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.

It is known that ZrCl4 can be used in the chlorination process of spent nuclear fuel. However, its solubility in high temperature molten salt is very small, making it difficult to dissolve a large amount of ZrCl4. Therefore, in this study, a flange-type sealed reactor was manufactured to observe the reaction characteristics of LiCl-KCl salt and ZrCl4. LiCl-KCl salt and ZrCl4 were placed in each alumina crucible, the reactor was sealed, and heated. The temperature at the reactor surface was above 500°C and maintained at that temperature for 48 hours. After completion of the reaction, the reactor was opened and the reaction products were recovered from each alumina crucible. The crystal structure of the reaction product was identified through XRD analysis, and the concentration of Zr was analyzed using ICP. Reaction characteristics were observed according to the molar ratio of ZrCl4 added to the number of moles of KCl in LiCl-KCl salt. The molar ratios of ZrCl4 to KCl were 0.5, 1, 2, and 3, respectively. As a result of each experiment, more than 95% of the injected ZrCl4 was vaporized and there was almost no residue in the ZrCl4 crucible. In the LiCl- KCl crucible, the weight increased in proportion to the amount of ZrCl4 added. As a result of XRD analysis, K2ZrCl6 was confirmed in all LiCl-KCl salt product. When the ZrCl4/KCl molar ratio was 2 and 3, LiCl-KCl could not be confirmed. Additionally, when the ZrCl4/KCl molar ratio was 1, LiCl was identified, but KCl was not found. Almost all of the KCl appears to have reacted with ZrCl4. ICP analysis results showed that the Zr concentration was proportional to the amount of ZrCl4 added in each LiCl-KCl salt, and exceeding the number of moles of reaction with KCl in the LiCl-KCl salt was observed. Therefore, these experimental results showed that ZrCl4 can be dissolved in LiCl-KCl salt at a maximum concentration higher than its solubility.

As a method for chlorinating spent nuclear fuel, a method of using ZrCl4 in high-temperature molten salt is known. However, ZrCl4 has a sublimation property that vaporizes at a temperature similar to the melting temperature of molten salt. Since solubility of ZrCl4 in molten salt is very low, it is difficult to dissolve a large amount of ZrCl4 in molten salt. However, once ZrCl4 can be dissolved together with the molten salt, it remains in the molten salt without vaporizing. That is, it is known that when vaporized ZrCl4 reacts with molten salt in a sealed reactor, it dissolves into the molten salt, and ZrCl4 above the solubility remains in the molten salt in the form of M2ZrCl6. Here, M represents an alkali element. Therefore, in this study, a flange-type sealed reactor was fabricated to dissolve a large amount of ZrCl4 in LiCl-KCl salt, and LiCl-KCl salt in which ZrCl4 was dissolved as K2ZrCl6 was prepared. LiCl-KCl, KCl, and ZrCl4 salts were charged into alumina crucibles and placed in a sealed reactor. The reactor was heated to 500°C and the reaction time was about 20 hours. The temperature of the reactor surface was about 480°C. After completion of the reactions, each crucible was recovered from the inside of the reactor. All of the ZrCl4 vaporized and there was no residue in the crucible. Both KCl and LiCl-KCl salts appear to have dissolved and then cooled, with respective weight gains. XRD analysis was performed to observe the structure of the recovered salts, and ICP analysis was performed to measure the Zr element content in each salt. As a result of XRD analysis, the structure of K2ZrCl6 was found in the KCl salt, but not in the LiCl-KCl salt. As a results of ICP analysis, it was found that the LiCl-KCl salt contained about 33wt% of ZrCl4, and about 25wt% was dissolved in the KCl salt. In other words, it was shown that ZrCl4 above the solubility can be dissolved in the LiCl-KCl molten salt.

As temporary storage facilities for spent nuclear fuel (SNF) are becoming saturated, there is a growing interest in finding solutions for treating SNF, which is recognized as an urgent task. Although direct disposal is a common method for handling SNF, it results in the entire fuel assembly being classified as high-level waste, which increases the burden of disposal. Therefore, it is necessary to develop SNF treatment technologies that can minimize the disposal burden while improving long-term storage safety, and this requires continuous efforts from a national policy perspective. In this context, this study focused on reducing the volume of high-level waste from light water reactor fuel by separating uranium, which represents the majority of SNF. We confirmed the chlorination characteristics of uranium (U), rare earth (RE), and strontium (Sr) oxides with ammonium chloride (NH4Cl) in previous study. Therefore, we prepared U-RE-SrOx simulated fuel by pelletizing each elements which was sintered at high temperature. The sintered fuel was again powdered by heating under air environment. The powdered fuel was reacted with NH4Cl to selectively chlorinate the RE and Sr elements for the separation. We will share and discuss the detailed results of our study.

Molten Salt Reactor (MSR) is one of Generation-IV nuclear reactors that uses molten salts as a fuel and coolant in liquid forms at high temperatures. The advantages of MSR, such as safety, economic feasibility, and scalability, are attributed from the fact that the molten salt fuel in a liquid state is chemically stable and has excellent thermo-physical properties. MSR combines the fuel and coolant by dissolving the actinides (U, Th, TRU, etc.) in the molten salt coolant, eliminating the possibility of a core meltdown accident due to loss of coolant (LOCA). Even if the molten salt fuel leaks, the radioactive fission products dissolved in the molten salt will solidify with the fuel salt at room temperature, preventing potential leakage to the outside. MSR was first demonstrated at ORNL starting with the Aircraft Reactor Experiment (ARE) in 1954 and was extended to the 7.4 MWth MSRE developed in 1964 and operated for 5 years. Recently, various start-ups, including TerraPower, Terrestrial Energy, Moltex Energy, and Seaborg, have been conducting research and development on various types of MSR, particularly focusing on its inherent safety and simplicity. While in the past, fluoride-based molten salt fuels were used for thermal neutron reactors, recently, a chlorine-based molten salt fuel with a relatively high solubility for actinides and advantageous for the transmutation of spent nuclear fuel and online reprocessing has been developing for fast neutron spectrum MSRs. This paper describes the development status of the process and equipment for producing highpurity UCl3, a fuel material for the chlorine-based molten salt fuel, and the development status of the gas fission product capturing technologies to remove the gaseous fission products generated during MSR operation. In addition, the results of the corrosion property evaluation of structural materials using a natural circulation molten salt loop will also be included.

The electrochemical behavior was investigated during the electrolysis of nickel oxide in LiCl-Li2O salt mixture at 650℃ by changing several components. The focus of this work is to improve anode design and shroud design to increase current densities. The tested components were ceramic anode shroud porosity, porosity size, anode geometry, anode material, and metallic porous anode shroud. The goal of these experiments was to optimize and improve the reduction process. The highest contributors to higher current densities were anode shroud porosity and anode geometry.

Interests in molten salt reactor (MSR) using a fast spectrum (FS) have been increased not only for having a high power density but for burning the high-level waste generated from nuclear power plants. For developing the FS-MSR technologies, chloride-based fuels are considered due to the advantage of higher solubility of actinides and lanthanides over fluoride-based salts. Despite significant progress in development of MSR technology, the manufacturing technology for production of the fuel is still insufficiently understood. One of the option to prepare the MSR fuel is to use products from pyroprocessing where oxide form of spent nuclear fuel is reduced into metal form and useful elements can be collected via electrochemical methods in molten salt system at high temperature. In order to chlorinate the products into chloride form, previous study used NH4Cl to chlorinate U metal into UCl3 in an airtight reactor. It was found that the U metal was completely chlorinated into chloride forms; however, impurities generated by the reaction of NH4Cl and reactor wall were found in the product. Therefore, in this work, the air tight reactor was re-deigned to avoid the reaction of reactor wall by insertion of Al2O3 crucible inside of the reactor. In addition, the reactor size was increased to produce UCl3 over 100 g. Using the newly designed reactor, U metal chlorination experiments using NH4Cl chlorinating agent were performed to confirm the optimal experimental conditions. The detailed results will be further discussed.

The effect of Li2O addition on precipitation behavior of uranium in LiCl-KCl-UCl3 has been investigated in this study. 99.99% LiCl-KCl eutectic salt is mixed with 10wt% UCl3 chips at 550°C in the Pyrex tube in argon atmosphere glove box, with 10 ppm O2 and 1 ppm H2O. Then, Li2O chunks are added in mixed LiCl-KCl-UCl3 and the system has been cooled down to room temperature for 10 hours to form enough UO2 particles in the salt. The solid salt has been taken out from the glove box, and cut into three sections (top, middle and bottom) by low-speed saw for further microscopic analysis. Three pieces of solid salt are dissolved in deionized water at room temperature and the solution is filtered by a filter paper to collect non-dissolved particles. The filter paper with particles is baked in vacuum oven at 120°C for 6 hours to evaporate remaining moisture from the filter paper. Further analysis was performed for the powder remaining on the filter paper, and periphery of the powder (cake) on the filter paper. Scanning electron microscopy (SEM), electron diffraction spectroscopy (EDS), and X-ray powder diffraction (XRD) are adopted to analysis the characteristic of the particles. From SEM analysis, the powders are consisted of small particles which have 5 to 10 m diameter, and EDS analysis shows they are likely UO2 with 23 at. % of uranium and 77 at. % oxygen. Cake is also analyzed by SEM and EDS, and needle like structures are widely observed on the particle. The length of needle is distributed from 5 to 20 m, and it has 6 to 10 at. % of chlorine, which are not fully dissolved into deionized water at room temperature. From XRD analysis, the particles show the peak position of UO2, and the result is well matched with the SEM-EDS results. We are planning to add more Li2O in the system for fully reacting uranium in UCl3, and compare the results to find the effect of Li2O concentration on UO2 precipitation.

Thermodynamically, TRUOx, REOx, and SrOx can be chlorinated using ammonium chloride (NH4Cl) as a chlorinating agent, whereas uranium oxides (U3O8 and UO2) remain in the oxide form. In the preliminary experiments of this study, U3O8 and CeO2 are reacted separately with NH4Cl at 623 K in a sealed reactor. CeO2 is highly reactive with NH4Cl and becomes chlorinated into CeCl3. The chlorination yield ranges from 96% to 100%. By contrast, U3O8 remains as UO2 even after chlorination. We produced U/REOx- and U/SrOx-simulated fuels to understand the chlorination characteristics of the oxide compounds. Each simulated fuel is chlorinated with NH4Cl, and the products are dissolved in LiCl-KCl salt to separate the oxide compounds from the chloride salt. The oxide compounds precipitate at the bottom. The precipitate and salt phases are sampled and analyzed via X-ray diffraction, scanning electron microscope-energy dispersive spectroscopy, and inductively coupled plasma-optical emission spectroscopy. The analysis results indicate that REOx and SrOx can be easily chlorinated from the simulated fuels; however, only a few of U oxide phases is chlorinated, particularly from the U/SrOx-simulated fuels.

Facing the problem of saturation of spent nuclear fuel (SNF) stored in temporary storage facilities on sites, interest in the treatment of SNF is increasing, and it is recognized as a task that needs to be solved promptly. Although direct disposal is a general method for dealing with SNF, the entire fuel assembly is classified as high-level waste; thus, the burden of disposal is high. In order to minimize the disposal burden with enhancing safety for long term storage, it is necessary to develop SNF treatment technologies and continuous efforts are required from a national policy perspective. The present study focused on minimizing the volume of high level waste from light water reactor fuel by separation of uranium, which accounts for most of SNF. The chlorination characteristics of uranium (U), rare earth (RE) oxides were confirmed through lab-scale experiments, and the possibility of uranium separation from U-RE simulated fuel was evaluated using NH4Cl chlorinating agent. The detailed results will be posted and discussed.

To estimate the removal efficiency of TRU and rare earth elements in an oxide spent fuel, basic dissolution experiments were performed for the reaction of rare earth elements from the prepared simfuel with chlorination reagents in LiCl-KCl molten salt. Based on the literature survey, NH4Cl, UCl3, and ZrCl4 were selected as chlorination reagent. CeO2 and Gd2O3 powders were mixed with uranium oxide as a representative material of rare earth elements. Simfuel pellets were prepared through molding and sintering processes, and mechanically pulverized to a powder form. The experiments for the reaction of the simfuel powder and chlorination reagents were carried out in a LiCl-KCl molten salt at 500°C. To observe the dissolution behavior of rare earth elements, molten salt samples were collected before and after the reactions, and concentration analysis was performed using ICP. After the reaction completed, the remaining oxide was washed with water and separated from the molten salt, and XRD was used for structural analysis. As a result of salt concentration analysis, the dissolution performance of rare earth elements was confirmed in the reaction experiments of all chlorination reagents. In an experiment using NH4Cl and ZrCl4, the uranium concentration in the molten salt was also measured. In other words, it seemed that not only rare elements but also uranium oxide, which is a main component of simfuel, was dissolved. Therefore, it is thought that the dissolution of rare earth elements is also possible due to the collapse of the uranium oxide structure of the solid powder and the reaction with the oxide of rare earth elements exposed to molten salt. As a result of analyzing the concentration changes of Simfuel before and after each reaction, there was little loss of uranium and rare earth elements (Ce/Gd) in the NH4Cl experiment, but a significant amount of rare earth elements were found to be reduced in the UCl3 experiment, and a large amount of rare earth elements were reduced in the ZrCl4 reaction.

Molten Salt Reactor (MSR) is one of the generation-IV advanced nuclear reactors in which hightemperature molten salt mixture is used as the primary coolant, or even the fuel itself unlike most nuclear reactors that adopt solid fuels. The MSR has received a great attention because of its excellent thermal efficiency, high power density, and structural simplicity. In particular, since the MSR uses molten salts with boiling points higher than the exit temperature of the reactor core, there is no severe accident such as a core melt-down which leads to a hydrogen explosion. In addition, it is possible to remove the residual heat through a completely passive way and when the fuel salt leaks to the outside, it solidifies at room-temperature without releasing radioactive fission products such as cesium, which make the MSR inherently safe. Both fluoride and chloride mixtures can be used as liquid fuel salts by adding actinide halides for MSRs. However, the MSRs using chloride-based salt fuels can be operated for a long time without adding nuclear fuel or online reprocessing because the actinide solubility in chloride salts is about six times higher than that in fluoride salts. Therefore, the chloride-based MSRs are more effective for the transmutation of long-lived radionuclides such as transuranic elements than the fluoride-based MSRs, which is beneficial to resolve the high radioactive spent nuclear fuel generated from light water reactors (LWRs). This paper examines liquid fuel fabrication using an improved U chlorination process for the chloride-based MSRs and presents the strategy for the management of gaseous fission products generated during the operation of MSR.

This study proposes a method of separating uranium (U) and minor actinides from rare earth (RE) elements in the LiCl-KCl salt system. Several RE metals were used to reduce UCl3 and MgCl2 from the eutectic LiCl-KCl salt systems. Five experiments were performed on drawdown U and plutonium (Pu) surrogate elements from RECl3-enriched LiCl-KCl salt systems at 773 K. Via the introduction of RE metals into the salt system, it was observed that the UCl3 concentration can be lowered below 100 ppm. In addition, UCl3 was reduced into a powdery form that easily settled at the bottom and was successfully collected by a salt distillation operation. When the RE metals come into contact with a metallic structure, a galvanic interaction occurs dominantly, seemingly accelerating the U recovery reaction. These results elucidate the development of an effective and simple process that selectively removes actinides from electrorefining salt, thus contributing to the minimization of the influx of actinides into the nuclear fuel waste stream.

희토류(Rare Earth) 함량이 높은 TRU 생성물 중의 RE 원소를 감소시키기 위하여 RE 원소와 UCl3의 산화반응을 이용한 RE 제거 공정의 타당성을 HSC Chemistry 코드를 이용하여 검토하였다. 사용후핵연료에 포함된 TRU 원소 및 RE 원소의 조성 및 열역학적 자료를 검토하였으며, UCl3와의 산화 반응에 따른 평형 자료를 계산하여 공정 가능성을 검토하였다. 실제 파이로 프로세싱 처리를 가정한 물질수지로부터 TRU 생성물의 RE 함량이 다른 두 가지 경우에 대하여 RE 원소 제거율과 TRU 회수율을 평가하였다. TRU 생성물을 산화제인 UCl3와 반응시켰을 때 각 원소의 Gibbs free energy의 차이에 의한 선택적 산화 반응이 일어났다. 투입된 UCl3 양을 조절하여 TRU 회수율을 최대로 유지하면서도 RE 원소를 제거하여 최종생성물의 TRU/ RE 비를 증가시킬 수 있는 가능성을 계산 결과로 확인하였다. 본 연구의 결과들은 열역학적 평형 자료에 기반한 결과이므로 실제 공정에 적용하기에는 많은 차이점이 존재한다. 그러나 TRU 물질을 취급하기 어려운 환경에서 파이로프로세싱의 TRU 생성물을 고속로의 핵연료로 공급하기 위한 공정 설계에 중요한 자료로 활용될 것으로 기대된다.