Pyroprocessing technology has emerged as a viable alternative for the treatment of metal/oxide used fuel within the nuclear fuel cycle. This innovative approach involves an oxide reduction process wherein spent fuel in oxide form is placed within a cathode basket immersed in a molten LiCl-Li2O salt operating at 923 K. The chemical reduction of these oxide materials into their metallic counterparts occurs through a reaction with Li metal, which is electrochemically deposited onto the cathode. However, during process, the generation of Li2O within the fuel basket is inevitable, and due to the limited reduction efficiency, a significant portion of rare earth oxides (REOx) remains in their oxide state. The presence of these impurities, specifically Li2O and REOx, necessitates their transfer into the electrorefining system, leading to several challenges. Both Li2O and REOx exhibit reactivity with UCl3, the primary electrolyte within the electrorefining system, causing a continuous reduction in UCl3 concentration throughout the process. Furthermore, the formation of fine UO2 powder within the salt system, resulting from chemical reactions, poses a potential long-term operational and safety concern within the electrorefining process.Various techniques have been developed to address the issue of UO2 fine particle removal from the salt, utilizing both chemical and mechanical methods. However, it is crucial that these methods do not interfere with the core pyroprocessing procedure. This study aims to investigate the impact of Li2O and REOx introduced from the electrolytic reduction process on the electrorefining system. Additionally, we propose a method to effectively eliminate the generated UO2 fine powder, thereby enhancing the long-term operational stability of the electrorefining process. The efficiency of this proposed solution in removing oxidized powder has been confirmed through laboratory-scale testing, and we will provide a comprehensive discussion of the detailed results.

In pyroprocessing, the residual salts (LiCl containing Li and Li2O) in the metallic fuel produced by the oxide reduction (OR) process are removed by salt distillation and fed into electrorefining. This study undertook an investigation into the potential viability of employing a separate LiCl salt rinsing process as an innovative alternative to conventional salt distillation techniques. The primary objective of this novel approach was to mitigate the presence of Li and Li2O within the residual OR salt of metallic fuel, subsequently facilitating its suitability for electrorefining processes. The process of rinsing the metallic fuel involved immersing it in a LiCl salt environment at a temperature of 650°C. During this immersion process, the residual OR salt contained within the fuel underwent dissolution, thereby reducing the concentrations of Li2O and Li generated during the OR process. Furthermore, the Li and Li2O dissolved within the LiCl salt were effectively consumed through chemical reactions with ZrO2 particles present within the salt. Importantly, even after the metallic fuel had been subjected to rinsing in a conventional LiCl salt solution, the concentration of Li and Li2O within the salt remained consistent with its initial levels, due to the utilization of ZrO2. Moreover, it was observed that the Li- Li2O content within the metallic fuel was significantly diluted as a result of the rinsing process.

삼불화알루미늄(AlF3)이 포함된 염화물-불화물 혼합 용융염에서 ZIRLO 튜브를 이용한 지르코늄 전해정련공정을 실증하였다. 순환 전압전류실험 결과, AlF3의 농도가 증가함에 따라 금속환원의 개시 전위가 일정하게 증가하고 지르코늄-알루미늄 합금형성과 관련된 추가적인 peak의 크기가 점차 증가하는 것으로 나타났다. 전류조절 전착법과 달리, −1.2 V의 일정전위 에서 수행한 지르코늄 전해정련에서 방사형 판 구조의 지르코늄 성장이 염의 상단 표면에서 확연하게 나타났으며, 전착물 지름의 크기는 AlF3의 농도에 따라 점차 증가하는 것으로 나타났다. 주사전자현미경(SEM)과 에너지 분산 X선 분광기(EDX) 와 X선 광전자 분광기(XPS)를 이용하여 판 구조의 지르코늄 전착물을 분석한 결과, 극미량의 알루미늄이 지르코늄-알루미늄 합금 형태로 존재하며, 전착물의 상단과 하단 간에 서로 다른 화학성분구조를 갖는 것으로 나타났다. AlF3의 첨가는 전착물 내 잔류염 양을 줄이고, 지르코늄 회수를 위한 전류효율을 향상시키는 데 효과적인 것으로 나타났다.