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.

In the production of zirconium cladding tube, a pickling acid solution is used to remove surface contaminants, which generates tons of pickling acid waste. The waste pickling solution is a valuable resource of Hf-free Zr. Many studies have investigated separating the Hf-free Zr source from the waste pickling acid. The results showed that Ba2ZrF8 precipitates prepared from the waste pickling acid were useful as an electrolyte for the electrorefining of Zr in molten salt. In the present work, electrorefining was performed in a Ba2ZrF8-LiF binary electrolyte to recover Zr from a Hf-free CuZr ingot anode prepared by electroreduction. Before electrorefining, two pretreatments are performed. First, electrolyte melting was carried out to determine the eutectic temperature, and second, the electrolyte was treated to eliminate impurities, mainly hydride. After electrorefining, the cathode deposits were analyzed by O2 gas analyzer and SEM-EDX to explore the possibility of recovering nuclear-grade Zr metal. Moreover, the anode was analyzed by SEM-EDX to determine the Zr dissolution depth.

The production of nuclear fuel cladding tube is expected to increase with the nuclear power plant expansion. Zirconium(Zr) scrap that is generated during manufacturing is also expected to increase. Zr electrorefining experiment was carried out in the fluoride salt of LiF-KF-ZrF4 using multiple electrode for scale up and improving throughput Zr electrorefiner development. The Zr reduction peak observed at -0.8 V(vs.Ni). Polarization behavior showed that the amount of applied current increases because of decreasing cell resistance as the number of cathode increases. Experimental results showed the highest recovery rate about 98% at lowest current density of 25.64 mA/cm2 using 6 electrodes. XRD and TG analysis result show that pure Zr was recovered 99.92% and ICP analysis shows that lower impurity content than conventional impurity content of the Anode(97.8%). Electrorefining consumes energy about 7.15 kWh/kg less than 39.7% compared to the Kroll process using 6 electrode width of 20 mm and height of 65 mm. Because of increasing cell efficiency and recovery rate, using multiple cathode is determined as an efficient technique for scale up electrorefining Zr scrap.

사용후핵연료로부터 유용한 물질을 회수하는 파이로 공정의 주요 공정 중 하나인 전해정련 기술과 국내의 전해정련 장치 개발에 대해 고찰하였다. 전해정련 반응은 LiCl-KCl 용융염 전해질 내에 우라늄과 초우란금속 및 희토류 등을 함유하는 사용후핵연료 금속전환체를 담은 양극 바스켓과 고체음극으로 구성되고, 양극에서 는 산화(용해)반응이 음극에서는 환원(석출)반응이 진행되며 순수한 우라늄만을 회수한다. 흑연음극이 가진 자발탈리하는 특성과 아래로 모아진 우라늄 석출물을 스크류 이송장치로 자동 회수하는 개념을 도입하여 처 리용량이 20 kgU/day 규모의 연속식 고성능 전해정련장치를 개발하였다

흑연음극을 이용하여 LiCl-KCl공융염내에서 금속우라늄의 전해정련을 수행하였다. Uraniurn-Graphite Intercalation Compound(U-GIC)의 형성에 의하여 우라늄 전착물의 sell-scraping이 일어나며 전해정련에서 stripping과정을 생략함으로서 전해효율을 높일 수 있다. 우라늄 전착물내의 희토류 원소 오염은 무시할 만 하였으나 약 300ppm정도의 탄소가 오염되어 있는 것으로 관찰되었다. 탄소 오염은 이트륨을 이용한 정제공정 등을 거칠 경우 제거 가능하리라 사료된다. 회수된 우라늄 전착물의 조직 특성을 분석하였으며, 스틸 음극에 의해 회수된 전착물과 비교하였다. 이 결과는 초기 실험결과 이며 보다 심층적 연구를 통하여 사용 후 금속핵연료의 전해정련 개념을 개선시킬 수 있을 것으로 판단된다.