Phase Equilibria in Systems Relevant to Pyroprocessing

Pyroprocessing has many advantages for the recovery and recycle of actinides, especially the transuranic elements, in used nuclear fuel. It has several unique features that distinguish it from other used fuel treatment technologies such as the ability to handle short-cooled fuel, a small process footprint, and production of metallic uranium and uranium - transuranic (U/TRU) products that can be directly fabricated into metallic fuel for advanced reactors. Recovery of the uranium and U/TRU products from the used fuel occurs in an electrorefining step. Uranium and transuranics in the used fuel (metal or reduced oxide) are dissolved at the anode in a molten chloride electrolyte, and electrodeposited at two different cathodes - one for uranium and another for the uranium - transuranic product. During this process, fission products less noble than uranium and transuranics (i.e., lanthanides, alkali and alkaline earth) anodically dissolve into the electrolyte, while only uranium and U/TRU are electrodeposited at the respective cathodes. Thus, there is a buildup of active metal and lanthanide fission products in the molten salt electrolyte. The goal of this work is to improve the fundamental understanding of the chemistry of actinides and transuranics in this complex, multicomponent solution. The fundamental thermodynamic properties of the multi-component molten salt electrolytes are complicated due to the formation of ternary and more complex compounds. As the actinides anodically dissolve at the anode and deposited at the cathode, a gradient in the concentration develops at the anode/electrolyte and the cathode/electrolyte interfaces. Ternary phase formation could impact the performance of the electrorefining system by influencing the chemical activity and thus the redox potentials of the actinide chlorides in the molten salt solution. Literature data on the LiCl-KCl-UCl₃ system is limited, sometimes conflicting, and may reflect the use of older analytical instrumentation, which was less accurate than that currently available. In addition, there has not been any investigation of the low UCl₃ concentration region of the system, which is the region relevant to electrorefining. (authors)