The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. In this study, we focus the enhancement for CAQS to provide the cations due to the chemical affinity between hydrogen isotope and unsaturated sites by cations in zeolite beads. Cation exchanged zeolite beads was synthesized with cobalt, copper, nickel, iron and silver in zeolite 4A beads. Synthesized cation exchanged zeolite was analyzed for the surface area and pore size in N2 and adsorption behaviors of hydrogen isotopes (D2/H2) for various cation exchanged zeolite beads using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption results will provide a foundation for future processes for tritium separation.

Tritium is radioactive isotope, emitting beta ray, released as tritiated water from nuclear power plants. Due to the danger of radioactive isotope, the appropriate separation of tritium is essentially carried out for environment and safety. Further, it is also promising material for energy production and research. The tritiated water can be treated by diverse techniques such as water distillation, cryogenic distillation, Girdler-sulfide process, and catalytic exchange. After treatment, it is more desirable to convert as gas phase for storage, comparing to liquid phase. However, achieving complete separation of hydrogen gases with very similar physical and chemical properties is significantly challenging. Thus, it is necessary to develop materials with effective separation properties in gas separation. In this presentation, we present hydrogen isotope separation in the gas phase using modified mesoporous silica. Mesoporous silica is a form of silica that is characterized by its mesoporous structure possessing pores that range from 2 to 50 nm in diameter. This material can be functionalized to selectively capture and separate molecules having specific size and affinity. Here, the silver and copper incorporated mesoporous silica was synthesized to tailor a chemical affinity quantum sieving effect, thereby providing separation efficiency in D2/H2. The adsorption quantities of H2 and D2 were determined by sorption study, and the textural properties of each mesoporous silica were analyzed using N2 physisorption. The selectivity (D2/H2) in diverse feed composition (1:1, 1:9, and 1:99 of D2/H2) was estimated by applying ideal adsorbed solution theory to predict the loading of the gas mixture on bare, Ag- and Cu-mesoporous silica based on their sorption study. Further, the performance of each mesoporous silica was evaluated in the breakthrough adsorption under 1:1 mixture of D2 and H2 at 77 K.

Carbon 14 (14C) is radioactive isotope of carbon which emits beta ray with long half-life (5730±30 years). Since the 14C is significantly hazardous for human being, the appropriate process to treat 14C is necessary. From the nuclear power plant, the ion exchange resin, graphite, and activated carbon are the main source of 14C. During the effort to reduce the volume of those wastes, the 14C is inevitably occurred as carbon dioxide (CO2) form, so called 14CO2. Thus, the development of technology to permanently capture and safely dispose 14CO2 is required. In this presentation, we introduce the decommissioning technology ranging from 14CO2 capture to solidification. First, the new class of glass adsorbent is developed which can irreversibly capture CO2 even under mild conditions. This material promotes the dissolution of alkaline earth ions due to the unstable glass structure. Then, the physical and chemical optimization of glass adsorbent enhances the performance of CO2 capture. Further, room temperature geopolymeric solidification is also performed to safely dispose 14C without any potential release.

Pt/C catalysts were prepared using black carbon (CB), and evaluated for their potential application as a catalyst of liquid-phase catalystic exchange for tritium treatment. CB was treated with 10% H2O2 solution for 0 and 2 hours at 105°C, Ethylene glycol and 40wt% Pt were added to the dried treated sample to prepare a Pt/C catalyst. The physical and chemical properties of the prepared catalysts were evaluated by BET, XRD, elemental analysis (EA), and TEM analyses. As a result of BET analysis, the surface area of CB without 10% H2O2 was 237.2 m2·g-1, and after treatment with 10% H2O2, it decreased to 181.2 m2·g-1 for 2 hours. However, the internal surface area increased, indicating the possibility that more Pt could be distributed inside the CB treated with 10% H2O2. In the XRD analysis results, the presence of Pt was confirmed by observing the Pt peak in the prepared Pt/C catalyst, and it was also observed through TEM analysis that Pt was evenly distributed within the CB. The elemental analysis (EA) results showed that the ratio of S and N decreased and the ratio of O increased with increasing 10% H2O2 treatment time. The H2O2 treated carbon supported Pt catalysts and polytetrafluoroethylene were then loaded together on a foamed nickel carrier to obtain hydrophobic catalysts. Our hydrophobic Pt catalyst using H2O2 treated black carbon are expected to be usefully used in the tritium treatment system.

The separation of hydrogen isotopes is a critical issue in various fields, such as deuterium or tritium production and the treatment of radioactively contaminated water. In this presentation, we describe the pervaporative separation of hydrogen isotopes using proton conductive membranes and underlying separation mechanism. We investigated the H/D separation factors of perfluorosulfonic acid (Nafion) and polybenzimidazole membranes using pervaporation, and found that both membranes exhibited similar separation factors of approximately 1.026. Water permeation flux through the membranes was highly dependent on their thickness and type, and increased with operation temperature. However, the effect of temperature on H/D separation factor was negligible. We also demonstrated the cascade separation of H/D, indicating the potential application of multi-stage operation. We found that surface transport mechanisms such as hydron hopping contributed the most to H/D separation during the pervaporation process of proton conductive membranes.

Radioactive carbon dioxide (14CO2) capture using innovative materials is desirable due to associated radiological hazards, and growing climate change. Mineral carbonation technology (MCT) is amenable to irreversibly capture CO2. Typically, MCT is attractive because capturing carbon through the chemical reaction between alkaline earth metal ions and CO2 forms insoluble and significantly stable carbonates. However, most applications of MCT have an intrinsic restriction regarding their operational conditions since no forward reaction occurs within realistic time scales. Thereby, the CO2 capture performance, such as CO2 capacity and carbonation reaction rate, of MCTs and their applications are severely restricted by the difficulty of operations under mild conditions. For example, natural minerals require aggressive carbonation reaction conditions e.g. high pressure (≥ 20 bar), high temperature (> 373 K), and pH-adjusted carrier solutions. To overcome such obstacles, the fabrication of alkaline earth oxides impregnated into an amorphous glass structure have been recently developed. They show enhanced rates of dissolution of alkaline earth metal ions and carbonation reaction due to the loosely packed glass structure and the generation of a surface coating silica gel, consequently facilitating CO2 capture under mild conditions. In this presentation, we report the synthesis and application of a crystallized glass tailored by controlled heat treatment for CO2 capture under mild conditions. The controlled heat treatment of an alkaline earth oxide-containing glass gives rise to a structural transformation from amorphous to crystalline. The structural characterizations and CO2 capture performance, including CO2 capacity, carbonation reaction rate, and the dissolution rate of alkaline earth metal ion, were analyzed to reveal the impact of controlled heat treatment and phase transformation.

The physicochemical similarities of hydrogen isotopes have made their separation a challenging task. Conventional methods such as cryogenic distillation, Girdler sulfide process, chromatography, and thermal cycling absorption have low separation factors and are energy-intensive. To overcome these limitations, research has focused on kinetic quantum sieving (KQS) and chemical affinity quantum sieving (CAQS) effects for selective separation of hydrogen isotopes. Porous materials such as metal-organic frameworks (MOF), covalent organic frameworks (COF), zeolites, carbon, and organic cages have been studied for hydrogen separation. This study have the literature review for previous research on D2/H2 adsorption and analyzes the D2/H2 adsorption behaviors of hydrogen isotopes for various zeolite using BET at 77 K. The study predicts the D2/H2 adsorption selectivity based on the results obtained with BET. These hydrogen isotope adsorption fundamentals provide a foundation for future processes for tritium separation.

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.

Metakaolin-based geopolymers have shown promise as suitable candidates for 14C immobilization and final disposal. It has been shown that the physicochemical properties of metakaolin wasteforms meet, and often far exceeding, the strict compression strength and leaching acceptance criteria of the South Korea radioactive waste disposal site. However, it is not possible to analyze and characterize the internal structure of the geopolymer wasteform by conventional characterization techniques such as microscopy without destruction of the wasteform; an impractical solution for inspecting wasteforms destined for final disposal. Internal inspection is important for ensuring wastes are homogenously mixed throughout the wasteform and that the wasteform itself does not pose any significant defects that may have formed either during formulation and curing or as a result of testing prior to final disposal. X-ray Computed Tomography (XCT) enables Non-Destructive Evaluation (NDE) of objects, such as final wasteforms, allowing for both their internal and external, characterization without destruction. However, for accurate quantification of an objects dimensions the spatial resolution (length and volume measures) must be know to a high degree of precision and accuracy. This often requires extensive knowledge of the equipment being used, its precise set-up, maintenance and calibration, as well as expert operation to yield the best results. A spatial resolution target consists of manufactured defects of uniformed dimensions and geometries which can be measured to a high degree of accuracy. Implementing the use of a spatial resolution target, the dimensions of which are known and certified independently, would allow for rapid dimensional calibration of XCT systems for the purpose of object metrology. However, for a spatial resolution target to be practical it should be made of the same material as the intended specimen, or at least exhibit comparable X-ray attenuation. In this study, attempts have been made to manufacture spatial resolution targets using geopolymer, silica glass, and alumina rods, as well as 3D printed materials with varying degrees of success. The metakaolin was activated by an alkaline activator KOH to from a geopolymer paste that was moulded into a cylinder (Diameter approx. 25 mm). The solidified geopolymer cylinder as well as both the silica glass rod and alumina rod (Diameter approx. 25 mm) we cut to approximately 4 mm ± 0.5 mm height with additional end caps cut measuring 17.5 mm ± 2.5 mm height. All parts were then polished to a high finish and visually inspected for their suitability as spatial resolution targets.

Hydrogen isotopes (H, D, T) separation technologies have received great interest for treatments of tritiated liquid waste produced in Fukushima. In addition, the separated deuterium and tritium can be utilized in various industries such as semiconductors and nuclear fusion as expensive and rare resources. However, separating hydrogen isotopes in gas and liquid forms still requires energyintensive processes. To improve efficiency and performance of hydrogen isotope separation, we are developing water electrolysis, cryosorption, distillation, isotope exchange, and hydrophobic catalyst technologies. Furthermore, an analytical method is studied to evaluate the separation of hydrogen isotopes. This presentation introduces the current status of hydrogen isotope research in this research group.

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.

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.

Facing the decommissioning era of nuclear facility, it is necessary to develop technology for treating wastewater containing nuclides. Among variety of nuclides, Cs/Sr/Co are the major nuclides considering quantity and radioactivity. In this presentation, we report the performance of nanofiltration and reverse osmosis membranes for nuclides separation. Reverse osmosis membranes have quite effective for the separation of Cs, Sr, and Co. Rejection is above 93% for single component and even higher for mixed nuclides separation, > 98%. This study indicates that polymeric membranes can be potential candidate for nuclides separation.

본 연구는 고온 열분해를 통한 Cs, Sr 등 고방사성핵종의 고정화를 위하여 각각 Cs이 흡착된 CHA (K형 Chabazite zeolite)-Cs, CHA-PCFC (potassium cobalt ferrocyanide)-Cs 및 Sr이 흡착된 4A-Sr, BaA-Sr 등의 제올라이트 계에서 TGA 및 XRD에 의한 배소 온도 변화에 따른 상변환을 고찰하였다. CHA-Cs 제올라이트 계의 경우 900℃ 까지는 CHA-Cs의 형태를 유지하고 있으며, 1,000℃에서 무정형 단계를 거친 후 1,100℃에서 pollucite (CsAlSi2O6)로 재결정 되었다. 반면에 CHA-CFC-Cs 제올라이 트 계는 700℃ 까지는 CHA-PCFC-Cs 형태를 유지하고 있으나, 900∼1,000℃ 사이에서 구조가 파괴되어 무정형으로 상변환 된 후 1,100℃에서 pollucite로 재결정 되었다. 한편 4A-Sr 제올라이트 계의 경우 700℃ 까지는 4A-Sr의 구조를 유지하고 있 으며, 800℃에서 무정형으로 상변환 된 다음 900℃에서는 Sr-feldspar (SrAl2Si2O8, hexagonal)으로, 1,100℃에서 SrAl2Si2O8 (triclinic)로 재결정 되었다. 그러나 BaA-Sr 제올라이트 계의 경우는 500℃ 이하부터 구조가 파괴되기 시작하여 500∼900℃ 에서 무정형 단계를 거친 후, 1,100℃에서 Ba/Sr-feldspar (Ba0.9Sr0.1Al2Si2O8 및 Ba0.5Sr0.5Al2Si2O8 공존)로 재결정 되었다. 상기 제올라이트 계 모두 온도 증가에 따라 탈수/(분해)→ 무정형→ 재결정의 단계를 거쳐 광물상으로 재결정 되었으며, 고온 열 분해 과정에서의 Cs 및 Sr의 휘발성, 침출성 등의 추가 연구가 요구되지만 각 제올라이트 계에 흡착된 Cs 및 Sr은 pollucite나 Sr-feldspar, Ba/Sr-feldspar 등으로 광물화 하여 Cs과 Sr을 배소체/(고화체) 내에 완전히 고정화 시킬 수 있을 것으로 보인다.

Heavy metal ion separation of commercial polymeric membranes is investigated to elucidate the permeation mechanism and possibility on applying treatment of wastewater from various origins. Since wastewater contains significant amount of heavy metal ions, their treatment to recycle or reuse is necessary. Polyamide based commercial membranes are prepared to test their separation performance on single- & multi-component heavy metal aqueous solutions. This study indicates that polymeric membranes can be potential candidate for heavy metal separation.