Various types of radioactive liquid and solid wastes are generated during the operation and decommissioning of nuclear power plants. To remove radionuclides Co-60, Cs-137 etc. from a liquid waste, the ion-exchange process based on organic resins has been commonly used for the operation of nuclear facilities. Due to the considerations for the final disposal of process endproduct, other treatment methods such as adsorption, precipitation using some inorganic materials have been suggested to prepare for large amounts of waste during decommissioning. This study evaluated sintering characteristics for radioactive precipitates generated during the liquid waste treatment process. The volume reduction efficiency and compressive strength of sintered pellets were the major parameters for the evaluation. Major components of a simulated precipitate were some coagulated (oxy) hydroxides containing light elements, such as Si, Al, Mg, Ca, and zeolite particles. Green pellets compressed to around 100 MPa were heated at a range of 750~850°C to synthesize sintered pellets. It was observed that the volume reduction percentages were higher than 50% in the appropriate sintering conditions. The volume reduction was caused by the reduction of void space between particles, which is an evidence of partial glassification and ceramization of the precipitates. This result can also be attributed to conversion reactions of zeolite particles into other minerals. The compressive strength ranged from 6 to 19 MPa. These results also showed a significant correlation with the volume reduction of sintered body. Although our lab-scale experiments showed many benefits of sintering for the precipitates, optimized conditions are needed for large-scale practical applications. Evaluation of sintering characteristics as a function of pellet size and further testing will be conducted in the future.

Various dry active wastes (DAWs) have been accumulated in nuclear power plants since the DAWs are mostly combustible. KAERI has developed a thermochemical treatment process for the used decontamination paper as an operational waste to substitute for incineration process and to decontaminate radionuclides from the DAWs. The thermochemical process is composed of thermal decomposition in a closed vessel, chlorination of carbonated DAWs, separation of soluble chlorides captured in water by hydroxide precipitation, and immobilization of the precipitate. This study examined the third and fourth steps in the process to immobilize Co-60 by fabricating a stable wasteform. Precipitation behaviors were investigated in the chloride solution by adding 10 M KOH. It was shown that the precipitates were composed of Mg(OH)2 and Al(OH)3. Then, the glass-ceramic wasteform for the precipitates were produced by adding additive mixtures in which silica and boron oxide were blended with various ratios. The wasteform was evaluated in terms of volume reduction ratio, bulk density, compressive strength, and leachability.

The process of carbonization followed by a high-temperature halogenation removal of radionuclides is a promising approach to convert low-radioactivity spent ion-exchange (IE) resins into freereleasable non-radioactive waste. The first step of this process is to convert spent ion-exchange resins into the carbon granules that are stable under high-temperature and corrosive-gas flowing conditions. This study investigated the kinetics of carbonization of cation exchange resin (CER) and the changes in structures during the course of carbonization to 1,273 K. Both of model-free and modelfitted kinetic analysis of mixed reactions occurring during the course of carbonization were first conducted based on the non-isothermal TGAs and TGA-FTIR analysis of CER to 1,272 K. The structural changes during the course of carbonization were investigated using the high-resolution FTIR and C-13 NMR of CER samples pyrolyzed to the peak temperature of each reaction steps established by the kinetic analysis. Four individual reaction steps were identified during the course of carbonization to 1,273 K. The first and the third steps were identified as the dehydration and the dissociation of the functional group of —SO3-H+ into SO2 and H2O, respectively. The second and the fourth steps were identified as the cleavage of styrene divinyl benzene copolymer and carbonization of pyrolysis product after the cleavage, respectively. The temperature and time positions of the peaks in the DTG plot are nearly identical to those of the peaks of the Gram Schmidt intensity of FTIR. The structural changes in carbonization identified by high-resolution FTIR and DTG are in agreement with those by C-13 NMR. The results of a detailed examination of the structural changes according to NMR and FTIR were in agreement with the pyrolysis gas evolution characteristics as examined by TGA-FTIR.

In pyroprocessing, the residual salts (LiCl containing Li and Li2O) in the metallic fuel produced by the oxide reduction (OR) process are removed by salt distillation and fed into electrorefining. This study undertook an investigation into the potential viability of employing a separate LiCl salt rinsing process as an innovative alternative to conventional salt distillation techniques. The primary objective of this novel approach was to mitigate the presence of Li and Li2O within the residual OR salt of metallic fuel, subsequently facilitating its suitability for electrorefining processes. The process of rinsing the metallic fuel involved immersing it in a LiCl salt environment at a temperature of 650°C. During this immersion process, the residual OR salt contained within the fuel underwent dissolution, thereby reducing the concentrations of Li2O and Li generated during the OR process. Furthermore, the Li and Li2O dissolved within the LiCl salt were effectively consumed through chemical reactions with ZrO2 particles present within the salt. Importantly, even after the metallic fuel had been subjected to rinsing in a conventional LiCl salt solution, the concentration of Li and Li2O within the salt remained consistent with its initial levels, due to the utilization of ZrO2. Moreover, it was observed that the Li- Li2O content within the metallic fuel was significantly diluted as a result of the rinsing process.

Heavy water (D2O) is a coolant as well as a moderator of pressurized heavy water reactors (PHWRs). During operation of PHWRs, deuterium (H-2, D) in heavy water is gradually converted to tritium (H-3, T), which is a radioactive nuclide with a half-life of 12.3 years, by capturing neutron. Various radioactive wastes contaminated by T are generated upon the PHWR operation. Owing to the similarity of D and T, they behave together a form of water (either liquid or vapor) in a normal circumstance. To handle D and T with the water form is quite difficult because it is not a solid and is highly mobile in nature. In this study, a mineralization technique to fix D and T in a solid form is suggested. It is considered that hydroxide minerals, which have low solubility in water, might tightly bind D and T in non-mobile, solid-state media. Feasibility of this strategy is studied by using a copper-based hydroxide mineral, atacamite. Atacamite is a natural mineral found in copper deposits with chemical formula of Cu2Cl(OH)3. Atacamite can be simply synthesized in laboratories by a precipitation method using copper chloride and calcium carbonate as precursors. Both chemicals were added into heavy water to obtain pale-green precipitates. Heavy water is the only source for D in this reaction and thus deuterated mineral is expected to be form. The obtained deuterated mineral, suspected to be Cu2Cl(OD)3, was then immersed in natural deionized water (extremely low D2O concentration) for several days to identify how fast D in Cu2Cl(OD)3 dissolves into water. In a preliminary Fourier transform infrared (FTIR) spectroscopy, absorption peaks related to HDO and D2O were not observed in the deionized water which is recovered after the immersion test, suggesting that D remained stable in the synthesized mineral. However, owing to low detection limit of FTIR, more precise analysis should be taken to clearly identify the stability of D of the deuterated atacamite. If deuterated hydroxide minerals are found to have sufficiently high D stability in natural water, they can be further treated with cement or other stabilization media to form a final wasteform for underground disposal.

Various dry actives wastes (e.g., gloves, wipers, shoes, clothes) are generated during operation and maintenance of nuclear facilities. Among those, latex gloves gets interest because they contain both organic and inorganic compounds. CaCO3 is a common filler material for production of latex rubbers. Here, latex gloves were thermally treated in a closed vessel to separate the organic and inorganic compounds. Using the closed vessel is beneficial as it can prevent escape of any species, including radioactive nuclides in a real case, generated during the treatment. It was found that thermal decomposition of latex gloves occurred above 250°C. Latex gloves were decomposed to gas, liquid, and solid compounds. The gas product is thought to be volatile organic compounds (VOCs). The liquid product seems to be a mixture of oils and water. A CaCO3 phase was identified in the solid product, as expected. The VOCs can be easily separated at room temperature by purging in vacuum or inert atmosphere. The liquid-solid mixture can be separated by distillation. It is thought that gammaemitting nuclides, such as Cs-137, Sr-90, and Co-60, dominantly remain in the solid product. In the best situation, the solid product is the only subject to be transferred to final wasteform fabrication stream and thus volume of final waste can be reduced. Surrogates of contaminated latex gloves (containing Cs, Sr, and Co) were prepared and they were treated at 350°C in the closed vessel. How these contaminants behaves in this thermal process will be discussed in the presentation.

Dry active wastes (DAWs) are a type of combustible radioactive solid waste, which includes decontamination paper, protective clothing, filters, plastic bags, etc. generated from operating nuclear facilities and decommissioning projects. The volume of DAWs could be increased over time, disadvantage to higher disposal costs and space utilitization of disposal site. Additionally, incineration methods cannot be applied to DAWs, unlike general environmental waste, due to concerns about air pollution and the release of harmful chemicals with radioactive nuclides into the atmosphere. Recently, KAERI developed an alternative thermochemical process for reducing the volume of DAW, which involves a step-wise approach, including carbonization, chlorination, and solidification. The purpose of this process is to selectively separate the radioactive nuclides from carbonized DAWs that are less than clearance criteria, which can be disposed of as non-radioactive waste. In this research, we investigated the thermal decomposition characteristics of DAWs using nonisothermal thermogravimetric analysis, which was performed with different categorized wastes and heating conditions. As a result, the cellulose DAWs such as decontamination paper and cotton were thermally decomposed in three or four-step depending on the heating conditions. On the other hand, the hydrocarbon and rubber DAWs such as plastic bags and latex were thermally decomposed in one or two-step. Therefore, it could be suggested the thermochemical treatment conditions that minimize the decomposition of DAWs by controlling the reaction steps, and we will try to apply these results for cellulose type DAWs such as decontamination paper and cotton, which is generated majorly from the nuclear facilities in the future.

This study evaluated the synthesis of optimal materials for high efficiency adsorption and removal characteristics of Cs-137 for radioactive contaminated water, and considered thermal treatment methods to stabilize the spent adsorbent generated after treatment. We synthesized a composite adsorbent with a combination of impregnating metal ferrocyanide that improves the selectivity of Cs adsorption with zeolite capable of removing Cs as a support. The Cs removal efficiency of the composite adsorbent was evaluated, and the stability change of Cs according to the high-temperature sintering was evaluated as a stabilization method of the spent adsorbent. The metal ferrocyanide content of the adsorbent was in the range of 11.8~36.0%. The adsorption experiments were performed using a simulated liquid waste to have a total Cs concentration of 1 mg/L while containing a trace amount of Cs-137, and then gamma radioactivity was analyzed. In order to evaluate the stabilization of the spent adsorbent, heat treatment was performed in the range of 500~1,100°C, and the volatilization rate of Cs during heat treatment and the leaching rate of Cs after heat treatment were compared. In the adsorption experiment, the Cs removal efficiency was higher than 99%, regardless of the amount of metal ferrocyanide in the composite adsorbent. In the sintering experiment on the spent adsorbent, it was confirmed that there was no volatilization of Cs up to 850°C, and then the volatilization rate increased as the heating temperature increased. On the other hand, the leaching rate of Cs in the sintered adsorbent tends to significantly decrease as the heating temperature increases, so that Cs can be stabilized in the sintered body. In addition, as the content of metal ferrocyanide increases, the volatilization rate of Cs rapidly increases, indicating that the unstable metal ferrocyanide in the adsorbent may adversely affect the removal of Cs as well as the thermal treatment stability.

Radioactive waste generated in large quantities from NPP decommissioning has various physicochemical and radiological characteristics, and therefore treatment technologies suitable for those characteristics should be developed. Radioactively contaminated concrete waste is one of major decommissioning wastes. The disposal cost of radioactive concrete waste is considerable portion for the total budget of NPP decommissioning. In this study, we developed an integrated technology with thermomechanical and chemical methods for volume reduction of concrete waste and stabilization of secondary waste. The unit devices for the treatment process were also studied at bench-scale tests. The volume of radioactive concrete waste was effectively reduced by separating clean aggregate from the concrete. The separated aggregate satisfied the clearance criteria in the test using radionuclides. The treatment of secondary waste from the chemical separation step was optimally designed, and the stabilization method was found for the waste form to meet the final disposal criteria in the repository site. The final volume reduction rates of 56.4~75.4% were possible according to the application scenario of our processes under simulated conditions. The commercial-scale system designs for the thermomechanical and chemical processes were completed. Also, it was found that the disposal cost for the contaminated concrete waste at domestic NPP could be reduced by more than 20 billion won per each unit. Therefore, it is expected that the application of this technology will improve the utilization of the radioactive waste disposal space and significantly reduce the waste disposal cost.

The Korea government decided to shut down Kori-1 and Wolsung-1 nuclear power plants (NPPs) in 2017 and 2019, respectively, and their decommissioning plans are underway. Decommissioning of a NPP generates various types of radioactive wastes such as concrete, metal, liquid, plastic, paper, and clothe. Among the various radioactive wastes, we focused on radioactive-combustible waste due to its large amount (10,000–40,000 drums/NPP) and environmental issues. Incineration has been the traditional way to minimize volume of combustible waste, however, it is no longer available for this amount of waste. Accordingly, an alternative technique is required which can accomplish both high volume reduction and low emission of carbon dioxide. Recently, KAERI proposed a new decontamination process for volume reduction of radioactivecombustible waste generated during operation and decommissioning of NPPs. This thermochemical process operates via serial steps of carbonization-chlorination-solidification. The key function of the thermochemical decontamination process is to selectively recover and solidify radioactive metals so that radioactivity of the decontaminated carbon meets the release criteria. In this work, a preliminary version of mass flow diagram of the thermochemical decontamination process was established for representative wastes. Mass balance of each step was calculated based on physical and chemical properties of each constituent atoms. The mass flow diagram provides a platform to organize experimental results leading to key information of the process such as the final decontamination factor and radioactivity of each product.

In this study, a chlorination technique for recycling Li2ZrO3, a reaction product of ZrO2-assisted rinsing process, was investigated to minimize the generation of secondary radioactive pyroprocessing waste. It was found that the reaction temperature was a key parameter that determined the reaction rate and maximum conversion ratio. In the temperature range of 400−600℃, an increase in the reaction temperature resulted in a profound increase in the reaction rate. Hence, according to the experimental results, a reaction temperature of at least 450℃ was proposed to ensure a Li2ZrO3 conversion ratio that exceeded 80% within 8 h of the reaction time. The activation energy was found to be 102 ± 2 kJ·mol−1·K−1 between 450 and 500℃. The formation of LiCl and ZrO2 as reaction products was confirmed by X-ray diffraction analysis. The experimental results obtained at various total flow rates revealed that the overall reaction rate depends on the Cl2 mass transfer rate in the experimental condition. The results of this study prove that the chlorination technique provides a solution to minimize the amount of radioactive waste generated during the ZrO2-assisted rinsing process.

Solid-state mechanochemical reduction combined with subsequent melting consolidation was suggested as a technical option for the oxide reduction in pyroprocessing. Ni ingot was produced from NiO as a starting material through this technique while Li metal was used as a reducing agent. To determine the technical feasibility of this approach for pyroprocessing, which handles spent nuclear fuels, thermodynamic calculations of the phase stabilities of various metal oxides of U and other fission elements were made when several alkaline and alkali-earth metals were used as reducing agents. This technique is expected to be beneficial, not only for oxide reduction but also for other unit processes involved in pyroprocessing.

The reaction between Li2CO3 and Cl2 was investigated to verify its occurrence during a carbon-anode-based oxide reduction (OR) process. The reaction temperature was identified as a key factor that determines the reaction rate and maximum conversion ratio. It was found that the reaction should be conducted at or above 500℃ to convert more than 90% of the Li2CO3 to LiCl. Experiments conducted at various total flow rate (Q) / initial sample weight (W i) ratios revealed that the reaction rate was controlled by the Cl2 mass transfer under the experimental conditions adopted in this work. A linear increase in the progress of reaction with an increase in Cl2 partial pressure (pCl2) was observed in the pCl2 region of 2.03–10.1 kPa for a constant Q of 100 mL∙min−1 and W i of 1.00 g. The results of this study indicate that the reaction between Li2CO3 and Cl2 is fast at 650℃ and the reaction is feasible during the OR process.