Solution actinide process

The redox salt which decomposes at 100°C, evolving nitrogen and oxygen [1] is overall an oxidant but has been used as a reducant in actinide processing [2]. Even in the absence of actinides dilute solutions for this may concentrate by evaporation of watrer until there is an autocatalytic runaway. A widely publicised explosion from this cause (there have been others) generated official reports [6]. Stability studies... 

COMPOSITION OF ACTUAL AND SYNTHETIC ACTINIDE PROCESS WASTE SOLUTIONS... 

Feed Solutions. The process is applicable to solutions of trivalent actinides or lanthanides in either dilute acid or a variety of salt solutions in either nitrate or chloride or mixed media. Sodium concentrations up to 3 M can be tolerated, but lithium begins to have adverse effects above 2 M and potassium is objectionable even at 0.5 M. Certain special constituents can be tolerated in the feed if specific precautions (described later) are taken. 

Nuclear Waste Reprocessing. Liquid waste remaining from processing of spent reactor fuel for military plutonium production is typically acidic and contains substantial transuranic residues. The cleanup of such waste in 1996 is a higher priority than military plutonium processing. Cleanup requires removal of long-Hved actinides from nitric or hydrochloric acid solutions. The transuranium extraction (Tmex) process has been developed for... 

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. 

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... 

Swanson, (31 ) Smith,(32) Phillips, ( 33 ) and others have described many aspects of "EHe Zirflex process but, unfortunately, not the form or charge of plutonium and other actinides in spent decladding solution. Presumably, soluble amounts of these elements are present as fluoride complexes, but this remains to be proven. 

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. 

Waste Treatment. Figure 2 outlines the current waste recovery and treatment processes, and proposed changes. Acid waste streams are sent through nitric acid and secondary plutonium recovery processes before being neutralized with potassium hydroxide and filtered. This stream and basic and laundry waste streams are sent to waste treatment. During waste treatment, the actinides in the aqueous waste are removed by three stages of hydroxide-iron carrier-flocculant precipitation. The filtrate solution is then evaporated to a solid with a spray dryer and the solids are cemented and sent to retrievable storage. 

A ferrite waste treatment process is being investigated to determine if it can more effectively remove actinides from waste solution with less solid waste generation than the flocculant precipitation method presently used (18). 

Conceptual Flowsheet for the Extraction of Actinides from HLLW. Figure 5 shows a conceptual flowsheet for the extraction of all the actinides (U, Np, Pu, Am, and Cm) from HLLW using 0.4 M 0< >D[IB]CMP0 in DEB. The CMPO compound was selected for this process because of the high D m values attainable with a small concentration of extractant and because of the absence of macro-concentrations of uranyl ion. Distribution ratios relevant to the flowsheet are shown in previous tables, IV, V, VI, and VII and figures 1 and 2. One of the key features of the flowsheet is that plutonium is extracted from the feed solution and stripped from the organic phase without the addition of any nitric acid or use of ferrous sulfamate. However, oxalic acid is added to complex Zr and Mo (see Table IV). The presence of oxalic acid reduces any Np(VI) to Np(IV) (15). The presence of ferrous ion, which is... 

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. 

Another area where titration calorimetry has found intensive application, and where the importance of heat flow versus isoperibol calorimetry has been growing, is the energetics of metal-ligand complexation. Morss, Nash, and Ensor [225], for example, used potenciometric titrations and heat flow isothermal titration calorimetry to study the complexation of UO "1" and trivalent lanthanide cations by tetrahydrofuran-2,3,4,5-tetracarboxylic acid (THFTCA), in aqueous solution. Their general goal was to investigate the potential application of THFTCA for actinide and lanthanide separation, and nuclear fuels processing. The obtained results (table 11.1) indicated that the 1 1 complexes formed in the reaction (M = La, Nd, Eu, Dy, andTm)... 

Of the many radioactive and inert constituents in waste solutions, only Tc and lanthanides coextract with actinides into the Truex process solvent. Trivalent lanthanides follow Am and Cm when the latter are stripped with dilute HNO3 depending on the disposition of the americium and... 

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. 

Electrodeposition of Pa metal has been performed from both aqueous and nonaqueous solutions. An isopropanol solution of 10-20 p,gmL Pa from 8M HCl/0.01 M HE/Pa stock was employed for quantitative electrodeposition [41]. The cell consisted of a gold-plated A1 cathode and a Pt wire anode. During deposition the current was maintained at 1 mA, which produced a potential of 400-600 V during the 90-min electrolysis. The progress of the electrolysis was externally monitored by alpha-counting of the electrolysis solution before and during the electrodeposition. Deposition studies of metal from aqueous solutions are more common. Pa was electrodeposited on platinum in 95% yield at tracer concentrations from an electrolyte of [NH4]C1/HC1 [42]. Electrochemical and chemical conditions of the plating process were described for Pu solutions, which served as a model for the other actinide elements studied. Another tracer... 

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