Actinides solvent extraction

We have considered typical examples of lanthanide and actinide solvent extraction by chelate formation, involving complexes with citric acid and with TTA, to prove that the labelling of a stable element by one of its radioactive isotopes can help to produce accurate data on the stability constants for complex formation. The method is applicable to elements with radioisotopes having a half-life allowing an ion concentration of 10 6m or less. Other methods of partition such as radiopolarography and radio-coulometry also result in accurate thermodynamical data when the same procedure of labelling is used (29). 

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. 

Because of the technical importance of solvent extraction, ion-exchange and precipitation processes for the actinides, a major part of their coordination chemistry has been concerned with aqueous solutions, particularly that involving uranium. It is, however, evident that the actinides as a whole have a much stronger tendency to form complexes than the lanthanides and, as a result of the wider range of available oxidation states, their coordination chemistry is more varied. 

Solvent extraction in the separation of rare earths and trivalent actinides. B. Weaver, Ion Exch. Solvent Extr., 1974, 6,190-277 (538). 

In addition to fuel and targets(15J6) from SRP reactors, SRP also reprocesses a wide variety of fuels from offsite research reactors and a wide range of unirradiated plutonium scrap materials.(17) Following customary Savannah River practice, initial processing of each offsite material is designed to transform the actinides to a solution that is compatible with one of the solvent extraction cycles in either of the separations areas. A major advantage of this practice is that the... 

Waste Handling for Unirradiated Plutonium Processing. Higher capacity, better-performing, and more radiation-resistant separation materials such as new ion exchange resins(21) and solvent extractants, similar to dihexyl-N,N-di ethyl carbamoyl methylphosphonate,(22) are needed to selectively recover actinides from acidic wastes. The application of membranes and other new techniques should be explored. 

We are not aware of any previous studies of the removal of plutonium or americium from (NH )2ZrF6-NHltF-NH N03 solutions. For ready plant-scale application, precipitation, sorption on inorganic materials, or batch solvent extraction processes may all be satisfactory. An inexpensive inorganic material with great selectivity and capacity for sorbing actinides, and with suitable hydraulic properties, would be especially attractive. 

The application of these methods is described in some detail for recovery of base metals and platinum group metals in Sections 9.17.5-9.17.6 focusing mainly on solution-based hydrometal-lurgical operations, largely those involving solvent extraction, because the nature of the metal complexes formed is usually best understood in such systems. NB. Extraction of lanthanides and actinides is not included as this subject is treated separately in Chapters 3.2 and 3.3. 

Clanex A solvent extraction process for converting solutions of the nitrates of actinides and lanthanides into their corresponding chlorides. The extractant is a solution of an aliphatic amine in diethylbenzene. 

Studies of sulfoxide complexes of other actinide elements have appeared, (38, 40), but insufficient data are available to make any meaningful comparisons along the series. Work on the solvent extraction of actinide elements by sulfoxides has been reported (423). 

Lisa Townsend, a technician in the Radiochemistry section of the Actinide Analytical Chemistry Group, analyzes bulk components and impurities in plutonium-238 materials used to fabricate heat sources used in space exploration. She utilizes a combination of ion exchange and solvent extraction techniques and determines component concentrations using alpha and gamma radio-counting instrumentation. 

The HSAB principle is useful in solvent extraction, as it provides a guide to choosing ligands that react strongly (high log P) to give extractable complexes. For example, the actinide elements would be expected to, and do, complex strongly with the P-diketonates, R3C—CO—CHj—CO—CR3 (where R = H... 

A guiding principle for the solvent extraction chemist is to produce an uncharged species that has its maximum coordination number satisfied by lipophilic substances (reactants). Eor trivalent lanthanides and actinides (Ln and An, respectively), the thermodynamic data suggest a model in which addition of one molecule of TBP displaces more than one hydrate molecule ... 

In the year 2000, 15% of the world s electric power was produced by 433 nuclear power reactors 169 located in Europe, 120 in the United States, and 90 in the Far East. These reactors consumed 6,400 tons of fresh enriched uranium that was obtained through the production of 35,000 tons of pure natural uranium in 23 different nations the main purification step was solvent extraction. In the reactors, the nuclear transmutation process yielded fission products and actinides (about 1000 tons of Pu) equivalent to the amount of uranium consumed, and heat that powered steam-driven turbines to produce 2,400 TWh of electricity in 2000. 

SOLVENT EXTRACTION OF ACTINIDES FROM WASTE SOLUTIONS... 

Often the products of nuclear reactions have very short half-lives. This is especially true for the heaviest elements obtained by bombardment of heavy targets with heavy ions. To identify and characterize such short-lived nuclides, fast separations are required solvent extraction techniques are well suited to provide the required fast separations. For example, the SISAK method [68] has been successfully used in conjunction with in-line gas jet separators at heavy ion accelerators to identify short half-life actinide isotopes produced by collision of heavy atoms. The Sisak method involves use of centrifugal contactors, with phase residence times as low as tenths of a second, in conjunction with in-line radiometric detection equipment. 

Of course, even without engineering-scale economic and technical drivers, studies of new nuclear solvent extraction technology can and will proceed at academic and national laboratory institutions. Areas for which new technology could be beneficial include, among others, development of extractants that can be readily incinerated detailed information concerning the kinetics of extraction of various solutes and perhaps, development of contactors with very short residence times. Extraction kinetics must be more carefully investigated in the future to be able to take advantage of kinetic differences, especially between the actinides and the fi -transition elements. 

M = Am, Cm, Bk, Cf, and Es) has been investigated by solvent extraction processes using bis-(2-ethylhexyl)phosphoric acid. The stability of [M(NCS)] and [M(NCS)2] increased gradually across the series in accord with expectations based on the actinide contraction, and there was evidence for the tetrad... 

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. 

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