• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.8 no.1
• /
• pp.77-84
• /
• 2010

Reduction of oxides has been investigated for the volume reduction and recycling of the spent oxide fuel from commercial nuclear power plants. Various oxide reduction methods were proposed and KAERI (Korea Atomic Energy Research Institute) is currently developing an electrochemical reduction process using a LiCl-$Li_2O$ molten salt as a reaction medium. The electrochemical reduction process, the front end of the pyroprocessing, can connect the PWR (Pressurized Water Reactor) oxide fuel cycle to a metal fuel cycle of the sodium cooled fast reactor. This paper summarizes KAERI efforts on the development, improvement, and scale-up of the oxide reduction process.

• Nuclear Engineering and Technology
• /
• v.48 no.4
• /
• pp.997-1001
• /
• 2016

Conductive ceramics are being developed to replace current Pt anodes in the electrolytic reduction of spent oxide fuels in pyroprocessing. While several conductive ceramics have shown promising electrochemical properties in small-scale experiments, their long-term stabilities have not yet been investigated. In this study, the chemical stability of conductive $La_{0.33}Sr_{0.67}MnO_3$ in $LiCl-Li_2O$ molten salt at $650^{\circ}C$ was investigated to examine its feasibility as an anode material. Dissolution of Sr at the anode surface led to structural collapse, thereby indicating that the lifetime of the $La_{0.33}Sr_{0.67}MnO_3$ anode is limited. The dissolution rate of Sr is likely to be influenced by the local environment around Sr in the perovskite framework.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.3 no.2
• /
• pp.105-112
• /
• 2005

The electrolytic reduction of uranium oxide in a LiCl-Li$_{2}$O molten salt system has been studied in a 10 g U$_{3}$O$_{8}$ /batch-scale experimental apparatus with an integrated cathode assembly at 650$^{\circ}C$. The integrated cathode assembly consists of an electric conductor, the uranium oxide to be reduced and the membrane for loading the uranium oxide. From the cyclic voltammograms for the LiCl-3 wt$\%$ Li$_{2}$O system and the U$_{3}$O$_{8}$-LiCl-3 wt$\%$ Li$_{2}$O system according to the materials of the membrane in the cathode assembly, the mechanisms of the predominant reduction reactions in the electrolytic reactor cell were to be understood; direct and indirect electrolytic reduction of uranium oxide. Direct and indirect electrolytic reductions have been performed with the integrated cathode assembly. Using the 325-mesh stainless steel screen the uranium oxide failed to be reduced to uranium metal by a direct and indirect electrolytic reduction because of a low current efficiency and with the porous magnesia membrane the uranium oxide was reduced successfully to uranium metal by an indirect electrolytic reduction because of a high current efficiency.

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.19 no.2
• /
• pp.271-278
• /
• 2021

In this study, a chlorination technique for recycling Li₂ZrO₃, a reaction product of ZrO₂-assisted rinsing process, was investigated to minimize the generation of secondary radioactive pyroprocessing waste. It was found that the reaction temperature was a key parameter that determined the reaction rate and maximum conversion ratio. In the temperature range of 400-600℃, an increase in the reaction temperature resulted in a profound increase in the reaction rate. Hence, according to the experimental results, a reaction temperature of at least 450℃ was proposed to ensure a Li₂ZrO₃ conversion ratio that exceeded 80% within 8 h of the reaction time. The activation energy was found to be 102 ± 2 kJ·mol^-1·K^-1 between 450 and 500℃. The formation of LiCl and ZrO₂ as reaction products was confirmed by X-ray diffraction analysis. The experimental results obtained at various total flow rates revealed that the overall reaction rate depends on the Cl₂ mass transfer rate in the experimental condition. The results of this study prove that the chlorination technique provides a solution to minimize the amount of radioactive waste generated during the ZrO₂-assisted rinsing process.

• Proceedings of the Korean Radioactive Waste Society Conference
• /
• 2003.11a
• /
• pp.447-452
• /
• 2003

We had clarified the reactions of the rare earth oxides($RE_2O_3$) with lithium oxide produced in lithium reduction process of oxide fuels. Oxides of scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, ytterbium and lutetium reacted with lithium oxide in the higher concentration than the respective certain critical concentration of lithium oxide and formed complex oxides($LiREO_2$). The critical lithium oxide concentrations for the formation of complex oxides of scandium, yttrium, praseodymium, neodymium, samarium, europium, gadolinium, ytterbium and lutetium oxide were respectively 0.1 wt%, 1.9 wt%, 5.3 wt%, 5.0 wt%, 3.0 wt%, 3.9 wt% 2.9 wt%, 2.6 wt% and 0.3 wt%. Cerium and lanthanum oxide did not react with lithium oxide. These complex oxides obtained from experiments have limited solubility in lithium chloride at $650^{\circ}C$.

• Proceedings of the Korean Radioactive Waste Society Conference
• /
• 2004.11a
• /
• pp.145-147
• /
• 2004

• Proceedings of the Korean Nuclear Society Conference
• /
• 2005.05a
• /
• pp.281-282
• /
• 2005

• Proceedings of the Korean Radioactive Waste Society Conference
• /
• 2018.11a
• /
• pp.581-581
• /
• 2018

• Journal of Nuclear Fuel Cycle and Waste Technology(JNFCWT)
• /
• v.3 no.2
• /
• pp.85-93
• /
• 2005

Isotopes of alkali and alkaline earth metals (AM and AEM) are the main contributors to the heat load and the radiotoxicity of spent fuel (SF) . These components are separated from the SF and dissolved in a molten LiCl in an electrolytic reduction process. A mass transfer model is developed to describe the diffusion behavior of Cs, Sr, and Ba in the SF into the molten salt. The model is an analytical solution of Fick's second law of diffusion for a cylinder which is the shape of a cathode in the electrolytic reduction process. And the model is also applied to depict the concentration profile of the oxygen ion which is produced by the electrolysis of Li$_{2}$O. The regressed diffusion coefficients of the model correlating the experimentally measured data are evaluated to be greater in the order of Ba, Cs, and Sr for the metal ions and the diffusion of the oxygen ion is slower than the metal ions which implies that different mechanisms govern the diffusion of the metal ions and the oxygen ions in a molten LiCl.

• Journal of the Korean Electrochemical Society
• /
• v.18 no.3
• /
• pp.121-129
• /
• 2015

The platinum anode for the electrolytic reduction process is generally surrounded by a nonporous ceramic shroud with an open bottom to offer a path for $O_2$ gas produced on the anode surface and prevent the corrosion of the electrolytic reducer. However, the $O^{2-}$ ions generated from the cathode are transported only in a limited fashion through the open bottom of the anode shroud because the nonporous shroud hinders the transport of the $O^{2-}$ ions to the anode surface, which leads to a decrease in the current density and an increase in the operation time of the process. In the present study, we demonstrate the electrolytic reduction of 1 kg-uranium oxide ($UO_2$) using the porous shroud to investigate its long-term stability. The $UO_2$ with the size of 1~4mm and the density of $10.30{\sim}10.41g/cm^3$ was used for the cathode. The platinum and 5-layer STS mesh were used for the anode and its shroud, respectively. After the termination of the electrolytic reduction run in 1.5 wt.% $Li_2O-LiCl$ molten salt, it was revealed that the U metal was successfully converted from the $UO_2$ and the anode and its shroud were used without any significant damage.