Various disposal methods for spent nuclear fuels (SNFs) are being researched, and one of these methods involves separating high heat-generating nuclear isotopes such as Strontium-90 (90Sr) and Cesium-137 (137Cs) for deep disposal. These isotopes has relatively short half-lives and substantial decay energies. Especially, 90Sr undergoes decay through Yttrium-90 to Zirconium-90, emitting intense heat with beta radiation. Therefore, the removal of these high heat-generating isotopes will significantly contribute to reducing disposal site area. To remove 90Sr from SNFs, molten salt was utilized in KAERI. During this process, it was discovered that 90Sr dissolves in the molten salt in the form of SrCl2 and/or Sr4OCl6. Afterwards, it is crucial to recover 90Sr in the form of oxide from the salt to create immobilized forms for disposal. This can be achieved by reactive distillation with K2CO3. However, the amount of 90Sr within the SNFs is only 0.121wt%, and even if all the 90Sr in the SNFs were to leach into the molten salt, the quantity of 90Sr in the molten slat would still be very small. Therefore, adding K2CO3 to the molten salt for reactive distillation could result in significant possibilities of side reactions occurring. In this study, a two-step process was employed to mitigate the side reactions: the 1st step involves evaporating the all molten salts and the 2nd step includes adding K2CO3 to make oxides through solid-solid reaction. Eutectic LiCl-KCl, which is the most commonly used salt, was employed. The eutectic LiCl-KCl with SrCl2 was heated at 850°C for 2 h to evaporate the salts under a vacuum (> 0.02 torr). However, after examining the distillation product before the solid-solid reaction, it was observed that SrCl2 reacted with KCl in the salt, resulting in the formation of KSr2Cl5. It means that salts containing KCl are not suitable candidates for reactive distillation aimed at producing immobilized forms. As an alternative, MgCl2 could be a highly promising candidate because it is inert to SrCl2 and according to a recent study in KAERI, MgCl2 exhibited the most efficient separation of Sr among various salts. Therefore, we plan to proceed with the two-step reactive distillation using MgCl2 for the future work.
It has been investigated on the management of Strontium-90 in KAERI. It is needed to separate the solute from the salt solution for the recovery of strontium after the chlorination of the strontium oxide in molten salt. A vacuum distillation technology was used for the separation of strontium from the molten salt in our previous study. Strontium chloride was successfully carbonated by reactive distillation of SrCl2 – K2CO3 – LiCl – KCl system. In this study, it was tried to develop another route to recover strontium from the salt solution by a solid-solid reaction for avoiding the entrainment of product and the salt-K2CO3 reaction. Reactive distillation experiments were carried out for SrCl2 - K2CO3 – LiCl – KCl system. The carbonation temperature and pressure were 520°C and 0.8 bar. After the carbonation reaction, the temperature was elevated to 820°C to remove KCl from the reaction product. SrCO3 and KCl peaks were found in the XRD analysis of the residual product. It could be concluded that SrCl2 can be successfully carbonated after salt removal by the solid-solid reaction.
It has been investigated on the management of the nuclides in KAERI. Strontium-90 is a high heatgenerating nuclide in spent nuclear fuel. It is needed to separate the salt from the salt solution for the recovery of strontium after the chlorination of the strontium oxide in molten salt. A vacuum distillation technology was used for the separation of strontium from the molten salt. It was investigated on operating conditions of reactive distillation process for the recovery of the strontium from the salt solution. At a reduced pressure, considerable amount of the carbonation agents such as K2CO3 and Li2CO3 were reduced during heating in the distiller due to the thermal decomposition. Therefore, the two step process was proposed, which is composed of a reaction step at an atmospheric pressure and a salt distillation step at a reduced pressure. In the reaction step, the condition of low temperature and high pressure is suitable to suppress the decomposition of the carbonation agent. In the salt distillation step, reduced pressure is preferable at a suitable temperature depending on the evaporation rate of the salt.
It has been studied on the disposal area reduction for the used nuclear fuel by the management of high decay-heat nuclides, long-lived nuclides, and highly mobile nuclides. It was investigated on the management of the nuclides in KAERI. Strontium-90 is a high heat-generating nuclide in spent nuclear fuel. It is needed to separate the salt from the salt solution for the recovery of strontium after the chlorination of the strontium oxide in molten salt. Vacuum distillation was used for the separation of strontium from the molten salt. Potassium carbonate was chosen as a reactive distillation reagent for SrCl2 – LiCl – KCl system by the thermodynamic calculation. Reactive distillation experiments were carried out. The residual was mainly SrCO3 in the XRD analysis. It could be concluded that K2CO3 could be one of the suitable reagents for the reactive distillation. The salt in the long–lived nuclide powders should be removed to prepare the block for disposal. Experiments were carried out using W powders (surrogate) and U3O8 powders to develop a process for the removal of the residual salt from UOx powders. The salts were successfully removed from the W and U3O8 powders by distillation.
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.
용융염 전해정련공정은 사용후핵연료로부터 전기화학적인 방법을 통해 음극에서 우라늄을 회수 하는 공정이다. 이 때 우라 늄은 약 30wt%의 염을 포함하고 있어 순수한 우라늄을 얻기 위해서는 염을 제거하는 Cathode Process (CP)가 필수적이다. CP는 대량의 우라늄을 처리해야 하므로 파이로공정의 난관중의 하나로 인식되고 있으며, 우라늄의 순도가 최종적으로 결정 되는 단계이므로 매우 중요한 공정이다. 현재, 이에 대한 연구는 주로 실험적 방법에 근거 하고 있어 염 제거 공정 중 온도, 압력, 염 가스의 거동을 관찰하기 어렵다. 따라서 본 연구에서는, 공정의 운전 조건에 대해 적합한 수학적 모델을 이용하여 전산모사 해석을 진행하였다. 본 연구는 증류부에서 염 가스의 증류 량, 확산계수에 의해 계산된 장치 내 염 가스의 이동 그 리고 응축부에서의 응결속도를 중점적으로 연구하였다. 장치내의 각각의 염 가스 거동을 정의하기 위해 Hertz-Langmuir 관 계식, Chapman-Enskog Theory, ANSYS-CFX의 상용 코드를 사용하였다. 그리고 HSC Chemistry에서 염의 물성 값을 이용 하여 모델을 구성하였다. 본 연구의 전산모사 해석을 통해 얻은 연구 결과를 이용하여 염 가스의 거동과 장치의 최적 운전 조건을 예측하였다. 따라서 본 해석 결과는 CP의 물리적 현상을 깊게 이해하는데 쓰일 뿐 아니라, 공학규모의 CP 장치를 상 용규모로 확장하는데 이용 할 수 있다.