In NPP (nuclear power plant), boric acid is used as a neutron absorbent. So radioactive boric acid waste are generated from various waste streams such as discharge or leakage of reactor coolant water, floor drains, drainage of equipment for operation or maintenance, reactor letdown flows and etc. Depending on KHNP, 20,015 drum (200 L drum) of concentrated boric acid waste were stored in KOREA NPP until 2019. In previous study, our group suggested the waste upcycling process synthesizing B4C neutron absorber using boric acid waste and activated carbon waste to innovatively reduce radioactive wastes. Radioactive activated carbon waste was utilized in off gas treatment system of NPP to capture nuclide such as I-131, C-14 and H-3. Activated carbon waste is treated as low-level radioactive waste and pre-treatment system for removing nuclide from the activated carbon waste is needed to use B4C up-cycling process. In this study, microwave treatment system is suggested to treat the activated carbon waste. Activated carbon waste was exposed to microwave for a few minutes and temperature of the waste was dramatically increased over 400°C. Nuclide in the activated carbon waste were selectively removed from the waste without massive production of secondary off gas waste.

Radioactive iodine-129, a byproduct of nuclear fission in nuclear power plants, presents significant environmental and health risks due to its high solubility in water and volatility. Iodine-129, with its half-life of 1.57×1017 years, necessitates safe management and disposal. Therefore, safely capturing and managing I-129 during spent nuclear fuel reprocessing is of paramount importance. To address these challenges, various glass waste forms containing silver iodide have been developed, such as borosilicate, silver phosphate, silver vanadate, and silver tellurite glasses. These glasses effectively immobilize iodine, but the high cost of silver raises affordability concerns. This study introduces CuI·Cu2O·TeO2 glass waste forms for iodine immobilization, a novel approach. The cost-effectiveness of copper, in contrast to silver, makes it an attractive alternative. The CuI·Cu2O·TeO2 glass waste forms were synthesized with varying CuI content (x) in (1-x)(0.3Cu2O·0.7TeO2) glass matrices. Xray diffraction (XRD) confirmed amorphous structures, and X-ray fluorescence (XRF) quantified composition. X-ray photoelectron spectroscopy (XPS) and Raman spectroscopy provided insights into structural properties. Durability assessments using a 7-day product consistency test (PCT-A) and inductively coupled plasma-mass spectrometry (ICP-MS) revealed compliance with U.S. glass regulations, making CuI·Cu2O·TeO2 glasses a promising choice for iodine immobilization in radioactive waste.

The nuclide management process for reducing the environmental burden being developed by the Korea Atomic Energy Research Institute is performed in molten salts, resulting in contaminated salt wastes containing fission products such as Cs, Sr, Ba, and rare-earth nuclides. In addition, the spent fuel of a molten salt reactor (MSR) contains a variety of fission products, and a purification process may be required for the reuse of the salt and the separation and disposal of the fission products in the spent nuclear fuel. The melt-crystallization method is a technique used for the purification and separation of chemicals or metals based on the different melting points of the different substances. In a recent study, our group developed a reactive-crystallization method using Li2CO3 precipitation agent to precipitate metal corrosion from the reactor through a chlorination reaction by HCl and Cl2, which may occur in chloride molten salt, and successfully precipitated the metal precipitate and purified and recovered LiCl salt. In this study, reactive-crystallization method has been established for removing fission products and corrosive materials. Using the reactive crystallization method, white LiCl-KCl salt that was not discolored by metal corrosion was recovered through the crystallization plates, and fission products and metal elements were shown to be suppressed to several ppm in the purified salt. Consequently, high-purity salts were recovered with high nuclide and corrosive separation efficiencies. The reactive crystallization procedure can also be applied to other salt waste systems, such as MSR nuclear fuel treatment and molten salt chemistry for the elimination of corrosive substances.

The intermediate level spent resins waste generated from water purification for the the moderator and primary heat transport system during operaioin of heavy water reactor (HWR). Especially, moderator resins contain high level activity largely because of their C-14 content. So spent resins are considered as a problematirc solid waste and require special treatment to meet the waste acceptance criteria for a disposal site. Various methods have been studied for the treatment of spent resins which include thermal, destructive, and stripping methods. In the case of solidification methods, cement, bitument or organic polymers were suggested. In the 1990s, acid stripping using nitric acid and thermal treatment methods were actively investigated in Canada to remove C-14 nuclide from waste resin. In Japan, thermal distructive method was studied in the 1990s. Since 2005, KAERI developed acid stripping method using phosphate salt. However, acid stripping method are not suitable due to large amounts of 2nd waste containing acid solution with various nuclides. To solve this probelm, KAERI has been suggested the microwave treatment method for C-14 selective removal from waste resin in the 2010s. Pilot scale demonstration tests using radioactive waste resin generated from Wolsung unit 1 and unit 2 were successfully conducted and 95% of C-14 was selectively removed from the radioactive waste resin. In recent years, price of C-14 source is dramatically increased due to market growth of C-14 utilization and exclusive supply chain depending on China and Russia. High purity of C-14 were captured in HWR waste resin. Interest of C-14 recovery research from HWR waste resin is currently increased in Canada. In this study, microwave method is suggested to treat HWR waste resin with C-14 recovery process. Additionally, status of waste resin management and research trends of HWR waste resin treatment are introduced.

Mixed-bed ion exchange resin consist of anion exchange resin and cation exchange resin is used to treat liquid radioactive waste in nuclear power plants. C-14 from heavy water reactors (HWR) is adsorbed on the anion exchange resin and is considered intermediate-level radioactive waste. The total amount of radioactivity of C-14 in spent ion exchange resin exceeds the activity limits for the disposal facility. Therefore, it is necessary to reduce the radioactivity through pre-treatment. There are thermal and non-thermal methods for the treatment of spent ion exchange resin. However, destructive methods have the problem of emitting off-gas containing radionuclides. To solve this challenge, various methods have been developed such as acid stripping, PLO process, activity stripping, thermal treatment and others. In this study, spent ion exchange resin (spent resin) was treated using microwave. The reaction characteristics of the resin to microwave were used to selectively remove the C-14 on the functional groups. Simulated spent anion exchange resin and spent resin from Wolseong NPP were treated with the microwave method, and the desorption rate was over 95%. An integrated process system of 1 kg/batch was built to produce operating data. After the operation of the process, characterization and evaluation of post-treatment for condensate water and adsorbent used in the process were performed. When the process system was applied to treat simulated spent resin and real spent resin, both showed a desorption rated of more than 97%. It means that the C-14 was successfully removed from the radioactive spent resin.

Many countries have used nuclear power to generate electricity. Uranium-235, which is used as fuel in nuclear power plants, produces many fission products. Among them, iodine-129 is problematic due to its long half-life (1.57×107 years) and high diffusivity in the environment. If it is released into the environment without any treatment, it could have a major impact on humans and ecosystems. Therefore, it must be treated into a stable form through capture and solidification. Iodine can be captured in the form of AgI through silver-loaded zeolite filters in off-gas treatment processes. However, AgI could be decomposed in the reducing atmosphere of groundwater, so it must be converted into a stable form. In this study, Al2O3, Bi2O3, PbO, V2O5, MoO3, or WO3 were added to the iodine solidification matrix, AgI-Ag2O-TeO2 glass. The glass precursors were mixed to the appropriate composition and placed in an alumina crucible. After heat treatment at 800°C for 1 hour, the melt was quenched in a carbon crucible. The leaching behavior and thermal properties of the glass samples were evaluated. The PCT-A test for leaching evaluation showed that the normalized releases of all elements were below 2 g/m2, which satisfied the U.S. glass wasteform leaching regulations. Diffrential scanning calorimetry (DSC) was performed to evaluate the thermal properties of all glass samples. The addition of MoO3 or WO3 to the AgI-Ag2O-TeO2 glass increased the glass transition temperature (Tg) and crystallization temperature (Tc) while maintaining the glass stability. The similar relative electro-static filed values of MoO3, and WO3 which are approxibately three times that of the glass network former TeO2, could provide sufficient force to the TeO2 interacting with the non-bridging oxygen forming Te-O-M (M=V, Mo, W) links. The high electrostatic forces of Mo and W increased the glass network cohension and prevented the crystallization of the glass.

Heat-generating nuclides such as Cs-137 and Sr-90 should be separated from spent nuclear fuel to reduce the short-term thermal load on the repository facility. In particular, Sr-90 must be separated because its decay process generates high temperatures. Recently, the Korea Atomic Energy Research Institute (KEARI) has been developing a waste burden minimization technology to reduce the environmental burden resulting from the disposal of spent nuclear fuel and maximize the utilization of the disposal facility. The technology incorporates a nuclide management process that maximizes disposal efficiency by selectively separating and accumulating key nuclides from spent nuclear fuel, such as Cs, Sr, I, TRU/RE, and Tc/Se. Sr nuclides dissolve in the chloride phase during the chlorination process of spent nuclear fuel and are recovered as carbonate or oxide through reactive distillation or reactive crystallization. Due to their chemical similarity, Ba nuclides are recovered along with Sr nuclides during this process. In this study, we prepared a ceramic waste form for group II nuclides, Ba(x)Sr(1-x)TiO3 (x=0, 0.25, 0.5, 0.75, 1), using the solid-state reaction method, taking into account the different ratios of Sr/Ba nuclides produced during the nuclide management process. Regardless of the Sr/Ba ratio, the established waste form fabrication process was able to produce a stable waste form. Physicochemical properties, including leaching and thermal properties, were evaluated to determine the stability of group II waste forms. In addition, the radiological properties of waste forms of Ba(x)Sr(1-x)TiO3 with varying Sr/Ba ratios were evaluated. These results provided fundamental data for the long-term storage and management of waste forms containing group II nuclides.

Se-79, a fission product of uranium, is present in spent nuclear fuel. Selenium is volatilized from the spent nuclear fuel during the pretreatment of pyroprocessing, and a filter composed of calcium oxide can capture gaseous selenium in the form of CaSeO3. Because Se-79 has a long half-life (3.27E5 years) and selenite ions have high mobility in groundwater, they must be immobilized in a chemically stable form for final disposal. This study used a composition of 50 TeO2 - 10 Al2O3 - 10 B2O3 - 10 Na2O - 10 CaO - 10 ZnO (mol%). High-purity powders of TeO2, Al2O3, H3BO3, Na2CO3, CaCO3, and ZnO were used as glass precursors. The mixed powders were placed in alumina crucibles and melted in an electric furnace under an ambient atmosphere at 800°C for 1 h before being cast on a carbon mold. The obtained glasses were ground into fine powders and then mixed with CaSeO3 powders. The powders were melted in alumina crucibles at 800°C for 1 h. To simulate a seleniumcaptured calcium filter, CaSeO3 was synthesized by a precipitation method using sodium selenite (Na2SeO3) and calcium nitrate (Ca(NO3)2) solutions. The glass samples were analyzed by an X-ray diffractometer (XRD). Retention of Se in tellurite glasses was analyzed by an X-ray fluorescence spectrometer (XRF) and inductively coupled plasma (ICP). The chemical durability of tellurite glass was evaluated through the PCT method.

Uranium-235, used in nuclear power generation, produces a lot of radioactive waste. Among radioactive waste nuclides, I-129 is problematic due to its long half-life (1.57×107 y) with high mobility in the environment. It should be captured and immobilized into a geological disposal environment through a stable waste form. In this study, various additives including Al, Bi, Pb, V, Mo and W were added to silver tellurite glass to prepare a matrix for immobilizing iodine, and its thermal and leaching properties were evaluated. To prepare glass, the glass precursor mixture was placed in alumina crucibles and heated at 800°C for 1 h. Except for aluminum, there was no significant loss of constituent elements. The loading of iodine in the matrix was approximately 11-15% by weigh, excluding oxygen. The normalized releases of all the elements obtained by PCT-A were below the order of 10-1 g/m2, which satisfies US regulation (2 g/m2). Differential scanning calorimetry was performed to evaluate the thermal properties of the glass samples. The glass transition temperature (Tg) increased by adding such as V2O5, MoO3, or WO3. The similar relative electrostatic field values of V2O5, MoO3, and WO3 could provide sufficient electro static field to the TeO2 interacting with the non-bridging oxygen forming Te-O-M (M = V, Mo, W) links. The addition of MoO3 or WO3 in the silver tellurite glass system increased glass transition temperature (Tg) and crystallization temperature (Tc) while maintaining the glass stability.

Radioactive cesium is a heat generated and semi-volitile nuclide in spent nuclear fuel (SNF). It is released gasous phase by head-end treatment which is a pretreatment of pyroprocessing. One of the capturing methods of gasous radioactive cesium is using zeolite. After ion-exchanged zeolite, it is transformed to ceramic waste form which is durable ceramic structure by heat treatment. Various ceramic wasteforms for Cs immobilization have been researched such as cesium aluminosilicate (CsAlSi2O6), cesium zirconium phosphate (CsZr2(PO4)3), cesium titanate (CsxAlxTi8-xO16, Cs2TiNb6O18) and CsZr0.5W1.5O6. The cesium pollucite is composed to aluminosilicate framework and cesium ion incorporated in matrix materials lattices. Many researchers are reported that the pollucite have high chemical durability. In this study, the Cesium pollucite was fabricated using mixtures of aluminosilicate denoted Absorbent product (AP) and Cs2CO3 by calcination and pelletized by cold pressing. The characterization of fabricated pollucite powder and pellets was analyzed by XRD, TGA, SEM, SEMEDS and XRF. The chemical durability of pollucite powder was evaulated by PCT-A and ICP-MS and OES. Thus, the optimal pressure condition without breaking the pellets which is low Cs2O/AP ratio and pelletizing pressure was selected. The long-term leaching test was performed using MCC-1 method for 28 days with the fabricated pollucite pellets. The leachate of leaching test was allard groundwaster and Deionized water and replaced 5 contact periods which is 3 hours, 3 days, 7 days, 14 days and 28 days and analyzed by ICPMS. The leaching rate was shown two stages. The first stage was rapid and relatively large amount of nuclides were leached. The leaching rate was decreased in the second stage. The fractional release rate of this study was shown same trend. These results were similar to previous studies.

To minimize the short-term thermal load on the repository facility, heat generating nuclides such as Cs-137 and Sr-90 should be separated from the spent nuclear fuel for efficiency of repository facility. In particular, Sr-90 must be separated because it generates high heat during the decay process. Recently, Korea Atomic Energy Research Institute (KEARI) is developing a waste burden minimization technology to reduce the environmental burden caused by the disposal of spent nuclear fuel and maximize the utilization of the disposal facility. The technology includes a nuclide management process that can maximize disposal efficiency by selectively separating and collecting major nuclides such as Cs, Sr, I, TRU/RE, and Tc/Se from spent nuclear fuel. Among the major nuclides, Sr nuclides dissolve in chloride phase during the chlorination process of spent nuclear fuel and recovered in the form of carbonate or oxide via reactive distillation. In this process, Ba nuclides are also recovered along with Sr nuclides due to their chemical similarity. In this study, we prepared group II nuclide ceramic waste form, Ba(x)Sr(1-x)TiO3 (x=0, 0.25, 0.5, 0.75, 1), using the solid-state reaction method by considering the various ratio of Sr/Ba nuclides generated from nuclide management process. The established waste form fabrication process was able to produce a stable waste form regardless of the ratio of Sr/Ba nuclides. To evaluate the stability of group II waste form, physicochemical properties such as leaching and thermal properties were evaluated. Also, the radiological properties of the Ba(x)Sr(1-x)TiO3 waste forms with various Sr/Ba ratios were evaluated, and the estimation of centerline temperature was carried out using the experimental thermal property data. These results provided fundamental data for long-term storage and management of group II nuclides waste form.

Inorganic and organic ion exchange materials were generally applied to liquid processes in nuclear reactor. In the case of heavy-water reactor (HWR), zeolite, active carbon, anion resin, and cation resin were used to treat liquid processes such as reactor primary coolant cleanup and liquid radioactive waste management system. Then, used ion exchangers were stored at storage tanks. Various kinds of nuclides were adsorbed in ion exchange materials. Especially, C-14, long half-life nuclide, was highly concentrated in anion resin, and waste resin was treated as intermediated level radioactive waste (ILW). Thermal and non-thermal methods such as pyrolysis, incineration, catalytic extraction, acid digestion, and wet oxidation have been studied for treating spent resin. However, destructive methods are not suitable due to massive off gas waste containing radioactive species. To solve this problem, various kinds of processes were developed such as acid stripping, PLO process, activity stripping, thermal treatment, and etc. In this study, microwave method is suggested to treat HWR waste resin. C-14 nuclide was selectively removed from waste resin without decomposition of main structure in waste resin. Radioactive waste resin generated from Wolsung HWR unit 1 and unit 2 was treated using microwave method and 95% of C-14 was successfully removed from the radioactive waste resin.

In this study, an aerosol process was introduced to produce CaCO3. The possibility of producing CaCO3 by the aerosol process was evaluated. The characteristics of CaCO3 prepared by the aerosol process were also evaluated. In the CaCO3 prepared in this study, as the heat treatment proceeded, the calcite phase disappeared. The portlandite phase and the lime phase were formed by the heat treatment. Even if the CO2 component is removed from the calcite phase, there is a possibility that the converted CO2 component could be adsorbed into the Ca component to form a calcite phase again. Therefore, in order to remove the calcite phase, carbon components should be removed first. The lime phase was formed when CO2 was removed from the calcite phase, while the portlandite phase was formed by the introducing of H2O to the lime phase. Therefore, the order in which each phase formed could be in the order of calcite, lime, and portlandite. The reason for the simultaneous presence of the portlandite phase and the lime phase is that the hydroxyl group (OH−) introduced by H2O was not removed completely due to low temperature and/or insufficient heating time. When the sufficient temperature (900°C) and heating time (60 min) were applied, the hydroxyl group (OH−) was removed to transform into lime phase. Since the precursor contained the hydrogen component, it could be possible that the moisture (H2O) and/or the hydroxyl group (OH−) were introduced during the heat treatment process.

Uranium-235, used for nuclear power generation, has brought radioactive waste. It could be released into the environment during reprocessing or recycling of the spent nuclear fuel. Among the radioactive waste nuclides, I-129 occurs problems due to its long half-life (1.57×107 y) with high mobility in the environment. Therefore, it should be captured and immobilized into a geological disposal system through a stable waste form. One of the methods to capture iodine in the off-gas treatment process is to use silver loaded zeolite filter. It converts radioactive iodine into AgI, one of the most stable iodine forms in the solid state. However, it is difficult to directly dispose of AgI itself in an underground repository because of its aqueous dissolution under reducing condition with Fe2+. It must be immobilized in the matrix materials to prevent release of iodine as a result of chemical reaction. Among the matrix glasses, silver tellurite glass has been proposed. In this study, additives including Al, Bi, Pb, V, Mo, and W were added into the silver tellurite glass. The thermal properties of each matrix for radioactive iodine immobilization were evaluated. The glasses were prepared by the melt-quenching method at 800°C for 1 h. Differential scanning calorimetry (DSC) was performed to evaluate the thermal properties of the glass samples. From the study, the glass transition temperature (Tg) was increased by adding additives such as V2O5, MoO3, or WO3 in the silver tellurite glass. The relative electro-static field (REF) values of V2O5, MoO3, and WO3 are about three times higher than that of the glass network former, TeO2. It could provide sufficient electro-static field (EF) to the TeO2 interacting with the non-bridging oxygen forming Te-O-M (M = V, Mo, W) links. Therefore, the addition of V2O5, MoO3, or WO3 reinforced the glass network cohesion to increase the Tg of the glass. The addition of MoO3or WO3 in the silver tellurite glass increased Tg and crystallization temperature (Tc) with remaining the glass stability.

During the treatment of spent nuclear fuel, radioactive iodine is generated in a liquefied or gaseous form in a specific process. In the case of iodine 129, it is a long-lived nuclide with a very long halflife and has high groundwater mobility under repository conditions. Despite showing a low radioactivity value, research on the management of radioactive iodine from a long-term perspective is continuously being performed. Although research has been conducted using borosilicate glass as a medium for solidifying iodine, compatibility of I in borosilicate glass is very small and the volatility is high in the solidification process. So it is not suitable as a solidified substance of iodine. Therefore, studies on other solidification media to replace them are continuously being conducted. Our research team tried to develop a new medium that can contain iodine in a solidified body stably through a simple heat treatment process and can improve problems such as volatility and waste loading. Iodine is captured as AgI in the Ag ion-exchanged zeolite. So, TeO2, Ag2O, and Bi2O3 having a high AgI loading rate were used as main components. It was named TAB after taking the first letter of each element. In previous studies, the physical properties, structure, and chemical stability of TAB materials were confirmed. PCT (Product Consistent test) was performed to confirm chemical stability. It is mainly used to compare the chemical stability of glass materials with other glass materials, but there are limitations in evaluating the long-term chemical stability of materials. In this experiment, we tried to evaluate the long-term stability of TAB and compare it with borosilicate, which is conventionally used to treat radioactive waste. In addition, we tried to understand the leaching behavior inside the TAB medium. For this purpose, ASTM C1308 test was performed for 365 days, and distilled water and KURT groundwater were used as leachates to examine the effect of ions in the groundwater on the solidified body. To analyze the leaching behavior, ICP-MS and ICP-OES analyses were performed, and the cross-section of the sample after leaching was observed through SEM.

Radioactive Cesium is fission products of spent nuclear fuelwith high heat generating nuclide, having a 30 years half-life. Particularly, it is important to make stable waste form because Cs-137 have high solubility and mobility at ground water. The ceramic waste form has higher thermal and structural stability and lower solubility than glass and cement waste form. Various ceramic waste forms for Cs immobilization have been researched such as aluminosilicate (CsAlSi2O6), phosphate (CsZr2(PO4)3), titanate (CsxAlxTi8-XO16) and CsZr0.4W1.5O6. Cs pollucite is incorporated radio-Cesium to aluminosilicate framework by inorganic ion-exchange with zeolite. Therefore, it is an extremely stable structure. In previous study, we are prepared Cs pollucite pellet with various ratio of Cs precursor/matrix materials, and attempted to evaluate applicability as ceramic waste form. Cs pollucite is produced by mixing Mullite and SiO2 obtained by heat treatment Kaolinite with Cs2CO3 in ratios of 0.5, 0.6, 0.7, 0.8. Optimized ratio was 0.5 revealed single pollucite phase and the others exhibited CsAlSiO4 phase with pollucite. Cs pollucite of ratio 0.5 was pelletized under various conditions and evaluated performance as waste form. herein, the pellets were cracked on surface and edges broken. Therefore, Cs pollucite having high ratio of matrix materials contained Si and Al was prepared and pelletized, and then waste form was evaluated. The Cs pollucite powder is ratio of Cs precursor/matrix materials were 0.1, 0.2, 0.3, 0.4. Pollucite powder was mixed with 1.5, 2.0wt% Polyvinyl alcohol as binder, and dried at 70°C for overnight. Afterward, these powders obtained were pressed using punch-die apparatus at 50, 100 bar for 1 hour and the pellets with about dia. 25 mm and height 10 mm was acquired. These pellets were sintered at 1,400°C for 5 hours. Subsequently, the waste forms were evaluated physicochemical test such as compression strength, thermal conductivity, thermal expansion and leaching properties analysis.

To reduce the environmental burden caused by the disposal of spent nuclear fuel and maximize the utilization of the repository facility, waste burden minimization technology is currently being developed at the Korea Atomic Energy Research Institute (KEARI). The technology includes a nuclide management process that can maximize disposal efficiency by selectively separating and collecting major nuclides in spent nuclear fuel. In addition, for efficient storage facility utilization, the short-term decay heat generated by spent nuclear fuel must be removed from the waste stream. To minimize the short-term thermal load on the repository facility, it is necessary to separate heat generating nuclides such as Cs-137 and Sr-90 from the spent fuel. In particular, Sr-90 must be separated because it generates high heat during the decay process. KAERI has developed a technology for separating Sr nuclides from Group II nuclides separated through the nuclide management process. In this study, we prepared Sr ceramic waste form, SrTiO3, by using the solid-state reaction method for long-term storage for the decay of separated Sr nuclides and evaluated the physicochemical properties of the waste form. Also, the radiological and thermal characteristics of the Sr waste form were evaluated by predicting the composition of Sr nuclides separated through the nuclide management process, and the estimation of centerline temperature was carried out using the experimental thermal data and steady state conduction equation in a long and solid cylinder type waste form. These results provided fundamental data for long-term storage and management of Sr waste.