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.

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.