DISTRIBUTION OF ACTINIDES BETWEEN THE AQUEOUS AND ORGANIC PHASES IN THE TALSPEAK PROCESS

One objective of the US Department of Energy's Office of Nuclear Energy (DOE-NE) is the development of sustainable nuclear fuel cycles which improve uranium resource utilization, maximize energy generation, minimize waste generation, improve safety, and complement institutional measures limiting proliferation risks. Activities in progress which support this objective include the development of advanced separation technologies to recover the actinides from used nuclear fuels. With the increased interest in the development of technology to allow closure of the nuclear fuel cycle, the TALSPEAK process is being considered for the separation of Am and Cm from the lanthanide fission products in a next generation reprocessing plant. However, at this time, the level of understanding associated with the chemistry and the control of the process variables is not acceptable for deployment of the process on an industrial scale. To address this issue, DOE-NE is supporting basic scientific studies focused on the TALSPEAK process through its Fuel Cycle Research and Development (R&D) program. One aspect of these studies is an experimental program at the Savannah River National Laboratory (SRNL) in which temperature-dependent distribution coefficients for the extraction of actinide elements in the TALSPEAK process were measured. The data were subsequently used to calculate conditional enthalpies and entropies of extraction by van't Hoff analysis to better understand the thermodynamic driving forces for the TALSPEAK process. In the SRNL studies, the distribution of Pu(III) in the TALSPEAK process was of particular interest. A small amount of Pu(III) would be present in the feed due to process losses and valence adjustment in prior recovery operations. Actinide elements such as Np and Pu have multiple stable oxidation states in aqueous solutions; therefore the oxidation state for these elements must be controlled in the TALSPEAK process, as the extraction chemistry is dependent upon the actinide's valence. Since our plans included the measurement of Pu(III) distribution coefficients using a Np(V) solution containing small amounts of {sup 238}Pu, it was necessary to demonstrate that the desired oxidation states of Np and Pu are produced and could be stabilized in a buffered lactate solution containing diethylenetriaminepentaacetic (DTPA). The stability of Np(V) and Pu(III) in lactic acid/DTPA solutions was evaluated by ultraviolet-visible (UV-vis) spectroscopy. To perform the evaluation, Np and Pu were added to solutions containing either hydroxylamine nitrate (HAN) or ferrous sulfamate (FS) as the reductant and nominally 1.5 M lactic acid/0.05 M DTPA. The pH of the solution was subsequently adjusted to nominally 2.8 as would be performed in the TALSPEAK process. In the valence adjustment study, we found that it was necessary to reduce Pu to Pu(III) prior to combining with the lactic acid and DTPA. The Pu reduction was performed using either HAN or FS. When FS was used, Np was reduced to Np(IV). The spectroscopic studies showed that Np(V) and Pu(III) are not stable in lactic acid/DTPA solutions. The stability of Np(IV)- and Pu(IV)-DTPA complexes are much greater than the stability of the Np(V)- and Pu(III)-DTPA complexes, and as a result, Np is slowly reduced to Np(IV) and Pu is slowly oxidized to Pu(IV) due to the reduced activity of the more stable complexes. When Np(V) was added to a solution containing a 1.5 M lactic acid/ammonium lactate buffer and 0.05 M DTPA, approximately 50% of the Np was reduced to Np(IV) in the first day. The fraction of Np(V) in the solution continued to diminish with time and was essentially reduced to Np(IV) after one week. When Pu(III) was added to a lactic acid/DTPA solution of the same composition, the spectrum recorded following at least two days after preparation of the solution continued to show some sign of Pu(III). The Pu(III) was completely oxidized to Pu(IV) after 3-4 days. The UV-vis spectroscopy demonstrated that Np(V) and Pu(III) were the predominate valences in the lactic acid/DTPA solution for the better part of a day following solution preparation. Based on these results, we chose to initially add HAN to the actinide tracer solution prepared for the distribution coefficient measurements (to produce Pu(III)) prior to combining with lactic acid and DTPA. The distribution coefficient measurements were expected to be complete in 2-3 h; therefore, Np(V) and Pu(III) valences would predominate in the solution during this time. Prior to adding the HAN to the actinide tracers, we added sufficient Am(III) activity to allow the measurement of distribution coefficients during the extraction experiments. Protactinium (V) distribution coefficients were also measured using the activity which was in secular equilibrium with the {sup 237}Np. The actinide distribution coefficients were measured at pH 2.8 and 3.5 and covered a range of temperatures from nominally 20 to 60 C