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A pyrochemical process is being developed to recover the longlived alpha-decaying radioactive nuclides from PUREX (plutonium uranium extraction), high-level wastes generated by the reprocessing of spent nuclear fuel. 1 These aqueous wastes contain fission products (noble metals, rare earths, transition metals, rubidium, strontium, cesium, barium, cadmium, tin, selenium) and actinides, the former being predominately short-lived, the latter containing many long-lived radionuclides. Removal of these alpha-decaying actinides from the residues reduces the long-term radiotoxicity and simplifies waste management. 2,3 Molten LiCl-KCl eutectic salt, cadmium and bismuth are used as solvents in the TRUMP-S (transuranic management by pyropartitioning separation) process. Process goals are to remove 99% of the actinides (U, Np, Pu, Am, and Cm) from chlorinated PUREX residues and to recover a product that is greater than 90% actinides by weight. The process separates the waste 4 into four fractions: actinides, rare earths, metals more noble than actinides, and metals more active than the rare earths. Separation of actinides and rare earths as a group from noble and active metals is accomplished by reductive extraction from the chlorinated high-level waste (HLW) residues into liquid Cd. The actinides are separated from the rare earths by electrorefining and countercurrent reductive extraction into liquid bismuth. A full set of consistent thermodynamic property measurements for the actinides and rare earths in the process solvents is required to predict actinide/rare earth separation. Data for the major trivalent actinides were reported previously. 5 Thermodynamic data obtained from measurements for the trivalent rare earths and americium are reported in this paper.Electrochemical potentials were measured and used to calculate the standard Gibbs free energy of formation of the metal chlorides in LiCl-KCl eutectic. Potential measurements at the LiCl-KCl/Cd and LiCl-KCl/Bi interfaces were made to calculate the activity coefficients for Am in the liquid Cd and Bi phases. These thermodynamic properties provide a basis for predicting composition in the salt and metal phases and of the separation products from electrorefining and extraction processes.Equilibrium potential measurements in LiCl-KCl eutectic have been reported previously for the actinides 5 and rare earths. 6 The previously reported rare earth data did not show the same degree of consistency with theory (i.e., calculated ion valence, standard potential temperature dependence) as for the reported actinide results.New data for the rare earths and Am are reported here. Improvements to the electrochemical cell design and experimental procedures were implemented for the experiments reported. For the rare earth chlorides, rare earth metal was deposited onto a Ta cathode to ensure a reliable electrical contact to the rare earth metal in equilibrium with the salt. A thoroughly characterized AgCl-LiCl-KCl salt was used in the reference electrodes. Relatively large amounts of Am a...

To increase the uranium recovery rate of molten salt electrorefining step in pyrometallurgical reprocessing of metallic fast reactor fuels, tests were carried out using electrorefiners equipped with mechanisms for scraping cathode deposits. After the modifications in the design of the anode basket and scraper mechanism, no stalling of the anode and scraper rotation due to interference by cathode deposits occurred. Under the condition that codissolution of zirconium and uranium was allowed in order to obtain maximum throughput, a current of 400-450 A was maintained until 82% of the initially loaded uranium was recovered. The uranium recovery rate for the same duration reached 789 g U/h (32.9 g U/hÁL per electrode volume). On the assumption that an electrorefiner operates for 20 h/d and 200 d/y in an actual pyrometallugical reprocessing facility, this result corresponds to a uranium recovery rate of 3.16 t U/y using only one electrode assembly of about 30 cm diameter, which should be a sufficiently high performance for practical use. From these results, the engineering feasibility of uranium recovery using an electrorefiner with cathode deposit scraper mechanism has been demonstrated.

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