Curium separation

Americium-Curium Separation by Means of Selective Extraction of Hexavalent Americium Using a Centrifugal Contactor... 

Americium-curium separations have always posed a challenge to chemists, mainly for two reasons ... 

The use of larger particles in the cyclotron, for example carbon, nitrogen or oxygen ions, enabled elements of several units of atomic number beyond uranium to be synthesised. Einsteinium and fermium were obtained by this method and separated by ion-exchange. and indeed first identified by the appearance of their concentration peaks on the elution graph at the places expected for atomic numbers 99 and 100. The concentrations available when this was done were measured not in gcm but in atoms cm. The same elements became available in greater quantity when the first hydrogen bomb was exploded, when they were found in the fission products. Element 101, mendelevium, was made by a-particle bombardment of einsteinium, and nobelium (102) by fusion of curium and the carbon-13 isotope. 

Ion exchange (qv see also Chromatography) is an important procedure for the separation and chemical identification of curium and higher elements. This technique is selective and rapid and has been the key to the discovery of the transcurium elements, in that the elution order and approximate peak position for the undiscovered elements were predicted with considerable confidence (9). Thus the first experimental observation of the chemical behavior of a new actinide element has often been its ion-exchange behavior—an observation coincident with its identification. Further exploration of the chemistry of the element often depended on the production of larger amounts by this method. Solvent extraction is another useful method for separating and purifying actinide elements. 

EXTRACTANT CONCENTRATION GRADIENT IN THE AMERICIUM(III) / CURIUM(III) SEPARATION BY COUNTERCURRENT CHROMATOGRAPHY... 

Street, K., and G. T. Seaborg Separation of Americium and Curium from... 

Dr. Glenn T. Seaborg proposed the term actinide for the new heavy elements that were predicted to follow the lanthanide series (Z-57 to Z-71). Dr. Seaborg believed that the actinides would be difficult to discover, and he proposed they would be trivalent homo-logues to the elements in the lanthanide series in which the 4f orbitals would be filled. His team at the Lawrence Berkeley National Laboratory (LBNL), located at the University of California s Berkeley campus, separated Z-95 (americium) and Z-96 (curium) as trivalent homologues of two of the elements in the lanthanide series located just above them in the periodic table. 

Americium may be separated from other elements, particularly from the lanthanides or other actinide elements, by techniques involving oxidation, ion exchange and solvent extraction. One oxidation method involves precipitation of the metal in its trivalent state as oxalate (controlled precipitation). Alternatively, it may be separated by precipitating out lanthanide elements as fluorosilicates leaving americium in the solution. Americium may also he oxidized from trivalent to pentavalent state by hypochlorite in potassium carbonate solution. The product potassium americium (V) carbonate precipitates out. Curium and rare earth metals remain in the solution. An alternative approach is to oxidize Am3+ to Am022+ in dilute acid using peroxydisulfate. Am02 is soluble in fluoride solution, while trivalent curium and lanthanides are insoluble. 

Americium and other actinide elements may be separated from lanthanides by solvent extraction. Lithium chloride solution and an eight to nine carbon tertiary amine are used in the process. Americium is then separated from curium by the above methods. 

Curium is produced in small amounts as a by-product of nuclear power production, but this material consists predominantly of the short-lived and extremely hazardous 244Cm isotope. Under prolonged irradiation, a series of neutron captures occurs, forming all the isotopes up to 249Cm. The 247Cm content in such instances never exceeds about 1%, and its separation from the other isotopes, by factors up to 106, would be a prodigious task. 

Weaver, B.S., Kappelmann, F.A. 1964. Talspeak A new method of separating americium and curium from lanthanides by extraction from an aqueous solution of aminopo-lyacetic acid complex with a monoacidic phosphate or phosphonate. ORNL-3559. 

This collection of the state-of-the-art papers emphasizes the continuing importance of industrial-scale production, separation, and recovery of transplutonium elements. Americium (At. No. 95) and curium (At. No. 96) were first isolated in weighable amounts during and immediately after World War II. Berkelium and californium were isolated in 1958 and einsteinium in 1961. These five man-made elements, in each case, subsequently became available in increasing quantities. 

Treatment of irradiated targets. The chemical operations relative to the production of transplutonium elements (americium 243, curium 244) are all performed using a nitric acid medium. The highly corrosive nature of the solutions concentrated with Cl" ions, which were used in the USA for the development of the Tramex process (JO, and the instability of SCN" ions to radiation (12), led us to select nitric acid solution to perform the chemical separations. Once the medium was selected, it was necessary to find an adequate additive which, in combination with a suitable extractant, would allow solution of the main problem namely separation of the trivalent actinides from triva-lent lanthanides. 

The second problem raised by the production of americium 243 and curium 244 resides in their mutual separation. The first experiment developed in France O) was based on a chromatographic Am/Cm separation on Dowex 1x8 anion exchange resin (200/400 mesh) in NO" form. After the fixation of Am(III) on the resin from an ethaiiolic (80 vol %) solution of composition... 

Furthermore, this method is not reasonably applicable to Am/Cm mixtures in which curium is present in macroconcentration. Recently (9) > we adapted the separation method developed by Mason, Bollmeier and Peppard (JO) to handle macroconcentrations of Am. This method consists of a selective extraction of americium, after its oxidation to Am(VI), by an extractant with outstanding selectivity properties, HD(DiBM)P. It can be implemented either by liquid-liquid extraction, requiring the use of centrifugal extractors (V7)> or by extraction chromatography, a simpler and less costly technique. 

Americium und Curium) was given to this pilot project (4). These plans were abandoned when the PACT project was terminated in 1973. Thus, demonstration of the separation process with actual HLW is lacking, and no judgement can be made on its performance. 

Americium was isolated first from plutonium, then from lanthanum and other impurities, by a combination of precipitation, solvent extraction, and ion exchange processes. Parallel with the separation, a vigorous program of research began. Beginning in 1950, a series of publications (1-24) on americium put into the world literature much of the classic chemistry of americium, including discussion of the hexavalent state, the soluble tetravalent state, oxidation potentials, disproportionation, the crystal structure(s) of the metal, and many compounds of americium. In particular, use of peroxydisulfate or ozone to oxidize americium to the (V) or (VI) states still provides the basis for americium removal from other elements. Irradiation of americium, first at Chalk River (Ontario, Canada) and later at the Materials Testing Reactor (Idaho), yielded curium for study. Indeed, the oxidation of americium and its separation from curium provided the clue utilized by others in a patented process for separation of americium from the rare earths. 

The clarified Tramex product solution is divided into two or three batches (<35 g of curium or <19 g of 244 Qm pgr batch) and processed by LiCl-based anion exchange, which is discussed in detail in another paper at this symposium (10), to obtain further decontamination from rare earths and to separate curium from the heavier elements. In each run, the transplutonium and rare-earth elements are sorbed on Dowex 1-X10 ion exchange resin from a 12 hi LiCl solution. Rare earths are eluted with 10 hi LiCl, curium with 9 M LiCl, and the transcurium elements with 8 jl HC1. About 5% of the curium is purposely eluted along with the transcurium elements to prevent losses of 2498 which elutes immediately after the curium and is not distinguishable by the in-line instrumentation. The transcurium element fractions from each run are combined and processed in a second-cycle run, using new resin, to remove most of the excess curium. 

Ross, R. G. Wiggins, J. T. "Preparation of Curium-Americium Oxide Microspheres by Resin-Bead Loading", paper presented at Symposium on Industrial Scale Production-Separation-Recovery of Transplutonium Elements, 2nd Chem. Congr. North American Continent, Las Vegas, NV, 1980. 

A second solvent extraction process (Pharex) was developed to partition the transcurium actinides from the americium and curium in the Tramex product ( 3) The Pharex process utilized 2-ethylhexyl phenylphosphonic acid as the extractant for the transcurium actinides. During early operations/ the selectivity of the Pharex extractant was found to be severely reduced by the presence of zirconium ions, which were introduced into the process solutions by corrosion of Zircaloy-2 equipment in TRU. At zirconium concentrations above 10 ppm, the achievable separation began to be diminished and, at 100 ppm, a practical separation could not be made (4). Thus, a replacement for the Pharex process was needed, and the LiCl AIX process was the most immediate alternative ... 

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