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.

The potential use of cost-effective carbon anodes, as an alternative to expensive platinum, in the reduction of oxides within LiCl-Li2O molten salt at elevated cell potentials presents a promising avenue. However, this elevated potential gives rise to the generation of a complex mixture of anodic gases, including hazardous and corrosive species such as chlorine (Cl2), oxygen (O2), carbon monoxide (CO), and carbon dioxide (CO2). In this study, we investigate the influence of applied potential and salt composition on the composition of the generated gas mixture. Real-time gas analysis was conducted during the TiO reduction reaction in the molten salt at 650°C using a MAX-300-LG gas analyzer. Simultaneously, electronic signals, including current, potential, and salt composition, were monitored throughout the oxide reduction process. Additionally, XRD investigations were performed to verify the crystal structure of the resulting products. This research provides valuable insights into optimizing carbon anode-based reduction processes for improved efficiency and safety.

The separation efficiency of nuclides in molten salt systems was investigated, with a focus on the influence of apparatus configuration and experimental conditions. A prior study revealed that achieving effective Sr separation from simulated oxide fuel required up to 96 hours, reaching a separation efficiency of approximately 90% using a static dissolution reaction in a porous alumina basket. In this study, we explored the impact of agitation on improving Sr separation efficiency and dissolution rates. The simulated oxide fuel composition consisted of 2wt% Sr, 3wt% Ba, 2wt% Ce, 3wt% Nd, 3wt% Zr, 2wt% Mo, and 89wt% U. To quantify the Sr concentration in the salt, we utilized ICP analysis after salt sampling via a dip-stick technique. Furthermore, we conducted ICPOES analysis over a 55-hour duration to assess the separated nuclides. Complementing these analyses, SEM and XRD investigations were performed to validate the crystal structure and morphology of the oxide products.

Pyroprocessing is a crucial method for recovering nuclear fuel materials, particularly uranium and transuranic elements (TRU), through electrochemical reactions in a LiCl or LiCl-KCl molten salt system, which is highly stable medium at elevated temperatures. In the electrochemical reduction stage, actinide metal oxides are effectively transformed into their metallic forms and retained at the cathode within a molten LiCl-Li2O environment at 650°C. Simultaneously, oxygen ions (O2-) are generated at the cathode and then transported through the molten salt to be discharged at the anode, where they combine to form oxygen gas (O2) on the anode’s surface. One notable challenge in this electrochemical process is the generation of various byproducts during the anode oxide reduction step, including oxygen, chlorine, carbon dioxide, and carbon monoxide. Consequently, significant amounts of corrosion products tend to accumulate on the upper region of the anode’s immersion area over time. This report introduces a novel solution to mitigate corrosion-related challenges within the specified temperature range. We propose a selective oxidation treatment for the NiCrAl-based 214 Haynes alloy, involving exposure to 1,100°C in a reducing atmosphere. The objective is to stimulate the growth of protective α-Al2O3 scales on the alloy’s surface. The resulting oxide scales have undergone thorough characterization using SEM, EDS, and XRD techniques. The pre-grown alumina scale has demonstrated commendable adherence and thermal stability, even when subjected to a chlorine-oxygen mixed atmosphere at the specified temperature.

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.

Separating nuclides from spent nuclear fuel is crucial to reduce the final disposal area. The use of molten salt offers a potential method for nuclide separation without requiring electricity, similar to the oxide reduction process in pyroprocessing. In this study, a molten salt leaching technique was evaluated for its ability to separate nuclides from simulated oxide fuel in MgCl2 molten salts at 800°C. The simulated oxide fuel contained 2wt% Sr, 3wt% Ba, 2wt% Ce, 3wt% Nd, 3wt% Zr, 2wt% Mo, and 89wt% U. The separation of Sr from the simulated oxide fuel was achieved by loading it into a porous alumina basket and immersing it in the molten salt. The concentration of Sr in the salt was measured using ICP analysis after sampling the salt outside the basket with a dip-stick technique. The separated nuclides were analyzed with ICP-OES up to a duration of 156 hours. The results indicate that Ba and Sr can be successfully separated from the simulated fuel in MgCl2, while Ce, Nd, and U were not effectively separated.

Instead of using expensive platinum, carbon anodes could potentially be utilized in the process of reducing oxides in LiCl-Li2O molten salt at a high cell potential. However, this high potential leads to the generation of a mixture of anodic gases containing toxic and corrosive gases such as chlorine (Cl2), oxygen (O2), carbon monoxide (CO), and carbon dioxide (CO2). To better understand this gas mixture, we conducted real-time analyses of the gases generated on the carbon anode during the TiO reduction reaction in the molten salt at 650°C, using a MAX-300-LG gas analyzer. Our results indicate that the ratio of CO/O2/CO2/Cl2 in the gas mixture is significantly influenced by the composition of the salt, and that removing the sources of oxygen ions in the salt increases the likelihood of generating toxic and corrosive Cl2 gas.

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.

Separation of high heat generating-radioactive isotopes from spent nuclear fuel is an important issue because it can reduce the final disposal area. As one of the technologies that can selectively separate only high heat generating-radioactive isotopes without dissolving spent fuel, the methods using molten salt have recently attracted attention. Although studies on chemical changes of Sr oxides in molten salts have been reported, they have limitation in that alternative oxide reagents rather than oxide fuel were used. In this study, the separation behaviors of Sr from simulated oxide fuel using various molten salts were investigated. A powder type containing 95.7wt% of U and 0.123wt% of Sr was used as the simulated oxide fuel. LiCl, LiCl-CaCl2, MgCl2, LiCl-KCl-MgCl2 and NaCl-MgCl2 were used as molten chloride salts. The separation of Sr from the simulated oxide fuel was conducted by loading it in porous alumina basket and immersing it in a salt. The concentration of Sr in the salt was measured by ICP analysis after sampling the salt outside the basket using dip-stick technique. The separation efficiencies of Sr from simulated oxide fuel using the salts were compared. Furthermore, the causes of their separation efficiency were systematically investigated.

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.

Molten salt immersion technique has been tested with several Sr oxides, SrZrO3, SrMoO4 and U2SrOy, and MgCl2 based molten salts for the Sr nuclide separation. Reaction time, temperature, and salt composition were varied to effectively separate Sr in chloride forms. ICP-OES, XRD, and SEM analysis were conducted for the conversion efficiency and structure and morphology analysis. It is confirmed that all experiments of SrZrO3 with MgCl2 at 800°C for reaction time 5, 10, 20 hours showed higher conversion efficiency than 99% and in LiCl-KCl-MgCl2 and NaCl-MgCl2 molten salts at 500°C or 600°C, conversion efficiency higher than 97% was obtained. SrMoO4 in MgCl2 immersion experiments for 10 hours showed higher conversion efficiency than 99% when the molar ratio of salt/oxide powder is 7. U2SrOy was also tested with MgCl2 molten salt at 800°C and higher efficiency than 99% and mainly MgUO4 were produced as a reaction product.

Strontium-90 is a high heat-generating nuclide in spent nuclear fuel. The removal of the nuclide separation is indispensable to reduce the burden of storage and disposal of high-level radioactive waste. Korea Atomic Energy Research Institute has developed the molten salt immersion technique to separate the strontium by the chlorination of the strontium oxide in molten salt. It is needed to separate the salt for the recovery of strontium from the salt solution after the chlorination reaction. In this study, it was investigated on the recovery of the strontium from the salt. Vacuum distillation was used for the separation of strontium from the molten salt. The vapor pressures of the candidate salts were calculated by HSC chemistry and the apparent evaporation rates (AER) were measured at 830°C to evaluate the salts for strontium recovery. The candidate salts were LiCl, KCl, MgCl2, NaCl and CaCl2. The AERs of MgCl2 and NaCl were 1.9 and 1.3 g/cm2-h, respectively. Those two salts can be separated from the strontium compound even though the AER values are much lower than those of LiCl-KCl (~ 8 g/cm2-h). CaCl2 salt was rarely evaporated (AER < 0.03 g/cm2-h) and it is not suitable to use as a strontium recovery salt. Therefore, MgCl2, NaCl, LiCl and KCl can be regarded as candidates for a strontium recovery salt.

Strontium is known as a salt-soluble element during the electrolytic oxide reduction (EOR) process. The chemical behavior of SrO during EOR was investigated via thermodynamic calculations to provide quantitative data on the chemical status of Sr. To achieve this, thermodynamic calculations were conducted using HSC chemistry software for various EOR conditions. It was revealed that SrO reacts with LiCl salt to produce SrCl2, even in the presence of Li2O, and that the ratio of SrCl2 depends on the initial concentration of Li2O dissolved in LiCl. It was found that SrO reacts with Li to produce Sr during EOR and that the reduced Sr reacts with LiCl salt to produce SrCl2. As a result, the proportions of metallic forms were lower in Sr than in La and Nd under various EOR conditions. The thermodynamic calculations indicated that the three chemical forms of SrO, SrCl2, and Sr co-exist in the EOR system under an equilibrium with Li, Li2O, and LiCl.

The corrosion behavior of the Inconel X-750 alloy was investigated for its potential application under a Cl2-O2 mixed gas flow in an Ar atmosphere. The corrosion rate was found to be negligible at temperatures up to 400℃ under a flow rate of 30 mL·min-1 Cl2 + 170 mL·min-1 Ar, whereas an exponential increase was observed in the corrosion rate at temperatures greater than 500℃. The suppression of the corrosion reaction due to the presence of O2 was verified experimentally at flow rates of 30 mL·min-1 Cl2 (4.96 g·m-2·h-1), 20 mL·min-1 Cl2 + 10 mL·min-1 O2 (2.02 g·m-2·h-1), and 10 mL·min-1 Cl2 + 20 mL·min-1 O2 (1.34 g·m-2·h-1) under a constant Ar flow rate of 170 mL·min-1 at 600℃ for 8 h. The surface morphology analysis results revealed that porous surfaces with tunnel-type holes were produced under the Cl2-O2 mixed-gas condition. Furthermore, the effects of the Cl2 flow rate on the corrosion rate were investigated, indicating that its impact was negligible within the range of 5–30 mL·min-1 Cl2 at 600℃.