu 2+ , Zn 2+ , UO 2 2+ , Fe 3+ , Nd 3+ , Eu 3+ , Th 4+ ) were considered; we have concluded that depending on the anionic complex of these metals formed in acidic media, we can observe either an adsorption at the micellar interface or not. This adsorption has a large influence of the surfactant aggregation properties and determines the limits of the application in term of ionic strength, temperature and surfactant concentration. (author) [fr

Solvent extraction separations of trivalent lanthanide and actinide ions using an aqueous aminomethanediphosphonic acid

International Nuclear Information System (INIS)

Jensen, M. P.

1998-01-01

The possibility of separating the trivalent lanthanides, represented by EU 3+ , and actinides, represented by Cf 3+ , using HDEHP in toluene and an aqueous phase containing N-piperidinomethane-1,1-diphosphotic acid, PMDPA, has been investigated. This modified aqueous phase offers potential advantages over the diethylenetriaminepentaacetic acid based TALSPEAK process because of the improved complexation properties of PMDPA in acidic solutions, and the ability to decompose PMDPA before disposal. Extraction experiments were conducted at 25 C in 2 M NaClO 4 between -log [H + ] 1 and 2. The studies enabled us to derive the aqueous phase speciation, the stability constants of the aqueous complexes, and the Cf/Eu separation factors. Despite the presence of an amino group in PMDPA that should favor the retention of the actinides in the aqueous phase, the Cf/Eu separation factors are near unity under the conditions studied

Extracting properties of N,N,N'N'-tetraalkyl-2 alkyl propane -1,3 diamides

International Nuclear Information System (INIS)

Nigond, L.

1992-01-01

N,N,N',N'-tetraalkyl -2 alkyl propane -1,3 diamides (RR'NCO) 2 CHR'' are investigated in the aim to separate actinides from nuclear wastes. N,N'-dimethyl N,N'-dibutyl tetradecylmalonamide (DMDBTDMA) was selected. This molecule can extract trivalent actinides in aliphatic diluents. Americium extraction is faster than iron extraction, hydrolytic degradation and solubility in aqueous phase are satisfactory. In non acidic media, diamides form aggregates, the size of which is function of diluent and diamide concentration. Extraction equilibria of HNO 3 , UO 2 2+ , Pu 4+ , Am 3+ and Fe 3+ are investigated.Four complexes are formed with nitric acid: L 2 HNO 3 , LHNO 3 , L 2 (HNO 3 ) 2 and L(HNO 3 ) 3 with L=DMDBTDMA. UO 2 2+ and Pu 4+ extraction takes place via the formation of neutral complexes: LUO 2 (NO 3 ) 2 , LPu(NO 3 ) 4 and L 2 Pu(NO 3 ) 4 for any nitric acid concentration. Am 3+ extraction takes place via the formation of LAm(NO 3 ) 3 and L 2 Am(NO 3 ) 3 for low nitric acid concentration and L x H y Am(NO 3 ) 3+y at higher acidity. Fe 3+ extraction involves anionic complexes L x HFe(NO 3 ) 4 for any acid concentration. In the presence of metallic cations, two kinds of interactions are observed: in the inner sphere of the metal diamide-metal ion complexation and in the outer sphere diamide-metallic complex interaction. The malonamide DMDBTDMA can be used to separate (III), (IV) and (VI) actinides from radioactive wastes

Development of fast reactor metal fuels containing minor actinides

International Nuclear Information System (INIS)

Ohta, Hirokazu; Ogata, Takanari; Kurata, Masaki; Koyama, Tadafumi; Papaioannou, Dimitrios; Glatz, Jean-Paul; Rondinella, Vincenzo V.

2011-01-01

Fast reactor metal fuels containing minor actinides (MAs) Np, Am, and Cm and rare earths (REs) Y, Nd, Ce, and Gd are being developed by the Central Research Institute of Electric Power Industry (CRIEPI) in collaboration with the Institute for Transuranium Elements (ITU) in the METAPHIX project. The basic properties of U-Pu-Zr alloys containing MA (and RE) were characterized by performing ex-reactor experiments. On the basis of the results, test fuel pins including U-Pu-Zr-MA(-RE) alloy ingots in parts of the fuel stack were fabricated and irradiated up to a maximum burnup of ∼10 at% in the Phenix fast reactor (France). Nondestructive postirradiation tests confirmed that no significant damage to the fuel pins occurred. At present, detailed destructive postirradiation examinations are being carried out at ITU. (author)

Pyrometallurgical processes for recovery of actinide elements

International Nuclear Information System (INIS)

Battles, J.E.; Laidler, J.J.; McPheeters, C.C.; Miller, W.E.

1994-01-01

A metallic fuel alloy, nominally U-20-Pu-lOZr, is the key element of the Integral Fast Reactor (IFR) fuel cycle. Metallic fuel permits the use of an innovative, simple pyrometallurgical process, known as pyroprocessing, (the subject of this report), which features fused salt electrorefining of the spent fuel. Electrorefining separates the actinide elements from fission products, without producing a separate stream of plutonium. The plutonium-bearing product is contaminated with higher actinides and with a minor amount of rare earth fission products, making it diversion resistant while still suitable as a fuel material in the fast spectrum of the IFR core. The engineering-scale demonstration of this process will be conducted in the refurbished EBR-II Fuel Cycle Facility, which has entered the start-up phase. An additional pyrometallurgical process is under development for extracting transuranic (TRU) elements from Light Water Reactor (LWR) spent fuel in a form suitable for use as a feed to the IFR fuel cycle. Four candidate extraction processes have been investigated and shown to be chemically feasible. The main steps in each process are oxide reduction with calcium or lithium, regeneration of the reductant and recycle of the salt, and separation of the TRU product from the bulk uranium. Two processes, referred to as the lithium and salt transport (calcium reductant) processes, have been selected for engineering-scale demonstration, which is expected to start in late 1993. An integral part of pyroprocessing development is the treatment and packaging of high-level waste materials arising from the operations, along with the qualification of these waste forms for disposal in a geologic repository

Pyrometallurgical processes for recovery of actinide elements

Energy Technology Data Exchange (ETDEWEB)

Battles, J.E.; Laidler, J.J.; McPheeters, C.C.; Miller, W.E.

1994-01-01

A metallic fuel alloy, nominally U-20-Pu-lOZr, is the key element of the Integral Fast Reactor (IFR) fuel cycle. Metallic fuel permits the use of an innovative, simple pyrometallurgical process, known as pyroprocessing, (the subject of this report), which features fused salt electrorefining of the spent fuel. Electrorefining separates the actinide elements from fission products, without producing a separate stream of plutonium. The plutonium-bearing product is contaminated with higher actinides and with a minor amount of rare earth fission products, making it diversion resistant while still suitable as a fuel material in the fast spectrum of the IFR core. The engineering-scale demonstration of this process will be conducted in the refurbished EBR-II Fuel Cycle Facility, which has entered the start-up phase. An additional pyrometallurgical process is under development for extracting transuranic (TRU) elements from Light Water Reactor (LWR) spent fuel in a form suitable for use as a feed to the IFR fuel cycle. Four candidate extraction processes have been investigated and shown to be chemically feasible. The main steps in each process are oxide reduction with calcium or lithium, regeneration of the reductant and recycle of the salt, and separation of the TRU product from the bulk uranium. Two processes, referred to as the lithium and salt transport (calcium reductant) processes, have been selected for engineering-scale demonstration, which is expected to start in late 1993. An integral part of pyroprocessing development is the treatment and packaging of high-level waste materials arising from the operations, along with the qualification of these waste forms for disposal in a geologic repository.

Functionalization of mesoporous materials for lanthanide and actinide extraction.

Science.gov (United States)

Florek, Justyna; Giret, Simon; Juère, Estelle; Larivière, Dominic; Kleitz, Freddy

2016-10-14

Among the energy sources currently available that could address our insatiable appetite for energy and minimize our CO2 emission, solar, wind, and nuclear energy currently occupy an increasing portion of our energy portfolio. The energy associated with these sources can however only be harnessed after mineral resources containing valuable constituents such as actinides (Ac) and rare earth elements (REEs) are extracted, purified and transformed into components necessary for the conversion of energy into electricity. Unfortunately, the environmental impacts resulting from their manufacture including the generation of undesirable and, sometimes, radioactive wastes and the non-renewable nature of the mineral resources, to name a few, have emerged as challenges that should be addressed by the scientific community. In this perspective, the recent development of functionalized solid materials dedicated to selective elemental separation/pre-concentration could provide answers to several of the above-mentioned challenges. This review focuses on recent advances in the field of mesoporous solid-phase (SP) sorbents designed for REEs and Ac liquid-solid extraction. Particular attention will be devoted to silica and carbon sorbents functionalized with commonly known ligands, such as phosphorus or amide-containing functionalities. The extraction performances of these new systems are discussed in terms of sorption capacity and selectivity. In order to support potential industrial applications of the silica and carbon-based sorbents, their main drawbacks and advantages are highlighted and discussed.

Selective partitioning of mercury from co-extracted actinides in a simulated acidic ICPP waste stream

International Nuclear Information System (INIS)

Brewer, K.N.; Herbst, R.S.; Tranter, T.J.

1995-01-01

The TRUEX process is being evaluated at the Idaho Chemical Processing Plant (ICPP) as a means to partition the actinides from acidic sodium-bearing waste (SBW). The mercury content of this waste averages 1 g/l. Because the chemistry of mercury has not been extensively evaluated in the TRUEX process, mercury was singled out as an element of interest. Radioactive mercury, 203 Hg, was spiked into a simulated solution of SBW containing 1 g/l mercury. Successive extraction batch contacts with the mercury spiked waste simulant and successive scrubbing and stripping batch contacts of the mercury loaded TRUEX solvent (0.2 M CMPO-1.4 M TBP in dodecane) show that mercury will extract into and strip from the solvent. The extraction distribution coefficient for mercury, as HgCl 2 from SBW having a nitric acid concentration of 1.4 M and a chloride concentration of 0.035 M was found to be 3. The stripping distribution coefficient was found to be 0.5 with 5 M HNO 3 and 0.077 with 0.25 M Na 2 CO 3 . An experimental flowsheet was designed from the batch contact tests and tested counter-currently using 5.5 cm centrifugal contactors. Results from the counter-current test show that mercury can be removed from the acidic mixed SBW simulant and recovered separately from the actinides

Removal of actinides from selected nuclear fuel reprocessing wastes

International Nuclear Information System (INIS)

Navratil, J.D.; Thompson, G.H.

1979-01-01

The US Department of Energy awarded Oak Ridge National Laboratory a program to develop a cost-risk-benefit analysis of partitioning long-lived nuclides from waste and transmuting them to shorter lived or stable nuclides. Two subtasks of this program were investigated at Rocky Flats. In the first subtask, methods for solubilizing actinides in incinerator ash were tested. Two methods appear to be preferable: reaction with ceric ion in nitric acid or carbonate-nitrate fusion. The ceric-nitric acid system solubilizes 95% of the actinides in ash; this can be increased by 2 to 4% by pretreating ash with sodium hydroxide to solubilize silica. The carbonate-nitrate fusion method solubilizes greater than or equal to 98% of the actinides, but requires sodium hydroxide pretreatment. Two additional disadvantages are that it is a high-temperature process, and that it generates a lot of salt waste. The second subtask comprises removing actinides from salt wastes likely to be produced during reactor fuel fabrication and reprocessing. A preliminary feasibility study of solvent extraction methods has been completed. The use of a two-step solvent extraction system - tributyl phosphate (TBP) followed by extraction with a bidentate organophosphorous extractant (DHDECMP) - appears to be the most efficient for removing actinides from salt waste. The TBP step would remove most of the plutonium and > 99.99% of the uranium. The second step using DHDECMP would remove > 99.91% of the americium and the remaining plutonium (> 99.98%) and other actinides from the acidified salt waste. 8 figures, 11 tables

Research on the chemical speciation of actinides

International Nuclear Information System (INIS)

Jung, Euo Chang; Park, K. K.; Cho, H. R.

2010-04-01

A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

Aggregation of dialkyl-substituted diphosphonic acids and its effect on metal ion extraction.

Energy Technology Data Exchange (ETDEWEB)

Chiarizia, R.; Barrans, R. E., Jr.; Ferraro, J. R. Herlinger, A. W.; McAlister, D. R.

1999-10-22

Solvent extraction reagents containing the diphosphonic acid group exhibit an extraordinary affinity for tri-, tetra- and hexavalent actinides. Their use has been considered for actinide separation and pre-concentration procedures. Solvent extraction data obtained with P,P{prime}-di(2-ethylhexyl) methane-, ethane- and butanediphosphonic acids exhibit features that are difficult to explain without Knowledge of the aggregation state of the extractants. Information about the aggregation of the dialkyl-substituted diphosphonic acids in aromatic diluents has been obtained using the complementary techniques of vapor pressure osmometry (VPO), small angle neutron scattering (SANS), infrared spectroscopy and molecular mechanics. The results from these techniques provide an understanding of the aggregation behavior of these extractants that is fully compatible with the solvent extraction data. The most important results and their relevance to solvent extraction are reviewed in this paper.

Hydrothermal decomposition of actinide(IV oxalates: a new aqueous route towards reactive actinide oxide nanocrystals

Directory of Open Access Journals (Sweden)

Walter Olaf

2016-01-01

Full Text Available The hydrothermal decomposition of actinide(IV oxalates (An= Th, U, Pu at temperatures between 95 and 250 °C is shown to lead to the production of highly crystalline, reactive actinide oxide nanocrystals (NCs. This aqueous process proved to be quantitative, reproducible and fast (depending on temperature. The NCs obtained were characterised by X-ray diffraction and TEM showing their size to be smaller than 15 nm. Attempts to extend this general approach towards transition metal or lanthanide oxalates failed in the 95–250 °C temperature range. The hydrothermal decomposition of actinide oxalates is therefore a clean, flexible and powerful approach towards NCs of AnO2 with possible scale-up potential.

Burning minor actinides in a HTR energy spectrum

International Nuclear Information System (INIS)

Pohl, Christoph; Rütten, H. Jochem

2012-01-01

Highlights: ► Burn-up analysis for varying plutonium/minor actinide fuel compositions. ► The influence of varying heavy metal fuel element loads is investigated. ► Significant burn-up via radiative capture and subsequently fission is observed. ► Difference observed between fuel element burn-up and total actinide burning rate. - Abstract: The generation of nuclear energy by means of the existing nuclear reactor systems is based mainly on the fission of U-235. But this comes along with the capture of neutrons by the U-238 faction and results in a build-up of plutonium isotopes and minor actinides as neptunium, americium and curium. These actinides are dominant for the long time assessment of the radiological risk of a final disposal therefore a minimization of the long living isotopes is aspired. Burning the actinides in a high temperature helium cooled graphite moderated reactor (HTR) is one of these options. The use of plutonium isotopes to sustain the criticality of the system is intended to avoid on the one hand highly enriched uranium because of international regulations and on the other hand low enriched uranium because of the build up of new actinides from neutron capture in the U-238 fraction. Because initial minor actinide isotopes are typically not fissionable by thermal neutrons the idea is to fission instead the intermediate isotopes generated by the first neutron capture. This paper comprises calculations for plutonium/minor actinides/thorium fuel compositions and their correlated final burn-up for a generic pebble bed HTR based on the reference design of the 400 MW PBMR. In particular the cross sections and the neutron balance of the different minor actinide isotopes in the higher thermal energy spectrum of a HTR will be discussed. For a fuel mixture of plutonium and minor actinides a significant burn-up of these actinides up to 20% can be achieved but at the expense of a higher residual fraction of plutonium in the burned fuel. Combining

JOWOG 22/2 - Actinide Chemical Technology (July 9-13, 2012)

Energy Technology Data Exchange (ETDEWEB)

Jackson, Jay M. [Los Alamos National Laboratory; Lopez, Jacquelyn C. [Los Alamos National Laboratory; Wayne, David M. [Los Alamos National Laboratory; Schulte, Louis D. [Los Alamos National Laboratory; Finstad, Casey C. [Los Alamos National Laboratory; Stroud, Mary Ann [Los Alamos National Laboratory; Mulford, Roberta Nancy [Los Alamos National Laboratory; MacDonald, John M. [Los Alamos National Laboratory; Turner, Cameron J. [Los Alamos National Laboratory; Lee, Sonya M. [Los Alamos National Laboratory

2012-07-05

The Plutonium Science and Manufacturing Directorate provides world-class, safe, secure, and reliable special nuclear material research, process development, technology demonstration, and manufacturing capabilities that support the nation's defense, energy, and environmental needs. We safely and efficiently process plutonium, uranium, and other actinide materials to meet national program requirements, while expanding the scientific and engineering basis of nuclear weapons-based manufacturing, and while producing the next generation of nuclear engineers and scientists. Actinide Process Chemistry (NCO-2) safely and efficiently processes plutonium and other actinide compounds to meet the nation's nuclear defense program needs. All of our processing activities are done in a world class and highly regulated nuclear facility. NCO-2's plutonium processing activities consist of direct oxide reduction, metal chlorination, americium extraction, and electrorefining. In addition, NCO-2 uses hydrochloric and nitric acid dissolutions for both plutonium processing and reduction of hazardous components in the waste streams. Finally, NCO-2 is a key team member in the processing of plutonium oxide from disassembled pits and the subsequent stabilization of plutonium oxide for safe and stable long-term storage.

Fermi surface measurements in actinide metals and compounds

International Nuclear Information System (INIS)

Arko, A.J.; Schirber, J.E.

1978-01-01

The various techniques of measuring Fermi Surface parameters are briefly discussed in terms f application to actinide systems. Particular emphasis is given the dHvA effect. Some general results found in the dHvA studies of actinide compounds are given. The dHvA effect has been measured in α-U and is presented in detail. None of the observed frequencies corresponds to closed surfaces. Results are compared to the calculations of Freeman, Koelling and Watson-Yang where qualitative agreement is observed

Actinide-Aluminate Speciation in Alkaline Radioactive Waste

International Nuclear Information System (INIS)

Clark, David L.; Fedosseev, Alexander M.

2001-01-01

Investigation of behavior of actinides in alkaline media containing AL(III) showed that no aluminate complexes of actinides in oxidation states (IIII-VIII) were formed in alkaline solutions. At alkaline precipitation IPH (10-14) of actinides in presence of AL(III) formation of aluminate compounds is not observed. However, in precipitates contained actinides (IIV)<(VI), and to a lesser degree actinides (III), some interference of components takes place that is reflected in change of solid phase properties in comparison with pure components or their mechanical mixture. The interference decreases with rise of precipitation PH and at PH 14 is exhibited very feebly. In the case of NP(VII) the individual compound with AL(III) is obtained, however it is not aluminate of neptunium(VII), but neptunate of aluminium(III) similar to neptunates of other metals obtained earlier

Calculation of critical concentrations of actinides in an infinite medium of silicon dioxide

International Nuclear Information System (INIS)

Okuno, Hiroshi; Sato, Shohei; Kawasaki, Hiromitsu

2009-01-01

The critical concentrations of actinides in metal-silicon-dioxide (SiO 2 ) and in metal-water (H 2 O) mixtures were calculated for 26 actinides including 233,235 U, 239,241 Pu, 242m Am, 243,245,247 Cm, and 249,251 Cf. The calculations were performed using the Monte Carlo neutron transport calculation code MCNP5 combined with the evaluated nuclear data library JENDL3.3. The results showed that the critical concentration of actinide in metal-SiO 2 mixtures was about 1/5 of that in metal-H 2 O mixtures for all the fissile nuclides investigated. The k ∞ 's of metal-SiO 2 and metal-H 2 O at one-half of the respective critical concentration of actinide, which was assumed as the subcritical concentration limit, were found to be less than 0.8 for all the actinides considered. By applying the sum-of-fractions rule to the concentrations of six nuclides in metal-SiO 2 mixtures, the subcriticality of high-level radioactive wastes was confirmed for a reported sample. The effects of different nuclear data libraries on the results of critical concentrations were found to be large for 242 Cm, 247 Cm, and 250 Cf by comparison with the results calculated with another evaluated nuclear data library, ENDF/B-VI. (author)

Extraction processes and solvents for recovery of cesium, strontium, rare earth elements, technetium and actinides from liquid radioactive waste

Science.gov (United States)

Zaitsev, Boris N.; Esimantovskiy, Vyacheslav M.; Lazarev, Leonard N.; Dzekun, Evgeniy G.; Romanovskiy, Valeriy N.; Todd, Terry A.; Brewer, Ken N.; Herbst, Ronald S.; Law, Jack D.

2001-01-01

Cesium and strontium are extracted from aqueous acidic radioactive waste containing rare earth elements, technetium and actinides, by contacting the waste with a composition of a complex organoboron compound and polyethylene glycol in an organofluorine diluent mixture. In a preferred embodiment the complex organoboron compound is chlorinated cobalt dicarbollide, the polyethylene glycol has the formula RC.sub.6 H.sub.4 (OCH.sub.2 CH.sub.2).sub.n OH, and the organofluorine diluent is a mixture of bis-tetrafluoropropyl ether of diethylene glycol with at least one of bis-tetrafluoropropyl ether of ethylene glycol and bis-tetrafluoropropyl formal. The rare earths, technetium and the actinides (especially uranium, plutonium and americium), are extracted from the aqueous phase using a phosphine oxide in a hydrocarbon diluent, and reextracted from the resulting organic phase into an aqueous phase by using a suitable strip reagent.

Evaluation and testing of sequestering agents for the removal of actinides from waste streams

Energy Technology Data Exchange (ETDEWEB)

Hoffman, D.C.; Romanovski, V.V.; Veeck, A.C. [Lawrence Livermore National Lab., CA (United States)] [and others

1997-10-01

The purpose of this project is to evaluate and test the complexing ability of a variety of promising new complexing agents synthesized by Professor Kenneth Raymond`s group at the University of California, Berkeley (ESP-CP TTP Number SF16C311). Some of these derivatives have already shown the potential for selectivity binding Pu(IV) in a wide range of solutions in the presence of other metals. Professor Raymond`s group uses molecular modeling to design and synthesize ligands based on modification of natural siderophores, or their analogs, for chelation of actinides. The ligands are then modified for use as liquid/liquid and solid/liquid extractants. The authors` group at the Glenn T. Seaborg Institute for Transactinium Science (ITS) at Lawrence Livermore National Laboratory determines the complex formation constants between the ligands and actinide ions, the capacity and time dependence for uptake on the resins, and the effect of other metal ions and pH.

Separation of actinides and their transmutation

International Nuclear Information System (INIS)

Bouchard, M.; Bathelier, M.; Cousin, M.

1978-08-01

Neutron irradiation of long-half-life actinides for transmutation into elements with shorter half-life is investigated as a means to reduce the long-term hazards of these actinides. The effectiveness of the method is analysed by applying it to fission product solutions from the first extraction cycle of fuel reprocessing plants. Basic principles, separation techniques and transmutation efficiencies are studied and discussed in detail

Comparative Study of f-Element Electronic Structure across a Series of Multimetallic Actinide, Lanthanide-Actinide and Lanthanum-Actinide Complexes Possessing Redox-Active Bridging Ligands

Energy Technology Data Exchange (ETDEWEB)

Schelter, Eric J.; Wu, Ruilian; Veauthier, Jacqueline M.; Bauer, Eric D.; Booth, Corwin H.; Thomson, Robert K.; Graves, Christopher R.; John, Kevin D.; Scott, Brian L.; Thompson, Joe D.; Morris, David E.; Kiplinger, Jaqueline L.

2010-02-24

A comparative examination of the electronic interactions across a series of trimetallic actinide and mixed lanthanide-actinide and lanthanum-actinide complexes is presented. Using reduced, radical terpyridyl ligands as conduits in a bridging framework to promote intramolecular metal-metal communication, studies containing structural, electrochemical, and X-ray absorption spectroscopy are presented for (C{sub 5}Me{sub 5}){sub 2}An[-N=C(Bn)(tpy-M{l_brace}C{sub 5}Me4R{r_brace}{sub 2})]{sub 2} (where An = Th{sup IV}, U{sup IV}; Bn = CH{sub 2}C{sub 6}H{sub 5}; M = La{sup III}, Sm{sup III}, Yb{sup III}, U{sup III}; R = H, Me, Et) to reveal effects dependent on the identities of the metal ions and R-groups. The electrochemical results show differences in redox energetics at the peripheral 'M' site between complexes and significant wave splitting of the metal- and ligand-based processes indicating substantial electronic interactions between multiple redox sites across the actinide-containing bridge. Most striking is the appearance of strong electronic coupling for the trimetallic Yb{sup III}-U{sup IV}-Yb{sup III}, Sm{sup III}-U{sup IV}-Sm{sup III}, and La{sup III}-U{sup IV}-La{sup III} complexes, [8]{sup -}, [9b]{sup -} and [10b]{sup -}, respectively, whose calculated comproportionation constant K{sub c} is slightly larger than that reported for the benchmark Creutz-Taube ion. X-ray absorption studies for monometallic metallocene complexes of U{sup III}, U{sup IV}, and U{sup V} reveal small but detectable energy differences in the 'white-line' feature of the uranium L{sub III}-edges consistent with these variations in nominal oxidation state. The sum of this data provides evidence of 5f/6d-orbital participation in bonding and electronic delocalization in these multimetallic f-element complexes. An improved, high-yielding synthesis of 4{prime}-cyano-2,2{prime}:6{prime},2{double_prime}-terpyridine is also reported.

Fabrication of U-Pu-Zr metallic fuel containing minor actinides

International Nuclear Information System (INIS)

Kurata, Masaki; Sasahara, Akihiro; Inoue, Tadashi; Betti, M.; Babelot, J.F.; Spirlet, J.C.; Koch, L.

1997-01-01

Rods of UPuZr alloy containing 5% minor actinides, 2% minor actinides and 2% rare-earth elements, and 5% minor actinides and 5% rare-earth elements have been fabricated by casting in yttria molds. Parts of the ingots were cut off for quantitative analysis and the rods characterized to the required extent, which included measurement of length, weight, diameter, and bending. For selected samples, metallographic study was carried out to examine the dispersion of the various phases contained in the alloy. Finally, the rods were encapsulated in stainless steel pin with the UPuZr reference after sodium bonding for the irradiation study. (author)

Adventures in Actinide Chemistry: A Year of Exploring Uranium and Thorium in Los Alamos

Energy Technology Data Exchange (ETDEWEB)

Pagano, Justin [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-01-08

The first part of this collection of slides is concerned with considerations when working with actinides. The topics discussed in the document as a whole are the following: Actinide chemistry vs. transition metal chemistry--tools we can use; New synthetic methods to obtain actinide hydrides; Actinide metallacycles: synthesis, structure, and properties; and Reactivity of actinide metallacycles.

Handbook on the physics and chemistry of rare earths: Volume 19: Lanthanides/Actinides: Physics, 2

International Nuclear Information System (INIS)

Gschneidner, Karl A.; Eyring, LeRoy; Choppin, G.R.; Lander, G.H.

1994-01-01

This handbook comprises five chapters on the lanthanide and actinide materials. In the first chapter the inelastic neutron scattering behaviors of the lanthanides and actinides are compared. In the next chapter the focus is on neutron scattering by heavy fermion single crystal materials, including metallic materials with a paramagnetic ground state, superconductors, metallic and semiconducting antiferromagnets and nearly insulating paramagnets. In chapter three a comprehensive review of intermediate valence and heavy fermions in a wide variety of lanthanide and actinide compounds is given, ranging from metallic to insulating materials. In chapter four two issues on the high pressure behaviours of anomalous cerium, ytterbium and uranium compounds are dealt with. In the final chapter an extensive review is given the thermodynamic properties of lanthanide and actinide metallic systems

Noble metal extraction and sorption concentrating

International Nuclear Information System (INIS)

Petrukhin, O.M.; Malofeeva, G.I.

1985-01-01

Works performed in the USSR Academy of Sciences GEOCHI laboratory of extraction methods and devoted to selectivity problems of extraction and sorption methods of platinum metal, cadmium and indium concentrating in analytical chemistry are discussed. On choosing complexino. reagent main attention is paid to the selectivity variation based on different stability of metal complexes. Platinum metals are extracted in the form of ion associates when usinq hard, mainly oxyqen-containing, extractants. Coordination-solvated metal complexes are extracted white usinq extractants containing sulfur, trivalent phosphorus and aromatic nitroqen as donor anions. Selectivity is maximum for sulfur- and nitroren-containinq extractants and sorbents. In case of the group extraction of platinum metals sorption is preferable and in case of selective extraction of individual metals, especially, in case of need of relative concentratinq extraction is preferable

New solvent extraction processes for minor actinides: CIEMAT contribution to the partnew project: EU contract n. FIKW-CT2000-0087: first semestral period 2001 september 2000-february 2001

International Nuclear Information System (INIS)

2002-01-01

This report includes the work developed at CIEMAT into the partnew project: '' New solvent extraction processes for minor actinides, during the first semestral period (september 2000 to february 2001), CIEMAT is involved in the following task: the study of the actinides (AN) and lanthanides (LN) extracting properties of new compounds with chemical structure based on two malonamide groups linked to an aromatic platform. The study of new-bearing extractants with chemical structure similar to malonamides aforementioned, changing the 0 atoms by s atoms, and the determination of the selectivity of these new thiomalonamides for AN(III) extraction. (Author)

Minor actinide transmutation - a waste management option

International Nuclear Information System (INIS)

Koch, L.

1986-01-01

The incentive to recycle minor actinides results from the reduction of the long-term α-radiological risk rather than from a better utilization of the uranium resources. Nevertheless, the gain in generated electricity by minor actinide transmutation in a fast breeder reactor can compensate for the costs of their recovery and make-up into fuel elements. Different recycling options of minor actinides are discussed: transmutation in liquid metal fast breeder reactors (LMFBRs) is possible as long as plutonium is not recycled in light water reactors (LWRs). In this case a minor actinide burner with fuel of different composition has to be introduced. The development of appropriate minor actinide fuels and their properties are described. The irradiation experiments underway or planned are summarized. A review of minor actinide partitioning from the PUREX waste stream is given. From the present constraints of LMFBR technology a reduction of the long-term α-radiological risk by a factor of 200 is deduced relative to that from the direct storage of spent LWR fuel. Though the present accumulation of minor actinides is low, nuclear transmutation may be needed when nuclear energy production has grown. (orig.)

Research on the chemical speciation of actinides

International Nuclear Information System (INIS)

Jung, Euo Chang; Park, K. K.; Cho, H. R.

2012-04-01

A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

Final Project Report for ER15351 ''A Study of New Actinide Zintl Ions Materials''

International Nuclear Information System (INIS)

Peter K. Dorhout

2007-01-01

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorus-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metal salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples

Interaction between actinides and protein: the calmodulin

International Nuclear Information System (INIS)

Brulfert, Florian

2016-01-01

Considering the environmental impact of the Fukushima nuclear accident, it is fundamental to study the mechanisms governing the effects of the released radionuclides on the biosphere and thus identify the molecular processes generating the transport and deposition of actinides, such as neptunium and uranium. However, the information about the microscopic aspect of the interaction between actinides and biological molecules (peptides, proteins...) is scarce. The data being mostly reported from a physiological point of view, the structure of the coordination sites remains largely unknown. These microscopic data are indeed essential for the understanding of the interdependency between structural aspect, function and affinity.The Calmodulin (CaM) (abbreviation for Calcium-Modulated protein), also known for its affinity towards actinides, acts as a metabolic regulator of calcium. This protein is a Ca carrier, which is present ubiquitously in the human body, may also bind other metals such as actinides. Thus, in case of a contamination, actinides that bind to CaM could avoid the protein to perform properly and lead to repercussions on a large range of vital functions.The complexation of Np and U was studied by EXAFS spectroscopy which showed that actinides were incorporated in a calcium coordination site. Once the thermodynamical and structural aspects studied, the impact of the coordination site distortion on the biological efficiency was analyzed. In order to evaluate these consequences, a calorimetric method based on enzyme kinetics was developed. This experiment, which was conducted with both uranium (50 - 500 nM) and neptunium (30 - 250 nM) showed a decrease of the heat produced by the enzymatic reaction with an increasing concentration of actinides in the medium. Our findings showed that the Calmodulin actinide complex works as an enzymatic inhibitor. Furthermore, at higher neptunium (250 nM) and uranium (500 nM) concentration the metals seem to have a poison

Study on remain actinides recovery in pyro reprocessing

International Nuclear Information System (INIS)

Suharto, Bambang

1996-01-01

The spent fuel reprocessing by dry process called pyro reprocessing have been studied. Most of U, Pu and MA (minor actinides) from the spent fuel will be recovered and be fed back to the reactor as new fuel. Accumulation of remain actinides will be separated by extraction process with liquid cadmium solvent. The research was conducted by computer simulation to calculate the stage number required. The calculation's results showed on the 20 stages extractor more than 99% actinides can be separated. (author)

Molecular and electronic structure of actinide hexa-cyanoferrates; Structure moleculaire et electronique des hexacyanoferrates d'actinides

Energy Technology Data Exchange (ETDEWEB)

Bonhoure, I

2001-07-01

The goal of this work is to improve our knowledge on the actinide-ligand bond properties. To this end, the hexacyanoferrate entities have been used as pre-organized ligand. We have synthesized, using mild chemistry, the following series of complexes: An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Th, U, Np, Pu); Am{sup III}[Fe{sup III}(CN){sub 6}].xH{sub 2}O; Pu {sup III}[Co{sup III}(CN){sub 6}].xH{sub 2}O and K(H?)An{sup III}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Pu, Am). The metal oxidation states have been obtained thanks to the {nu}{sub CN}, stretching vibration and to the actinide L{sub III} absorption edge studies. As Prussian Blue, the An{sup IV}[Fe{sup II}(CN){sub 6}].xH{sub 2}O (An = Np, Pu) are class II of Robin and Day compounds. X-ray Diffraction has shown besides that these complexes crystallize in the P6{sub 3}/m space group, as the isomorphic LaKFe(CN){sub 6}.4H{sub 2}O complex used as structural model. The EXAFS oscillations at the iron K edge and at the An L{sub III} edge allowed to determine the An-N, An-O, Fe-C and Fe-N distances. The display of the multiple scattering paths for both edges explains the actinide contribution absence at the iron edge, whereas the iron signature is present at the actinide edge. We have shown that the actinide coordination sphere in actinides hexa-cyanoferrates is comparable to the one of lanthanides. However, the actinides typical behavior towards the lanthanides is brought to the fore by the An{sup IV} versus Ln{sup III} ions presence in this family of complexes. Contrarily to the 4f electrons, the 5f electrons influence the electronic properties of the compounds of this family. However, the gap between the An-N and Ln-N distances towards the corresponding metals ionic radii do not show any covalence bond evolution between the actinide and lanthanide series. (author)

Robust membrane systems for actinide separations

International Nuclear Information System (INIS)

Jarvinen, Gordon D.; McCleskey, T. Mark; Bluhm, Elizabeth A.; Abney, Kent D.; Ehler, Deborah S.; Bauer, Eve; Le, Quyen T.; Young, Jennifer S.; Ford, Doris K.; Pesiri, David R.; Dye, Robert C.; Robison, Thomas W.; Jorgensen, Betty S.; Redondo, Antonio; Pratt, Lawrence R.; Rempe, Susan L.

2000-01-01

Our objective in this project is to develop very stable thin membrane structures containing ionic recognition sites that facilitate the selective transport of target metal ions, especially the actinides

Separation of actinides and long-lived fission products from high-level radioactive wastes (a review)

International Nuclear Information System (INIS)

Kolarik, Z.

1991-11-01

The management of high-level radioactive wastes is facilitated, if long-lived and radiotoxic actinides and fission products are separated before the final disposal. Especially important is the separation of americium, curium, plutonium, neptunium, strontium, cesium and technetium. The separated nuclides can be deposited separately from the bulk of the high-level waste, but their transmutation to short-lived nuclides is a muchmore favourable option. This report reviews the chemistry of the separation of actinides and fission products from radioactive wastes. The composition, nature and conditioning of the wastes are described. The main attention is paid to the solvent extraction chemistry of the elements and to the application of solvent extraction in unit operations of potential partitioning processes. Also reviewed is the behaviour of the elements in the ion exchange chromatography, precipitation, electrolysis from aqueous solutions and melts, and the distribution between molten salts and metals. Flowsheets of selected partitioning processes are shown and general aspects of the waste partitioning are shortly discussed. (orig.) [de

A new look at actinide recycle

International Nuclear Information System (INIS)

Burch, W.D.; Croff, A.G.; Rawlins, J.A.; Schulz, W.W.

1991-01-01

This paper will address the justification for reexamination of the value of recovering the minor actinides and certain fission products from spent light-water reactor fuels and describe some of the technical progress that has been made since the major studies of a decade ago. During this time, the US Environmental Protection Agency (EPA) and the Nuclear Regulatory Commission have begun establishing detailed criteria and regulations for geologic repositories. An examination of the hazards of waste disposal relative to the EPA release standards reveals that removal of 99.9% of the actinides (Pu, Am, and Np) reduces these hazards quite close to the EPA standards after 300 years' decay of the strontium and cesium. It may be also useful to remove and separately manage and dispose of certain of the long-lived fission products, such as 99 Tc and 129 I. Much additional work is required to fully assess the appropriate target recoveries as the hazards and risks are more closely examined and as the standards are reworked and refined. The two decades before the projected start of the US repository may present a window of opportunity to introduce several better management practices that act to simplify the repository safety issues. From a technical standpoint, significant progress has been made on recovery of the actinides from aqueous wastes though use of the TRUEX process. Additional work is required to demonstrate the application of the process to spent LWR fuels, but it appears straightforward. In addition, work at the Argonne National Laboratory on the liquid-metal reactor metal fuel cycle shows the relative simplicity of recycle of the actinides in that fast reactor cycle. Much work remains to fully demonstrate that actinides from all secondary waste streams can be removed to the target levels from both the aqueous reprocessing of LWR fuel and the pyro processes for the metal-fueled fast reactor. 9 refs., 2 figs

Self-interaction corrected local spin density calculations of actinides

DEFF Research Database (Denmark)

Petit, Leon; Svane, Axel; Szotek, Z

2010-01-01

We use the self-interaction corrected local spin-density approximation in order to describe localization-delocalization phenomena in the strongly correlated actinide materials. Based on total energy considerations, the methodology enables us to predict the ground-state valency configuration...... of the actinide ions in these compounds from first principles. Here we review a number of applications, ranging from electronic structure calculations of actinide metals, nitrides and carbides to the behaviour under pressure of intermetallics, and O vacancies in PuO2....

Concepts for immobilized extractants

International Nuclear Information System (INIS)

Paine, R.T.

1993-01-01

This paper addresses the problem of cleaning actinides from geomedia. In the past actinides were often released to the ground because of their tendency to bind tightly to forms of geomedia, and in addition spills have occurred over time. To remediate these areas involves finding ways to either guarantee the retention of the actinides in the geomedia, or finding ways to extract them and leave the soils clean. One possible way to clean soils is to wash them, which in order to extract actinides means the use of ligands which bind competitively with actinides in the presence of soil fractions. An array of organic ligands is known which bind with actinides, but the larger problem of handling these ligands in a manner which allows concentration of the actinides is still open. The author addresses work to bind such ligands to different types of matrices which can then be used in packed extraction columns to remove actindes from flow streams, and finally concentrated, by using minimal volume backflushing to extract the actinides from the column

Reversible optical sensor for the analysis of actinides in solution

International Nuclear Information System (INIS)

Lesage, B.; Picard, S.; Serein-Spirau, F.; Lereporte, J.P.

2007-01-01

In this work is presented a concept of reversible optical sensor for actinides. It is composed of a p doped conducing polymer support and of an anion complexing the actinides. The chosen conducing polymer is the thiophene-2,5-di-alkoxy-benzene whose solubility and conductivity are perfectly known. The actinides selective ligand is a lacunar poly-oxo-metallate such as P 2 W 17 O 61 10- or SiW 11 O 39 8- which are strong anionic complexing agents of actinides at the oxidation state (IV) even in a very acid medium. The sensor is prepared by spin coating of the composite mixture 'polymer + ligand' on a conducing glass electrode and then tested towards its optical and electrochemical answer in presence of uranium (IV). The absorption change due to the formation of cations complexes by poly-oxo-metallate reveals the presence of uranium (IV). After the measurement, the sensor is regenerated by anodic polarization of the support and oxidation of the uranium (IV) into uranium (VI) which weakly interacts with the poly-oxo-metallate and is then released in solution. (O.M.)

Ab Initio Enhanced calphad Modeling of Actinide-Rich Nuclear Fuels

Energy Technology Data Exchange (ETDEWEB)

Morgan, Dane [Univ. of Wisconsin, Madison, WI (United States); Yang, Yong Austin [Univ. of Wisconsin, Madison, WI (United States)

2013-10-28

The process of fuel recycling is central to the Advanced Fuel Cycle Initiative (AFCI), where plutonium and the minor actinides (MA) Am, Np, and Cm are extracted from spent fuel and fabricated into new fuel for a fast reactor. Metallic alloys of U-Pu-Zr-MA are leading candidates for fast reactor fuels and are the current basis for fast spectrum metal fuels in a fully recycled closed fuel cycle. Safe and optimal use of these fuels will require knowledge of their multicomponent phase stability and thermodynamics (Gibbs free energies). In additional to their use as nuclear fuels, U-Pu-Zr-MA contain elements and alloy phases that pose fundamental questions about electronic structure and energetics at the forefront of modern many-body electron theory. This project will validate state-of-the-art electronic structure approaches for these alloys and use the resulting energetics to model U-Pu-Zr-MA phase stability. In order to keep the work scope practical, researchers will focus on only U-Pu-Zr-{Np,Am}, leaving Cm for later study. The overall objectives of this project are to: Provide a thermodynamic model for U-Pu-Zr-MA for improving and controlling reactor fuels; and, Develop and validate an ab initio approach for predicting actinide alloy energetics for thermodynamic modeling.

Actinide recovery from pyrochemical residues

International Nuclear Information System (INIS)

Avens, L.R.; Clifton, D.G.; Vigil, A.R.

1984-01-01

A new process for recovery of plutonium and americium from pyrochemical waste has been demonstrated. It is based on chloride solution anion exchange at low acidity, which eliminates corrosive HCl fumes. Developmental experiments of the process flowsheet concentrated on molten salt extraction (MSE) residues and gave >95% plutonium and >90% americium recovery. The recovered plutonium contained 6 = from high chloride-low acid solution. Americium and other metals are washed from the ion exchange column with 1N HNO 3 -4.8M NaCl. The plutonium is recovered, after elution, via hydroxide precipitation, while the americium is recovered via NaHCO 3 precipitation. All filtrates from the process are discardable as low-level contaminated waste. Production-scale experiments are now in progress for MSE residues. Flow sheets for actinide recovery from electrorefining and direct oxide reduction residues are presented and discussed

Actinide recovery from pyrochemical residues

International Nuclear Information System (INIS)

Avens, L.R.; Clifton, D.G.; Vigil, A.R.

1985-05-01

We demonstrated a new process for recovering plutonium and americium from pyrochemical waste. The method is based on chloride solution anion exchange at low acidity, or acidity that eliminates corrosive HCl fumes. Developmental experiments of the process flow chart concentrated on molten salt extraction (MSE) residues and gave >95% plutonium and >90% americium recovery. The recovered plutonium contained 6 2- from high-chloride low-acid solution. Americium and other metals are washed from the ion exchange column with lN HNO 3 -4.8M NaCl. After elution, plutonium is recovered by hydroxide precipitation, and americium is recovered by NaHCO 3 precipitation. All filtrates from the process can be discardable as low-level contaminated waste. Production-scale experiments are in progress for MSE residues. Flow charts for actinide recovery from electro-refining and direct oxide reduction residues are presented and discussed

Evaluating the efficacy of a minor actinide burner

International Nuclear Information System (INIS)

Dobbin, K.D.; Kessler, S.F.; Nelson, J.V.; Omberg, R.P.; Wootan, D.W.

1993-06-01

The efficacy of a minor actinide burner can be evaluated by comparing safety and economic parameters to the support ratio. Minor actinide mass produced per unit time in this number of Light Water Reactors (LWRs) can be burned during the same time period in one burner system. The larger the support ratio for a given set of safety and economic parameters, the better. To illustrate this concept, the support ratio for selected Liquid Metal Reactor (LMR) burner core designs was compared with corresponding coolant void worths, a fundamental safety concern following the Chernobyl accident. Results can be used to evaluate the cost in reduced burning of minor actinides caused by LMR sodium void reduction efforts or to compare with other minor actinide burner systems

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

International Nuclear Information System (INIS)

Modolo, G.; Wilden, A.; Geist, A.; Magnusson, D.; Malmbeck, R.

2012-01-01

The selective partitioning (P) of long-lived minor actinides from highly 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 Juelich (FZJ), Karlsruher Institut fuer 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. (orig.)

Extraction of metal values

Energy Technology Data Exchange (ETDEWEB)

Dalton, R F

1988-10-19

Metal values (especially uranium values) are extracted from aqueous solutions of metal oxyions in the absence of halogen ion using an imidazole of defined formula. Especially preferred extractants are 1-alkyl imidazoles and benzimidazoles having from 7 to 25 carbon atoms in the alkyl group.

The actinides

International Nuclear Information System (INIS)

Bagnall, K.W.

1987-01-01

This chapter of coordination compound chemistry is devoted to the actinides and starts with a general survey. Most of the chapter relates to thorium and uranium but protactinium, neptunium and plutonium are included. There are sections on nitrogen, phosphorus, sulfur, selenium, tellurium and halogen ligands of the metals in their +3, +4, +5 and +6 oxidation states and of the transplutonium elements in their +2, +3, +4, and +5 oxidation states. (UK)

Extraction process for removing metallic impurities from alkalide metals

Science.gov (United States)

Royer, Lamar T.

1988-01-01

A development is described for removing metallic impurities from alkali metals by employing an extraction process wherein the metallic impurities are extracted from a molten alkali metal into molten lithium metal due to the immiscibility of the alkali metals in lithium and the miscibility of the metallic contaminants or impurities in the lithium. The purified alkali metal may be readily separated from the contaminant-containing lithium metal by simple decanting due to the differences in densities and melting temperatures of the alkali metals as compared to lithium.

The actinides-a beautiful ending of the Periodic Table

International Nuclear Information System (INIS)

Johansson, Boerje; Li, Sa

2007-01-01

The 5f elements, actinides, show many properties which have direct correspondence to the 4f transition metals, the lanthanides. The remarkable similarity between the solid state properties of compressed Ce and the actinide metals is pointed out in the present paper. The α-γ transition in Ce is considered as a Mott transition, namely, from delocalized to localized 4f states. An analogous behavior is also found for the actinide series, where the sudden volume increase from Pu to Am can be viewed upon as a Mott transition within the 5f shell as a function of the atomic number Z. On the itinerant side of the Mott transition, the earlier actinides (Pa-Pu) show low symmetry structures at ambient conditions; while across the border, the heavier elements (Am-Cf) present the dhcp structure, an atomic arrangement typical for the trivalent lanthanide elements with localized 4f magnetic moments. The reason for an isostructural Mott transition of the f electron in Ce, as opposed to the much more complicated cases in the actinides, is identified. The strange appearance of the δ-phase (fcc) in the phase diagram of Pu is another consequence of the border line behavior of the 5f electrons. The path leading from δ-Pu to α-Pu is identified

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

Energy Technology Data Exchange (ETDEWEB)

Francois, N [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

2000-07-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

Energy Technology Data Exchange (ETDEWEB)

Francois, N. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

2000-07-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

Uranium(VI) and ruthenium extraction by dialkyldithio-phosphoric acids

International Nuclear Information System (INIS)

Fitoussi, R.; Musikas, C.

1980-01-01

Oxygen donors like dialkylphosphoric acids are good extractants for actinide ions, but little is known about their sulfur homologs. Investigations of U(VI) and Ru extraction from various aqueous media are reported. This includes extraction of U(VI) from nitric, perchloric, and phosphoric acids by solutions of dialkyldithiophosphoric acids in dodecane or benzene. Extraction of U(VI) by synergistic mixtures, of which at least one of the components is a sulfur donor, has been investigated. The extracted species have been identified, and a comparison with the complexes obtained by extraction with the homologous oxygen donors is made. The sulfur-actinide bond is weaker than the oxygen-actinide one, but in some synergistic extractions the dialkyldithiophosphonates are more efficient than the oxygen donors. In addition to size effects, this behavior could be attributed to the weakness of the hydrogen bonds of the SH groups, which allows a greater variety of the ligands to enter the coordination sphere of the metal. Ruthenium, like the d-transition elements, gives strong bonds with the sulfur donors. However, its extraction from nitric acid is slow. We investigated the influence of several parameters on the distribution coefficients and found that the presence of a reagent which destroys nitrous ions is necessary to achieve quantitative extraction. The role of RuNO groups is also discussed

Halogen protected cobalt bis(dicarbollide) ions with covalently bonded CMPO functions as anionic extractants for trivalent lanthanide/actinide partitioning

Czech Academy of Sciences Publication Activity Database

Grüner, Bohumír; Švec, Petr; Selucký, P.; Bubeníková, M.

2012-01-01

Roč. 38, č. 1 (2012), s. 103-112 ISSN 0277-5387 R&D Projects: GA ČR GA104/09/0668 Institutional research plan: CEZ:AV0Z40320502 Keywords : carboranes * metallaboranes * dicarbollides * CMPR * liquid-liquid extraction * lanthanides * actinides Subject RIV: CA - Inorganic Chemistry Impact factor: 1.813, year: 2012

Rapid Separation Methods to Characterize Actinides and Metallic Impurities in Plutonium Scrap Materials at SRS

International Nuclear Information System (INIS)

Maxwell, S.L. III; Jones, V.D.

1998-07-01

The Nuclear Materials Stabilization and Storage Division at SRS plans to stabilize selected plutonium scrap residue materials for long term storage by dissolution processing and plans to stabilize other plutonium vault materials via high-temperature furnace processing. To support these nuclear material stabilization activities, the SRS Analytical Laboratories Department (ALD) will provide characterization of materials required prior to the dissolution or the high-firing of these materials. Lab renovations to install new analytical instrumentation are underway to support these activities that include glove boxes with simulated-process dissolution and high- pressure microwave dissolution capability. Inductively-coupled plasma atomic emission spectrometry (ICP-AES), inductively- coupled mass spectrometry (ICP-MS) and thermal-ionization mass spectrometry (TIMS) will be used to measure actinide isotopics and metallic impurities. New high-speed actinide separation methods have been developed that will be applied to isotopic characterization of nuclear materials by TIMS and ICP-MS to eliminate isobaric interferences between Pu-238 /U- 238 and Pu-241/Am-241. TEVA Resin, UTEVA Resin, and TRU Resin columns will be used with vacuum-assisted flow rates to minimize TIMS and ICP-MS sample turnaround times. For metallic impurity analysis, rapid column removal methods using UTEVA Resin, AGMP-1 anion resin and AG MP-50 cation resin have also been developed to remove plutonium and uranium matrix interferences prior to ICP-AES and ICP- MS measurements

Phoenix type concepts for transmutation of LWR waste minor actinides

International Nuclear Information System (INIS)

Segev, M.

1994-01-01

A number of variations on the original Phoenix theme were studied. The basic rationale of the Phoenix incinerator is making oxide fuel of the LWR waste minor actinides, loading it in an FFTF-like subcritical core, then bombarding the core with the high current beam accelerated protons to generate considerable energy through spallation and fission reactions. As originally assessed, if the machine is fed with 1600 MeV protons in a 102 mA current, then 8 core modules are driven to transmute the yearly minor actinides waste of 75 1000 MW LWRs into Pu 238 and fission products; in a 2 years cycle the energy extracted is 100000 MW d/T. This performance cannot be substantiated in a rigorous analysis. A calculational consistent methodology, based on a combined execution of the Hermes, NCNP, and Korigen codes, shows, nonetheless that changes in the original Phoenix parameters can upgrade its performance.The original Phoenix contains 26 tons minor actinides in 8 core modules; 1.15 m 3 module is shaped for 40% neutron leakage; with a beam of 102 mA the 8 modules are driven to 100000 MW/T in 10.5 years, burning out the yearly minor actinide waste of 15 LWRs; the operation must be assisted by grid electricity. If the 1.15 m 3 module is shaped to allow only 28% leakage, then a beam of 102 mA will drive the 8 modules to 100000 MW/T in 3.5 years, burning out the yearly minor actinides waste of 45 LWRs. Some net grid electricity will be generated. If 25 tons minor actinides are loaded into 5 modules, each 1.72 m 3 in volume and of 24% leakage, then a 97 mA beam will drive the module to 100000 MW/T in 2.5 years, burning out the yearly minor actinides waste of 70 LWRs. A considerable amount of net grid electricity will be generated. If the lattice is made of metal fuel, and 26 tons minor actinides are loaded into 32 small modules, 0.17 m 3 each, then a 102 mA beam will drive the modules to 100000 MW/T in 2 years, burning out the yearly minor actinides waste of 72 LWRs. A considerable

Predictive Modeling in Actinide Chemistry and Catalysis

Energy Technology Data Exchange (ETDEWEB)

Yang, Ping [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)

2016-05-16

These are slides from a presentation on predictive modeling in actinide chemistry and catalysis. The following topics are covered in these slides: Structures, bonding, and reactivity (bonding can be quantified by optical probes and theory, and electronic structures and reaction mechanisms of actinide complexes); Magnetic resonance properties (transition metal catalysts with multi-nuclear centers, and NMR/EPR parameters); Moving to more complex systems (surface chemistry of nanomaterials, and interactions of ligands with nanoparticles); Path forward and conclusions.

Actinide separations by supported liquid membranes

International Nuclear Information System (INIS)

Danesi, P.R.; Horwitz, E.P.; Rickert, P.; Chiarizia, R.

1984-01-01

The work has demonstrated that actinide removal from synthetic waste solutions using both flat-sheet and hollow-fiber SLM's is a feasible chemical process at the laboratory scale level. The process is characterized by the typical features of SLM's processes: very small quantities of extractant required; the potential for operations with high feed/strip volume ratios, resulting in a corresponding concentration factor of the actinides; and simplicity of operation. Major obstacles to the implementation of the SLM technology to the decontamination of liquid nuclear wastes are the probable low resistance of polypropylene supports to high radiation fields, which may prevent the application to high-level nuclear wastes; the unknown lifetime of the SLM; and the high Na content of the separated actinide solution

Predictive thermodynamic models for liquid--liquid extraction of single, binary and ternary lanthanides and actinides

International Nuclear Information System (INIS)

Hoh, Y.C.

1977-03-01

Chemically based thermodynamic models to predict the distribution coefficients and the separation factors for the liquid--liquid extraction of lanthanides-organophosphorus compounds were developed by assuming that the quotient of the activity coefficients of each species varies slightly with its concentrations, by using aqueous lanthanide or actinide complexes stoichiometric stability constants expressed as its degrees of formation, by making use of the extraction mechanism and the equilibrium constant for the extraction reaction. For a single component system, the thermodynamic model equations which predict the distribution coefficients, are dependent on the free organic concentration, the equilibrated ligand and hydrogen ion concentrations, the degree of formation, and on the extraction mechanism. For a binary component system, the thermodynamic model equation which predicts the separation factors is the same for all cases. This model equation is dependent on the degrees of formation of each species in their binary system and can be used in a ternary component system to predict the separation factors for the solutes relative to each other

Actinide recycling by pyro process for future nuclear fuel cycle system

International Nuclear Information System (INIS)

Inoue, T.

2001-01-01

Pyrometallurgical technology is one of the potential devices for the future nuclear fuel cycle. Not only economic advantage but also environmental safety and strong resistance for proliferation are required. So as to satisfy the requirements, actinide recycling applicable to LWR and FBR cycles by pyro-process has been developed over a ten-year period at the CRIEPI. The main technology is electrorefining for U and Pu separation and reductive extraction for TRU separation, which can be applied on oxide fuels through reduction process as well as metal fuels. The application of this technology for separation of TRU in HLLW through chlorination could contribute to the improvement of public acceptance with regard to geologic disposal. The main achievements are summarised as follows: - Elemental technologies such as electrorefining, reductive extraction, injection casting and salt waste treatment and solidification have been successfully developed with lots of experiments. - Fuel dissolution into molten salt and uranium recovery on solid cathode for electrorefining has been demonstrated at an engineering scale facility in Argonne National Laboratory using spent fuels and at the CRIEPI through uranium tests. - Single element tests using actinides showed Li reduction to be technically feasible; the subjects of technical feasibility on multi-element systems and on effective recycle of Li by electrolysis of Li 2 O remain to be addressed. - Concerning the treatment of HLLW for actinide separation, the conversion to chlorides through oxides has also been established through uranium tests. - It is confirmed that more than 99% of TRU nuclides can be recovered from high-level liquid waste by TRU tests. - Through these studies, the process flowsheets for reprocessing of metal and oxide fuels and for partitioning of TRU separation have been established. The subjects to be emphasised for further development are classified into three categories: process development (demonstration

Combining extractant systems for the simultaneous extraction of transuranic elements and selected fission products

International Nuclear Information System (INIS)

Horwitz, E.P.

1993-01-01

The popularity of solvent extraction (SX) stems from its ability to operate in a continuous mode, to achieve high throughputs and high decontamination factors of product streams, and to utilize relatively small quantities of very selective chemical compounds as metal ion complexants. The chemical pretreatment of nuclear waste for the purpose of waste minimization will probably utilize one or more SX processes. Because of the diversity and complexity of nuclear waste, perhaps the greatest difficulty for the separation chemist is to develop processes that remove not only actinides but also selected fission products in a single process. A stand alone acid-side SX process (TRUEX) for removal of uranium and transuranic elements (Np, Pu, Am) from nuclear waste has been widely reported. Recently, an acid-side SX process (SREX) to extract and recover 90 Sr from high-level nuclear waste has also been reported. Both the TRUEX and SREX processes extract Tc to a significant extent although not as efficiently as they extract transuranics and Sr. Ideally one would like to have a process that can extract and recover all actinides as well as 99 Tc, 90 Sr, and 137 Cs. A possible solution to multielement extraction is to mix two extractants with totally different properties into a single process solvent formulation. For this approach to be successful, both extractants must be essentially the same type, either neutral, liquid cationic, or liquid anionic. Experimental work has been carried out on mixed TRUEX and SREX processes, for synthetically created waste, and demonstrates the combined solvent formulation is effective at extracting both the actinides and Tc, as well as Sr. There is no evidence for the presence of either synergistic or antagonistic effects between the two extractants. This demonstates the feasibility of at least part of a combined solvent extraction scheme

Spin–orbit coupling in actinide cations

DEFF Research Database (Denmark)

Bagus, Paul S.; Ilton, Eugene S.; Martin, Richard L.

2012-01-01

The limiting case of Russell–Saunders coupling, which leads to a maximum spin alignment for the open shell electrons, usually explains the properties of high spin ionic crystals with transition metals. For actinide compounds, the spin–orbit splitting is large enough to cause a significantly reduced...... spin alignment. Novel concepts are used to explain the dependence of the spin alignment on the 5f shell occupation. We present evidence that the XPS of ionic actinide materials may provide direct information about the angular momentum coupling within the 5f shell....

Moessbauer effect studies with actinides

International Nuclear Information System (INIS)

Stone, J.A.

1966-01-01

Moessbauer resonance studies in the actinide elements offer a new technique for measuring solid-state properties to a region of the periodic chart where such information is relatively sparse. It is well known that the actinides, the elements with atomic numbers from 90 to 103, form a transition series due to filling of the 5f electron shell, analogous to the rare-earth series in which the 4f shell is filled. Like the rare earths, the actinide metals and compounds are expected to exhibit a variety of interesting magnetic properties, but, unlike the rare earths, there have been few studies of the magnetic behaviour of actinides, and these properties are largely unknown. The chemical properties of the actinides have been studied somewhat more extensively, and, in contrast to the rare earths, form a multiplicity of stable valence states, especially in the lighter members of the series. It is just these properties, magnetic and chemical, for which the Moessbauer effect is a valuable probe, sensitive to the magnetic and electric environment of an atom. The rare-earth series has been a particularly fruitful region in terms of the number of elements which have been shown to exhibit the Moessbauer effect, and for this reason the exploitation of the Moessbauer effect to yield new solid-state and chemical information on the rare earths is a highly active field of research today. There is every reason to believe that the actinides can be similarly studied by the Moessbauer effect. 43 refs, 6 figs, 4 tabs

Partitioning of actinide from simulated high level wastes arising from reprocessing of PHWR fuels: counter current extraction studies using CMPO

International Nuclear Information System (INIS)

Deshingkar, D.S.; Chitnis, R.R.; Wattal, P.K.; Theyyunni, T.K.; Nair, M.K.T.; Ramanujam, A.; Dhami, P.S.; Gopalakrishnan, V.; Rao, M.K.; Mathur, J.N.; Murali, M.S.; Iyer, R.H.; Badheka, L.P.; Banerji, A.

1994-01-01

High level wastes (HLW) arising from reprocessing of pressurised heavy water reactor (PHWR) fuels contain actinides like neptunium, americium and cerium which are not extracted in the Purex process. They also contain small quantities of uranium and plutonium in addition to fission products. Removal of these actinides prior to vitrification of HLW can effectively reduce the active surveillance period of final waste form. Counter current studies using indigenously synthesised octyl (phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) were taken up as a follow-up of successful runs with simulated sulphate bearing low acid HLW solutions. The simulated HLW arising from reprocessing of PHWR fuel was prepared based on presumed burnup of 6500 MWd/Te of uranium, 3 years cooling period and 800 litres of waste generation per tonne of fuel reprocessed. The alpha activity of the HLW raffinate after extraction with the CMPO-TBP mixture could be brought down to near background level. (author). 13 refs., 2 tabs., 12 figs

Partitioning of actinide from simulated high level wastes arising from reprocessing of PHWR fuels: counter current extraction studies using CMPO

Energy Technology Data Exchange (ETDEWEB)

Deshingkar, D S; Chitnis, R R; Wattal, P K; Theyyunni, T K; Nair, M K.T. [Bhabha Atomic Research Centre, Bombay (India). Process Engineering and Systems Development Div.; Ramanujam, A; Dhami, P S; Gopalakrishnan, V; Rao, M K [Bhabha Atomic Research Centre, Bombay (India). Fuel Reprocessing Group; Mathur, J N; Murali, M S; Iyer, R H [Bhabha Atomic Research Centre, Bombay (India). Radiochemistry Div.; Badheka, L P; Banerji, A [Bhabha Atomic Research Centre, Bombay (India). Bio-organic Div.

1994-12-31

High level wastes (HLW) arising from reprocessing of pressurised heavy water reactor (PHWR) fuels contain actinides like neptunium, americium and cerium which are not extracted in the Purex process. They also contain small quantities of uranium and plutonium in addition to fission products. Removal of these actinides prior to vitrification of HLW can effectively reduce the active surveillance period of final waste form. Counter current studies using indigenously synthesised octyl (phenyl)-N, N-diisobutylcarbamoylmethylphosphine oxide (CMPO) were taken up as a follow-up of successful runs with simulated sulphate bearing low acid HLW solutions. The simulated HLW arising from reprocessing of PHWR fuel was prepared based on presumed burnup of 6500 MWd/Te of uranium, 3 years cooling period and 800 litres of waste generation per tonne of fuel reprocessed. The alpha activity of the HLW raffinate after extraction with the CMPO-TBP mixture could be brought down to near background level. (author). 13 refs., 2 tabs., 12 figs.

Actinide analytical program for characterization of Hanford waste

International Nuclear Information System (INIS)

Johnson, S.J.; Winters, W.I.

1977-01-01

The objective of this program has been to develop faster, more accurate methods for the concentration and determination of actinides at their maximum permissible concentration (MPC) levels in a controlled zone. These analyses are needed to characterize various forms of Hanford high rad waste and to support characterization of products and effluents from new waste management processes. The most acceptable methods developed for the determination of 239 Pu, 238 Pu, 237 Np, 241 Am, and 243 Cm employ solvent extraction with the addition of tracer isotopes. Plutonium and neptunium are extracted from acidified waste solutions into Aliquat-336. Americium and curium are then extracted from the waste solution at the same acidity into dihexyl-N,N-diethylcarbamylmethylenephosphonate (DHDECMP). After back extraction into an aqueous matrix, these actinides are electrodeposited on steel disks for alpha energy analysis. Total uranium and total thorium are also isolated by solvent extraction and determined spectrophotometrically

Ionic Liquid and Supercritical Fluid Hyphenated Techniques for Dissolution and Separation of Lanthanides, Actinides, and Fission Products

International Nuclear Information System (INIS)

Wai, Chien M.; Mincher, Bruce

2012-01-01

This project is investigating techniques involving ionic liquids (IL) and supercritical (SC) fluids for dissolution and separation of lanthanides, actinides, and fission products. The research project consists of the following tasks: Study direct dissolution of lanthanide oxides, uranium dioxide and other actinide oxides in [bmin][Tf 2 N] with TBP(HNO 3 ) 1.8 (H 2 O) 0.6 and similar types of Lewis acid-Lewis base complexing agents; Measure distributions of dissolved metal species between the IL and the sc-CO 2 phases under various temperature and pressure conditions; Investigate the chemistry of the dissolved metal species in both IL and sc-CO 2 phases using spectroscopic and chemical methods; Evaluate potential applications of the new extraction techniques for nuclear waste management and for other projects. Supercritical carbon dioxide (sc-CO 2 ) and ionic liquids are considered green solvents for chemical reactions and separations. Above the critical point, CO 2 has both gas- and liquid-like properties, making it capable of penetrating small pores of solids and dissolving organic compounds in the solid matrix. One application of sc-CO 2 extraction technology is nuclear waste management. Ionic liquids are low-melting salts composed of an organic cation and an anion of various forms, with unique properties making them attractive replacements for the volatile organic solvents traditionally used in liquid-liquid extraction processes. One type of room temperature ionic liquid (RTIL) based on the 1-alkyl-3-methylimidazolium cation [bmin] with bis(trifluoromethylsulfonyl)imide anion [Tf 2 N] is of particular interest for extraction of metal ions due to its water stability, relative low viscosity, high conductivity, and good electrochemical and thermal stability. Recent studies indicate that a coupled IL sc-CO 2 extraction system can effectively transfer trivalent lanthanide and uranyl ions from nitric acid solutions. Advantages of this technique include operation at

Use of fast reactors for actinide transmutation. Proceedings of a specialists meeting held in Obninsk, Russian Federation, 22-24 September 1992

Energy Technology Data Exchange (ETDEWEB)

1993-03-15

The management of radioactive waste is one of the key issues in today`s discussions on nuclear energy, especially the long term disposal of high level radioactive wastes. The recycling of plutonium in liquid metal fast breeder reactors (LMFBRs) would allow `burning` of the associated extremely long life transuranic waste, particularly actinides, thus reducing the required isolation time for high level waste from tens of thousands of years to hundreds of years for fission products only. The International Working Group on Fast Reactors (IWGFR) decided to include the topic of actinide transmutation in liquid metal fast breeder reactors in its programme. The IAEA organized the Specialists Meeting on Use of Fast Breeder Reactors for Actinide Transmutation in Obninsk, Russian Federation, from 22 to 24 September 1992. The specialists agree that future progress in solving transmutation problems could be achieved by improvements in: Radiochemical partitioning and extraction of the actinides from the spent fuel (at least 98% for Np and Cm and 99.9% for Pu and Am isotopes); technological research and development on the design, fabrication and irradiation of the minor actinides (MAs) containing fuels; nuclear constants measurement and evaluation (selective cross-sections, fission fragments yields, delayed neutron parameters) especially for MA burners; demonstration of the feasibility of the safe and economic MA burner cores; knowledge of the impact of maximum tolerable amount of rare earths in americium containing fuels. Refs, figs and tabs.

Actinide burning in the integral fast reactor

International Nuclear Information System (INIS)

Chang, Y.I.

1993-01-01

During the past few years, Argonne National Laboratory has been developing the integral fast reactor (IFR), an advanced liquid-metal reactor concept. In the IFR, the inherent properties of liquid-metal cooling are combined with a new metallic fuel and a radically different refining process to allow breakthroughs in passive safety, fuel cycle economics, and waste management. A key feature of the IFR concept is its unique pyroprocessing. Pyroprocessing has the potential to radically improve long-term waste management strategies by exploiting the following attributes: 1. Minor actinides accompany plutonium product stream; therefore, actinide recycling occurs naturally. Actinides, the primary source of long-term radiological toxicity, are removed from the waste stream and returned to the reactor for in situ burning, generating useful energy. 2. High-level waste volume from pyroprocessing call be reduced substantially as compared with direct disposal of spent fuel. 3. Decay heat loading in the repository can be reduced by a large factor, especially for the long-term burden. 4. Low-level waste generation is minimal. 5. Troublesome fission products, such as 99 Tc, 129 I, and 14 C, are contained and immobilized. Singly or in combination, the foregoing attributes provide important improvements in long-term waste management in terms of the ease in meeting technical performance requirements (perhaps even the feasibility of demonstrating that technical performance requirements can be met) and perhaps also in ultimate public acceptance. Actinide recycling, if successfully developed, could well help the current repository program by providing an opportunity to enhance capacity utilization and by deferring the need for future repositories. It also represents a viable technical backup option in the event unforeseen difficulties arise in the repository licensing process

Actinide uptake by transferrin and ferritin metalloproteins

International Nuclear Information System (INIS)

Den Auwer, C.; Llorens, I.; Moisy, Ph.; Vidaud, C.; Goudard, F.; Barbot, C.; Solari, P.L.; Funke, H.

2005-01-01

In order to better understand the mechanisms of actinide uptake by specific biomolecules, it is essential to explore the intramolecular interactions between the cation and the protein binding site. Although this has long been done for widely investigated transition metals, very few studies have been devoted to complexation mechanisms of actinides by active chelation sites of metalloproteins. In this field, X-ray absorption spectroscopy has been extensively used as a structural and electronic metal cation probe. The two examples that are presented here are related to two metalloproteins in charge of iron transport and storage in eukaryote cells: transferrin and ferritin. U(VI)O 2 2+ , Np(IV) and Pu(IV) have been selected because of their possible role as contaminant from the geosphere. (orig.)

Electrochemical properties of LiMn2O4 cathode material doped with an actinide

International Nuclear Information System (INIS)

Eftekhari, Ali; Moghaddam, Abdolmajid Bayandori; Solati-Hashjin, Mehran

2006-01-01

Metal substation as an efficient approach for improvement of battery performance of LiMn 2 O 4 was performed by an actinide dopant. Uranium as the last natural element and most common actinide was employed for this purpose. Cyclic voltammetric studies revealed that incorporation of uranium into LiMn 2 O 4 spinel significantly improves electrochemical performance. It also strengthens the spinel stability to exhibit better cycleability. Surprisingly, the capacity increases upon cycling of LiU 0.01 Mn 1.99 O 4 cathode. This inverse behavior is attributed to uniform distribution of dopant during insertion/extraction process. In other words, this is an electrochemical refinement of the nanostructure which is not detectable in microscale morphology, as rearrangement of dopant in nanoscale occurs and this is an unexceptional nanostructural ordering. In addition, uranium doping strengthens the Li diffusion, particularly at redox potentials

Use of fast-spectrum reactors for actinide burning

International Nuclear Information System (INIS)

Chang, Yoon I.

1991-01-01

Finally, Integral Fast Reactor (IFR) pyroprocessing has been developed only in recent years and it appears to have potential as a relatively uncomplicated, effective actinide recovery process. In fact, actinide recycling occurs naturally in the IFR fuel cycle. Although still very much developmental, the entire IFR fuel cycle will be demonstrated on prototype-scale in conjunction with the EBR-II and its refurbished Fuel Cycle Facility starting in late 1991. A logical extension to this work, therefore, is to establish whether this IFR pyrochemical processing can be applied to extracting actinides from LWR spent fuel. This paper summarizes current thinking on the rationale for actinide recycle, its ramifications on the geologic repository and the current high-level waste management plans, and the necessary development programs. 4 figs., 4 tabs

Actinide speciation in the environment

International Nuclear Information System (INIS)

Choppin, G.R.

2007-01-01

Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is much more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK sp ≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO 2 2+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO 3 ) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH) 4 , in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is

Critical masses for the even-neutron-numbered transuranium actinides

International Nuclear Information System (INIS)

Westfall, R.M.

1981-01-01

As part of a standards effort of the American Nuclear Society to establish subcritical mass limits for the transuranium actinides, critical masses were calculated for seven actinides, critical masses were calculated for seven actinide elements in bare, water-reflected, and steel-reflected metal systems. For the nuclides /sup 242/Pu and /sup 241/Am, values obtained with ENDF/B-V cross-section data were in much better agreement with values inferred from experimental measurement than were initial values calculated with ENDF/B-IV data. A brief description of the analytical methods employed is followed by a presentation of the results. 10 refs

Electrochemical reduction of actinides oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.

2011-01-01

Reactive metals are currently produced from their oxide by multiple steps reduction techniques. A one step route from the oxide to the metal has been suggested for metallic titanium production by electrolysis in high temperature molten chloride salts. In the so-called FFC process, titanium oxide is electrochemically reduced at the cathode, generating O 2- ions, which are converted on a graphite anode into carbon oxide or dioxide. After this process, the spent salt can in principle be reused for several batches which is particularly attractive for a nuclear application in terms of waste minimization. In this work, the electrochemical reduction process of cerium oxide (IV) is studied in CaCl 2 and CaCl 2 -KCl melts to understand the oxide reduction mechanism. Cerium is used as a chemical analogue of actinides. Electrolysis on 10 grams of cerium oxide are made to find optimal conditions for the conversion of actinides oxides into metals. The scale-up to hundred grams of oxide is also discussed. (author) [fr

Waste management analysis for the nuclear fuel cycle. I. Actinide recovery from aqueous salt wastes

International Nuclear Information System (INIS)

Martella, L.L.; Navratil, J.D.

1979-01-01

A preliminary feasibility study of solvent extraction methods has been completed for removing actinides from selected salt wastes likely to be produced during reactor fuel fabrication and reprocessing. The use of a two-step solvent extraction system, tributyl phosphate (TBP) followed by a bidentate organophosphorus extractant (DHDECMP), appears most efficient for removing actinides from salt waste. The TBP step would remove most of the plutonium and >99.99% of the uranium. The second step, using DHDECMP, would remove >99.91% of the americium, the remaining plutonium (>99.98%), and other actinides from the acidified salt waste

Actinides and fission products partitioning from high level liquid waste

International Nuclear Information System (INIS)

Yamaura, Mitiko

1999-01-01

The presence of small amount of mixed actinides and long-lived heat generators fission products as 137 Cs and 90 Sr are the major problems for safety handling and disposal of high level nuclear wastes. In this work, actinides and fission products partitioning process, as an alternative process for waste treatment is proposed. First of all, ammonium phosphotungstate (PWA), a selective inorganic exchanger for cesium separation was chosen and a new procedure for synthesizing PWA into the organic resin was developed. An strong anionic resin loaded with tungstate or phosphotungstate anion enables the precipitation of PWA directly in the resinous structure by adding the ammonium nitrate in acid medium (R-PWA). Parameters as W/P ratio, pH, reactants, temperature and aging were studied. The R-PWA obtained by using phosphotungstate solution prepared with W/P=9.6, 9 hours digestion time at 94-106 deg C and 4 to 5 months aging time showed the best capacity for cesium retention. On the other hand, Sr separation was performed by technique of extraction chromatography, using DH18C6 impregnated on XAD7 resin as stationary phase. Sr is selectively extracted from acid solution and >99% was recovered from loaded column using distilled water as eluent. Concerning to actinides separations, two extraction chromatographic columns were used. In the first one, TBP(XAD7) column, U and Pu were extracted and its separations were carried-out using HNO 3 and hydroxylamine nitrate + HNO 3 as eluent. In the second one, CMP0-TBP(XAD7) column, the actinides were retained on the column and the separations were done by using (NH 4 ) 2 C 2 O 4 , DTPA, HNO 3 and HCl as eluent. The behavior of some fission products were also verified in both columns. Based on the obtained data, actinides and fission products Cs and Sr partitioning process, using TBP(XAD7) and CMP0-TBP(XAD7) columns for actinides separation, R-PWA column for cesium retention and DH18C6(XAD7) column for Sr isolation was performed

Interactions of Microbes found at Aespoe Underground Lab with Actinides such as Curium, Plutonium and Uranium

Energy Technology Data Exchange (ETDEWEB)

Moll, H.; Merroun, M.; Geipel, G.; Rossberg, A.; Hennig, C.; Selenska-Pobell , S.; Bernhard, G. [Forschungszentrum Dresden-Rossendorf e.V., Inst. fuer Radioc hemie, 01314 Dresden (Germany)]. e-mail: h.moll@fzd.de; Stumpf, Th. [Forschungszentru m Karlsruhe, Inst. fuer Nukleare Entsorgung, 76021 Karlsruhe (Germany)

2007-06-15

Sulfate-reducing bacteria (SRB) frequently occur in the deep granitic rock aquifers at the Aespoe Hard Rock Laboratory (Aespoe HRL), Sweden. The new SRB strain Desulfovibrio aespoeensis could be isolated. Results describing the basic interaction mechanisms of uranium, curium, and plutonium with cells of D. aespoeensis DSM 10631T will be presented. The interaction experiments with the actinides showed that the cells are able to remove all three actinides from the surrounding solution. The amount of removed actinide and the interaction mechanism varied among the different actinides. The main U(VI) removal occurred after the first 24 h. The contact time, pH and [U(VI)]initial influence the U removal efficiency. The presence of uranium caused a damaging of the cell membranes. TEM revealed an accumulation of U inside the bacterial cell. D. aespoeensis are able to form U(IV). A complex interaction mechanism takes place consisting of biosorption, bioreduction and bioaccumulation. In the case of {sup 242}Pu, solvent extractions, UV-vis- and XANES spectroscopy were used to determine the speciation of the Pu oxidation states. In the first step, the Pu(VI) and Pu(IV)-polymers are bound to the biomass. Solvent extractions showed that 97 % of the initially present Pu(VI) is reduced to Pu(V) due to the activity of the cells within the first 24 h. Most of the formed Pu(V) dissolves from the cell envelope back to the aqueous solution due to the weak complexing properties of this plutonium oxidation state. In the case of curium at a much lower metal concentration of 3x10{sup -7} M, a pure biosorption of Cm(III) on the cell envelope forming an inner-sphere surface complex most likely with organic phosphate groups was detected. To summarize, the strength of the interaction of D. aespoeensis with the selected actinides at pH 5 and actinide concentrations = 10 mg/L ([Cm] 0.07 mg/L) follows the pattern: Cm > U > Pu >> Np.

The chemistry of the actinide elements. Volume I

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1986-01-01

The Chemistry of the Actinide Elements is a comprehensive, contemporary and authoritative exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

Pyrochemical reprocessing of molten salt fast reactor fuel: focus on the reductive extraction step

Directory of Open Access Journals (Sweden)

Rodrigues Davide

2015-12-01

Full Text Available The nuclear fuel reprocessing is a prerequisite for nuclear energy to be a clean and sustainable energy. In the case of the molten salt reactor containing a liquid fuel, pyrometallurgical way is an obvious way. The method for treatment of the liquid fuel is divided into two parts. In-situ injection of helium gas into the fuel leads to extract the gaseous fission products and a part of the noble metals. The second part of the reprocessing is performed by ‘batch’. It aims to recover the fissile material and to separate the minor actinides from fission products. The reprocessing involves several chemical steps based on redox and acido-basic properties of the various elements contained in the fuel salt. One challenge is to perform a selective extraction of actinides and lanthanides in spent liquid fuel. Extraction of actinides and lanthanides are successively performed by a reductive extraction in liquid bismuth pool containing metallic lithium as a reductive reagent. The objective of this paper is to give a description of the several steps of the reprocessing retained for the molten salt fast reactor (MSFR concept and to present the initial results obtained for the reductive extraction experiments realized in static conditions by contacting LiF-ThF4-UF4-NdF3 with a lab-made Bi-Li pool and for which extraction efficiencies of 0.7% for neodymium and 14.0% for uranium were measured. It was concluded that in static conditions, the extraction is governed by a kinetic limitation and not by the thermodynamic equilibrium.

Electro-spray Ionization Mass Spectrometry Investigation of BTBP - Lanthanide(III) and Actinide(III) Complexes

Energy Technology Data Exchange (ETDEWEB)

Retegan, T.; Ekberg, Ch. [Chalmers, Dept Chem and Biol Engn, SE-41296 Gothenburg, (Sweden); Berthon, L.; Zorz, N. [DEN DRCP SCPS LCSE, CEA Marcoule, Bagnols Sur Ceze, (France)

2009-07-01

In the framework of nuclear waste reprocessing, the separation processes of minor actinides from fission products are developed using liquid-liquid extraction. To gain an understanding of the mechanism involved in the extraction process, a complex formation of actinides and lanthanides with BTBPs (6, 6'-bis(5, 6-dialkyl-1, 2, 4-triazin-3-yl)-2, 2'-bipyridines) was characterized using the Electro-spray Ionization Mass Spectrometry (ESI-MS) technique. This study was carried out to compare the influence of diluents and side groups of the extractants on complex formation. Three different diluents, nitrobenzene, octanol and cyclohexanone, and two extractants, C5-BTBP and CyMe{sub 4}-BTBP, were selected for this experiment. It was found that the change of the diluent and of the substituent on the BTBP moiety does not modify the stoichiometry of the complexes which is L{sub 2}M(NO{sub 3}){sub 3}. It is proposed that one nitrate is directly coordinated to the metal ion, the two other anions probably remaining in the outer coordination sphere. The difference observed in extracting properties is probably due to the solvation of the complexes by the diluent. The noncovalent force that holds complexes together are likely to be largely governed by electrostatic interactions even if the hydrophobic exterior of the complexes plays an important role in the complexation/extraction mechanism. The study of the stability of the ions in the gas phase shows that the C5-BTBP ligand has a labile hydrogen atom, which is a fragility point of C5-BTBP. (authors)

Demonstration of innovative partitioning processes for minor actinide recycling from high active waste solutions

International Nuclear Information System (INIS)

Modolo, G.; Wilden, A.; Geist, A.; Malmbeck, R.; Taylor, R.

2014-01-01

The recycling of the minor actinides (MA) using the Partitioning and Transmutation strategy (P and T) could contribute significantly to reducing the volume of high level waste in a geological repository and to decreasing the waste's longterm hazards originating from the long half-life of the actinides. Several extraction processes have been developed worldwide for the separation and recovery of MA from highly active raffinates (HAR, e.g. the PUREX raffinate). A multi-cycle separation strategy has been developed within the framework of European collaborative projects. The multi-cycle processes, on the one hand, make use of different extractants for every single process. Within the recent FP7 European research project ACSEPT (Actinide reCycling by SEParation and Transmutation), the development of new innovative separation processes with a reduced number of cycles was envisaged. In the so-called 'innovative SANEX' concept, the trivalent actinides and lanthanides are co-extracted from the PUREX raffinate by a DIAMEX like process (e.g. TODGA). Then, the loaded solvent is subjected to several stripping steps. The first one concerns selectively stripping the actinides(III) with selective water-soluble ligands (SO3-Ph-BTB), followed by the subsequent stripping of trivalent lanthanides. A more challenging route studied also within our laboratories is the direct actinide(III) separation from a PUREX-type raffinate using a mixture of CyMe 4 BTBP and TODGA as extractants, the so-called One cycle SANEX process. A new approach, which was also studied within the ACSEPT project, is the GANEX (Grouped ActiNide EXtraction) concept addressing the simultaneous partitioning of all transuranium (TRU) elements for their homogeneous recycling in advanced generation IV reactor systems. Bulk uranium is removed in the GANEX 1st cycle, e.g. using a monoamide extractant and the GANEX 2nd cycle then separates the TRU. A solvent composed of TODGA + DMDOHEMA in kerosene has been shown to

Actinide elements in aquatic and terrestrial environments

International Nuclear Information System (INIS)

Bondietti, E.A.; Bogle, M.A.; Brantley, J.N.

1979-01-01

Progress is reported on the following research projects: water-sediment interactions of U, Pu, Am, and Cm; relative availability of actinide elements from abiotic to aquatic biota; comparative uptake of transuranic elements by biota bordering Pond 3513; metabolic reduction of 239 Np from Np(V) to Np(IV) in cotton rats; evaluation of hazards associated with transuranium releases to the biosphere; predicting Pu in bone; adsorption--solubility--complexation phenomena in actinide partitioning between sorbents and solution; comparative soil extraction data; and comparative plant uptake data

Use of two-phase aqueous systems based on water-soluble polymers in thin-layer and extraction chromatography for recovery and separtion of actinides

International Nuclear Information System (INIS)

Molochnikova, N.P.; Shkinev, V.M.; Myasoedov, B.F.

1995-01-01

The feasibility has been demonstrated of using two-phase aqueous systems based on water-soluble polymers, polyethylene glycol and dextran sulfate, in thin-layer and extraction chromatography for recovery and separation of actinides. A convenient method has been proposed for continuous recovery of 239 Np from 243 Am, originating from differences in sorption of tri- and pentavalent actinides from sulfate solutions containing potassium phosphotungstate by silica gel impregnated with polyethylene glycol. New plates for thin-layer chromatography using water-soluble polymers have been developed. These plates were used to study behavior of americium in various oxidation states in thin sorbent layers

Advanced Aqueous Separation Systems for Actinide Partitioning

Energy Technology Data Exchange (ETDEWEB)

Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lumetta, Gregg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-04-02

One of the most challenging aspects of advanced processing of used nuclear fuel is the separation of transplutonium actinides from fission product lanthanides. This separation is essential if actinide transmutation options are to be pursued in advanced fuel cycles, as lanthanides compete with actinides for neutrons in both thermal and fast reactors, thus limiting efficiency. The separation is difficult because the chemistry of Am3+ and Cm3+ is nearly identical to that of the trivalent lanthanides (Ln3+). The prior literature teaches that two approaches offer the greatest probability of devising a successful group separation process based on aqueous processes: 1) the application of complexing agents containing ligand donor atoms that are softer than oxygen (N, S, Cl-) or 2) changing the oxidation state of Am to the IV, V, or VI state to increase the essential differences between Am and lanthanide chemistry (an approach utilized in the PUREX process to selectively remove Pu4+ and UO22+ from fission products). The latter approach offers the additional benefit of enabling a separation of Am from Cm, as Cm(III) is resistant to oxidation and so can easily be made to follow the lanthanides. The fundamental limitations of these approaches are that 1) the soft(er) donor atoms that interact more strongly with actinide cations than lanthanides form substantially weaker bonds than oxygen atoms, thus necessitating modification of extraction conditions for adequate phase transfer efficiency, 2) soft donor reagents have been seen to suffer slow phase transfer kinetics and hydro-/radiolytic stability limitations and 3) the upper oxidation states of Am are all moderately strong oxidants, hence of only transient stability in media representative of conventional aqueous separations systems. There are examples in the literature of both approaches having been described. However, it is not clear at present that any extant process is sufficiently robust for application at the scale

Radiation-chemical behaviour of actinides in extraction systems

International Nuclear Information System (INIS)

Vladimirova, M.V.; Fedoseev, D.A.; Bojkova, I.A.; Milovanova, A.S.

1987-01-01

Radiation-chemical behaviour of Pu(4) in γ-irradiated triisoamyl phosphate (TIAP) solutions in n-dodecane with metal concentration of 9.5x10 -3 mol/l is investigated by spectrophotometric and extraction methods within the interval of γ-irradiation absorbed dose values from 1.5x10 4 to 1.0x10 5 Gy. Absorption spectra of Pu(4) complexes with TIAP and diisoamylphosphoric acid (DIAPA) are taken for the first time and their extinction molar coefficients (e.m.c.) are determined. Apparent stability constants of Pu(4) complexes with DIAPA with molar ratio of acid to metal of 1:1 and 2:1 are determined. It is as certained, that in the result of organic solution γ-irradiation Pu(4) does not change its valent state, but forms complexes with DIAPA. Radiation-chemical yield of these complexes formation G D practically does not differ from G D for Pu(4) dibutylphosphate complexes and makes up 1.0±0.2 molec./100 eV. It is shown, that coefficients of Pu(4) distribution between γ-irradiated TIAP solutions in n-dodecane and HNO 3 aqueous solutions (0.1 ml/l) linearly increase with E γ growth. Absorption spectrum configuration and e.m.c. values of Pu(4) organic solutions after fourfold re-extraction testify to the fact, that nonextractable Pu(4) constitutes complexes with DIAPA with molar ratio of acid to metal of 1:1 and 2:1

Actinide burning and waste disposal

Energy Technology Data Exchange (ETDEWEB)

Pigford, T H [University of California, Berkeley, CA (United States)

1990-07-01

Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

Actinide burning and waste disposal

International Nuclear Information System (INIS)

Pigford, T.H.

1990-01-01

Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

Measurements of actinide-fission product yields in Caliban and Prospero metallic core reactor fission neutron fields

Energy Technology Data Exchange (ETDEWEB)

Casoli, P.; Authier, N. [CEA, Centre de Valduc, 21120 Is-sur-Tille (France); Laurec, J.; Bauge, E.; Granier, T. [CEA, Centre DIF, 91297 Arpajon (France)

2011-07-01

In the 1970's and early 1980's, an experimental program was performed on the facilities of the CEA Valduc Research Center to measure several actinide-fission product yields. Experiments were, in particular, completed on the Caliban and Prospero metallic core reactors to study fission-neutron-induced reactions on {sup 233}U, {sup 235}U, and {sup 239}Pu. Thick actinide samples were irradiated and the number of nuclei of each fission product was determined by gamma spectrometry. Fission chambers were irradiated simultaneously to measure the numbers of fissions in thin deposits of the same actinides. The masses of the thick samples and the thin deposits were determined by mass spectrometry and alpha spectrometry. The results of these experiments will be fully presented in this paper for the first time. A description of the Caliban and Prospero reactors, their characteristics and performances, and explanations about the experimental approach will also be given in the article. A recent work has been completed to analyze and reinterpret these measurements and particularly to evaluate the associated uncertainties. In this context, calculations have also been carried out with the Monte Carlo transport code Tripoli-4, using the published benchmarked Caliban description and a three-dimensional model of Prospero, to determine the average neutron energy causing fission. Simulation results will be discussed in this paper. Finally, new fission yield measurements will be proposed on Caliban and Prospero reactors to strengthen the results of the first experiments. (authors)

Synergistic extraction of transition metal cations from aqueous media by two separated organic phases

International Nuclear Information System (INIS)

Goldberg, I.

1991-12-01

We have therefore initiated novel approaches to the study of the mechanism of the synergistic extraction of metal ions by means of two separated organic phases, which are brought in contact with the same aqueous phase. The present work is concerned with the extraction of transition metals and actinides ions from nitric acid by chelating agents e.g., HTTA thenoyltrifluoroacetone in a diluent - the first organic phase, and by natural donor, e.g., TBP, tri-butyl phosphate in a diluent the second organic phase. The adduct formation was studied by means of spectrochemical and radiochemical methods. In the first approach the aqueous phase was attacked with both organic phases simultanously (the static or parallel extraction). In this method organic phase are separated one from the other. It was shown that even in the absence of mixing, synergism is observed under this experimental conditions. The results indicate, that adduct formation occurs in both organic phases. Nevertheless the enhanchment of extraction in the TBP phase is by far greater than that in the HTTA containing phase. This approach has one disadvatage, viz., the experiments are very time consuming, a typical experiment requiring over 10 days. In order to overcome this difficulty, the following experiments were carried out: the aqueous phase were first shaken with diluent containing an anionic ligand and the phases were allowed to separate. Then the aqueous solution were shaken with diluent containing a netural donor and the phase again were allowed to separate. The concentration of the metal ions in all the phases were determined. The experiments were repeated with an other diluent replacing the first diluent in one or both organic phases. In this way eight sequences of experiments were carried out for each concentration set chosen. The results thus point out that this experimental approach open new possibilities to investigate the mechanism and the kinetics of synergistic extraction processes. (author) the

Titanium metal: extraction to application

Energy Technology Data Exchange (ETDEWEB)

Gambogi, Joseph (USGS, Reston, VA); Gerdemann, Stephen J.

2002-09-01

In 1998, approximately 57,000 tons of titanium metal was consumed in the form of mill products (1). Only about 5% of the 4 million tons of titanium minerals consumed each year is used to produce titanium metal, with the remainder primarily used to produce titanium dioxide pigment. Titanium metal production is primarily based on the direct chlorination of rutile to produce titanium tetrachloride, which is then reduced to metal using the Kroll magnesium reduction process. The use of titanium is tied to its high strength-to-weight ratio and corrosion resistance. Aerospace is the largest application for titanium. In this paper, we discuss all aspects of the titanium industry from ore deposits through extraction to present and future applications. The methods of both primary (mining of ore, extraction, and purification) and secondary (forming and machining) operations will be analyzed. The chemical and physical properties of titanium metal will be briefly examined. Present and future applications for titanium will be discussed. Finally, the economics of titanium metal production also are analyzed as well as the advantages and disadvantages of various alternative extraction methods.

Applications of DHDECMP extraction chromatography to nuclear analytical chemistry

International Nuclear Information System (INIS)

Marsh, S.F.; Simi, O.R.

1981-01-01

Dihexyl-N,N-diethylcarbamylmethylenephosphonate (DHDECMP) is a highly selective extractant for actinides and lanthanides. This reagent, extensively studied for process-scale operations, also has valuable analytical applications. Extraction chromatographic columns of DHDECMP, supported on inert, porous, polymer beads effectively separate most metallic impurity elements from the retained inner transition elements. The retained elements can be separated into individual fractions of (1) lanthanides, (2) americium, (3) plutonium, and (4) uranium by mixed-solvent anion exchange

Optimisation of composite metallic fuel for minor actinide transmutation in an accelerator-driven system

Science.gov (United States)

Uyttenhove, W.; Sobolev, V.; Maschek, W.

2011-09-01

A potential option for neutralization of minor actinides (MA) accumulated in spent nuclear fuel of light water reactors (LWRs) is their transmutation in dedicated accelerator-driven systems (ADS). A promising fuel candidate dedicated to MA transmutation is a CERMET composite with Mo metal matrix and (Pu, Np, Am, Cm)O 2-x fuel particles. Results of optimisation studies of the CERMET fuel targeting to increasing the MA transmutation efficiency of the EFIT (European Facility for Industrial Transmutation) core are presented. In the adopted strategy of MA burning the plutonium (Pu) balance of the core is minimized, allowing a reduction in the reactivity swing and the peak power form-factor deviation and an extension of the cycle duration. The MA/Pu ratio is used as a variable for the fuel optimisation studies. The efficiency of MA transmutation is close to the foreseen theoretical value of 42 kg TW -1 h -1 when level of Pu in the actinide mixture is about 40 wt.%. The obtained results are compared with the reference case of the EFIT core loaded with the composite CERCER fuel, where fuel particles are incorporated in a ceramic magnesia matrix. The results of this study offer additional information for the EFIT fuel selection.

Optimisation of composite metallic fuel for minor actinide transmutation in an accelerator-driven system

International Nuclear Information System (INIS)

Uyttenhove, W.; Sobolev, V.; Maschek, W.

2011-01-01

A potential option for neutralization of minor actinides (MA) accumulated in spent nuclear fuel of light water reactors (LWRs) is their transmutation in dedicated accelerator-driven systems (ADS). A promising fuel candidate dedicated to MA transmutation is a CERMET composite with Mo metal matrix and (Pu, Np, Am, Cm)O 2-x fuel particles. Results of optimisation studies of the CERMET fuel targeting to increasing the MA transmutation efficiency of the EFIT (European Facility for Industrial Transmutation) core are presented. In the adopted strategy of MA burning the plutonium (Pu) balance of the core is minimized, allowing a reduction in the reactivity swing and the peak power form-factor deviation and an extension of the cycle duration. The MA/Pu ratio is used as a variable for the fuel optimisation studies. The efficiency of MA transmutation is close to the foreseen theoretical value of 42 kg TW -1 h -1 when level of Pu in the actinide mixture is about 40 wt.%. The obtained results are compared with the reference case of the EFIT core loaded with the composite CERCER fuel, where fuel particles are incorporated in a ceramic magnesia matrix. The results of this study offer additional information for the EFIT fuel selection.

Recent progress on R and D of innovative extractants and adsorbents for partitioning of minor actinides at JAEA

International Nuclear Information System (INIS)

Kimura, Takaumi; Morita, Yasuji; Koma, Yoshikazu

2010-01-01

The R and D effort on partitioning of minor actinides (MA) at the Japan Atomic Energy Agency (JAEA) has been concentrated on development and improvement of innovative extractants and adsorbents as the fundamental studies and of MA recovery process as the advanced aqueous reprocessing system in fast reactor cycle technology development (FaCT) project. This paper reviews current status and prospects of the R and D activities on the partitioning of MA at JAEA. (authors)

Study of the actinide-lanthanide separation from nuclear waste by a new pyrochemical process; Etude de la separation actinides-lanthanides des dechets nucleaires par un procede pyrochimique nouveau

Energy Technology Data Exchange (ETDEWEB)

Lemort, F. [CEA Marcoule, Departement de Retraitement, des Dechets et du Demantelement, 30 - Bagnols-sur-Ceze (France)]|[Institut National Polytechnique, 38 - Grenoble (France)

1997-01-01

The theoretical extraction and separation of platinoids, actinides and lanthanides is allowed by thermodynamic using two adapted reducing agents: zinc and magnesium. Thereby, a pyrochemical method for the nuclear waste processing has been devised. The high temperature handling of the elements in fluoride forms and their processing by a reactive metallic phase required special precautions. The study of the behavior of matter in exploratory systems allowed the development of an experimental technology for the treatment and contacting of phases. The thermodynamical analysis of the experimental results shows the feasibility of the process. A model was developed to predict the distribution coefficients of zirconium, uranium and lanthanum as a function of the system composition. An estimation method was proposed in order to evaluate the distribution coefficients in diluted solution of all the actinides and lanthanides existing in the fission products between LiF CaF{sub 2} and Zn-Mg at 720 deg C. Coupled with the experimental results, the estimates results may be extrapolated to concentrated solutions allowing predictions of the separation of all actinides and lanthanides. The rapidity of element transfer is induced by a thermal effect caused by the high exothermicity of the reduction by magnesium. The kinetic coefficients have been linked with the reduction enthalpy of each element. Moreover, the kinetics seem limited by chemical reaction and not by mass transfer. (author) 66 refs.

Synergic extraction of some lanthanide and actinide elements by a mixture of bis(2-ethyl hexyl) phosphoric acid and dinonylnapthalene - sulfonic acid in aromatic diluents

International Nuclear Information System (INIS)

Raieh, M.A.; El-Dessouky, M.M.

1985-01-01

Extraction of lanthanides and actinides were found to be synergetically enhanced by a mixture of bis(2-ethyl hexyl) phosphoric acid (HA) and dinonylnaphthalene sulfonic acid (HD) in aromatic diluents covering a wide range of dielectric constants. The main extracted species is found to be MAsub(2)Hsub(m-1)Dsub(m). Experimental results indicate that the extraxtion mechanism is governed by the extraction of HD in the organic phase. (author)

Citrate based ''TALSPEAK'' lanthanide-actinide separation process

International Nuclear Information System (INIS)

Del Cul, G.D.; Bond, W.D.; Toth, L.M.; Davis, G.D.; Dai, S.; Metcalf, D.H.

1994-09-01

The potential hazard posed to future generations by long-lived radionuclides such as the transuranic elements (TRU) is perceived as a major problem associated with the use of nuclear power. TRU wastes have to remain isolated from the environment for ''geological'' periods of time. The costs of building, maintaining, and operating a ''geological TRU repository'' can be very high. Therefore, there are significant economical advantages in segregating the relatively low volume of TRU wastes from other nuclear wastes. The chemical behavior of lanthanides and actinides, 4f and 5f elements respectively, is rather similar. As a consequence, the separation of these two groups is difficult. The ''TALSPEAK'' process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. The method is based on the preferential complexation of the trivalent actinides by an aminopolyacetic acid. Cold experiments showed that by using citric acid the deleterious effects produced by impurities such as zirconium are greatly reduced

Nuclear fuel cycle-oriented actinides separation in China

Energy Technology Data Exchange (ETDEWEB)

Chen, Jing; He, Xihong; Wang, Jianchen [Tsinghua Univ., Beijing (China). Inst. of Nuclear and New Energy Technology

2014-04-01

In the last decades, the separation of actinides was widely and continuously studied in China. A few kinds of salt-free reductants to adjust Pu and Np valences have been investigated. N,N-dimethylhydroxylamine is a good reductant with high reduction rate constants for the co-reduction of Pu(IV) and Np(VI), and monomethylhydrazine is a simple compound for the individual reduction of Np(VI). Advanced PUREX based on Organic Reductants (APOR) was proposed. Trialkylphosphine oxide (TRPO) with a single functional group was found to possess strong affinity to tri-, tetra- and hexa-valent actinides. TRPO process has been first explored in China for actinides partitioning from high level waste and the good partitioning performance was demonstrated by the hot test. High extraction selectivity for trivalent actinides over lanthanides by dialkyldithiophosphinic acids was originally found in China. A separation process based on purified Cyanex 301 for the separation of Am from lanthanides was presented and successfully tested in a battery of miniature centrifugal contactors. (orig.)

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 2. Flowsheet Test with Actinide-spiked Simulant

Energy Technology Data Exchange (ETDEWEB)

Wilden, Andreas [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Lumetta, Gregg J. [Nuclear Science and Engineering Group, Pacific Northwest National Laboratory, Richland, DC, USA; Sadowski, Fabian [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Schmidt, Holger [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Schneider, Dimitri [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Gerdes, Markus [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Law, Jack D. [Aqueous Separations and Radiochemistry Department, Idaho National Laboratory, Idaho Falls, ID, USA; Geist, Andreas [Karlsruhe Institute of Technology (KIT), Institute for Nuclear Waste Disposal (INE), Karlsruhe, Germany; Bosbach, Dirk [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Modolo, Giuseppe [Forschungszentrum Jülich GmbH, Institut für Energie – und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany

2017-08-17

A solvent extraction system has been developed for separating trivalent actinides from lanthanides. This “Advanced TALSPEAK” system uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanides into a n-dodecane-based solvent phase, while the actinides are retained in a citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid. Batch distribution measurements indicate that the separation of americium from the light lanthanides decreases as the pH decreases. For example, the separation factor between La and Am increases from 2.5 at pH 2.0 to 19.3 at pH 3.0. However, previous investigations indicated that the extraction rates for the heavier lanthanides decrease with increasing pH. So, a balance between these two competing effects is required. An aqueous phase in which the pH was set at 2.6 was chosen for further process development because this offered optimal separation, with a minimum separation factor of ~8.4, based on the separation between La and Am. Centrifugal contactor single-stage efficiencies were measured to characterize the performance of the system under flow conditions.

Neutronics design study on a minor actinide burner for transmuting spent fuel

International Nuclear Information System (INIS)

Choi, Hang Bok

1998-08-01

A liquid metal reactor was designed for the primary purpose of burning the minor actinide waste from commercial light water reactors. The design was constrained to maintain acceptable safety performance as measured by the burnup reactivity swing, the doppler coefficient, and the sodium void worth. Sensitivity studies were performed for homogeneous and decoupled core designs, and a minor actinide burner design was determined to maximize actinide consumption and satisfy safety constraints. One of the principal innovations was the use of two core regions, with a fissile plutonium outer core and an inner core consisting only of minor actinides. The physics studies performed here indicate that a 1200 MWth core is able to transmute the annual minor actinide inventory of about 16 LWRs and still exhibit reasonable safety characteristics. (author). 34 refs., 22 tabs., 14 figs

Actinide science with soft x-ray synchrotron radiation

International Nuclear Information System (INIS)

Shuh, D.

2002-01-01

Several workshops, some dating back more than fifteen years, recognised both the potential scientific impact and opportunities that would be made available by the capability to investigate actinide materials in the vacuum ultraviolet (VUV)/soft X-ray region of the synchrotron radiation (SR) spectrum. This spectral region revolutionized the approach to surface materials chemistry and physics nearly two decades ego. The actinide science community was unable to capitalize on these SR methodologies for the study of actinide materials until recently because of radiological safety concerns. ,The Advanced Light Source (ALS) at LBNL is a third-generation light source providing state-of-the-art performance in the VUV/soft X-ray region. Along with corresponding improvements in detector and vacuum technology, the ALS has rendered experiments with small amounts of actinide materials possible. In particular, it has been the emergence and development of micro-spectroscopic techniques that have enabled investigations of actinide materials at the ALS. The primary methods for the experimental investigation of actinide materials in the VUV/soft X-ray region are the complementary photoelectron spectroscopies, near-edge X-ray absorption fine structure (NEXAFS) and X-ray emission spectroscopy (XES) techniques. Resonant photo-emission is capable of resolving the 5f electron contributions to actinide bonding and can be used to characterise the electronic structure of actinide materials. This technique is clearly a most important methodology afforded by the tunable SR source. Core level and valence band photoelectron spectroscopies are valuable for the characterisation of the electronic properties of actinide materials, as well as for general analytical purposes. High-resolution core-level photo-emission and resonant photo-emission measurements from the a (monoclinic) and δ (FCC) allotropic phases of plutonium metal have been collected on beam line 7.0 at the ALS and the spectra show

Application of liquid metals for the extraction of solid metals

International Nuclear Information System (INIS)

Borgstedt, H.U.

1996-01-01

Liquid metals dissolve several solid metals in considerable amounts at moderate temperatures. The dissolution processes may be based upon simple physical solubility, formation of intermetallic phases. Even chemical reactions are often observed in which non-metallic elements might be involved. Thus, the capacity to dissolve metals and chemical properties of the liquid metals play a role in these processes. Besides the solubility also chemical properties and thermochemical data are of importance. The dissolution of metals in liquid metals can be applied to separate the solutes from other metals or non-metallic phases. Relatively noble metals can be chemically reduced by the liquid phases. Such solution processes can be applied in the extractive metallurgy, for instance to extract metals from metallic waste. The recycling of metals is of high economical and ecological importance. Examples of possible processes are discussed. (author)

Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

International Nuclear Information System (INIS)

Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K.; Rao, C.V.S. Brahmmananda; Jayalakshmi, S.

2015-01-01

The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

Chemistry of the actinide elements. Second edition

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1987-01-01

This is an exhaustive, updated discourse on the chemistry of Actinides, Volume 1 contains a systematic coverage of the elements Ac, Th, Pa, U, Np, and Pu, which constitutes Part 1 of the work. The characterization of each element is discussed in terms of its nuclear properties, occurrence, preparation, atomic and metallic properties, chemistry of specific compounds, and solution chemistry. The first part of Volume 2 follows the same format as Volume 1 but is confined to the elements Am, Cm, Bk, Cf, and Es, plus a more condensed coverage of the Transeinsteinium elements (Fm, Md, No, Lw, and 104-109). Part 2 of this volume is devoted to a discussion of the actinide elements in general, with a specific focus on electronic spectra, thermodynamic and magnetic properties, the metallic state, structural chemistry, solution kinetics, organometallic chemistry for σ- and π-bonded compounds, and some concluding remarks on the superheavy elements

Systematic thermodynamic properties of actinide metal-oxygen systems at high temperatures: Emphasis on lower valence states

International Nuclear Information System (INIS)

Ackermann, R.J.; Chandrasekharaiah, M.S.

1975-01-01

The thermodynamic data for the actinide metals and oxides (thorium to curium ) have been assessed, examined for consistency, and compared with the lanthanides. Correlations relating the enthalpies of formation of the solid oxides with the corresponding aquo ions make possible the estimation of the thermodynamic properties of AmO 2 (s) and Am 2 O 3 (s) which are in accordance with vaporization data. The known thermodynamic properties of the substoichiometric dioxides MOsub(2-x)(s) at high temperatures demonstrate the relative stabilities of valence states less than 4+ and lead to the examination of stability requirements for the sesquioxides M 2 O 3 (s) and the monoxides MO(s). Sequential trends in the gaseous metals, monoxides and dioxides are examined, compared, and contrasted with the lanthanides. (author)

Recent trends in metals extraction

Directory of Open Access Journals (Sweden)

Regel-Rosocka, M.

2013-08-01

Full Text Available After near 70 years of practical usage, solvent extraction is a perfectly mastered technique of separation, widely used on an industrial scale for the separation of metals mainly from raw materials. However, currently, in the era of depleting natural resources and increasingly less accessible deposits, environmental restrictions, etc., an increasing interest, both from social and economical constrains, is being directed at the extraction of metals from the secondary sources (such as batteries, electronic scrap. In many cases, solvent extraction, due to its operational characteristics, can be considered as the Best Available Technology for the purpose of separating multielemental metal solutions. This paper provides a brief overview of past achievements and present scenario of solvent extraction investigations and developments, describing some recently commissioned solvent extraction plants, whereas the Skorpion Zinc plant (Namibia for zinc extraction from raw materials and caesium removal from radioactive High Level Wastes (HLWs are told over in detail as case studies. The paper also presents some proposals for the use of liquid-liquid extraction to separate metal ions from secondary sources (e.g. cobalt from industrial waste streams. The review highlights the emerging use of ionic liquids as new extractants for metals, providing an insight into this exciting research field. Despite its detractors, solvent extraction has entered in force into XXI century as a leading separation technology for metals.Después de casi 70 años de uso práctico, la extracción líquido-líquido o extracción con disolventes es una técnica de separación muy evolucionada, utilizándose a escala industrial en el beneficio de metales obtenidos de diversas materias primas. Sin embargo, con el agotamiento de los recursos naturales y el aumento de depósitos minerales de más difícil acceso, restricciones medio ambientales, etc., ha aumentado el interés, tanto desde

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands

International Nuclear Information System (INIS)

Francois, N.

2000-01-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

Partitioning-separation of metal ions using heterocyclic ligands

International Nuclear Information System (INIS)

Hudson, M.J.; Drew, M.G.B.; Iveson, P.B.; Russell, M.L.

2001-01-01

Some guidelines are proposed for the effective design of heterocyclic ligands for partitioning because there is no doubt that the correct design of a molecular extractant is required for the effective separation of metal ions such as actinides(III) from lanthanides(III). Heterocyclic ligands with aromatic ring systems have a rich chemistry, which is only now becoming sufficiently well understood in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-carboxy-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with lanthanide ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazole-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. (author)

Calculated Bulk Properties of the Actinide Metals

DEFF Research Database (Denmark)

Skriver, Hans Lomholt; Andersen, O. K.; Johansson, B.

1978-01-01

Self-consistent relativistic calculations of the electronic properties for seven actinides (Ac-Am) have been performed using the linear muffin-tin orbitals method within the atomic-sphere approximation. Exchange and correlation were included in the local spin-density scheme. The theory explains...... the variation of the atomic volume and the bulk modulus through the 5f series in terms of an increasing 5f binding up to plutonium followed by a sudden localisation (through complete spin polarisation) in americium...

Medium temperature reaction between lanthanide and actinide carbides and hydrogen

International Nuclear Information System (INIS)

Dean, G.; Lorenzelli, R.; Pascard, R.

1964-01-01

Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C 1-x , H 2x ). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [fr

Synthesis of tetravalent actinide chlorides. Versatile compounds for actinide chemistry

Energy Technology Data Exchange (ETDEWEB)

Maerz, Juliane [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements

2016-07-01

Anhydrous actinide tetrachlorides (AnCl{sub 4}) were synthesized under mild conditions to provide versatile compounds for actinide chemistry. They enable a direct access to actinide complexes with organic and inorganic ligands.

The R-Process Alliance: 2MASS J09544277+5246414, the Most Actinide-enhanced R-II Star Known

Science.gov (United States)

Holmbeck, Erika M.; Beers, Timothy C.; Roederer, Ian U.; Placco, Vinicius M.; Hansen, Terese T.; Sakari, Charli M.; Sneden, Christopher; Liu, Chao; Lee, Young Sun; Cowan, John J.; Frebel, Anna

2018-06-01

We report the discovery of a new actinide-boost star, 2MASS J09544277+5246414, originally identified as a very bright (V = 10.1), extremely metal-poor ([Fe/H] = ‑2.99) K giant in the LAMOST survey, and found to be highly r-process-enhanced (r-II; [Eu/Fe] = +1.28]), during the snapshot phase of the R-Process Alliance (RPA). Based on a high signal-to-noise ratio (S/N), high-resolution spectrum obtained with the Harlan J. Smith 2.7 m telescope, this star is the first confirmed actinide-boost star found by RPA efforts. With an enhancement of [Th/Eu] = +0.37, 2MASS J09544277+5246414 is also the most actinide-enhanced r-II star yet discovered, and only the sixth metal-poor star with a measured uranium abundance ([U/Fe] = +1.40). Using the Th/U chronometer, we estimate an age of 13.0 ± 4.7 Gyr for this star. The unambiguous actinide-boost signature of this extremely metal-poor star, combined with additional r-process-enhanced and actinide-boost stars identified by the RPA, will provide strong constraints on the nature and origin of the r-process at early times.

Actinide/crown ether chemistry

International Nuclear Information System (INIS)

Benning, M.M.

1988-01-01

A structural survey of actinide/crown ether compounds was conducted in order to investigate the solid state chemistry of these complexes. Several parameters - the metal size, crown type, counterion, solvent systems and reaction and crystallization conditions - were varied to correlate their importance in complexation. Under atmospheric conditions, two types of complexes were isolated, those containing only hydrogen-bonded crown interactions and instances where the crown interacts directly with the metal center. In both cases, water seems to play a very important role. When coordinated to the metal, water molecules exhibit the necessary donor properties required for the formation of hydrogen-bonded contacts. The water molecules also provide fierce competition with the crown ethers for metal-binding sites and in most cases prohibit the formation of complexes in which direct metal-ligand association exists. The results of this study indicate that direct interaction between the metal atoms and the crown ethers, in the presence of water, can only occur with polyether conformations which limit the steric replusions within the metal coordination sphere

Actinide science. Fundamental and environmental aspects

International Nuclear Information System (INIS)

Choppin, Gregory R.

2005-01-01

Nuclear test explosions and reactor wastes have deposited an estimated 16x10 15 Bq of plutonium into the world's aquatic systems. However, plutonium concentration in open ocean waters is orders of magnitude less, indicating that most of the plutonium is quite insolvable in marine waters and has been incorporated into sediments. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides were introduced into the aquatic system. Actinide solubility depends on such factors as pH(hydrolysis), E H (oxidation state), reaction with complexants (e.g. carbonate, phosphate, humic acid, etc.) sorption to surfaces of minerals and/or colloids, etc., in the water. The most significant of these variables is the oxidation sate of the metal ion. The simultaneous presence of more than one oxidation state for some actinides (e.g. plutonium) in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation but can undergo reduction to the Pu(IV) oxidation state with its different elemental behavior. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK SP - 56). The net solubility of hexavalent UO 2 2+ in sea water is also limited by hydrolysis; however, it has a relatively high concentration due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(CO) 3 (OH), is the limiting species for the solubility of Am(III) in sea water. Thorium is found exclusively as the tetravalent species and its solubility is limited by the formation of quite insoluble Th(OH) 4 . The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in

Method for the concentration and separation of actinides from biological and environmental samples

International Nuclear Information System (INIS)

Horwitz, E.P.; Dietz, M.L.

1989-01-01

A method and apparatus for the quantitative recover of actinide values from biological and environmental sample by passing appropriately prepared samples in a mineral acid solution through a separation column of a dialkyl(phenyl)-N,N-dialylcarbamoylmethylphosphine oxide dissolved in tri-n-butyl phosphate on an inert substrate which selectively extracts the actinide values. The actinide values can be eluted either as a group or individually and their presence quantitatively detected by alpha counting. 3 figs

Separation of Am(III) from Eu(III) by mixtures of triazynylbipyridine and bis(dicarbollide) extractants. The composition of the metal complexes extracted

International Nuclear Information System (INIS)

Narbutt, J.; Krejzler, J.

2006-01-01

Separation of trivalent actinides, in particular americium and curium, from lanthanides is an important step in an advanced partitioning process for future reprocessing of spent nuclear fuels. The use of soft donor (N and S) ligands makes it possible to separate the two groups of elements, probably because of the more covalent character in the complexes with actinides compared to the lanthanides. The aim of present work was to study solvent extraction of Am(III) and Eu(III) in a similar system with diethylhemi-BTP and COSAN: protonated bis(chlorodicarbollido)cobalt(III) or commo-3,3-cobalta-bis(8,9,12-trichlora-1,2-dicarbaclosododecaborane)ic acid. The present research was focused on both the determination of conditions for the separation of 241 Am(III) from 152 Eu in aqueous nitrate solution by using a synergistic extraction system and on the modelling of the process by slope analysis. Obtained values of the separation factors supported by the computer modelling permitted drawing the conclusions on the mechanism of the process and on the structure of extracted species

Proceedings of the symposium Actinides 2006 - Basic Science, Applications and Technology

International Nuclear Information System (INIS)

Blobaum, Kerri J.M.; Chandler, Elaine A.; Havela, Ladislav; Maple, M. Brian; Neu, Mary P.

2007-01-01

These proceedings from the September 2006 symposium includes papers presented on experimental and modeling work with the intention of broadening understanding of the field of actinide research. Actinides have gained attention recently because of their roles in the threat of nuclear terrorism (e.g., 'dirty bombs') and the use of nuclear power to offset fossil fuel consumption. Actinide science is the study of the elements with atomic numbers in the range of 90 to 103, which includes uranium and plutonium. Beyond the well-known nuclear reactions of these heavy radioactive metals, the large electron clouds with 5f electrons in the outer shell yield fascinating and complex chemistries, crystal structures, and physical properties. Traditionally, actinide research has been divided among three scientific disciplines: chemistry (nuclear chemistry and radiochemistry); physics (condensed matter physics and electronic structure); and materials science (metallurgy). Modern actinide research, however, has become an interdisciplinary blend of these traditional fields, and it also incorporates developing fields such as environmental chemistry and superconductivity. Improved scientific understanding of actinides is needed for development of materials for actinide detection and nuclear fuels, and for safer management of nuclear waste. Recently, there has been a resurgence of actinide science at national laboratories and universities. The current multidisciplinary approach to actinide science lays the groundwork for understanding the connection between the 5f electronic structure and observed chemical reactions and physical properties such as structural phase transformations and novel ground states. This work provides many opportunities for new researchers in actinide science. These proceedings gather 25 selected papers among the 53 presentations given at this symposium

Polymer Inclusion Membrane Containing a Tripodal Diglycolamide Ligand: Actinide Ion Uptake and Transport Studies

NARCIS (Netherlands)

Mahanty, B.; Mohapatra, P.K.; Raut, D.R.; Das, D.K.; Behere, P.G.; Afzal, M.; Verboom, Willem

2016-01-01

A cellulose triacetate (CTA)-based polymer inclusion membrane (PIM) containing a C-pivot tripodal diglycolamide (T-DGA) as the carrier extractant and 2-nitrophenyl octyl ether (NPOE) as the plasticizer shows potential for the uptake of actinides from acidic feed solutions. The uptake of actinides

On solvent extraction of metals by macrocyclic polyethers

International Nuclear Information System (INIS)

Ionov, V.P.

1984-01-01

The Ksub(γ) parameter characterizing effective ion charges in ionic associates of metal salts is suggested; these charges parallel with other factors determine the metals extraction by macrocyclic polyethers (crown-ethers). The dependence of metal extraction constant on the Ksub(γ) parameter is discussed. It is shown that the less effective cation charge of alkali metal ionic associates, the more probable its entering the crown-ether cavity. The synergetic crown-ethers extraction is bound as well with Ksub(γ) of metal salts. The differences in the cation extraction constants having the same ionic radius are explained with account of different values of Ksub(γ) parameters of these salts

The chemistry of molten salt mixtures: application to the reductive extraction of lanthanides and actinides by a liquid metal; Chimie des melanges de sels fondus. Application a l'extraction reductrice d'actinides et de lanthanides par un metal liquide

Energy Technology Data Exchange (ETDEWEB)

Finne, J

2005-10-15

The design of a process of An/Ln separation by liquid - liquid extraction can be used for on-line purification of the molten salt in a molten salt nuclear reactor (Generation IV) as well as reprocessing various spent fuels. In order to establish the chemical properties of An and Ln in molten salt mediums, E - pO{sub 2} - diagrams were established for the relevant chemical elements. With the purpose of checking the possibilities of separating the An from Ln, the real activity coefficients in liquid metals were measured. An experimental protocol was developed and validated on the Gd/Ga system. It was then transferred to radioactive environment to measure the activity coefficient of Pu in Ga. The results made it possible to estimate the effectiveness of the Pu extraction and its separation from Gd and Ce. The selectivity was shown to decrease with the temperature and Al and Ga showed a good selectivity between Pu and the Ce in fluoride medium. (author)

Actinide separation by electrorefining

International Nuclear Information System (INIS)

Fusselman, S.P.; Gay, R.L.; Grantham, L.F.; Grimmett, D.L.; Roy, J.J.; Inoue, T.; Hijikata, T.; Krueger, C.L.; Storvick, T.S.; Takahashi, N.

1995-01-01

TRUMP-S is a pyrochemical process being developed for the recovery of actinides from PUREX wastes. This paper describes development of the electrochemical partitioning step for recovery of actinides in the TRUMP-S process. The objectives are to remove 99 % of each actinide from PUREX wastes, with a product that is > 90 % actinides. Laboratory tests indicate that > 99 % of actinides can be removed in the electrochemical partitioning step. A dynamic (not equilibrium) process model predicts that 90 wt % product actinide content can be achieved through 99 % actinide removal. Accuracy of model simulation results were confirmed in tests with rare earths. (authors)

Innovative SANEX process for trivalent actinides separation from PUREX raffinate

International Nuclear Information System (INIS)

Sypula, Michal

2013-01-01

Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF Ln/Am obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as a Zr

Innovative SANEX process for trivalent actinides separation from PUREX raffinate

Energy Technology Data Exchange (ETDEWEB)

Sypula, Michal

2013-07-01

Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF{sub Ln/Am} obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as

Experimental studies of narrow band effects in the actinides

Energy Technology Data Exchange (ETDEWEB)

Brodsky, M.B.

1976-01-01

In many actinide metallic systems the f-electrons exhibit band behavior. This is a consequence of direct f-f wave function overlap or hybridization of f-electrons with s-, p-, and d-electrons. The f-bands can be responsible for large electronic densities of states at the Fermi level which may lead to band magnetism of various types. Although the concept of valence instabilities must be approached cautiously especially in the light actinides, it would not be surprising to observe them in the future, especially in Am compounds.

Experimental studies of narrow band effects in the actinides

International Nuclear Information System (INIS)

Brodsky, M.B.

1976-01-01

In many actinide metallic systems the f-electrons exhibit band behavior. This is a consequence of direct f-f wave function overlap or hybridization of f-electrons with s-, p-, and d-electrons. The f-bands can be responsible for large electronic densities of states at the Fermi level which may lead to band magnetism of various types. Although the concept of valence instabilities must be approached cautiously especially in the light actinides, it would not be surprising to observe them in the future, especially in Am compounds

Benzene-centered tripodal diglycolamides : Synthesis, metal ion extraction, luminescence spectroscopy, and DFT studies

NARCIS (Netherlands)

Leoncini, Andrea; Ansari, Seraj Ahmad; Mohapatra, Prasanta Kumar; Boda, Anil; Musharaf Ali, Sheikh; Sengupta, Arijit; Huskens, Jurriaan; Verboom, Willem

2017-01-01

Three benzene-centered tripodal diglycolamides (Bz-T-DGAs) were synthesized and evaluated for actinide, lanthanide, and fission product ion extraction. 1,3,5-Triethylbenzene-based tripodal DGA (LI) showed high distribution ratio (D) values for Am3+ and Eu3+ in a mixture of 95% n-dodecane and 5%

Conception, synthesis and application of tripodands in actinide/lanthanide separation

International Nuclear Information System (INIS)

Bobet, Josselin

1997-01-01

The purpose of this work is the synthesis of C, H, O and N containing compounds able to separate '4f' and '5f' elements by liquid/liquid extraction. In a first part, the literature's study allow us to point out actinide and lanthanide ions actual nature and the different ways offered by organic chemistry to share two metallic ions between two liquid phases. On one hand, these trivalent cations' high coordination numbers drive us to synthesize tripodands with hard sites which were fitted for complexation. On the other hand, it appeared that carboxylate or even less-hard site like pyridine chelate selectively actinides, allowing separation. In a second part, 60 ligands were synthesized. In each of the ligands families, a structural parameter changes (site nature, distance between two neighbouring sites, sites respective orientation, lipophilicity and rigidity). 2,2-dihydroxymethyl-dodecanol and 1,3,5- tri(chlorocarbonyl) benzene were chosen as core. O-alkylation and amidation reactions were also peculiarly studied. Rekker's proceeding for lipophilicity calculation was used in order to establish a structure-activity relationship. In a third part, extraction assays with radioactive effluents ( 152 Eu and 241 Am) point out extraction and separation abilities of our compounds. Different operating ways were used according as ligand is soluble in aqueous or organic phase. Organic phase-soluble compounds were compared to DcH18C6, pyridine ones to 2,4,6-tri(2-pyridyl)-l,3,5-triazine (TPTZ) and carboxylate ones to diethylenetriamine-tetracetic acid (DTPA, Talspeak proceeding). The third phase phenomenon was encountered and studied. Influence of salt, pH and organic phase were also studied. (author) [fr

Medium temperature reaction between lanthanide and actinide carbides and hydrogen; Reaction a temperature moyenne entre les monocarbures de lanthanides et d'actinides et l'hydrogene

Energy Technology Data Exchange (ETDEWEB)

Dean, G; Lorenzelli, R; Pascard, R [Commissariat a l' Energie Atomique, Fontenay-aux-Roses (France). Centre d' Etudes Nucleaires

1964-07-01

Hydrogen is fixed reversibly by the lanthanide and actinide mono carbides in the range 25 - 400 C, as for pure corresponding metals. Hydrogen goes into the carbides lattice through carbon vacancies and the total fixed amount is approximately equal to two hydrogen atoms per initial vacancy. Final products c.n thus be considered as carbo-hydrides of general formula M(C{sub 1-x}, H{sub 2x}). The primitive CFC, NaCl type, structure remains unchanged but expands strongly in the case of actinide carbides. With lanthanide carbides, hydrogenation induces a phase transformation with reappearance of the metal structure (HCP). Hydrogen decomposition pressures of all the studied carbo-hydrides are greater than those of the corresponding di-hydrides. (authors) [French] Les monocarbures d'actinides et de lanthanides fixent reversiblement de l'hydrogene a temperature peu elevee, a peu pres dans les memes conditions que les metaux purs correspondants. L'hydrogene penetre dans le reseau des carbures par l'intermediaire des lacunes de carbone, et la quantite totale fixee est approximativement egale a deux atomes d'hydrogene par lacune initiale. Les produits obtenus peuvent donc etre consideres comme des carbohydrures de formule generale M(C{sub 1-x}, H{sub 2x}). La structure d'origine CFC, type NaCl est conservee, mais avec une forte expansion, dans le cas des carbures d'actinides. En revanche, l'hydrogenation entraine un changement de phase cristalline avec retour a la structure du metal (HC) pour les carbures de lanthanides. Tous les carbohydrures etudies ont des tensions de decomposition en hydrogene superieures a celles des dihydrures correspondants. (auteurs)

The separation of extractants implemented in the DIAMEX-SANEX process

Energy Technology Data Exchange (ETDEWEB)

Heres, Xavier [CEA-Marcoule, DEN/MAR/DRCP/SCPS, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Baron, P.; Hill, C.; Ameil, E.; Martinez, I. [CEA-Marcoule, DEN/MAR/DRCP/SCPS, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France); Rivalier, P. [CEA-Marcoule, DEN/MAR/DTEC/SGCS, BP 17171, 30207 Bagnols-sur-Ceze Cedex (France)

2008-07-01

DIAMEX-SANEX is a process developed at the Cea to recover selectively the actinides(III) after a COEX{sup TM} or a PUREX process, in order to significantly decrease the radiotoxicity of the ultimate waste produced by the nuclear industry. This liquid-liquid extraction process is based on the DIAMEX process, using a malonamide supplemented by an acidic extractant. Besides an actinide extraction step and a lanthanide stripping step are implemented an actinide(III) stripping step and an extractant splitting step. The latter is carried out to avoid interactions between these two extractants during the first co-extraction step of the actinides and the lanthanides. This paper gives some results obtained with di-n-hexyl phosphoric acid (HDHP), which fulfills the required criteria for process development. Batch experiments or cold counter-current tests showed that it is possible to separate this extractant from DMDOHEMA. HDHP can moreover maintain the lanthanides(III) in the organic phase when the actinides(III) are back extracted from the organic phase. (authors)

The separation of extractants implemented in the DIAMEX-SANEX process

International Nuclear Information System (INIS)

Heres, Xavier; Baron, P.; Hill, C.; Ameil, E.; Martinez, I.; Rivalier, P.

2008-01-01

DIAMEX-SANEX is a process developed at the Cea to recover selectively the actinides(III) after a COEX TM or a PUREX process, in order to significantly decrease the radiotoxicity of the ultimate waste produced by the nuclear industry. This liquid-liquid extraction process is based on the DIAMEX process, using a malonamide supplemented by an acidic extractant. Besides an actinide extraction step and a lanthanide stripping step are implemented an actinide(III) stripping step and an extractant splitting step. The latter is carried out to avoid interactions between these two extractants during the first co-extraction step of the actinides and the lanthanides. This paper gives some results obtained with di-n-hexyl phosphoric acid (HDHP), which fulfills the required criteria for process development. Batch experiments or cold counter-current tests showed that it is possible to separate this extractant from DMDOHEMA. HDHP can moreover maintain the lanthanides(III) in the organic phase when the actinides(III) are back extracted from the organic phase. (authors)

Methods for separating actinides from reprocessing and refabrication plant wastes

International Nuclear Information System (INIS)

Tedder, D.W.; Finney, B.C.; Blomeke, J.O.

1979-01-01

Chemical processing flowsheets have been developed to partition actinides from all actinide-bearing LWR fuel reprocessing and refabrication plant wastes. These wastes include high-activity-level liquids, scrap recovery liquors, HEPA filters and incinerator ashes, and chemical salt wastes such as sodium carbonate scrub solutions, detergent cleanup streams, and alkaline off-gas scrubber liquors. The separations processes that were adopted for this study are based on solvent extraction, cation exchange chromatography, and leaching with Ce 4+ -HNO 3 solution

Valence instabilities as a source of actinide system inconsistencies

International Nuclear Information System (INIS)

Sandenaw, T.A.

1979-01-01

Light actinide elements alone, and in some of their alloys, may exist as a static or dynamic mixture of two configurations. Such a state can explain both a resistivity maximum and lack of magnetic order observed in so many actinide materials, and still be compatible with the existence of f-electrons in narrow bands. Impurity elements may stabilize slightly different intermediate valence states in U, Np, and Pu, thus contributing to inconsistencies in published results. The physical property behavior of mixed-valence, rare-earth compounds is very much like that observed in development of antiphase (martensitic) structures. Martensitic transformations in U, Np, and Pu, from high-temperature b. c. c. to alpha phase, may be a way of ordering an alloy-like metal of mixed or intermediate valence. The relative stability of each phase structure may depend upon its electron-valence ratio. A Hubbard model for electron correlations in a narrow energy band has been invoked in most recent theories for explaining light actinide behavior. Such a model may also be applicable to crystal symmetry changes in martensitic transformations in actinides

Applicability of a valence fluctuation model to the observed physical property response of actinide materials

International Nuclear Information System (INIS)

Sandenaw, T.A.

1978-01-01

It is shown that the physical property behavior of the light actinide elements, U, Np, and Pu, and certain of their alloys, is like that of known mixed-valence, R.E. metallic compounds. It is inferred that interconfiguration fluctuation (ICF) theory should also be applicable to actinide materials

Rapid Computer Aided Ligand Design and Screening of Precious Metal Extractants from TRUEX Raffinate with Experimental Validation

International Nuclear Information System (INIS)

Clark, Aurora Sue; Wall, Nathalie; Benny, Paul

2015-01-01

Rhodium is the most extensively used metal in catalytic applications; it occurs in mixed ores with platinum group metals (PGMs) in the earth's crust in low concentrations (0.4 - 10 ppb). It is resistant to aerial oxidation and insoluble in all acids, including aqua regia, making classical purification methods time-consuming and inefficient. To ensure adequate purity, several precipitation and dissolution steps are necessary during separation. Low abundance, high demand, and extensive processing make rhodium the most expensive of all PGMs. From alternative sources, rhodium is also produced in sufficient quantities (0.47 kg per ton initial heavy metal (tIHM)) during the fission of U-235 in nuclear reactors along with other PGMs (i.e. Ag, Pd, Ru). A typical power water reactor operating with UO 2 fuel after cooling can generate PGMs in quantities greater than found in the earth's crust (0.5-2 kg/tIHM). This currently untapped supply of PGMs has the potential to yield $5,000-30,000/tIHM. It is estimated that by the year 2030, the amount of rhodium generated in reactors could exceed natural reserves. Typical SNF processing removes the heavier lanthanides and actinides and can leave PGMs at ambient temperatures in aqueous acidic (Cl - or NO 3 - ; pH < 1) solutions at various activities. While the retrieval of these precious metals from SNF would minimize waste generation and improve resource utilization, it has been difficult to achieve thus far. Two general strategies have been utilized to extract Rh(III) from chloride media: ion pairing and coordination complexation. Ion pairing mechanisms have been studied primarily with the tertiary and quaternary amines. Additionally, mixed mechanism extractions have been observed in which ion pairing is the initial mechanism, and longer extraction equilibrium time generated coordination complexes. Very few coordination complexation extraction ligands have been studied. This project approached this problem through the

Rapid Computer Aided Ligand Design and Screening of Precious Metal Extractants from TRUEX Raffinate with Experimental Validation

Energy Technology Data Exchange (ETDEWEB)

Clark, Aurora Sue [Washington State Univ., Pullman, WA (United States); Wall, Nathalie [Washington State Univ., Pullman, WA (United States); Benny, Paul [Washington State Univ., Pullman, WA (United States)

2015-11-16

Rhodium is the most extensively used metal in catalytic applications; it occurs in mixed ores with platinum group metals (PGMs) in the earth’s crust in low concentrations (0.4 - 10 ppb). It is resistant to aerial oxidation and insoluble in all acids, including aqua regia, making classical purification methods time-consuming and inefficient. To ensure adequate purity, several precipitation and dissolution steps are necessary during separation. Low abundance, high demand, and extensive processing make rhodium the most expensive of all PGMs. From alternative sources, rhodium is also produced in sufficient quantities (0.47 kg per ton initial heavy metal (tIHM)) during the fission of U-235 in nuclear reactors along with other PGMs (i.e., Ag, Pd, Ru). A typical power water reactor operating with UO₂ fuel after cooling can generate PGMs in quantities greater than found in the earth’s crust (0.5-2 kg/tIHM). This currently untapped supply of PGMs has the potential to yield $5,000-30,000/tIHM. It is estimated that by the year 2030, the amount of rhodium generated in reactors could exceed natural reserves. Typical SNF processing removes the heavier lanthanides and actinides and can leave PGMs at ambient temperatures in aqueous acidic (Cl⁻ or NO₃⁻; pH < 1) solutions at various activities. While the retrieval of these precious metals from SNF would minimize waste generation and improve resource utilization, it has been difficult to achieve thus far. Two general strategies have been utilized to extract Rh(III) from chloride media: ion pairing and coordination complexation. Ion pairing mechanisms have been studied primarily with the tertiary and quaternary amines. Additionally, mixed mechanism extractions have been observed in which ion pairing is the initial mechanism, and longer extraction equilibrium time generated coordination complexes. Very few coordination complexation extraction ligands have been studied. This project approached this problem

Study of the actinide-lanthanide separation from nuclear waste by a new pyrochemical process

International Nuclear Information System (INIS)

Lemort, F.

1997-01-01

The theoretical extraction and separation of platinoids, actinides and lanthanides is allowed by thermodynamic using two adapted reducing agents: zinc and magnesium. Thereby, a pyrochemical method for the nuclear waste processing has been devised. The high temperature handling of the elements in fluoride forms and their processing by a reactive metallic phase required special precautions. The study of the behavior of matter in exploratory systems allowed the development of an experimental technology for the treatment and contacting of phases. The thermodynamical analysis of the experimental results shows the feasibility of the process. A model was developed to predict the distribution coefficients of zirconium, uranium and lanthanum as a function of the system composition. An estimation method was proposed in order to evaluate the distribution coefficients in diluted solution of all the actinides and lanthanides existing in the fission products between LiF CaF 2 and Zn-Mg at 720 deg C. Coupled with the experimental results, the estimates results may be extrapolated to concentrated solutions allowing predictions of the separation of all actinides and lanthanides. The rapidity of element transfer is induced by a thermal effect caused by the high exothermicity of the reduction by magnesium. The kinetic coefficients have been linked with the reduction enthalpy of each element. Moreover, the kinetics seem limited by chemical reaction and not by mass transfer. (author)

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 1. Process Optimization and Flowsheet Development

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Levitskaia, Tatiana G. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Wilden, Andreas [Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Casella, Amanda J. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Hall, Gabriel B. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Lin, Leigh [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Sinkov, Sergey I. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Law, Jack D. [Idaho National Laboratory, Aqueous Separations and Radiochemistry Department, Idaho Falls, ID, USA; Modolo, Giuseppe [Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany

2017-08-18

A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration of the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.

Plutonium and americium extraction studies with bifunctional organophosphorus extractants

International Nuclear Information System (INIS)

Navratil, J.D.

1985-01-01

Neutral bifunctional organophosphorus extractants, such as octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and dihexyl-N,N-diethylcarbamoylmethylphosphonate (CMP), are under study at the Rocky Flats Plant (RFP) to remove plutonium and americium from the 7M nitric acid waste. These compounds extract trivalent actinides from strong nitric acid, a property which distinguishes them from monofunctional organiphosphorus reagents. Furthermore, the reagents extract hydroytic plutonium (IV) polymer which is present in the acid waste stream. The compounds extract trivalent actinides with a 3:1 stoichiometry, whereas tetra- and hexavalent actinides extract with a stoichiometry of 2:1. Preliminary studies indicate that the extracted plutonium polymer complex contains one to two molecules of CMP per plutonium ion and the plutonium(IV) maintains a polymeric structure. Recent studies by Horwitz and co-workers conclude that the CMPO and CMP reagents behave as monodentate ligands. At RFP, three techniques are being tested for using CMP and CMPO to remove plutonium and americium from nitric acid waste streams. The different techniques are liquid-liquid extraction, extraction chromatography, and solid-supported liquid membranes. Recent tests of the last two techniques will be briefly described. In all the experiments, CMP was an 84% pure material from Bray Oil Co. and CMPO was 98% pure from M and T Chemicals

Investigation on leaching of actinide oxides into supercritical fluids

International Nuclear Information System (INIS)

Shafikov, D.N.; Kamachev, V.A.; Babain, V.A.; Murzin, A.A.; Shadrin, A.Yu.; Podojnitsin, S.V.

2006-01-01

The extraction of actinide oxides into solutions of the TBP-HNO 3 complex in supercritical (SC) CO 2 was investigated. Experiments on the extraction of the TBP-HNO 3 complex into SC CO 2 were first conducted. It was found that a constant concentration of TBP in SC CO 2 of 13.5-14.8 % vol. can be attained using a constant molar ratio of [HNO 3 ]:[TBP] about 2.5 : 1. Joint leaching of uranium, plutonium and neptunium from mixtures of actinide oxides with solutions of TBP-HNO 3 in SC CO 2 was found feasible. If the leaching of uranium is about 95 %, its purification coefficients from major gamma-emitting radionuclides (Cs and Sr) exceed 100, while the purification coefficients of uranium from rare earth elements are 10-20

Ionic Liquids as Extraction Media for Metal Ions

Science.gov (United States)

Hirayama, Naoki

In solvent extraction separation of metal ions, recently, many researchers have investigated possible use of hydrophobic ionic liquids as extraction media instead of organic solvents. Ionic liquids are salts of liquid state around room temperature and can act not only as solvents but also as ion-exchangers. Therefore, the extraction mechanism of metal ions into ionic liquids is complicated. This review presents current overview and perspective on evaluation of nature of hydrophobic ionic liquids as extraction media for metal ions.

Supercritical fluid extraction of lanthanides and actinides from solid materials with a fluorinated β-diketone

International Nuclear Information System (INIS)

Lin, Y.; Brauer, R.D.; Laintz, K.E.; Wai, C.M.

1993-01-01

Direct extraction of metal ions by supercritical carbon dioxide is highly inefficient because of the charge neutralization requirement and the weak solute-solvent interactions. One suggested approach of extracting metal ions by supercritical carbon dioxide is to convert the charged species into metal chelates using a chelating agent in the fluid phase. This paper describes a method of extracting lanthanide and uranyl ions from a solid material by supercritical carbon dioxide containing a fluorinated beta-diketone, 2,2-dimethyl-6,6,7,7,8,8,8-heptafluoro-3,5-octanedione(FOD). Potential applications of this SFE method for separating the f-block elements from environmental samples are discussed. 13 refs., 2 tabs

Behavior of actinides in the Integral Fast Reactor fuel cycle

Energy Technology Data Exchange (ETDEWEB)

Courtney, J.C. [Louisiana State Univ., Baton Rouge, LA (United States). Nuclear Science Center; Lineberry, M.J. [Argonne National Lab., Idaho Falls, ID (United States). Technology Development Div.

1994-06-01

The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ({sup 237}Np, {sup 240}Pu, {sup 241}Am, and {sup 243}Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for ten day exposure in the Experimental Breeder Reactor-2 which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction-rates and neutron spectra. These experimental data increase the authors` confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs.

Actinide behavior in the Integral Fast Reactor. Final project report

Energy Technology Data Exchange (ETDEWEB)

Courtney, J.C.

1994-11-01

The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ({sup 237}Np, {sup 240}Pu, {sup 241}Am, and {sup 243}Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and weapons grade plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for seven day exposure in the Experimental Breeder Reactor-II which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction rates and neutron spectra. These experimental data increase the authors confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs.

Actinide behavior in the Integral Fast Reactor. Final project report

International Nuclear Information System (INIS)

Courtney, J.C.

1994-11-01

The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ( 237 Np, 240 Pu, 241 Am, and 243 Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and weapons grade plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for seven day exposure in the Experimental Breeder Reactor-II which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction rates and neutron spectra. These experimental data increase the authors confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs

Behavior of actinides in the Integral Fast Reactor fuel cycle

International Nuclear Information System (INIS)

Courtney, J.C.; Lineberry, M.J.

1994-01-01

The Integral Fast Reactor (IFR) under development by Argonne National Laboratory uses metallic fuels instead of ceramics. This allows electrorefining of spent fuels and presents opportunities for recycling minor actinide elements. Four minor actinides ( 237 Np, 240 Pu, 241 Am, and 243 Am) determine the waste storage requirements of spent fuel from all types of fission reactors. These nuclides behave the same as uranium and other plutonium isotopes in electrorefining, so they can be recycled back to the reactor without elaborate chemical processing. An experiment has been designed to demonstrate the effectiveness of the high-energy neutron spectra of the IFR in consuming these four nuclides and plutonium. Eighteen sets of seven actinide and five light metal targets have been selected for ten day exposure in the Experimental Breeder Reactor-2 which serves as a prototype of the IFR. Post-irradiation analyses of the exposed targets by gamma, alpha, and mass spectroscopy are used to determine nuclear reaction-rates and neutron spectra. These experimental data increase the authors' confidence in their ability to predict reaction rates in candidate IFR designs using a variety of neutron transport and diffusion programs

Recycle of LWR actinides to an IFR

International Nuclear Information System (INIS)

Pierce, R.D.; Ackerman, J.P.; Johnson, G.K.; Mulcahey, T.P.; Poa, D.S.

1991-01-01

Large quantities of actinide elements are present in irradiated light water reactor fuel that is stored throughout the world. Because of the high fission to capture ratio for the transuranium (TRU) elements with the high energy neutrons in metal-fueled integral fast reactors (IFR), that reactor can consume these elements effectively. The stored fuel may represent valuable resource for the expanding application of fast power reactors. In addition, the removal of TRU elements from spent LWR fuel has the potential for increasing the capacity of high level waste facilities by reducing the heat load and may increase the margin of safety in meeting licensing requirement. Argonne National Laboratory is developing a pyrochemical process, which is compatible with the IFR fuel cycle for the recovery of TRU elements from LWR fuel. The proposed product is a metallic actinide ingot, which can be introduced into the electrorefining step of the IFR process. Two pyrochemical processes, that is, salt transport process and blanket processing study, are discussed in this paper. Also the experimental studies are reported. (K.I.)

Systematics of criticality data of special actinide nuclides deduced through the Trombay criticality formula

International Nuclear Information System (INIS)

Srinivasan, M.; SubbaRao, K.; Garg, S.B.; Acharya, G.V.

1989-01-01

The authors describe a number of interesting systematics and correlations deduced by analyzing the criticality data of special actinide nuclides using concepts embodied in the Trombay critically formula (TCF). The κ ∞ of fast metal actinide nuclides gives a remarkable linear correlation with the fissility parameter Z 2 /A. The neutron leakage probability of all fast metal cores characterized using a constant parameter σ std enables computation of the critical mass value of any unknown fissile nuclide knowing only its Z 2 /A value. Since the neutron leakage probability from dilute fissile solutions is primarily governed by the scattering/slowing down properties of the hydrogen present in water, critical masses and subcritical limits can be predicted for any water-reflected system at any specified hydrogen-to-actinide atomic ratio knowing only the κ ∞ value of the given fissile solution

Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine

International Nuclear Information System (INIS)

Riviere, Ch.

2000-01-01

The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

Adsorption of actinides by chelating agents containing benzene rings, fixed on charcoal

International Nuclear Information System (INIS)

Valentini Ganzerli, M.T.; Crespi Caramella, V.; Maggi, L.

1999-01-01

The focus of this paper is on the analysis of the actinides in the hydrosphere to study their environmental dispersion. The 8-hydroxyquinoline family and the benzohydroxamic acid have a complexing ability towards the actinides, even if in different oxidation states. Taking advantage of this ability, their salts with some organic acids or bases were prepared. In this way compounds were obtained easily incorporated into active charcoal. Only a small amount of the prepared adsorber may be equilibrated with large sample volumes. Subsequently it can be recovered by filtration. The adsorbed ions may be then re-dissolved with a small volume of the appropriate eluting solution. The 8-hydroxy-quinolines and the 8-hydroxyquinoline produced salts with the benzilic acid. These compounds similarly behave and show wide adsorption coefficients for solutions of pH higher than 3. The adsorption takes place by means of the formation of a complex of the actinide ion with the hydroxyquinoline moiety and also with the benzilic anion. Provided that the active extracting agent is not dissolved in a medium but fixed into a solid phase, the whole adsorption process may be regarded as a solvent extraction reaction. The benzohydroxamic acid was treated with the diphenylamine or with the tribenzylamine to obtain salts, later adsorbed into the charcoal. The adsorption of actinide ions seems to take place by means of a precipitation mechanism of the actinide ions with the hydroxamate ions for solution of pH higher than 3.5. Also in this case high values were obtained for the distribution coefficients. The actinide ions act similarly in the +4 or +6 oxidation state towards the prepared adsorber series. Therefore, it is possible to use only one adsorber to concentrate all actinides. Methods of analysis of actinides in the environment may be suitably set up and the concentration step based on these new prepared adsorber may improve the whole procedure. (authors)

Biosorption of Metals from Multi-Component Bacterial Solutions

CERN Document Server

Tsertsvadze, L A; Petriashvili, Sh G; Chutkerashvili, D G; Kirkesali, E I; Frontasyeva, M V; Pavlov, S S; Gundorina, S F

2002-01-01

The method of extraction of metals from industrial solutions by means of economical and easy to apply biosorbents in subtropics such as products of tea manufacturing, moss, microorganisms is described. The multi-component solutions obtained in the process of leaching of ores, rocks and industrial wastes by peat suspension were used in the experiments. The element composition of sorbent biomass and solutions was investigated by epithermal neutron activation analysis and by atomic absorption spectrometry. The results obtained evidence that the used biosorbents are applicable for extraction of the whole set of heavy metals and actinides (U, Th, Cu, Mn, Fe, Pb, Li, Rb, Sr, Cd, As, Co and others) from industrial solutions.

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

Energy Technology Data Exchange (ETDEWEB)

Karahan, Aydin, E-mail: karahan@mit.edu [Center for Advanced Nuclear Energy Systems, Nuclear Science and Engineering Department, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge MA 24-204 (United States)

2011-07-15

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

Science.gov (United States)

Karahan, Aydın

2011-07-01

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

Extending FEAST-METAL for analysis of low content minor actinide bearing and zirconium rich metallic fuels for sodium fast reactors

International Nuclear Information System (INIS)

Karahan, Aydin

2011-01-01

Computational models in FEAST-METAL fuel behaviour code have been upgraded to simulate minor actinide bearing zirconium rich metallic fuels for use in sodium fast reactors. Increasing the zirconium content to 20-40 wt.% causes significant changes in fuel slug microstructure affecting thermal, mechanical, chemical, and fission gas behaviour. Inclusion of zirconium rich phase reduces the fission gas swelling rate significantly in early irradiation. Above the threshold fission gas swelling, formation of micro-cracks, and open pores increase material compliancy enhance diffusivity, leading to rapid fuel gas swelling, interconnected porosity development and release of the fission gases and helium. Production and release of helium was modelled empirically as a function of americium content and fission gas production, consistent with previous Idaho National Laboratory studies. Predicted fuel constituent redistribution is much smaller compared to typical U-Pu-10Zr fuel operated at EBR-II. Material properties such as fuel thermal conductivity, modulus of elasticity, and thermal expansion coefficient have been approximated using the available database. Creep rate and fission gas diffusivity of high zirconium fuel is lowered by an order of magnitude with respect to the reference low zirconium fuel based on limited database and in order to match experimental observations. The new code is benchmarked against the AFC-1F fuel assembly post irradiation examination results. Satisfactory match was obtained for fission gas release and swelling behaviour. Finally, the study considers a comparison of fuel behaviour between high zirconium content minor actinide bearing fuel and typical U-15Pu-6Zr fuel pins with 75% smear density. The new fuel has much higher fissile content, allowing for operating at lower neutron flux level compared to fuel with lower fissile density. This feature allows the designer to reach a much higher burnup before reaching the cladding dose limit. On the other

Solvent extraction of noble metals by formazans

International Nuclear Information System (INIS)

Grote, M.; Hueppe, U.; Kettrup, A.

1984-01-01

The extraction properties of ion-pairs composed of quaternary ammonium cations and a sulphonated formazan were compared with those of an unsulphonated formazan, for various solvent media. In dichloromethane the combined system behaves as a 'coloured anion-exchanger', with displacement of the sulphonated formazan, whereas in toluene Pd(II) and Ag(I) are extracted as the metal formazan chelates from aqueous medium. The rates of extraction are remarkably higher than with the simple extractants. Because of the higher stability only the simple chelating extraction systems afford satisfactory separation of Pd(II) from excess of Pt(IV) and of Ag(I) from Cu(II). The extracted metals can be stripped and the extractant regenerated. (author)

Trivalent lanthanide/actinide separation in the spent nuclear fuel wastes' reprocessing

International Nuclear Information System (INIS)

Narbutt, J.; Krejzler, J.

2006-01-01

Separation of trivalent actinides, in particular americium and curium, from lanthanides is an important step in an advanced partitioning process for future reprocessing of spent nuclear fuels. Since the trivalent actinides and lanthanides have similar chemistries, it is rather difficult to separate them from each other. The aim of presented work was to study solvent extraction of Am(III) and Eu(III) in a system containing diethylhemi-BTP (6-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine) and COSAN (protonated bis(chlorodicarbollido)cobalt(III)). The system was chosen by several groups working in the integrated EC research Project EUROPART. Several physicochemical properties of the extraction system were analyzed and discussed

Actinide oxide photodiode and nuclear battery

Energy Technology Data Exchange (ETDEWEB)

Sykora, Milan; Usov, Igor

2017-12-05

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

Thermodynamic Properties of Actinides and Actinide Compounds

Science.gov (United States)

Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean

The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.

Partitioning and Leaching Behavior of Actinides and Rare Earth Elements in a Zirconolite- Bearing Hydrothermal Vein System

International Nuclear Information System (INIS)

Payne, Timothy E.; Hart, Kaye P.; Lumpkin, Gregory R.; McGlinn, Peter J.; Giere, Reto

2007-01-01

Chemical extraction techniques and scanning electron microscopy were used to study the distribution and behavior of actinides and rare earth elements (REE) in hydrothermal veins at Adamello (Italy). The six samples discussed in this paper were from the phlogopite zone, which is one of the major vein zones. The samples were similar in their bulk chemical composition, mineralogy, and leaching behavior of major elements (determined by extraction with 9 M HCl). However, there were major differences in the extractability of REE and actinides. The most significant influence on the leaching characteristics appears to be the amounts of U, Th and REE incorporated in resistant host phases (zirconolite and titanite) rather than readily leached phases (such as apatite). Uranium and Th are very highly enriched in zirconolite grains. Actinides were more readily leached from samples with a higher content of U and Th, relative to the amount of zirconium. The results show that REE and actinides present in chemically resistant host minerals can be retained under aggressive leaching conditions. (authors)

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

Science.gov (United States)

2016-01-01

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

Metals extraction from sea water

International Nuclear Information System (INIS)

Chryssostomidis, C.; Larue, G.J.; Morgan, D.T.

1981-01-01

A method and system for continuously extracting metals from sea water by deploying adsorber sheets in a suitable current of sea water, recovering the adsorber sheets after they become loaded with metal and eluting the metal from the recovered sheets. The system involves the use of hollow, perforated bobbins on which the sheets are rolled as they are recovered and through which elutant is introduced

Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

International Nuclear Information System (INIS)

Ackerman, J.P.; Johnson, T.R.

1993-01-01

The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing

Partition of actinides and fission products between metal and molten salt phases: Theory, measurement, and application to IFR pyroprocess development

Energy Technology Data Exchange (ETDEWEB)

Ackerman, J.P.; Johnson, T.R.

1993-10-01

The chemical basis of Integral Fast Reactor fuel reprocessing (pyroprocessing) is partition of fuel, cladding, and fission product elements between molten LiCl-KCl and either a solid metal phase or a liquid cadmium phase. The partition reactions are described herein, and the thermodynamic basis for predicting distributions of actinides and fission products in the pyroprocess is discussed. The critical role of metal-phase activity coefficients, especially those of rare earth and the transuranic elements, is described. Measured separation factors, which are analogous to equilibrium constants but which involve concentrations rather than activities, are presented. The uses of thermodynamic calculations in process development are described, as are computer codes developed for calculating material flows and phase compositions in pyroprocessing.

Novel Strategies for the Removal of Toxic Metals from Soils and Waters

Science.gov (United States)

Roundhill, D. Max

2004-02-01

This article surveys the toxicities of mercury, cadmium, lead, copper, cadmium, and the actinides. Strategies for the removal of these metals include surfactants, aqueous biphasic systems, and liquid membranes. For soils, both in situ stabilization and detection are discussed. For extraction from soils, electrokinetic extraction, phytoremediation, and bioremediation methods are critically evaluated. This article provides an educator with the resources to set up a series of lectures on inorganic aspects of environmental chemistry.

Actinide partitioning from high level liquid waste using the Diamex process

International Nuclear Information System (INIS)

Madic, C.; Blanc, P.; Condamines, N.; Baron, P.; Berthon, L.; Nicol, C.; Pozo, C.; Lecomte, M.; Philippe, M.; Masson, M.; Hequet, C.

1994-01-01

The removal of long-lived radionuclides, which belong to the so-called minor actinides elements, neptunium, americium and curium, from the high level nuclear wastes separated during the reprocessing of the irradiated nuclear fuels in order to transmute them into short-lived nuclides, can substantially decrease the potential hazards associated with the management of these nuclear wastes. In order to separate minor actinides from high-level liquid wastes (HLLW), a liquid-liquid extraction process was considered, based on the use of diamide molecules, which display the property of being totally burnable, thus they do not generate secondary solid wastes. The main extracting properties of dimethyldibutyltetradecylmalonamide (DMDBTDMA), the diamide selected for the development of the DIAMEX process, are briefly described in this paper. Hot tests of the DIAMEX process (using DMDBTDMA) related to the treatment of an mixed oxide fuels (MOX) type HLLW, were successfully performed. The minor actinide decontamination factors of the HLLW obtained were encouraging. The main results of these tests are presented and discussed in this paper. (authors). 9 refs., 2 figs., 7 tabs

Comparative evaluation of DHDECMP [dihexyl-N,N-diethylcarbamoyl-methylphosphonate] and CMPO [octylphenyl-N,N,-diisobutylcarbamoylmethylphosphine oxide] as extractants for recovering actinides from nitric acid waste streams

International Nuclear Information System (INIS)

Marsh, S.F.; Yarbro, S.L.

1988-02-01

Certain neutral, bifunctional organophosphorous compounds are of special value to the nuclear industry. Dihexyl-N,N-diethylcarbomoylmethylphosphonate (DHDECMP) and octylphenyl-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) are highly selective extractants for removing actinide and lanthanide elements from nitric acid. We obtained these two extractants from newly available commercial sources and evaluated them for recovering Am(III), Pu(IV), and U(VI) from nitric acid waste streams of plutonium processing operations. Variables included the extractant (DHSECMP or CMPO), extractant/tributylphosphate ratio, diluent, nitrate concentration, nitrate salt/nitric acid ratio, fluoride concentration, and contact time. Based on these experimental data, we selected DHDECMP as the perferred extractant for this application. 18 refs., 30 figs

Method for fluorination of actinide fluorides and oxyfluorides using O/sub 2/F/sub 2/

Science.gov (United States)

Eller, P.G.; Malm, J.G.; Penneman, R.A.

1984-08-01

The present invention relates generally to methods of fluorination and more particularly to the use of O/sub 2/F/sub 2/ for the preparation of actinide hexafluorides, and for the extraction of deposited actinides and fluorides and oxyfluorides thereof from reaction vessels. The experiments set forth hereinabove demonstrate that the room temperature or below use of O/sub 2/F/sub 2/ will be highly beneficial for the preparation of pure actinide hexafluorides from their respective tetrafluorides without traces of HF being present as occurs using other fluorinating agents: and decontamination of equipment previously exposed to actinides: e.g., walls, feed lines, etc.

Citrate-based open-quotes Talspeakclose quotes actinide-lanthanide separation process

International Nuclear Information System (INIS)

Del Cul, G.D.; Toth, L.M.; Bond, W.D.

1997-01-01

Lanthanide elements are produced in relatively high yield by fission of 235 U. Almost all the lanthanide isotopes decay to stable nonradioactive lanthanide isotopes in a relatively short time. Consequently, it is highly advantageous to separate the relatively small actinide fraction from the relatively large quantities of lanthanide isotopes. The TALSPEAK process (Trivalent Actinide Lanthanide Separations by Phosphorus-reagent Extraction from Aqueous Complexes) is one of the few means available to separate the trivalent actinides from the lanthanides. Previous work based on the use of lactic or glycolic acid has shown deleterious effects of some impurity ions such as zirconium(IV), even at concentrations on the order of 10 -4 M. Other perceived problems were the need to maintain the pH and reagent concentrations within a narrow range and a significant solubility of the organic phase at high carboxylic acid concentrations. The authors' cold experiments showed that replacing the traditional extractants glycolic or lactic acid with citric acid eliminates or greatly reduces the deleterious effects produced by impurities such as zirconium. An extensive series of batch tests was done using a wide range of reagent concentrations at different pH values, temperatures, and contact times. The results demonstrated that the citrate-based TALSPEAK can tolerate appreciable changes in pH and reagent concentrations while maintaining an adequate lanthanide extraction. Experiments using a three-stage glass mixer-settler showed a good lanthanide extraction, appropriate phase disengagement, no appreciable deleterious effects due to the presence of impurities such as zirconium, excellent pH buffering, and no significant loss of organic phase

Heterogeneous all actinide recycling in LWR all actinide cycle closure concept

International Nuclear Information System (INIS)

Tondinelli, Luciano

1980-01-01

A project for the elimination of transuranium elements (Waste Actinides, WA) by neutron transmutation is developed in a commercial BWR with U-Pu (Fuel Actinides, FA) recycle. The project is based on the All Actinide Cycle Closure concept: 1) closure of the 'back end' of the fuel cycle, U-Pu coprocessing, 2) waste actinide disposal by neutron transmutation. The reactor core consists of Pu-island fuel assemblies containing WAs in target pins. Two parallel reprocessing lines for FAs and WAs are provided. Mass balance, hazard measure, spontaneous activity during 10 recycles are calculated. Conclusions are: the reduction in All Actinide inventory achieved by Heterogeneous All Actinide Recycling is on the order of 83% after 10 recycles. The U235 enrichment needed for a constant end of cycle reactivity decreases for increasing number of recycles after the 4th recycle. A diffusion-burnup calculation of the pin power peak factors in the fuel assembly shows that design limits can be satisfied. A strong effort should be devoted to the solution of the problems related to high values of spontaneous emission by the target pins

Actinides-1981

International Nuclear Information System (INIS)

1981-09-01

Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry

Actinides-1981

Energy Technology Data Exchange (ETDEWEB)

1981-09-01

Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

Actinides and environmental interfaces: striving for molecular-level understanding

International Nuclear Information System (INIS)

Heino Nitsche

2005-01-01

enhanced second harmonic generation can probe the electronic (UV-vis region) structure of metal species adsorbed at a surface or interface. Infrared-visible sum frequency generation spectroscopy probes the infrared vibrational spectrum of molecules adsorbed at the interface. SHG/SFG studies will greatly assist with understanding reactivity at interfaces of oxides and soil organic matter with heavy metals and radionuclides/actinides. Time-resolved Laser-fluorescence spectroscopy (TRLFS) is a highly sensitive tool for actinides that absorb light and de-excite by fluorescence emission, e.g., U(VI) and Cm(III), to probe changes in actinide speciation and coordination environment in solution. This method can also be used to differentiate whether adsorbed species form surface complexes or surface precipitates. Recently, it was shown that the intense synchrotron radiation can change the oxidation states of redox-sensitive actinide samples which may cause erroneous results, and low temperature measurements are now used to alleviate this shortcoming. X-ray Absorption Fine Structure (XAFS) Spectroscopy is composed of two component spectroscopies, X-ray absorption near edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) which provide element specific oxidation state and local structure information, respectively. EXAFS (Extended X-ray Absorption Fine Structure Spectroscopy) provides information on the chemical environment of particular actinide, in particular bond lengths and the number of neighboring atoms. Combining both methods, detailed knowledge of the different processes resulting from the interaction of the selected actinides with environmental interfaces can be gained. XANES and EXAFS measurements and TRLFS studies to obtain molecular-level mechanistic details of actinide interaction with common environmental solutions and interfaces will be presented together with first SHG/SFG characterization results of model systems for environmental interfaces

ACTINET-I3 Summer School on Analytical Innovation in the field of actinide recycling - Slides of the presentations

International Nuclear Information System (INIS)

Poinssot, Ch.; Nash, K.L.; Puget, P.; Szabo, Z.; Vallet, V.; Berthon, L.; Duhamet, J.; Wipff, G.; Dufreche, J.F.; Walter, P.; Thiebaut, D.; Toulhoat, P.; Aupiais, J.; Amatore, C.

2011-01-01

This conference dealt with 3 main topics: analytical innovation in separation processes (hyphenated techniques, analytical chips,...), actinide recycling (extraction, interfaces, processes,...) and chemistry and thermodynamics of actinides. This document is composed of the slides of the presentations

CMPO-functionalized C{sub 3}-symmetric tripodal ligands in liquid/liquid extractions : efficient, selective recognition of Pu(IV) with low affinity for 3+ metal ions.

Energy Technology Data Exchange (ETDEWEB)

Matloka, K.; Sah, A. K.; Peters, M. W.; Srinivasan, P.; Gelis, A. V.; Regalbuto, M.; Scott, M. J.; Univ. of Florida

2007-12-10

Structural modifications of carbamoylmethylphosphine oxide (CPMO)-functionalized triphenoxymethane platforms are described, and the influence of these changes on the ability of the ligand to extract actinides from simulated acidic nuclear waste streams has been evaluated. The ligand system has been shown to have excellent binding efficiency and a selectivity for An(IV) in comparison to the a simple monomeric CMPO ligand under analogous conditions. Both the extraction efficiency and selectivity are strongly dependent on the flexibility and electronic properties of the ligating units in the triphenoxymethane construct. The Tb(III) and Bi(III) nitrate complexes of tris-CMPO derivatives have been isolated, and their structures were elucidated by NMR, ESI FT-ICR MS, and X-ray analysis, providing information on the interactions between metal ions and the tris-CMPO molecules.

Liquid–liquid extraction of Pu(IV), U(VI) and Am(III) using malonamide in room temperature ionic liquid as diluent

International Nuclear Information System (INIS)

Rout, Alok; Venkatesan, K.A.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2012-01-01

Highlights: ► Extraction of actinides using malonamide in room temperature ionic liquid. ► High distribution ratios of actinides in room temperature ionic liquid. ► Ion exchange mechanism. ► Stoichiometry of extraction. ► High separation factors of U(VI) and Pu(IV) over Am(III) and fission products. - Abstract: The extraction behavior of U(VI), Pu(IV) and Am(III) from nitric acid medium by a solution of N,N-dimethyl-N,N-dioctyl-2-(2-hexyloxyethyl)malonamide (DMDOHEMA) in the room temperature ionic liquid, 1–butyl–3–methylimidazolium bis(trifluoromethanesulfonyl)imide (C 4 mimNTf 2 ), was studied. The distribution ratio of these actinides in DMDOHEMA/C 4 mimNTf 2 was measured as a function of various parameters such as the concentration of nitric acid, DMDOHEMA, NTf 2 − , alkyl chain length of ionic liquid. The extraction of actinides in the absence of DMDOHEMA was insignificant and the distribution ratio achieved in conjunction with C 4 mimNTf 2 , was remarkable. The separation factor of U(VI) and Pu(IV) achieved with the use of DMDOHEMA, ionic liquid was compared with Am(III) and other fission products. The stoichiometry of the metal-solvate was determined to be 1:2 for U(VI) and Pu(IV) and 1:3 for Am(III).

Removal of actinides from dilute waste waters using polymer filtration

International Nuclear Information System (INIS)

Smith, B.F.; Robison, T.W.; Gibson, R.R.

1995-01-01

More stringent US Department of Energy discharge regulations for waste waters containing radionuclides (30 pCi/L total alpha) require the development of new processes to meet the new discharge limits for actinide metal ions, particularly americium and plutonium, while minimizing waste. We have been investigating a new technology, polymer filtration, that has the potential for effectively meeting these new limits. Traditional technology uses basic iron precipitation which produces large amounts of waste sludge. The new technology is based on using water-soluble chelating polymers with ultrafiltration for physical separation. The actinide metal ions are selectively bound to the polymer and can not pass through the membrane. Small molecules and nonbinding metals pass through the membrane. Advantages of polymer filtration technology compared to ion, exchange include rapid kinetics because the binding is occurring in a homogenous solution and no mechanical strength requirement on the polymer. We will present our results on the systematic development of a new class of water-soluble chelating polymers and their binding ability from dilute acid to near neutral waters

Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures

International Nuclear Information System (INIS)

Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

1999-01-01

By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs

Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

Energy Technology Data Exchange (ETDEWEB)

Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

1999-02-12

By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

Complexes of actinides with naturally occuring organic substances - Literature survey

International Nuclear Information System (INIS)

Olofsson, U.; Allard, B.

1983-02-01

Properties of naturally occurring humic and fulvic acids and their formation of actinide complexes are reviewed. Actinides in all the oxdation states III, IV, V and VI would form complexes with many humic and fulvic acids, comparable in strength to the hydroxide and carbonate complexes. Preliminary experiments have shown, that the presence of predominantly humic acid complexes would significantly reduce the sorption of americium on geologic media. This does not, however, necessarily lead to a potentially enhanced mobility under environmental conditions, since humic and fulvic acids carrying trace metals also would be strongly bound to e.g. clayish material. (author)

Progress on the Application of Metallic Fuels for Actinide Transmutation

International Nuclear Information System (INIS)

Kennedy, J. Rory; Fielding, Randall; Janney, Dawn; Mariani, Robert; Teague, Melissa; Egeland, Gerald

2015-01-01

Full text of publication follows: Idaho National Laboratory (INL) is developing actinide bearing alloy metallic fuels intended for effecting the transmutation of long-lived isotopes in fast reactor application as part of a partitioning and transmutation strategy. This presentation will report on progress in three areas of this effort: demonstration of the fabrication of fuels under remote (hot cell) conditions directly coupled to the product from the Pyro-processing of spent fuel as part of the Joint Fuel Cycle Studies (JFCS) collaboration with the Korean Atomic Energy Research Institute (KAERI); the chemical sequestration of lanthanide fission products to mitigate fuel-cladding-chemical-interaction (FCCI); and transmission electron microscopy (TEM) and atom probe tomography (APT) studies on the as-cast microstructure of the metallic fuel alloy. For the JFCS efforts, we report on the implementation of the Glove-box Advanced Casting System (GACS) as a prototype casting furnace for eventual installation into the INL Hot Fuel Examination Facility (HFEF) where the recycled fuel will be cast. Results from optimising process parameters with respect to fuel characteristics, americium volatility, materials interaction, and lanthanide fission product carry over distribution will be discussed. With respect to the lanthanide carry over from the Pyro-processing product, encouraging studies on concepts to chemically sequester the FCCI promoting lanthanides within the fuel matrix thus inhibiting migration and interaction with the cladding will be presented. Finally, in relation to advanced modelling and simulation efforts, detailed investigations and interpretation on the nano-scale as cast microstructure of possible recycle fuel composition containing U, Pu, Am, Np as well as carry-over lanthanide species will be discussed. These studies are important for establishing the initial conditions from which advanced physics based fuel performance codes will run. (authors)

Process analytical chemistry applied to actinide waste streams

International Nuclear Information System (INIS)

Day, R.S.

1994-01-01

The Department of Energy is being called upon to clean up it's legacy of waste from the nuclear complex generated during the cold war period. Los Alamos National Laboratory is actively involved in waste minimization and waste stream polishing activities associated with this clean up. The Advanced Testing Line for Actinide Separations (ATLAS) at Los Alamos serves as a developmental test bed for integrating flow sheet development of nitric acid waste streams with process analytical chemistry and process control techniques. The wastes require processing in glove boxes because of the radioactive components, thus adding to the difficulties of making analytical measurements. Process analytical chemistry methods provide real-time chemical analysis in support of existing waste stream operations and enhances the development of new waste stream polishing initiatives. The instrumentation and methods being developed on ATLAS are designed to supply near-real time analyses on virtually all of the chemical parameters found in nitric acid processing of actinide waste. These measurements supply information on important processing parameters including actinide oxidation states, free acid concentration, interfering anions and metal impurities

Metal scarcity and sustainability, analyzing the necessity to reduce the extraction of scarce metals

NARCIS (Netherlands)

Henckens, M. L C M; Driessen, P. P J; Worrell, E.

2014-01-01

There is debate whether or not further growth of metal extraction from the earth's crust will be sustainable in connection with geologic scarcity. Will future generations possibly face a depletion of specific metals? We study whether, for which metals and to what extent the extraction rate would

Combined techniques for studying actinide complexes in room temperature ionic liquids

International Nuclear Information System (INIS)

Gaillard, C.; Billard, I.; Mekki, S.; Ouadi, A.; Hennig, Ch.; Denecke, M.A.

2007-01-01

Room temperature ionic liquids (RTILs) are a new class of solvents. Their main interest is related to their 'green' properties (non-volatile, non-flammable, etc.), but also from the variability of their physico-chemical properties (stability, hydrophobicity, viscosity) as a function of the RTIL cationic and anionic components. In the frame of the nuclear fuel reprocessing, RTILs are particularly attractive in order to improve existing processes or to develop new ones for actinide and lanthanide partitioning, in replacement of toxic solvents used nowadays, for metal electrodeposition or for liquid/liquid extraction by the use of task specific ionic liquids. However, despite the increasing number of publications devoted to ionic liquids, the solvation effects, the solute-solvent and solvent-solvent interactions are still hardly known. These fundamental aspects are of tremendous importance to the understanding of the solvating properties of these new solvents. In this frame, we have undertaken studies on the solvation and complexation of lanthanides (III) and actinides in RTILs, by the use of spectroscopic techniques. Experiments were led in various ionic liquids in order to highlight the role of the anionic part of the RTILs on the reactivity of the studied cations. Results have clearly shown that solvation phenomena in RTILs are not as 'simple' as in classical solvents. The dissolution of a Ln/An salt, even if complete, does not imply dissociation and solvation of the metal cation by the RTILs anions only. The nature of first co-ordination sphere of Ln/An depends on the competition between its counter-anions and the RTIL anions, which, in turn, influence the complexation reaction with other added anions such as chlorides. (authors)

Chelant extraction of heavy metals from contaminated soils

Energy Technology Data Exchange (ETDEWEB)

Peters, R.W. [Energy Systems Division, Argonne National Laboratory, 9700 South Cass Avenue, Argonne, IL 60439 (United States)

1999-04-23

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple

Chelant extraction of heavy metals from contaminated soils

International Nuclear Information System (INIS)

Peters, R.W.

1999-01-01

The current state of the art regarding the use of chelating agents to extract heavy metal contaminants has been addressed. Results are presented for treatability studies conducted as worst-case and representative soils from Aberdeen Proving Ground's J-Field for extraction of copper (Cu), lead (Pb), and zinc (Zn). The particle size distribution characteristics of the soils determined from hydrometer tests are approximately 60% sand, 30% silt, and 10% clay. Sequential extractions were performed on the 'as-received' soils (worst case and representative) to determine the speciation of the metal forms. The technique speciates the heavy metal distribution into an easily extractable (exchangeable) form, carbonates, reducible oxides, organically-bound, and residual forms. The results indicated that most of the metals are in forms that are amenable to soil washing (i.e. exchangeable+carbonate+reducible oxides). The metals Cu, Pb, Zn, and Cr have greater than 70% of their distribution in forms amenable to soil washing techniques, while Cd, Mn, and Fe are somewhat less amenable to soil washing using chelant extraction. However, the concentrations of Cd and Mn are low in the contaminated soil. From the batch chelant extraction studies, ethylenediaminetetraacetic acid (EDTA), citric acid, and nitrilotriacetic acid (NTA) were all effective in removing copper, lead, and zinc from the J-Field soils. Due to NTA being a Class II carcinogen, it is not recommended for use in remediating contaminated soils. EDTA and citric acid appear to offer the greatest potential as chelating agents to use in soil washing the Aberdeen Proving Ground soils. The other chelating agents studied (gluconate, oxalate, Citranox, ammonium acetate, and phosphoric acid, along with pH-adjusted water) were generally ineffective in mobilizing the heavy metals from the soils. The chelant solution removes the heavy metals (Cd, Cu, Pb, Zn, Fe, Cr, As, and Hg) simultaneously. Using a multiple-stage batch extraction

A micro hot test of the Chalmers-GANEX extraction system on used nuclear fuel

Energy Technology Data Exchange (ETDEWEB)

Bauhn, L.; Hedberg, M.; Aneheim, E.; Ekberg, C.; Loefstroem-Engdahl, E.; Skarnemark, G. [Department of Chemical and Biological Engineering, Nuclear Chemistry, Chalmers University of Technology, Kemivaegen 4, SE-412 96 Goeteborg (Sweden)

2013-07-01

In the present study, a 'micro hot test' has been performed using the Chalmers-GANEX (Group Actinide Extraction) system for partitioning of used nuclear fuel. The test included a pre-extraction step using N,N-di-2- ethylhexyl-butyramide (DEHBA) in n-octanol to remove the bulk part of the uranium. This pre-extraction was followed by a group extraction of actinides using the mixture of TBP and CyMe{sub 4}-BTBP in cyclohexanone as suggested in the Chalmers-GANEX process, and a three stage stripping of the extracted actinides. Distribution ratios for the extractions and stripping were determined based on a combination of γ- and α-spectrometry, as well as ICP-MS measurements. Successful extraction of uranium, plutonium and the minor actinides neptunium, americium and curium was achieved. However, measurements also indicated that co-extraction of europium occurs to some extent during the separation. These results were expected based on previous experiments using trace concentrations of actinides and lanthanides. Since this test was only performed in one stage with respect to the group actinide extraction, it is expected that multi stage tests will give even better results. (authors)

Subsurface interactions of actinide species and microorganisms. Implications for the bioremediation of actinide-organic mixtures

International Nuclear Information System (INIS)

Banaszak, J.E.; Rittmann, B.E.; Reed, D.T.

1999-01-01

By reviewing how microorganisms interact with actinides in subsurface environments, the way how bioremediation controls the fate of actinides is assessed. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. The way how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility is described. Why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions is explained. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. Development of mathematical models that link microbiological and geochemical reactions is described. Throughout, the key research needs are identified. (author)

Method for the recovery of actinide elements from nuclear reactor waste

International Nuclear Information System (INIS)

Horwitz, E.P.; Delphin, W.H.; Mason, G.W.

1979-01-01

A process is described for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid

A unified picture of the crystal structures of metals

Science.gov (United States)

Söderlind, Per; Eriksson, Olle; Johansson, Börje; Wills, J. M.; Boring, A. M.

1995-04-01

THE crystal structures of the light actinides have intrigued physicists and chemists for several decades1. Simple metals and transition metals have close-packed, high-symmetry structures, such as body-centred cubic, face-centred cubic and hexagonal close packing. In contrast, the structures of the light actinides are very loosely packed and of low symmetry-tetragonal, orthorhombic and monoclinic. To understand these differences, we have performed total-energy calculations, as a function of volume, for both high-and low-symmetry structures of a simple metal (aluminium), a non-magnetic transition metal (niobium), a ferromagnetic transition metal (iron) and a light actinide (uranium). We find that the crystal structure of all of these metals is determined by the balance between electrostatic (Madelung) interactions, which favour high symmetry, and a Peierls distortion of the crystal lattice, which favours low symmetry. We show that simple metals and transition metals can adopt low-symmetry structures on expansion of the lattice; and we predict that, conversely, the light actinides will undergo transitions to structures of higher symmetry on compression.

A unified picture of the crystal structures of metals

International Nuclear Information System (INIS)

Soederlind, P.; Eriksson, O.; Johansson, B.; Wills, J.M.; Boring, A.M.

1995-01-01

The crystal structures of the light actinides have intrigued physicists and chemists for several decades. Simple metals and transition metals have close-packed, high-symmetry structures, such as body-centred cubic, face-centred cubic hexagonal close packing. In contrast, the structures of the light actinides are very loosely packed and of low symmetry -tetragonal, orthorhombic and monoclinic. To understand these differences, we have have performed total-energy calculations, as a function of volume, for both high- and low-symmetry structures of a simple metal (aluminium), a non-magnetic transition metal (niobium), a ferromagnetic transition metal (iron) and a light actinide (uranium). We find that the crystal structure of all these metals is determined by the balance between electrostatic (Madelung) interactions, which favour high symmetry, and a Peierls distortion of the crystal lattice, which favours low symmetry. We show that simple metals and transition metals can adopt low-symmetry structures on expansion of the lattice; and we predict that, conversely, the light actinides will undergo transitions to structures of higher symmetry on compression. (author)

Actinide colloid generation in groundwater

International Nuclear Information System (INIS)

Kim, J.I.

1990-05-01

The progress made in the investigation of actinide colloid generation in groundwaters is summarized and discussed with particular examples relevant to an understanding of the migration behaviour of actinides in natural aquifer systems. The first part deals with the characterization of colloids: groundwater colloids, actinide real-colloids and actinide pseudocolloids. The second part concentrates on the generation processes and migration behaviour of actinide pseudocolloids, which are discussed with some notable experimental examples. Importance is stressed more on the chemical aspects of the actinide colloid generation in groundwater. This work is a contribution to the CEC project MIRAGE II, particularly, to research area: complexation and colloids. (orig.)

EUROPART: an European integrated project on actinide partitioning

International Nuclear Information System (INIS)

Madic, C.; Baron, P.; Hudson, M.J.

2006-01-01

Full text of publication follows: The EUROPART project is a scientific integrated project between 24 European partners, from 10 countries, mostly funded by the European Community within the FP6, together with CRIEPI from Japan and ANSTO from Australia. EUROPART aims at developing chemical partitioning processes for the so-called minor actinides (MA) contained in nuclear wastes, i.e. from Am to Cf. In the case of the treatment of dedicated spent fuels or targets, the actinides to be separated also include U, Pu and Np. The techniques considered for the separation of these radionuclides belong to the fields of hydrometallurgy and pyrometallurgy, as in the previous European FP5 programs named PARTNEW, CALIXPART and PYROREP, respectively. The two main axes of research within EUROPART are: 1/ the partitioning of MA (from Am to Cf) from wastes issuing from the reprocessing of high burn-up UOX fuels and multi-recycled MOX fuels, 2/ the partitioning of the whole actinide family of elements for recycling, as an option for advanced dedicated fuel cycles (this work will be connected to the studies to be performed within the EUROTRANS European integrated project). In hydrometallurgy, the research is organized in five Work Packages (WP). Four are dedicated to the study of partitioning methods mainly based on the use of solvent extraction methods and of solid extractants, one WP is dedicated to the development of actinide co-conversion methods for fuel or target preparations. The research in pyrometallurgy is organized into four WPs, listed hereafter: (i) study of the basic chemistry of transuranium elements and of some fission products in molten salts (chlorides, fluorides), (ii) development of actinide partitioning methods, (iii) study of the conditioning of the salt wastes, (iv) system studies. Moreover, a strong management team is concerned not only with the technical and financial issues arising from EUROPART, but also with information, communication and benefits for Europe

Extraction of metal ions by neutral β-diphosphoramides

International Nuclear Information System (INIS)

Madic, C.

1990-01-01

The extracting ability of β-diphosphoramides of the type R-N[P(O)(NMe 2 ) 2 ] 2 with R=-CH 3 (NIPA), -C 12 H 25 (ODIPA), or -C 16 H 33 (OHDIPA) for metal ions such as lanthanides, uranyl, and the transuranium elements Am(III) and Pu(IV) has been studied. Extraction yields depend on the nature of the ligand, the organic diluent (nitromethane, kerosene, tert-butylbenzene), the concentration of nitric acid in the aqueous phase, and the ligand-to-metal ratio, Q. The results show that the bidentate phosphoramides are very efficient extractants for all of the metals studied, even at low ratios Q. The presence of nitric acid generally enhances the extraction yields. On the other hand, selectivity is rather poor with these ligands. A particular effort has been made to determine the nature of extracted species by NMR spectroscopy

Determination of actinides by alpha spectrometric methods

International Nuclear Information System (INIS)

Galanda, D.

2011-01-01

The submitted thesis in its first part concern with content determination of plutonium, americium, uranium, thorium radionuclides, like the most significant representatives of actinides in environmental patterns, where by the primary consideration is a focusing on content of these actinides in samples of superior mycotic organisms - mushrooms. Following the published studies the mushrooms were monitored as organisms that could verify most of attributes putted on bioindicators in term of observation of substantial radionuclides in living environment. There were analyzed two groups of samples that came from two chosen locations, one of them is situated in Eastern Slovakia and the second one in West Slovakia. Except for mushrooms samples the examined radionuclides volumes were determined even in specimens of soil sub-base and some plants from chosen localities. The liquid - liquid extraction methods were used for determination of mass activities of actinides in samples for radiochemical separation of monitored radionuclides. The obtained results of plutonium and americium mass activities determination's lead us to carry out experiments that proved abilities of superior mycotic organisms to absorb and accumulate alpha radionuclides in their textures. We choose the oyster mushroom (Pleurotus ostreatus) species as an experimental object. Sporocarps of this mushroom were cultivated on substratum which is commercially exploited to cultivate it whereby this substratum was purposely contaminated by known activities of 239 Pu and 241 Am. We prepared five autonomous samples together. The values of mass activities of 239 Pu and 241 Am obtained by following analysis of prepared samples showed the ability of mushrooms to absorb observed actinides in their texture structures. On the basis of obtained mass activities it was possible to evaluate and numerically determine a transmitting factor's attributes of monitored radionuclides in sporocarps and in sub-base. Accordingly we

Multifaceted Modularity: A Key for Stepwise Building of Hierarchical Complexity in Actinide Metal–Organic Frameworks

Energy Technology Data Exchange (ETDEWEB)

Dolgopolova, Ekaterina A. [Department; Ejegbavwo, Otega A. [Department; Martin, Corey R. [Department; Smith, Mark D. [Department; Setyawan, Wahyu [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; Karakalos, Stavros G. [College; Henager, Charles H. [Pacific Northwest National Laboratory, Richland, Washington 99352, United States; zur Loye, Hans-Conrad [Department; Shustova, Natalia B. [Department

2017-11-07

Growing necessity for efficient nuclear waste management is a driving force for development of alternative architectures towards fundamental understanding of mechanisms involved in actinide integration inside extended structures. In this manuscript, metal-organic frameworks (MOFs) were investigated as a model system for engineering radionuclide containing materials through utilization of unprecedented MOF modularity, which cannot be replicated in any other type of materials. Through the implementation of recent synthetic advances in the MOF field, hierarchical complexity of An-materials were built stepwise, which was only feasible due to preparation of the first examples of actinide-based frameworks with “unsaturated” metal nodes. The first successful attempts of solid-state metathesis and metal node extension in An-MOFs are reported, and the results of the former approach revealed drastic differences in chemical behavior of extended structures versus molecular species. Successful utilization of MOF modularity also allowed us to structurally characterize the first example of bimetallic An-An nodes. To the best of our knowledge, through combination of solid-state metathesis, guest incorporation, and capping linker installation, we were able to achieve the highest Th wt% in mono- and bi-actinide frameworks with minimal structural density. Overall, combination of a multistep synthetic approach with homogeneous actinide distribution and moderate solvothermal conditions could make MOFs an exceptionally powerful tool to address fundamental questions responsible for chemical behavior of An-based extended structures, and therefore, shed light on possible optimization of nuclear waste administration.

Equipment, operation and some results from a hot test of the CTH actinide separation process

International Nuclear Information System (INIS)

Liljenzin, J.O.; Persson, G.

1981-01-01

The CTH actinide separation process has been tested by treating 16 l of 10 year old waste solution from PUREX reprocessing of metallic fuel. It was in general found to operate well and, in some respects, slightly better than design specifications. The extraction process removed more than 99.995% of initial alpha activity. After the sorption steps 5 Bq/l β-activity remained in solution. The modified reversed TALSPEAK process used to separate Am and Cm from the lanthanides gave an Am-Cm product with less than 0.7% of the lanthanides and vice versa. This result can probably be somewhat improved by continuous addition of lactic acid and closer pH control. (orig.)

Theoretical and experimental study of actinide complexes with monoamides and organophosphorus ligands in solution

International Nuclear Information System (INIS)

Ribokaite, Kristina

2013-01-01

Monoamides and organophosphate are of great interest for the nuclear fuel cycle. Such ligands can selectively extract actinides in liquid-liquid extraction processes. The structure of the extractant (its functional group and its alkyl substituents) has a predominant role in the selective separation of actinides. This thesis concerns the theoretical and experimental studies of model systems in the aim of better understanding of the effect on molecular structures of the complexes. Structures of actinides complexes formed with model ligands in simple media (water or methanol in the presence of nitrate ions) have been characterized. At first, the complexation of uranyl by monoamide and phosphine oxide was studied in water and methanol. Molecular Dynamics simulations and DFT calculations were used to quantify the stability of uranyl complexes with those ligands, and to determine their structural properties. The theoretical results were then compared with experimental results obtained by UV-visible, infrared, Raman and EXAFS on the same chemical systems. The results were used to highlight the greater stability of uranyl complexes with phosphine oxide and monoamides. Further spectroscopic measurements combined with molecular modeling were used to gain a better understanding of the coordination mode of nitrate ion around the uranyl in both water and methanol. Finally, DFT calculations were used to study the influence of the structure of the monoamide or organophosphorus ligand and their interaction with the actinides (IV, VI) including steric effects in the first coordination sphere. (author) [fr

European Europart integrated project on actinide partitioning

International Nuclear Information System (INIS)

Madic, C.; Hudson, M.J.

2005-01-01

This poster presents the objectives of EUROPART, a scientific integrated project between 24 European partners, mostly funded by the European Community within the FP6. EUROPART aims at developing chemical partitioning processes for the so-called minor actinides (MA) contained in nuclear wastes, i.e. from Am to Cf. In the case of dedicated spent fuels or targets, the actinides to be separated also include U, Pu and Np. The techniques considered for the separation of these radionuclides belong to the fields of hydrometallurgy and pyrometallurgy, as in the previous FP5 programs named PARTNEW and PYROREP. The two main axes of research within EUROPART will be: The partitioning of MA (from Am to Cf) from high burn-up UO x fuels and multi-recycled MOx fuels; the partitioning of the whole actinide family for recycling, as an option for advanced dedicated fuel cycles (and in connection with the studies to be performed in the EUROTRANS integrated project). In hydrometallurgy, the research is organised into five Work Packages (WP). Four WP are dedicated to the study of partitioning methods mainly based on the use of solvent extraction methods, one WP is dedicated to the development of actinide co-conversion methods for fuel or target preparation. The research in pyrometallurgy is organized into four WP, listed hereafter: development of actinide partitioning methods, study of the basic chemistry of trans-curium elements in molten salts, study of the conditioning of the wastes, some system studies. Moreover, a strong management team will be concerned not only with the technical and financial issues arising from EUROPART, but also with information, communication and benefits for Europe. Training and education of young researchers will also pertain to the project. EUROPART has also established collaboration with US DOE and Japanese CRIEPI. (authors)

Separation of platinum metals by theirs extraction as sulfides

International Nuclear Information System (INIS)

Pilipenko, A.T.; Ryabushko, O.P.; Ty Van Mak

1978-01-01

Separation of platinum metals by means of their sediment in the form of sulfides with subsequent extraction is studied. The optimum conditions of metal sulfide extraction are determined, the metal output dependence from acidness and aqueous phase composition and also the organic solvent nature are investigated. Ruthenium concentration was determined photometrically. Ruthenium sulfide is extracted by butyl spirit from 1-4 normal hydrochloric acid. The maximum extraction grade of 63% is reached in 3.2-normal acid. When the mixture of acetic and hydrochloric acids (2:1) is used for decomposition of ruthenium tiosalts, the grade of ruthenium extraction by amyl spirit or the mixture of anyl and butyl spirits (1:1) constitutes 100%

A first principles investigation of the electronic structure of actinide oxides

DEFF Research Database (Denmark)

Petit, Leon; Svane, Axel; Szotek, Zdzislawa

2010-01-01

The ground state electronic structures of the actinide oxides AO, A2O3 and AO2 (A=U, Np, Pu, Am, Cm, Bk, Cf) are determined from first-principles calculations using the selfinteraction corrected local spin-density approximation. Our study reveals a strong link between preferred oxidation number...... and degree of localization. The ionic nature of the actinide oxides emerges from the fact that those oxides where the ground state is calculated to be metallic do not exist in nature, as the corresponding delocalized f-states favour the accommodation of additional O atoms into the crystal lattice....

Research in actinide chemistry

International Nuclear Information System (INIS)

Choppin, G.R.

1993-01-01

This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH - , CO 3 2- , PO 4 3- , humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements

Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

Energy Technology Data Exchange (ETDEWEB)

Cassayre, L., E-mail: cassayre@chimie.ups-tlse.fr [Laboratoire de Genie Chimique (LGC), Departement Procedes Electrochimiques, CNRS-UMR 5503, Universite de Toulouse III - Paul Sabatier, 31062 Toulouse (France); Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany)

2011-07-01

Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl{sub 3}. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl{sub 3} alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl{sub 2}/UAl{sub 3} molar ratio, providing complete chlorination of the alloy without formation of volatile UCl{sub 5} and UCl{sub 6}. The results showed high efficient chlorination at a temperature of 150 deg. C.

Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

International Nuclear Information System (INIS)

Cassayre, L.; Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P.

2011-01-01

Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl 3 . A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl 3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl 2 /UAl 3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl 5 and UCl 6 . The results showed high efficient chlorination at a temperature of 150 deg. C.

Method for extracting copper, silver and related metals

Science.gov (United States)

Moyer, Bruce A.; McDowell, W. J.

1990-01-01

A process for selectively extracting precious metals such as silver and gold concurrent with copper extraction from aqueous solutions containing the same. The process utilizes tetrathiamacrocycles and high molecular weight organic acids that exhibit a synergistic relationship when complexing with certain metal ions thereby removing them from ore leach solutions.

Magnesium transport extraction of transuranium elements from LWR fuel

International Nuclear Information System (INIS)

Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Miller, W.E.; Pierce, R.D.

1992-01-01

This patent describes a process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuel containing rare earth and noble metal fission products as well as fission products of alkali metals, alkaline earth metals and iodine. It comprises reducing the oxide fuel with Ca metal in the presence of Ca halide; separating the Ca halide with the CaO and the fission products contained therein from the U-Fe alloy and the metal values dissolved therein and electrolytically contacting the calcium salts with a carbon electrode; contacting the liquid U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel with liquid Mg metal, thereafter separating the liquid Mg and the metals dissolved therein from the U-Fe alloy and the metal dissolved therein, distilling the Mg from the transuranium actinide and rare earth metals, recontacting the U-Fe alloy with liquid Mg metal a sufficient number of times until not less than about 99% by weight of the transuranium actinide values have been removed from the U-Fe alloy

Impurities that cause difficulty in stripping actinides from commercial tetraalkylcarbamoylmethylphosphonates

International Nuclear Information System (INIS)

Bahner, C.T.; Shoun, R.R.; McDowell, W.J.

1977-09-01

Dihexyl[(diethylcarbamoyl)methyl]phosphonate (DHDECMP) in diethylbenzene extracts actinides well from 6 M nitric acid solution, but commercially available DHDECMP contains impurities which interfere with stripping the actinides from the organic extract. DHDECMP purified by molecular distillation does not contain these impurities, but the pot residue contains increased concentrations of them. Heating the purified DHDECMP causes the formation of products which interfere with stripping in the same way, suggesting that high temperatures employed in the manufacture of DHDECMP may produce the offending impurities. These impurities can be separated from the heat-decomposed material or the pot residues by dilution with a large volume of hexanes (causing part of the impurities to separate as a second liquid phase) followed by equilibration of the hexane solution with dilute alkali. After the treatment with hexane and dilute alkali, the DHDECMP is readily recovered and functions well in the actinide extraction process. Dibutyl[(dibutylcarbamoyl)methyl]-phosphonate (DBDBCMP) and di(2-ethylhexyl)[(diethylcarbamoyl)-methyl]phosphonate (DEHDECMP) are purified less effectively by these methods. Similar separation methods using diethylbenzene or CCl 4 as solvent do not remove impurities as completely as the hexane process. Impurities can also be removed from a benzene solution of the DHDECMP pot residue by passing it through a column packed with silica gel or diethylaminoethyl cellulose. These impurities have been separated into fractions for analytical examination by use of various solvents and by column chromatography. Hexyl hydrogen [(diethylcarbamoyl)methyl]-phosphonate has been identified tentatively as a principal objectionable impurity. Dihexyl phosphoric acid and possibly dihexylphosphonate have been identified in other fractions

Some activities in the United States concerning the physics aspects of actinide waste recycling

International Nuclear Information System (INIS)

Raman, S.

1975-01-01

Reactor types being considered in the United States for the purpose of actinide waste recycling are discussed briefly. The reactor types include thermal reactors operating on the 3.3 percent 235 U-- 238 U and the 233 U-- 232 Th fuel cycles, liquid metal fast breeder reactors, reactors fueled entirely by actinide wastes, gaseous fuel reactors, and fusion reactors. Cross section measurements in progress or planned toward providing basic data for testing the recycle concept are also discussed

Method for the recovery of actinide elements from nuclear reactor waste

Science.gov (United States)

Horwitz, E. Philip; Delphin, Walter H.; Mason, George W.

1979-01-01

A process for partitioning and recovering actinide values from acidic waste solutions resulting from reprocessing of irradiated nuclear fuels by adding hydroxylammonium nitrate and hydrazine to the waste solution to adjust the valence of the neptunium and plutonium values in the solution to the +4 oxidation state, thus forming a feed solution and contacting the feed solution with an extractant of dihexoxyethyl phosphoric acid in an organic diluent whereby the actinide values, most of the rare earth values and some fission product values are taken up by the extractant. Separation is achieved by contacting the loaded extractant with two aqueous strip solutions, a nitric acid solution to selectively strip the americium, curium and rare earth values and an oxalate solution of tetramethylammonium hydrogen oxalate and oxalic acid or trimethylammonium hydrogen oxalate to selectively strip the neptunium, plutonium and fission product values. Uranium values remain in the extractant and may be recovered with a phosphoric acid strip. The neptunium and plutonium values are recovered from the oxalate by adding sufficient nitric acid to destroy the complexing ability of the oxalate, forming a second feed, and contacting the second feed with a second extractant of tricaprylmethylammonium nitrate in an inert diluent whereby the neptunium and plutonium values are selectively extracted. The values are recovered from the extractant with formic acid.

Actinides

International Nuclear Information System (INIS)

Martinot, L.; Fuger, J.

1985-01-01

The oxidation behavior of the actinides is explained on the basis of their electronic structure. The actinide elements, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and laurencium are included. For all except the last three elements, the points of discussion are oxidation states, Gibbs energies and potentials, and potential diagram for the element in acid solution; and thermodynamic properties of these same elements are tabulated. References are cited following discussion of each element with a total of 97 references being cited. 13 tables

Estimating the extractability of potentially toxic metals in urban soils: A comparison of several extracting solutions

International Nuclear Information System (INIS)

Madrid, F.; Reinoso, R.; Florido, M.C.; Diaz Barrientos, E.; Ajmone-Marsan, F.; Davidson, C.M.; Madrid, L.

2007-01-01

Metals released by the extraction with aqua regia, EDTA, dilute HCl and sequential extraction (SE) by the BCR protocol were studied in urban soils of Sevilla, Torino, and Glasgow. By multivariate analysis, the amounts of Cu, Pb and Zn liberated by any method were statistically associated with one another, whereas other metals were not. The mean amounts of all metals extracted by HCl and by SE were well correlated, but SE was clearly underestimated by HCl. Individual data for Cu, Pb and Zn by both methods were correlated only if each city was considered separately. Other metals gave poorer relationships. Similar conclusions were reached comparing EDTA and HCl, with much lower values for EDTA. Dilute HCl extraction cannot thus be recommended for general use as alternative to BCR SE in urban soils. - Dilute HCl extraction is tested as an alternative to the BCR sequential extraction in urban soils

Sigma Team for Minor Actinide Separation: PNNL FY 2011 Status Report

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Levitskaia, Tatiana G.; Carter, Jennifer C.; Warner, Marvin G.; Pittman, Jonathan W.

2011-08-13

This report summarizes work conducted in FY 2011 at PNNL to investigate new methods of separating the minor actinide elements (Am and Cm) from the trivalent lanthanide elements, and separation of Am from Cm. For the former, work focused on a solvent extraction system combining an acidic extractant (HDEHP) with a neutral extractant (CMPO) to form a hybrid solvent extraction system referred to as TRUSPEAK (combining the TRUEX and TALSPEAK processes). For the latter, ligands that strongly bing uranyl ion were investigated for stabilizing corresponding americyl ion.

Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides; Modelisation thermodynamique de l'extraction de nitrates de lanthanides par le CMPO et par un calixarene-CMPO en milieu acide nitrique concentre. Application a l'optimisation de la separation des lanthanides et des actinides/lanthanides

Energy Technology Data Exchange (ETDEWEB)

Belair, S

2003-07-01

The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO{sub 3}){sub 3}-HNO{sub 3}-H{sub 2}O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

Removal of actinide elements from liquid scintillation cocktail wastes using liquid-liquid extraction and demulsification techniques

International Nuclear Information System (INIS)

Foltz, K.; Landsberger, S.; Srinivasan, B.; Vandegrift, G.F.

1994-01-01

For many years liquid scintillation cocktail (LSC) wastes have been generated and stored at Argonne National Laboratory (ANL). These wastes are stored in thousands of 10--20 m scintillation vials, many of which contain elements with Z > 88. Because storage space is limited, disposal of this waste is pressing. These wastes could be commercially incinerated if the radionuclides with Z>88 are reduced to sufficiently low levels. However, there is currently no deminimus level for these radionuclides, and separation techniques are still being tested. The University of Illinois is conducting experiments to separate radionuclides with Z > 88 from simulated LSC wastes by using liquid-liquid extraction (LLX) and demulsification techniques. The actinide elements are removed from the LSC by extraction into an aqueous phase after the cocktail has been demulsified. The aqueous and organic phases are separated and the organic phase, now free from radionuclides with Z > 88, can be sent to a commercial incineration facility. The aqueous phase may be treated and disposed of using existing techniques. The LLX separation techniques used solutions of sodium oxalate, aluminum nitrate, and tetrasodium EDTA at varying concentrations. These extractants were mixed with the simulated waste in a 1:1 volume ratio. Using 1.0M Na 4 EDTA salt solutions, decontamination ratios as high as 230 were achieved

The solvent extraction of alkali metal ions with β-diketones

International Nuclear Information System (INIS)

Munakata, Megumu; Niina, Syozo; Shimoji, Noboru

1974-01-01

This work was undertaken to investigate effects of solvent and chelating-agent on the solvent extraction of alkali metal ions by seven β-diketones, acetylacetone (Acac), benzoylacetone (BzA), dipivaloylmethane (DPM), dibenzoylmethane (DBM), thenoyltrifluoloacetone (TTA), benzoyltrifluoroacetone (BFA) and hexafluoroacetylacetone (HFA), and to separate lithium from alkali metals. The extraction of alkali metals increase with increasing donor power of the solvent: i.e., benzene Na>K>Rb>Cs, which is also the order in which the adduct formation of these β-diketone chelates with donor solvents increase. The adduct formations between β-diketone chelates of alkali metals and donor solvents markedly enhance the solubilities of the chelates in solvents and, consequently, the extractabilities of alkali metals with β-diketones. Lithium was extracted with TTA in ether at such a low base concentration that sodium, potassium, rubidium and cesium were hardly extracted, and this enabled to separate lithium from other metals by the use of rubidium hydroxide (0.02 M). An attempt has been made to isolate alkali metal β-diketone chelates and some chelates have been obtained as crystals. The infrared absorption bands arising from C=O and C.=C of TTA shift to lower frequencies in the alkali metal chelates with TTA, and consequently, β-diketones is suggested to coordinate to alkali metal as a bidentate ligand. (JPN)

Systematic and structural studies of homogeneous and polymeric extractants for the separation and recovery of metal ion: Triennial performance report, August 1, 1983-July 31, 1986

International Nuclear Information System (INIS)

Alexandratos, S.D.

1986-04-01

Novel polymeric extractants have been synthesized and applied to the recovery of metal ions from dilute aqueous solutions. The new category of dual mechanism bifunctional polymers is introduced as a series of resins which permit highly selective extractions through the use of a reaction additional to ion exchange in the recovery process. The bifunctional phosphinic acid ion exchange/redox resins form the first class of resins within this category. Their synthesis and the recovery of metallic mercury, silver, gold, and copper from their ionic solutions is detailed. Under equilibrium conditions, these resins operate entirely by the redox mechanism until all of the primary phosphinic acid sites are oxidized, followed then by purely ion exchange. Kinetic studies show that the cation's reduction potential determines whether a redox reaction will occur while, at a given reduction potential, the oxidation state determines how rapidly. The significant coordinative ability of the phosphoryl oxygen is also important, though, and is responsible for extracting greater amounts of actinide ions than the sulfonic resins. For those processes where membranes would most appropriately be applied, the modification of polypropylene with interpenetrating polymer network extractants yields a recovery system with almost infinite lifetime. Such networks have been formed from polymers of di(undecenyl) phosphoric acid and found to display significantly enhanced retention within polystyrene bead supports. 10 refs

Novel extractants with high selectivity for valuable metals in seawater. Calixarene derivatives

International Nuclear Information System (INIS)

Kakoi, Takahiko; Goto, Masahiro

1997-01-01

Seawater contains various valuable metals such as uranium and lithium. Therefore, attempts are being made to develop highly selective extractants which recognize target metal ions in reclaimed seawater. In this review, we have focused our study on the application of novel cyclic compound calixarene based extractants. A novel host compound calixarene, which is a cyclic compound connecting some phenol rings, is capable of forming several different extractant ring sizes and introducing various kinds of functional groups towards targeting of metal ions in seawater. Therefore, calixarene derivatives are capable of extracting valuable metals such as uranium, alkaline metals, heavy metals, rare earth metals and noble metals selectively by varying structural ring size and functional groups. The novel host compound calixarene has given promising results which line it up as a potential extractant for the separation of valuable metal ions in seawater. (author)

Biotechnology for the extractive metals industries

Science.gov (United States)

Brierley, James A.

1990-01-01

Biotechnology is an alternative process for the extraction of metals, the beneficiation of ores, and the recovery of metals from aqueous systems. Currently, microbial-based processes are used for leaching copper and uranium, enhancing the recovery of gold from refractory ores, and treating industrial wastewater to recover metal values. Future developments, emanating from fundamental and applied research and advances through genetic engineering, are expected to increase the use and efficiency of these biotechnological processes.

Metal ion separations with proton-ionizable Lariat Ethers and their polymers

International Nuclear Information System (INIS)

Bartsch, R.A.

1993-01-01

The preparation of novel and specific organic complexing agents may lead to the development of new separation systems for aqueous metal ions. Thus the introduction of highly lipophilic oximes led to the current utilization of these compounds as commercial extractants for the hydrometallurgy of nonferrous metals. Crown ethers (macrocyclic polyethers) have been employed in the laboratory-scale solvent extraction of alkali-metal, alkaline-earth, and other metal cations into organic phases. Attachment of side arms to crown ethers gives lariat ethers. The presence of one or more potential coordination sites in the side arm of the lariat ether may produce substantial changes in the selectivity and efficiency of metal ion complexation. It has been demonstrated that concomitant transfer of an aqueous phase anion into the organic medium is not required for metal ion extraction. This factor is of immense importance to potential practical applications of these proton-ionizable crown ethers in which the common, hard, aqueous phase anions would be involved. Another advantage of proton-ionizable lariat ethers is the ease with which extracted metal ions may be stripped from the organic phase by shaking with aqueous mineral acid. Thus both metal ion extraction and stripping are facilitated by pendent proton-ionizable groups. Most of the hazardous metal ion species in the Hanford Site tank wastes are members of the alkali-metal, alkaline-earth, lanthanide, and actinide families. These hard metal ion species prefer association with hard donor atoms, such as oxygens. Therefore, crown and lariat ethers are well-suited for complexation with such metal ion species

Some activities in the United States concerning the physics aspects of actinide waste recycling

International Nuclear Information System (INIS)

Raman, S.

1976-01-01

This review paper briefly discusses the reactor types being considered in the United States for the purpose of actinide waste recycling. The reactor types include thermal reactors operating on the 3.3% 235 U- 238 U and the 233 U- 232 Th fuel cycles, liquid metal fast breeder reactors, reactors fueled entirely by actinide wastes, gaseous fuel reactors and fusion reactors. This paper also discusses cross section measurements in progress or planned toward providing basic data for testing the recycle concept. (author)

The correlation of metal content in medicinal plants and their water extracts

Directory of Open Access Journals (Sweden)

Ranđelović Saša S.

2013-01-01

Full Text Available The quality of some medicinal plants and their water extracts from South East Serbia is determined on the basis of metal content using atomic absorption spectrometry. The two methods were used for the preparation of water extracts, to examine the impact of the preparation on the content of metals in them. Content of investigated metals in both water extracts is markedly lower then in medicinal plants, but were higher in water extract prepared by method (I, with exception of lead content. The coefficients of extraction for the observed metal can be represented in the following order: Zn > Mn > Pb > Cu > Fe. Correlation coefficients between the metal concentration in the extract and total metal content in plant material vary in the range from 0.6369 to 0.9956. This indicates need the plants to be collected and grown in the unpolluted area and to examine the metal content. The content of heavy metals in the investigated medicinal plants and their water extracts is below the maximum allowable values, so they are safe to use.

Spectroscopic properties of tetravalent actinide ions in solids

International Nuclear Information System (INIS)

Krupa, J.C.

1987-01-01

Optical spectroscopy is a powerful tool to study the electronic structure of an optically active transition ion in the condensed phase media and consequently to study the interactions between the central ion and its environment. The main interactions that are essential for an understanding of the energy level distribution of an f N ion in solids is briefly examined and the deduced free-ion and crystal field parameters for Pa 4+ , U 4+ , Np 4+ are compared to those of the isoelectronic configuration lanthanide ions. At last, the actinide series offers an interesting situation since the 5f electrons in the metals are delocalized in the light actinides and then localized, that sould affect the nature of the chemical bonding in the two parts of the series. Is this trend reflected in the An 4+ spectroscopic parameters

Advanced counter-current multi-stage centrifugal extractor for solvent extraction process

International Nuclear Information System (INIS)

Ionita, Gheorghe; Mirica, Dumitru; Croitoru, Cornelia; Stefanescu, Ioan; Steflea, Dumitru; Mihaila, V.; Peteu, Gh.

2002-01-01

Total actinide recovery, lanthanide/actinide separation and the selective partitioning of actinide from high level waste (HLW) are nowadays of a major interest. Actinide partitioning with a view to safe disposing of HLW or utilization in many other applications of recovered elements involve an extraction process usually by means of mixer-settler, pulse column or centrifugal contactor. The latter, presents some doubtless advantages and responds to the above mentioned goals. A new type of counter-current multistage centrifugal extractor has been designed and built. The counter-current multi-stage centrifugal extractor is a stainless steel cylinder with an effective length of 346 mm, the effective diameter of 100 mm and a volume of 1.5 liters, having horizontal position as working position. The new internal structure and geometry of the new advanced centrifugal extractor is shown. It consists of nine cells (units): five rotation units, two mixing units, two propelling units and two final plates which ensures the counter-current running of the two phases. The central shaft having the rotation cells fixed on it is connected to an electric motor of high rotation speed. The extractor has been tested at 1000-3000 rot/min for a ratio of the aqueous/organic phase = 1. The mechanical and hydrodynamic behavior of the two phases in counter-current are described. The results showed that the performances have been generally good. The new facility appears to be a promising idea to increase extraction rate of radionuclides and metals from liquid effluents. (authors)

Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

Energy Technology Data Exchange (ETDEWEB)

Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2013-03-01

The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

Trivalent actinide-lanthanide extraction by DEHPA. Structure of organic complexes

International Nuclear Information System (INIS)

Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

1985-09-01

The di-2-ethylhexyldithiophosphoric acid HDEHDTP is a bidentate ligand with sulphur donor atoms which has a good affinity for soft acids. H 2 O H NMR and light diffraction let us demonstrate that HDEHDTP is a monomer and NaDEHDTP a reverse micelle. When La 3+ replaces Na + , the reverse micelle is preserved. In the same way when TBP expells H 2 O the polymerised state is preserved. Evidence of that is provided by low angle X-ray diffraction; the micelles are shell-shaped and the ions are strongly tied to the ligand. The mechanism of extraction has been determined with traces of metal for HDEHDTP and the synergistic system HDEHDTP, TBP. The substitution of H 2 O by TBP in the complex induces a shortening of the S-metal bound so that the 5f ions better ability to form covalent bounds is settled [fr

Actinides: from heavy fermions to plutonium metallurgy

International Nuclear Information System (INIS)

Smith, J.L.; Fisk, Z.; Hecker, S.S.

1984-01-01

The actinide elements mark the emergence of 5f electrons. The f electrons possess sufficiently unusual characteristics that their participation in atomic binding often result in dramatic changes in properties. This provides an excellent opportunity to study the question of localization of electrons; a question that is paramount in predicting the physical and chemical properties of d and f electron transition metals. The transition region between localized (magnetic) and itinerant (often superconducting) behavior provides for many interesting phenomena such as structural instabilities (polymorphism), spin fluctuations, mixed valences, charge density waves, exceptional catalytic activity and hydrogen storage. This region offers most interesting behavior such as that exhibited by the actinide compounds UBe 13 and UPt 3 . Both compounds are heavy-fermion superconductors in which both magnetic and superconducting behavior exist in the same electrons. The consequences of f-electron bonding (which appears greatest at Plutonium) show dramatic effects on phase stability, alloying behavior, phase transformations and mechanical behavior

Zirconium behaviour during electrorefining of actinide-zirconium alloy in molten LiCl-KCl on aluminium cathodes

Energy Technology Data Exchange (ETDEWEB)

Meier, R. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Heidelberg University, Institute of Physical Chemistry, Im Neuenheimer Feld 253, Heidelberg 69120 (Germany); Souček, P., E-mail: Pavel.Soucek@ec.europa.eu [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Malmbeck, R.; Krachler, M.; Rodrigues, A.; Claux, B.; Glatz, J.-P. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Fanghänel, Th. [European Commission, Joint Research Centre (JRC), Institute for Transuranium Elements (ITU), Postfach 2340, Karlsruhe 76125 (Germany); Heidelberg University, Institute of Physical Chemistry, Im Neuenheimer Feld 253, Heidelberg 69120 (Germany)

2016-04-15

A pyrochemical electrorefining process for the recovery of actinides from metallic nuclear fuel based on actinide-zirconium alloys (An–Zr) in a molten salt is being investigated. In this process actinides are group-selectively recovered on solid aluminium cathodes as An–Al alloys using a LiCl–KCl eutectic melt at a temperature of 450 °C. In the present study the electrochemical behaviour of zirconium during electrorefining was investigated. The maximum amount of actinides that can be oxidised without anodic co-dissolution of zirconium was determined at a selected constant cathodic current density. The experiment consisted of three steps to assess the different stages of the electrorefining process, each of which employing a fresh aluminium cathode. The results indicate that almost a complete dissolution of the actinides without co-dissolution of zirconium is possible under the applied experimental conditions. - Highlights: • Recovery of actinides was shown by electrorefining of U/Pu–Zr alloys in LiCl–KCl. • Constant current density of 20 mA/cm{sup 2} is applied. • Most of the actinides were dissolved avoiding zirconium co-dissolution. • Deterioration of the deposit quality by a small amount of co-deposited Zr is not observed.

Performance comparison of metallic, actinide burning fuel in lead-bismuth and sodium cooled fast reactors

International Nuclear Information System (INIS)

Weaver, K.D.; Herring, J.S.; Macdonald, P.E.

2001-01-01

Various methods have been proposed to ''incinerate'' or ''transmute'' the current inventory of transuranic waste (TRU) that exits in spent light-water-reactor (LWR) fuel, and weapons plutonium. These methods include both critical (e.g., fast reactors) and non-critical (e.g., accelerator transmutation) systems. The work discussed here is part of a larger effort at the Idaho National Engineering and Environmental Laboratory (INEEL) and at the Massachusetts Institute of Technology (MIT) to investigate the suitability of lead and lead-alloy cooled fast reactors for producing low-cost electricity as well as for actinide burning. The neutronics of non fertile fuel loaded with 20 or 30-wt% light water reactor (LWR) plutonium plus minor actinides for use in a lead-bismuth cooled fast reactor are discussed in this paper, with an emphasis on the fuel cycle life and isotopic content. Calculations show that the average actinide burn rate is similar for both the sodium and lead-bismuth cooled cases ranging from -1.02 to -1.16 g/MWd, compared to a typical LWR actinide generation rate of 0.303 g/MWd. However, when using the same parameters, the sodium-cooled case went subcritical after 0.2 to 0.8 effective full power years, and the lead-bismuth cooled case ranged from 1.5 to 4.5 effective full power years. (author)

Development of Radioanalytical and Microanalytical Procedures for the Determination of Actinides in Environmental Samples

International Nuclear Information System (INIS)

Macsik, Zsuzsanna; Vajda, Nora; Bene, Balazs; Varga, Zsolt

2008-01-01

A radio-analytical procedure has been developed for the simultaneous determination of actinides in swipe samples by alpha-spectrometry after the separation of the actinides by extraction chromatography. The procedure is based on the complete decomposition of the sample by destruction with microwave digestion or ashing in furnace. Actinides are separated on an extraction chromatographic column filled with TRU resin (product of Eichrom Industries Inc.). Alpha sources prepared from the separated fractions of americium, plutonium, thorium and uranium are counted by alpha spectrometry. Micro-analytical procedure is being developed for the location and identification of individual particles containing fissile material using solid state nuclear track detectors. The parameters of alpha and fission track detection have been optimized and a procedure has been elaborated to locate the particles on the sample by defining the coordinates of the tracks created by the particles on the track detector. Development of a procedure is planned to separate the located particles using micromanipulator and these particles will be examined individually by different micro- and radio-analytical techniques. (authors)

Development of Radioanalytical and Microanalytical Procedures for the Determination of Actinides in Environmental Samples

Energy Technology Data Exchange (ETDEWEB)

Macsik, Zsuzsanna [Institute of Nuclear Techniques, Moegyetem rakpart 9, H-1111 Budapest (Hungary); Vajda, Nora [RadAnal Ltd., Bimbo ut 119/a, H-1026 Budapest (Hungary); Bene, Balazs [National Institute of Standards and Technology, Gaithersburg, MD 20899 (United States); Varga, Zsolt [Institute of Isotopes, Konkoly-Thege M. ut 29-33, H-1121 Budapest (Hungary)

2008-07-01

A radio-analytical procedure has been developed for the simultaneous determination of actinides in swipe samples by alpha-spectrometry after the separation of the actinides by extraction chromatography. The procedure is based on the complete decomposition of the sample by destruction with microwave digestion or ashing in furnace. Actinides are separated on an extraction chromatographic column filled with TRU resin (product of Eichrom Industries Inc.). Alpha sources prepared from the separated fractions of americium, plutonium, thorium and uranium are counted by alpha spectrometry. Micro-analytical procedure is being developed for the location and identification of individual particles containing fissile material using solid state nuclear track detectors. The parameters of alpha and fission track detection have been optimized and a procedure has been elaborated to locate the particles on the sample by defining the coordinates of the tracks created by the particles on the track detector. Development of a procedure is planned to separate the located particles using micromanipulator and these particles will be examined individually by different micro- and radio-analytical techniques. (authors)

Actinide recycle

Energy Technology Data Exchange (ETDEWEB)

Till, C; Chang, Y [Argonne National Laboratory, Argonne, IL (United States)

1990-07-01

A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository.

Actinide recycle

International Nuclear Information System (INIS)

Till, C.; Chang, Y.

1990-01-01

A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository

Recovery of actinides from actinide-aluminium alloys by chlorination: Part III - Chlorination with HCl(g)

Science.gov (United States)

Meier, Roland; Souček, Pavel; Walter, Olaf; Malmbeck, Rikard; Rodrigues, Alcide; Glatz, Jean-Paul; Fanghänel, Thomas

2018-01-01

Two steps of a pyrochemical route for the recovery of actinides from spent metallic nuclear fuel are being investigated at JRC-Karlsruhe. The first step consists in electrorefining the fuel in molten salt medium implying aluminium cathodes. The second step is a chlorination process for the separation of actinides (An) from An-Al alloys formed on the cathodes. The chlorination process, in turn, consists of three steps; the distillation of adhered salt (1), the chlorination of An-Al by HCl/Cl2 under formation of AlCl3 and An chlorides (2), and the subsequent sublimation of AlCl3 (3). In the present work UAl2, UAl3, NpAl2, and PuAl2 were chlorinated with HCl(g) in a temperature range between 300 and 400 °C forming UCl4, NpCl4 or PuCl3 as the major An containing phases, respectively. Thermodynamic calculations were carried out to support the experimental work. The results showed a high chlorination efficiency for all used starting materials and indicated that the sublimation step may not be necessary when using HCl(g).

Determination of Pb-210 and actinides by extraction chromatography and anion exchange chromatography

International Nuclear Information System (INIS)

Kalmykov, St.N.; Sapozhnikov, Yu.A.

1997-01-01

This work is devoted to the determination of Pb-210 and actinides (Pu-238, Pu-239, Am-241, U-235, U-238, Th-232) by means of highly selective chromatographic resins and anion exchangers. The special interest was paid to the analysis of large quantities of samples with high concentration of competitive ions like ocean sediments, bone ash and others.The commercially available TRU-Spec chromatographic resins was used for separation of actinides from the matrix. Then U, Th, Am, and Pu were separated from other using anion exchange chromatography with AG-1X4 anionite in Cl - form, electro-deposed and α-counted.Pb-21- and Bi-210 were determined by liquid scintillation counting. The developed procedure is rather express, effective and could be adopted for the determination of radionuclides like Ba-133, Ra, Np-239

Thermodynamic modelling of the extraction of nitrates of lanthanides by CMPO and by CMPO-like calixarene in concentrated nitric acid medium. Application in the optimization of the separation of lanthanides and actinides/lanthanides

International Nuclear Information System (INIS)

Belair, S.

2003-01-01

The separation minor actinides / lanthanides in nitric acid medium is as one of problems of separative chemistry the most delicate within the framework of the processes allowing the recovery of long life radioelements present in the solutions of fission products. Previous studies showed that CMPO-substituted calix[4]arenes presents a better affinity for actinides than for lanthanides. To optimize the operating conditions of separation and to take into account the degree of non-ideality for the concentrated nitric solutions, we adopted a thermodynamic approach. The methodology taken to determine the number and the stoichiometry of the complexes formed in organic phase base on MIKULIN-SERGIEVSKII's model used through a software of data processing of experimental extraction isotherms. These tools are exploited at first on an extraction system engaging the CMPO, extractant reagent of actinides and lanthanides in concentrated nitric medium. The modelling of the system Ln(NO 3 ) 3 -HNO 3 -H 2 O/CMPO comes to confirm the results of several studies. At the same time, they allow to establish working hypotheses aiming at limiting the investigations of our researches towards the most stable complexes formed between lanthanides and CMPO-like calixarene to which the same method is then applied. An analytical expression of the selectivity of separation by the calixarene is established to determine the parameters and physico-chemical variables on which it depends. So, the ratio of the constants of extraction and the value of the activity of water of the system fixes the selectivity of separation of 2 elements. The exploitation of this relation allows to preview the influence of a variation of the concentration of nitric acid. Experiments of extraction confirm these forecasts and inform about the affinity of the calixarene with respect to lanthanides elements and to the americium. (author)

Liquid scintillation counting techniques for the determination of some alpha emitting actinides: a review

International Nuclear Information System (INIS)

Mirashi, N.N.; Chander, Keshav; Aggarwal, S.K.

2000-12-01

The present report is a review of the work on liquid scintillation counting techniques, for the determination of alpha emitting actinides like uranium, plutonium, americium etc; for the last three decades (1970-1999). It covers the progress that has taken place in conventional liquid scintillation counting employing various solvents, scintillators and extractants. There is gradual development in instrumentation from integral counting of alpha emitters to alpha liquid scintillation spectrometry to resolve and identify different alpha emitters. These advancements have led to Pulse Shape Analysis (PSA) and Photon Electron Rejecting Alpha Liquid Scintillation Spectrometry (PERALS) techniques for the determination of the alpha emitters in the presence of beta and gamma activity. These techniques allow the determination of actinides at very low levels which has increased their applications to almost all the fields of chemistry; be it biomedical, environmental, geological or process chemistry of nuclear fuels. The development of biphasic technique using various extractants to separate different elements and counting in presence of one another has been made possible. Inorganic scintillators have been recently developed which have the advantage of eliminating effects of quenching and presence of beta/gamma emitting actinides. This review will serve as a reference to those who want to carry out work in the field of determination of actinides using liquid scintillation counting techniques. (author)

Recent development in computational actinide chemistry

International Nuclear Information System (INIS)

Li Jun

2008-01-01

Ever since the Manhattan project in World War II, actinide chemistry has been essential for nuclear science and technology. Yet scientists still seek the ability to interpret and predict chemical and physical properties of actinide compounds and materials using first-principle theory and computational modeling. Actinide compounds are challenging to computational chemistry because of their complicated electron correlation effects and relativistic effects, including spin-orbit coupling effects. There have been significant developments in theoretical studies on actinide compounds in the past several years. The theoretical capabilities coupled with new experimental characterization techniques now offer a powerful combination for unraveling the complexities of actinide chemistry. In this talk, we will provide an overview of our own research in this field, with particular emphasis on applications of relativistic density functional and ab initio quantum chemical methods to the geometries, electronic structures, spectroscopy and excited-state properties of small actinide molecules such as CUO and UO 2 and some large actinide compounds relevant to separation and environment science. The performance of various density functional approaches and wavefunction theory-based electron correlation methods will be compared. The results of computational modeling on the vibrational, electronic, and NMR spectra of actinide compounds will be briefly discussed as well [1-4]. We will show that progress in relativistic quantum chemistry, computer hardware and computational chemistry software has enabled computational actinide chemistry to emerge as a powerful and predictive tool for research in actinide chemistry. (authors)

Application of chemical structure and bonding of actinide oxide materials for forensic science

International Nuclear Information System (INIS)

Wilkerson, Marianne Perry

2010-01-01

We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO 2 (An: U, Pu) to form non-stoichiometric species described as AnO 2+x . Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

Application of chemical structure and bonding of actinide oxide materials for forensic science

Energy Technology Data Exchange (ETDEWEB)

Wilkerson, Marianne Perry [Los Alamos National Laboratory

2010-01-01

We are interested in applying our understanding of actinide chemical structure and bonding to broaden the suite of analytical tools available for nuclear forensic analyses. Uranium- and plutonium-oxide systems form under a variety of conditions, and these chemical species exhibit some of the most complex behavior of metal oxide systems known. No less intriguing is the ability of AnO{sub 2} (An: U, Pu) to form non-stoichiometric species described as AnO{sub 2+x}. Environmental studies have shown the value of utilizing the chemical signatures of these actinide oxide materials to understand transport following release into the environment. Chemical speciation of actinide-oxide samples may also provide clues as to the age, source, or process history of the material. The scientific challenge is to identify, measure and understand those aspects of speciation of actinide analytes that carry information about material origin and history most relevant to forensics. Here, we will describe our efforts in material synthesis and analytical methods development that we will use to provide the fundamental science to characterize actinide oxide molecular structures for forensic science. Structural properties and initial results to measure structural variability of uranium oxide samples using synchrotron-based X-ray Absorption Fine Structure will be discussed.

Uranium chloride extraction of transuranium elements from LWR fuel

International Nuclear Information System (INIS)

Miller, W.E.; Ackerman, J.P.; Battles, J.E.; Johnson, T.R.; Pierce, R.D.

1992-01-01

A process of separating transuranium actinide values from uranium values present in spent nuclear oxide fuels containing rare earth and noble metal fission products as well as other fission products is disclosed. The oxide fuel is reduced with Ca metal in the presence of Ca chloride and a U-Fe alloy which is liquid at about 800 C to dissolve uranium metal and the noble metal fission product metals and transuranium actinide metals and rare earth fission product metals leaving Ca chloride having CaO and fission products of alkali metals and the alkali earth metals and iodine dissolved therein. The Ca chloride and CaO and the fission products contained therein are separated from the U-Fe alloy and the metal values dissolved therein. The U-Fe alloy having dissolved therein reduced metals from the spent nuclear fuel is contacted with a mixture of one or more alkali metal or alkaline earth metal halides selected from the class consisting of alkali metal or alkaline earth metal and Fe or U halide or a combination thereof to transfer transuranium actinide metals and rare earth metals to the halide salt leaving the uranium and some noble metal fission products in the U-Fe alloy and thereafter separating the halide salt and the transuranium metals dissolved therein from the U-Fe alloy and the metals dissolved therein. 1 figure

Actinide isotopic analysis systems

International Nuclear Information System (INIS)

Koenig, Z.M.; Ruhter, W.D.; Gunnink, R.

1990-01-01

This manual provides instructions and procedures for using the Lawrence Livermore National Laboratory's two-detector actinide isotope analysis system to measure plutonium samples with other possible actinides (including uranium, americium, and neptunium) by gamma-ray spectrometry. The computer program that controls the system and analyzes the gamma-ray spectral data is driven by a menu of one-, two-, or three-letter options chosen by the operator. Provided in this manual are descriptions of these options and their functions, plus detailed instructions (operator dialog) for choosing among the options. Also provided are general instructions for calibrating the actinide isotropic analysis system and for monitoring its performance. The inventory measurement of a sample's total plutonium and other actinides content is determined by two nondestructive measurements. One is a calorimetry measurement of the sample's heat or power output, and the other is a gamma-ray spectrometry measurement of its relative isotopic abundances. The isotopic measurements needed to interpret the observed calorimetric power measurement are the relative abundances of various plutonium and uranium isotopes and americium-241. The actinide analysis system carries out these measurements. 8 figs

Rapid method to determine actinides and 89/90Sr in limestone and marble samples

International Nuclear Information System (INIS)

Maxwell, S.L.; Culligan, Brian; Hutchison, J.B.; Utsey, R.C.; Sudowe, Ralf; McAlister, D.R.

2016-01-01

A new method for the determination of actinides and radiostrontium in limestone and marble samples has been developed that utilizes a rapid sodium hydroxide fusion to digest the sample. Following rapid pre-concentration steps to remove sample matrix interferences, the actinides and 89 / 90 Sr are separated using extraction chromatographic resins and measured radiometrically. The advantages of sodium hydroxide fusion versus other fusion techniques will be discussed. This approach has a sample preparation time for limestone and marble samples of <4 h. (author)

Influence of ionic liquids on actinides extraction by diphenyl(dibutyl)carbamoylmethylphosphine oxide in different solvents from nitric acid solution

International Nuclear Information System (INIS)

Pribylova, G.A.

2011-01-01

Influence of ionic liquids (ILs) addition (1-50 wt%) on extraction efficiency of actinides by diphenyl(dibutyl)carbamoylmethylphosphine oxide (Ph 2 Bu 2 ) from 3 M HNO 3 has been studied. Am(III) distribution ratios in two-phase systems 0.1 M Ph 2 Bu 2 in either DCE or CHCl 3 -3 M HNO 3 depending on the nature of additional ionic liquids: imidazolium-based ILs: [C 4 mim][PF 6 ], [C 4 mim][BF 4 ] and phosphonium-based ILs: PPF 6 , PBF 4 and PCl were determined. The highest value of Am(III) extraction ratio change (1040) was found on addition of PPF 6 to Ph 2 Bu 2 in CHCl 3 . Extraction of Pu(IV) and U(VI) by 0.001 M Ph 2 Bu 2 in the presence of [C 4 mim][PF 6 ] in DCE, CHCl 3 or meta-nitrobenzotrifluoride (NBTF) have been investigated. The greatest enhancement of extraction efficiency was observed using CHCl 3 , the least polar studied solvent. Using a mixture of conventional solvent and ionic liquid as a solvent for extractant enables one to increase distribution ratios and reduce viscosity of organic phase as compared with ionic liquid viscosity. The marked increase of Am(III), Pu(IV) and U(VI) extraction extent by Ph 2 Bu 2 on addition of ionic liquids to the extent of 10 wt% permit one essentially to diminish amounts considerably more expensive carbamoylmethylphosphine oxide(the general name is CMPO) used in TRUEX process. (author)

Study of the selectivity of poly-nitrogenous extracting molecules in the complexation of actinides (III) and lanthanides (III) in solution in anhydrous pyridine; Etude de la selectivite de molecules extractantes polyazotees dans la complexation des actinides (III) et des lanthanides (III) en solution dans la pyridine anhydre

Energy Technology Data Exchange (ETDEWEB)

Riviere, Ch

2000-10-05

The aim of this work is to better understand the factors which contribute to the separation of lanthanides(III) and actinides(III). Polydentate nitrogenous molecules present an interesting selectivity. A thermodynamic study of the complexation in pyridine of lanthanide and uranium by the bipyridine ligand (bipy) has been carried out. The formation constants and the thermodynamic values of the different complexes have been determined. It has been shown that the bipy complexes formation is controlled by the enthalpy and unfavored by the entropy. The conductometry has revealed too a significant difference in the uranium and lanthanides complexation by the bipyridine ligand. The use of the phenanthroline ligand induces a better complexation of the metallic ions but the selectivity is not improved. On the other hand, the decrease of the basicity and the increase of the ligand denticity (for instance in the case of the use of ter-pyridine) favour the selectivity without improving the complexation. The selectivity difference for the complexation of actinides(III) and lanthanides(III) by the different studied ligands (independent systems) has been confirmed by experiments of inter-metals competition. (O.M.)

Cobalt bis(dicarbollide) ions with covalently bonded CMPO groups as selective extraction agents for lanthanide and actinide cations from highly acidic nuclear waste solutions

International Nuclear Information System (INIS)

Gruner, B.; Plesek, J.; Baca, J.; Cisarova, I.; Dozol, J.F.; Rouquette, H.; Vinas, C.; Selucky, P.; Rais, J.

2002-01-01

A new series of boron substituted cobalt bis(dicarbollide)(1-) ion (1) derivatives of the general formula [(8-CMPO-(CH 2 -CH 2 O) 2 -1,2-C 2 B 9 H 10 )(1',2'-C 2 B 9 H 11 )-3,3'-Co] - (CMPO = Ph 2 P(O)-CH 2 C(O)NR, R = C 4 H 9 (3b), -C 12 H 25 (4b), -CH 2 -C 6 H 5 (5b)) was prepared by ring cleavage of the 8-dioxane-cobalt bis(dicarbollide) (2) bi-polar compound by the respective primary amines and by subsequent reaction of the resulting amino derivatives (3a-5a) with the nitrophenyl ester of diphenyl-phosphoryl-acetic acid. The compounds were synthesized with the aim to develop a new class of more efficient extraction agents for liquid/liquid extraction of polyvalent cations, i.e. lanthanides and actinides, from high-level activity nuclear waste. All compounds were characterized by a combination of 11 B NMR, 1 H high field NMR, Mass Spectrometry with Electro-spray and MALDI TOF ionisation, HPLC and other techniques. The molecular structure of the supramolecular Ln 3+ complex of the anion 5b was determined by single crystal X-ray diffraction analysis. Crystallographic results proved that the Ln(m) atom is bonded to three functionalized cobalt bis(dicarbollide) anions in a charge compensated complex. The cation is tightly coordinated by six oxygen atoms of the CMPO terminal groups (two of each ligand) and by three water molecules completing the metal coordination number to 9. Atoms occupying the primary coordination sphere form a tri-capped trigonal prismatic arrangement. Very high liquid-liquid extraction efficiency of all anionic species was observed. Moreover, less polar toluene can be applied as an auxiliary solvent replacing the less environmentally friendly nitro- and chlorinated solvents used in the current dicarbollide liquid-liquid extraction process. The extraction coefficients are sufficiently high for possible technological applications. (authors)

Metal ion extractant in microemulsions: where solvent extraction and surfactant science meet

International Nuclear Information System (INIS)

Bauer, C.

2011-01-01

The presented work describes the supramolecular structure of mixtures of a hydrophilic surfactant n-octyl-beta-glucoside (C8G1), and the hydrophobic metal ion extractant tributylphosphate (TBP) in n-dodecane/water as well as in the presence of salts. In the first part, basic solvent extraction system, composed of water, oil and extractant, will be introduced. The focus, however, lies on the extraction of multivalent metal ions from the aqueous phase. During this extraction process and in the following thermodynamic equilibrium, aggregation and phase transition in supramolecular assemblies occur, which are already described in literature. Notably, these reports rest on individual studies and specific conclusions, while a general concept is still missing. We therefore suggest the use of generalized phase diagrams to present the physico-chemical behaviour of (amphiphilic) extractant systems. These phase diagrams facilitated the development of a thermodynamic model based on molecular geometry and packing of the extractant molecules in the oil phase. As a result, we are now in the position to predict size and water content of extractant aggregates and, thus, verify the experimental results by calculation.Consequently, the second part presents a systematic study of the aqueous and organic phase of water/C8G1 and water/oil/TBP mixtures. The focus lies on understanding the interaction between metal ions and both amphiphilic molecules by means of small angle x-ray scattering (SAXS), dynamic light scattering (DLS) and UV-Vis spectroscopy. We confirmed the assumption that extraction of metal ions is driven by TBP, while C8G1 remains passive. In the third and last part, microemulsions of C8G1, TBP, water (and salt) and n-dodecane are characterized by small angle neutron scattering (SANS), and chemical analytics (Karl Fischer, total organic carbon, ICP-OES,...). The co-surfactant behaviour of TBP was highlighted by comparison to the classical n-alcohol (4≤n≤8) co