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.

A phosphorylation (phosphate precipitation) technology of metal chlorides is considering as a proper treatment method for recovering the fission products in a spent molten salt. In KAERI’s previous precipitation tests, the powder of lithium phosphate (Li3PO4) as a precipitation agent reacted with metal chlorides in a simulated LiCl-KCl molten salt. The reaction of metal chlorides containing actinides such as uranium and rare earths with lithium phosphate in a molten salt was known as solidliquid reaction. In order to increase the precipitation reaction rate the powder of lithium phosphate dispersed by stirring thoroughly in a molten salt. As one of the recovery methods of the metal phosphates precipitated on the bottom of the molten salt vessel cutting method at the lower part of the salt ingot is considered. On the other hand, a vacuum distillation method of all the molten salt containing the metal phosphates precipitates was proposed as another recovering method. In recent study, a new method for collecting the phosphorylation reaction products into a small recovering vessel was investigated resulting in some test data by using the lithium phosphate ingot in a molten salt containing uranium and three rare earth elements (Nd, Ce, and La). The phosphorylation experiments using lithium phosphate ingots carried out to collect the metal phosphate precipitates and the test result of this new method was feasible. However, the reaction rate of test using lithium phosphate ingot is very slower than that of test using lithium phosphate powder. In this presentation, the precipitation reactor design used for phosphorylation reaction shows that the amount of molten salt transferred to the distillation unit will reduce by collecting all of the metal phosphates that will be generated using lithium phosphate powder into a small recovering vessel.

The metal product from the electrolytic reduction of uranium oxide in LiCl molten salt retains about 10 ~ 20wt% of the residual salts. Salt vacuum distillation is conducted to separate the residual salt from the metal product and well-performed in a glove box in an argon atmosphere. A dimensionless analysis of the characteristics of a salt vacuum distiller needs to be scaled up for a high capacity process. The vacuum distillation apparatus can be of two different sizes (M-type and P-type). M-type equipment is small in size and exhibits a high recovery rate of more than 95%. A comparison of two salt vacuum distillers was conducted with the dimensionless analysis method. Heat and fluid flows are strongly influenced by the structure of the apparatus and phase transition phenomena of vacuum distillation. The several dimensionless parameters were calculated at the nozzle throat located between the evaporator and the receiver and at different operating temperatures. Both salt vacuum distillers had similar trends of dimensionless parameters. However, the distributions of the parameter values varied with the nozzle geometry and size. The results of the dimensionless analysis will aid the scaling up of the salt distillation process.

사용후핵연료 파이로프로세싱에서 발생하는 방사성폐기물의 양을 최소화하기 위해서는 방사성 핵종 함유 염폐기물을 효과 적으로 처리할 수 있는 기술개발이 필요하다. 이를 위해 탄산화물(Li2CO3, K2CO3)을 이용한 반응증류공정에서 LiCl-KCl 공융 염 내 NdCl3의 분리특성을 관찰하였다. HSC-Chemistry 프로그램을 이용한 탄산화물과 NdCl3의 반응모델결과에서 NdCl3는 탄산화물의 주입조건 및 온도변화에 따라 산염화물(NdOCl) 또는 산화물(Nd2O3) 형태로 전환됨이 확인되었으며, 탄산화물 의 주입조건에 따른 LiCl-KCl-NdCl3계의 반응증류시험에서 반응모델결과와 유사한 경향을 확인하였다. 이 결과들을 이용하 여 LiCl-KCl 공융염 내 NdCl3를 고화가 용이한 산화물 형태로 분리하기 위한 공정조건을 도출하였다.

비등온 및 등온조건에서의 열중량분석을 이용하여 다양한 압력조건(0.5 - 50 mmHg)에서 LiCl-KCl 공융염 증류속도를 우선 측정하였다. 비등온조건에서의 열중량분석결과로부터 온도의 함수로 표현될 수 있는 증류 속도식을 도출하였다. 이 속도식에 의해 계산된 휘발플럭스(flux)는 등온조건에서의 열중량분석을 통해 얻어 진 증류속도와 일치하였다. 1300 K 이하의 온도조건과 0.5 mmHg와 50 mmHg 사이의 감압조건에서 10-4- 10-5 mole cm-2 sec-1의 증류속도를 얻을 수 있다. 실험실규모 실험장치에서 50 mmHg의 압력과 1150 K 이상 의 온도 조건에서 한 시간 증류로 약 99%의 염이 분리되었다. 희토류 침전물내에 잔류하는 염을 증류에 의해 제거할 때 휘발시간이나, 온도를 증가시키는 것보다 휘발 계면적을 증가시키는 것이 효과가 더 큰 것으로 나타났으며, 휘발면적을 4.52 cm2에서 12.56 cm2로 증가시켜 한 시간 동안 증류하였을 때 99.95% 이상의 염이 분리되었다.

전해정련공정을 통해 생산된 우라늄 전착물은 약 30%의 용융염을 포함하고 있으므로, 순수한 우라늄을 회 수하여 금속 잉곳으로 용이하게 제조하기 위해서는 용융염을 먼저 제거하는 공정이 필요하다. 우라늄 전착물의 염증류 거동을 고찰하기 위해서는 염증류의 주요 공정변수인 유지온도와 진공압의 염제거율에 대한 영 향를 고찰해야 한다. 이전 연구에서 우라늄전착물에 대한 염증류 거동에 대해 Hertz-Langmuir 관계식을 적 용하여 각 용융염의 휘발 조건에 대해 염휘발계수를 얻을 수 있었으며 이로부터 우라늄 전착물에 대해 99% 이상의 염제거율을 나타내는 염증류공정의 조업조건을 도출하였다[1]. 한편, 염증류 장치에서 사용되는 재질 인 스테인리스강에 대해 우라늄 전착물에서 염휘발된 우라늄 금속이 스테인리스강의 주성분인 철, 니켈, 크 롬 등과 공정(eutectic melt)을 형성하지 않는 온도에서 염증류공정을 수행해야 하는 제한 조건이 따른다. 이 번 연구에서는 우라늄 금속과 스테인리스강과의 반응성을 검토함으로써 우라늄 전착물의 염을 99% 이상 제 거할 수 있는 조건을 확인하였다. 그리고 염증류 속도를 증진시키며 휘발된 염을 더 효율적으로 회수하기 위 해 공급되는 알곤 흐름에 의한 염증류 장치의 열해석을 수행함으로써 알곤 흐름에 의한 우라늄 전착물에 대 한 염증류 거동을 고찰하였다.