Recovery of silver from CEPOD anolyte solutions

The process known as Catalyzed Electrochemical Plutonium Oxide Dissolution (CEPOD) has been shown effective for removing plutonium from a variety of residues and solids. This process involves the electrochemical oxidation of PuO{sub 2} (and other Pu species) to (PuO{sub 2}){sup 2+}, and dissolution of the latter species in the anode solution (anolyte). Silver is used to transfer charge from the electrodes to the solid Pu oxide. Ag (1) is oxidized at the anode to Ag(II) and carried by the solution to the plutonium oxide solids, where the silver and oxide undergo a redox reaction that converts Pu(IV) to Pu(VI), and Ag(II) to Ag(I). Other metal ions [such as Ce(IV) and Co(III)] may also be used for this charge transfer, but have been found to be less effective than silver. The same process may be used to destroy various organic materials (such as paper and wood, oil and fuels, and synthetic polymer materials) by complete oxidation to CO{sub 2} or H{sub 2}O, for example. Upon completion of a CEPOD dissolver run, the anolyte may be processed to remove solution species of interest (i.e., Pu), or the anolyte may be recycled, or disposed. Because silver is a Resource Conservation and Recovery Actmore » (RCRA) land ban material, it must be removed from waste streams. Preliminary experiments, completed in FY 1991, demonstrated a simple, effective technique for silver removal from solutions. Ascorbic acid (C{sub 6}H{sub 8}O{sub 6}) Was Used to reduce silver ion to metallic silver, which precipitates from solution. The process was demonstrated effective on a bench scale using samples of actual CEPOD anolyte. Further experiments, in FY 1993, optimized these parameters and demonstrated the effectiveness of the technique on CEPOD anolyte on a larger, process scale (liters of solution). This report describes both the preliminary bench-scale experiments and the more recent process-scale experiments. The results are also compared to electro-deposition, another method of silver ion removal.« less