Advanced Aqueous Separation Systems for Actinide Partitioning

Abstract

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) donormore » 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 necessary for commercial fuel processing supporting transmutation of transplutonium elements. This research project continued basic themes investigated by this research group during the past decade. In the Fuel Cycle Research and Development program at DOE, the current favorite process for accomplishing the separation of trivalent actinides from fission product lanthanides is the TALSPEAK process. TALSPEAK is a solvent extraction method (developed at Oak Ridge National Lab in the 1960s) based on the combination of a cation exchanging extractant (e.g., HDEHP), an actinide-selective aminopolycarboxylate complexing agent (e.g., DTPA), and a carboxylic acid buffer to control pH in the range of 3-4. Considerable effort has been expended in this research group during the past 8 years to elaborate the details of TALSPEAK in the interest of developing improved approaches to the operation of TALSPEAK-like systems. In this project we focused on defining aggregation phenomena in conventional TALSPEAK separations, on supporting the development of Advanced TALSPEAK processes, on profiling the aqueous complexation kinetics of lanthanides in TALSPEAK relevant aqueous media, on the design of new diglycolamide and N-donor extractants, and on characterizing cation-cation complexes of pentavalent actinides.« less