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.

Nuclear weapon generates huge amount of radioactive fallout which is extremely dangerous. The fallout gradually falls to the ground and then covers every surface in city and nature. A hydrogel decontamination medium has been developed to clean the surface polluted by the fallout. The hydrogel is soluble in water so the used hydrogel can be simply removed from the surface by washing. However, significant amount of waste water, containing the radioactive fallout, is generated with this process. In this respect, it is necessary to secure alternative technical options for the used hydrogel recovery. In this study, a steam-suction process was suggested for the used hydrogel recovery. Contaminated stainless steel surface, with fixed simulated fallout particles, was prepared for test. The simulated fallout particles were obtained by high-temperature treatment of a mixture of natural soil, used concrete, and Fe2O3. The hydrogel, composed of poly-vinyl alcohol and borax, was spread onto the contaminated stainless steel surface. The hydrogel was soft at first and it gradually becomes rigid with time. The used hydrogel was recovered by suction with a simultaneous steam spraying to soften the rigid gel. As a result, the clean surface of the stainless steel without the simulated fallout particles was obtained, showing the feasibility of this technique for the used hydrogel recovery.

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.

경험식에 기반한 폭발 해석방법은 폭압-시간 이력곡선을 하중으로 적용하여 해석하는 방법이다. 이 방법은 모델링이 간단하고 해 석시간이 짧아 효율적이지만, 일부 연구에 따르면 근거리 폭발 해석에는 적합하지 않음이 보고되고 있다. 본 연구에서는 예로써 환산 거리 0.4~1.0의 근거리 폭발조건에 있는 RC 보에 대해 해석방법에 따른 결과의 차이 및 원인을 분석하였고, 이를 통해 경험식 방법을 이용한 해석의 적용 범위를 구체적으로 검토 및 확인할 수 있었다. 사용된 유한요소해석 프로그램은 LS-DYNA이다. 해석결과에 따르 면, 원거리 폭발 실험 데이터를 근거로 하는 경험식 해석방법은 충격량을 과소평가하고 있었다. 이로 인해 RC 보의 처짐은 측정된 처 짐 또는 ALE(Arbitrary Lagrangian Eulerian) 해석결과에 비해 작게 계산되었다. 구조체의 응답이 크게 나타나는 근거리 폭발에 대해 서는 ALE 해석방법을 사용하는 것이 더 적합할 것으로 사료된다.

Wide-area surface decontamination is essential in the emergency situation of release of radioisotopes to public such as nuclear accident or terrorist attack. Here, a self-generated hydrogel based on the reversible complex between poly (vinyl alcohol) (PVA) and phenylboronic acid-grafted poly (methyl vinyl ether-alt-mono-sodium maleate) (PBA-g-PVM-SM) was developed to remove the radioactive cesium from surface. Two aqueous polymeric solutions of PVA and PBA-g-PVM-SM containing sulfur-zeolite were simultaneously applied to surfaces, which subsequently self-generated a hydrogel based on the PBA-diol ester bond. The sulfur-zeolite suspended in hydrogel selectively remove the 137Cs from contaminated surface and easily separated from the dissociable used hydrogel by simple water rinsing. In radioactive tests, the resulting hydrogel containing sulfur-chabazite displayed high 137Cs removal efficiencies of 96.996% for painted cement and 63.404% for cement, which was 2.33 times higher than that of commercial strippable coating (Decongel). Considering the intrinsic various ion-exchange ability of zeolite, our hydrogel system has the excellent potential for the effective removal of various hazardous contamination including radionuclides from the surface.

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.