Molten salt consisting primarily of eutectic LiCl-KCl is currently being used in electrorefiners in the Fuel Conditioning Facility at Idaho National Laboratory. Options are currently being evaluated for storing this salt outside of the argon atmosphere hot cell. The hygroscopic nature of eutectic LiCl-KCl makes is susceptible to deliquescence in air followed by extreme corrosion of metallic cannisters. In this study, the effect of occluding the salt into a zeolite on water sorption/desorption was tested. Two zeolites were investigated: Na-Y and zeolite 4A. Na-Y was ineffective at occluding a high percentage of the salt at either 10 or 20wt% loading. Zeolite-4A was effective at occluding the salt with high efficiency at both loading levels. Weight gain in salt occluded zeolite-4A (SOZ) from water sorption at 20% relative humidity and 40℃ was 17wt% for 10% SOZ and 10wt% for 20% SOZ. In both cases, neither deliquescence nor corrosion occurred over a period of 31 days. After hydration, most of the water could be driven off by heating the hydrated salt occluded zeolite to 530℃. However, some HCl forms during dehydration due to salt hydrolysis. Over a wide range of temperatures (320–700℃) and ramp rates (5, 10, and 20℃ min−1), HCl formation was no more than 0.6% of the Cl− in the original salt.

Molten salt solutions consisting of eutectic LiCl-KCl and concentrations of samarium chloride (0.5 to 3.0 wt%) at 500℃ were analyzed using both cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The CV technique gave the average diffusion coefficient for Sm3+ over the concentration range. Equipped with Sm3+ diffusion coefficient, the Randles-Sevcik equation predicted Sm3+ concentration values that agree with the given experimental values. From CV measurements; the anodic, cathodic, and half-peak potentials were identified and subsequently used as a parameter to acquire EIS spectra. A six-element Voigt model was used to model the EIS data in terms of resistance-time constant pairs. The lowest resistances were observed at the half-peak potential with the associated resistance-time constant pairs characterizing the reversible reaction between Sm3+ and Sm2+. By extrapolation, the Voigt model estimated the polarization resistance and established a polarization resistance-concentration relationship.

A simplified flowsheet for pyroprocessing commercial spent fuel is proposed in which the only salt treatment step is actinide drawdown from electrorefiner salt. Actinide drawdown can be performed using a simple galvanic reduction process utilizing the reducing potential of gadolinium metal. Recent results of equilibrium reduction potentials for Gd, Ce, Nd, and La are summarized. A description of a recent experiment to demonstrate galvanic reduction with gadolinium is reviewed. Based on these experimental results and material balances of the flowsheet, this new variant of the pyroprocessing scheme is expected to meet the objectives of minimizing cost, maximizing processing rate, minimizing proliferation risk, and optimizing the utilization of geologic repository space.

The US Department of Energy’s Idaho National Laboratory (INL) has been operating a molten salt electrorefiner at their facility since 1996. The baseline method for disposal of the radioactive salt is the ceramic waste process which generates glass bonded sodalite loaded with chloride salts. This process starts with the high temperature absorption of the salt into zeolite-4A. The salt-loaded zeolite is then blended with glass frit and heated to form a sintered, glass-bonded sodalite. INL is currently assessing alternatives for disposal of the ER salt because of the lengthy processing times, costly equipment and large volume of waste associated with the baseline process. An alternative process was studied, where protonated zeolite was used instead of alkali metal-substituted zeolite. It was found that the metals contained in the salt can replace the protons in the zeolite which are evolved via formation of HCl. From the standpoint of generating a nuclear waste form, the evolution of HCl gas should reduce the weight of the final waste. It has been estimated that the volume of waste produced from immobilizing the INL electrorefiner salt could be reduced by a factor of three using this process followed by sintering the fission product loaded zeolite. Equipment requirements in the hot cell would be significantly simplified, and the time to process all of the waste salt would be reduced by almost a factor of 4. An investigation into the new process has been presented here.

Voltammetry has shown promise as a method to estimate the concentrations of actinides in the molten LiCl-KCl used as an electrolyte in spent nuclear fuel electrorefiners. This salt typically contains several actinides in addition to many active metal fission products (rare earths, Group I & II metals). However, most of the voltammetry studies to date have focused on a single actinide or lanthanide in eutectic LiCl-KCl. This paper examines experimental and analytical techniques that can be used to estimate the concentration of a molten salt mixture containing both lanthanum (III)- and gadolinium(III)-chloride in eutectic LiCl-KCl. The aspects of the experimental procedures and setup that are unique to a multi-lanthanide mixture are briefly discussed. Experimental results from qualitative and quantitative analyses of cyclic voltammetry and open-circuit potentiometry are presented. Due to the close proximity of their standard potentials, extensive analytical work is required to estimate the concentrations. Two approaches are used in this work: peak separation and multivariate analysis. The merits of these two methods will be analyzed and discussed.