Decommissioning waste is generated with various types and large quantities within a short period. Concrete, a significant building material for nuclear facilities, is one of the largest decommissioning wastes, which is mixed with aggregate, sand, and cement with water by the relevant mixing ratio. Recently, the proposed treatment method for volume reduction of radioactive concrete waste was proven up to scale-up testing using unit equipment, which involved sequentially thermomechanical and chemical treatment. According to studies, the aggregate as non-radioactive material is separated from cement components with contaminated radionuclides as less than clearance criteria, so the volume of radioactive concrete waste is decreased effectively. However, some supplementation points were presented to commercialize the process. Hence, the process requires efficiency as possible to minimize the interface parts, either by integration or rearranging the equipment. In this study, feasibility testing was performed using integrated heating and grinding equipment, to supplement the possible issue of generated powder and dust during the process. Previously, heat treatment and grinding devices were configured separately for pilot-scale testing. But some problems such as leakage and pipe blockage occurred during the transportation of generated fine powder, which caused difficulties in maintaining the equipment. For that reason, we studied to reduce the interface between the equipment by integrating and rearranging the equipment. To evaluate the thermal grinding performance, the fraction of coarse and concrete fines based on 1mm particle size was measured, and the amount of residual cement in each part was analyzed by wet analysis using 4M hydrochloric acid. The result was compared with previous studies and the thermomechanical equipment could be selected to enhance the process. Therefore, it is expected that the equipment for commercialization could be optimized and composed the process compactly by this study.

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.

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.

Decommissioning waste is generated at all stages during the decommissioning of nuclear facilities, and various types of radioactive waste are generated in large quantities within a short period. Concrete is a major building material for nuclear facilities. It is mixed with aggregate, sand, and cement with water by the relevant mixing ratio and dried for a certain period. Currently, the proposed treatment method for volume reduction of radioactive concrete waste was involved thermomechanical and chemical treatment sequentially. The aggregate as non-radioactive materials is separated from cement components as contaminated sources of radionuclides. However, to commercialize the process established in the laboratory, it is necessary to evaluate the scale-up potential by using the unit equipment. In this study, bench-scale testing was performed to evaluate the scale-up properties of the thermomechanical and chemical treatment process, which consisted of three stages (1: Thermomechanical treatment, 2: Chemical treatment, 3: Wastewater treatment). In the first stage, lab, bench, and pilot scale thermomechanical tests were performed to evaluate the treated coarse aggregate and fines. In the second stage, the fine particles generated by the thermomechanical treatment process, were chemically treated using dissolution equipment, after then the removal efficiency and residual of cement in the small aggregate was compared with laboratory results. The final stage, the secondary wastewater containing contaminant nuclides was treated, and the contaminant nuclides could be removed by chemical precipitation method in the scale-up reactors. Furthermore, an additional study was required on the solid-liquid separation, which connected each part of the equipment. It was conducted to optimize the separation method for the characteristics of the particles to be separated and the purpose of separation. Therefore, it is expected that the basic engineering data for commercialization was collected by this study.

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.

Concrete is one of the largest wastes, by volume, generated during the decommissioning of nuclear facilities, which significantly influences the projected costs for the disposal of decommissioning wastes. Concrete consists of aggregates and a cement binder. In radioactive concrete, the radioisotopes are mainly associated with the cement component. If the radioactive isotope can be separated from the concrete to below the clearance criteria, the volume of radioactive concrete waste could be reduced effectively. We were studied to separate the radioactive materials from the concrete by using the thermomechanical and chemical treatment processes, sequentially. From the study, separated aggregate could be treated to achieve the clearance level. However, these processes generate a large volume of secondary acidic radioactive wastewater, which might be a critical problem to reduce the volume of radioactive concrete waste. In this research, separating the 137Cs and 90Sr from dissolved concrete wastewater to below the discharge criteria by precipitation method, it would be released to the environment under industrial waste guidelines. The experiments were conducted to using a simulated radioactive wastewater, formed by the dissolution of concrete within HCl, which was spiking the 137Cs and 90Sr, respectively. In addition, we applied the chemical precipitation methods with wastewater, using ferrocyanide for 137Cs and BaSO4 coprecipitation for 90Sr. As a result, targeted radionuclides could be removed to the discharge level (137Cs: 0.05 Bq·ml−1, 90Sr: 0.02 Bq·ml−1) by precipitation method. Therefore, it could reduce the secondary wastewater effectively by precipitation method and enhance the additional volume reduction for radioactive concrete waste.

Radioactive carbon, C-14, can be generated by the neutron capture reaction of O-17 during the nuclear power plant operation. Since C-14 is classified as an intermediate level waste radionuclide, it is required that an effective separation process for C-14. C-14 is mainly absorbed on activated carbon in the air cleanup system. Therefore, the main generation source of C-14 during the nuclear power plant decommissioning is spent activated carbon. KAERI has been developing the treatment of spent activated carbon. In this process, C-14 can be desorbed as a gaseous oxide form from the spent activated carbon at high-temperature vacuum conditions. This radioactive carbon dioxide can be captured into alkaline earth metal incorporated glass and can be transformed into carbonate form. However, the carbonate (e.g. CaCO3 and SrCO3) is dispersive. When the radioactive carbonates are disposed into a geological repository, they should be immobilized to remove future uncertainty. This study examined the stabilization/immobilization of the radioactive carbonates by the cement hydration process. Cement wasteform incorporated with calcium carbonate and strontium carbonate was produced under various waste loading (e.g. 20wt%, 40wt%, and 60wt% of CaCO3 and SrCO3, respectively). Then we evaluated mechanical and chemical durability by measuring compressive strength and leachability according to standard test methods specified in the waste acceptance criteria of the Gyeongju low and intermediate level waste repository (WAC-SIL-2022-1). Also, microstructure and thermal characteristics were investigated by SEM-EDS and TGA analysis.