Radioactive contamination of soil on the site of a nuclear facility has a characteristic that radioactive nuclides are adsorbed into the pores between soil particles, making it quite difficult to decontaminate. For this reason, research on the development of various decontamination processes is being actively conducted. In this study, among various decontamination studies, a soil decontamination process using supercritical carbon dioxide was presented. The decontamination process uses supercritical carbon dioxide as the main solvent, which has a higher penetration power than other materials. Therefore, the process consists of the process of desorbing and extracting the target radionuclides between particles of soil. However, since nuclides exist as ions in the soil, polar chelating ligand material was introduced as an additive to nonpolar supercritical carbon dioxide for smooth chemical reactions in the soil. Thereafter, from the viewpoint of improving process continuity and efficiency, an alcohol material was introduced as an auxiliary solvent for liquefaction of chelating ligand in a solid state. Through prior research on the selection of a solvent for liquefaction of chelating ligand, ethanol and 2-propanol were finally selected based on whether the chelating ligand was dissolved. However, if the auxiliary solvent in which the chelating ligand is dissolved is to be combined with radionuclides in the soil, it must first be well dissolved in supercritical carbon dioxide, the main solvent. Therefore, in this study, the solubility of ethanol and 2-propanol in supercritical carbon dioxide was measured and the suitability was evaluated. The temperature conditions were carried out at 40°C, the same as the previously designed decontamination process, and the measurement was conducted by adjusting the pressure and volume through a syringe pump and a variable volume device. In addition, solubility was measured based on the observation of the ‘cloud point’ in which the image becomes cloudy and then bright. As a result of the experiment, several solubility points were measured at a pressure of 150 bar or less. If the flow rate ratio of supercritical carbon dioxide and auxiliary solvent derived from the results is applied to the soil decontamination process, it is expected that the process efficiency will increase in the future.

Korea faces decommissioning the nation’s first commercial nuclear power plant, the Kori-1 and Wolseong-1 reactors. In addition, other nuclear power plants that will continue to operate will also face decommissioning over time, so it is essential to develop independent nuclear facility decommissioning and site remediation technologies. Among these various technologies, soil decontamination is an essential not only in the site remediation after the decommissioning of the highly radioactive nuclear facility, but also in the case of site contamination caused by an accident during operation of the nuclear facility. But the soil, which is a porous material, is difficult to decontaminate because radionuclides are adsorbed into the pores. Therefore, with the current decontamination technology, it is difficult to achieve the two goals of high decontamination efficiency and secondary waste reduction at the same time. In this study, a soil decontamination process with supercritical carbon dioxide as the main solvent was presented, which has better permeability than other solvents and is easy to maintain critical conditions and change physical properties. Through prior research, a polar chelating ligand was introduced as an additive for smooth extraction reaction between radionuclides present as ions in soil and nonpolar supercritical carbon dioxide. In addition, for the purpose of continuity of the process, a candidate group of auxiliary solvents capable of liquefying the ligand was selected. In this research evaluated the decontamination efficiency by adding the selected auxiliary solvent candidates to the supercritical carbon dioxide decontamination process, and ethanol with the best characteristics was selected as the final auxiliary solvent. In addition, based on the decontamination effect under a single condition of the auxiliary solvent found in the Blank Test process, the possibility of a pre-treatment leaching process using alcohol was tested in addition to the decontamination process using supercritical carbon dioxide. Finally, in addition to the existing Cs and Sr, the possibility of decontamination process was tested by adding U nuclides as a source of contamination. As a result of this research, it is expected that by minimizing secondary waste after the process, waste treatment cost could be reduced and the environmental aspect could be contributed, and a virtuous cycle structure could be established through reuse of the separated carbon dioxide solvent. In addition, adding its own extraction capacity of ethanol used for liquefaction of solid-phase ligands is expected to maximize decontamination efficiency in the process of increasing the size of the process in the future.

As the number of nuclear power plants whose design life has expired worldwide increases, the attempts are continuing to complete the project of nuclear back-end cycle, the last task of the nuclear industry. Decontamination is essential in the process of dismantling nuclear facilities and restoration sites to remove all or some of the regulatory controls from an authorized facility. Among radioactive wastes, particularly contaminated soil is characterized by difficult physical decontamination because radionuclides are adsorbed between soil particles, that is, pores. Therefore, chemical decontamination is mainly used, which has the disadvantage of generating a lot of secondary waste. In order to overcome these disadvantages, an eco-friendly soil decontamination process is being developed that can drastically reduce the amount of secondary waste generated by using supercritical carbon dioxide. Supercritical carbon dioxide can easily control its physical properties and has both liquid and gas properties. However, since supercritical carbon dioxide is non-polar, additives are needed to extract polar metal ions, which are the goal of decontamination. Therefore, ligand with both CO2-philic and metal binding regions was selected. In previous studies, the decontamination efficiency of soil was evaluated by reacting contaminated soil with solid ligand and co-ligand at once. When solid ligands were used, the decontamination efficiency was lower than expected, which was expected because chemical substances were somewhat difficult to exchange in the closed process. In this study, in order to increase the efficiency of the decontamination process, the need for a process of liquefying ligand and continuously flowing it has been raised. Therefore, a co-solvent that dissolves well at the same time in SCCO2, ligand, and co-ligand was selected. In the selection process, a total of eight substances were selected by dividing into six polar substances and two non-polar substances through various criteria such as economic feasibility, eco-friendliness, and harmlessness. Thereafter, ethanol was finally selected through solubility evaluation for SCCO2 and additives. It is expected that a more effective decontamination process can be constructed when the additive is liquefied using a solvent selected from the results of this study.

Today, the domestic and international nuclear power industry is experiencing an acceleration in the scale of the nuclear facility decommissioning market. This phenomenon is also due to policy changes in some countries, but the main reason is the rapid increase in the proportion of old nuclear power plants in the world, mainly in countries that introduced nuclear power plants in the early stages. Decontamination is essential in the process of decommissioning nuclear facilities. Among various decontamination targets, radionuclides are adsorbed between pores in the soil, making physical decontamination quite difficult. Therefore, various chemical decontamination technologies are used for contaminated soil decontamination, and the current decontamination technologies have a problem of generating a large amount of secondary wastes. In this study, soil decontamination technology using supercritical carbon dioxide is proposed and aimed to make it into a process. This technology applies cleaning technology using supercritical fluids to decontamination of radioactive waste, it has important technical characteristics that do not fundamentally generate secondary wastes during radioactive waste treatment. Supercritical carbon dioxide is harmless and is a very useful fluid with advantages such as high dissolution, high diffusion coefficient, and low surface tension. However, since carbon dioxide, a non-polar material, shows limitations in removing polar and ionic metal wastes, a chelating ligand was introduced as an additive. In this study, a ligand material that can be dissolved in supercritical carbon dioxide and has high binding ability with polar metal ions was selected. In addition, in order to increase the decontamination efficiency, an experiment was conducted by adding an auxiliary ligand material and ultrasonic waves as additives. In this study, the possibility of liquefaction of chelating ligands and auxiliary ligands was tested for process continuity and efficiency, and the decontamination efficiency was compared by applying it to the actual soil classified according to the particle size. The decontamination efficiency was derived by measuring the concentration of target nuclides in the soil before and after decontamination through ICP-MS. As a result of the experiment, it was confirmed that the liquefaction of the additive had a positive effect on the decontamination efficiency, and a difference in the decontamination efficiency was confirmed according to the actual particle size of the soil. Through this study, it is expected that economic value can be created in addition to the social value of the technology by ensuring the continuity of the decontamination process using supercritical carbon dioxide.

본 연구에서는, 유기용매를 사용하지 않는 친 환경적인 건식 공정과 초임계 공정을 이용한 Thin-multiwalled carbon nanotube (TWNTs)/아민계 에폭시 첨가제의 복합체 제조에 관하여 연구를 하였다. 제조된 TWNTs/아민계 에폭시 첨가제의 복합체는 우레탄기반의 비스페놀 A 타입의 에폭시 레 진의 경화제로 사용하였다. TWNTs/아민계 에폭시 첨가제의 복합체를 경화제로 사용하여 제조된 에폭 시 레진의 열적 성질을 Dynamic mechanical analysis (DMA)를 이용하여 분석 하였으며, 메트릭스상의 carbon nanotube 의 높은 분산성은 SEM을 통하여 확인 하였다. 그 결과, 초임계 공정을 이용하여 제 조된 에폭시 레진의 열적 성질과 매트릭스내의 carbon nanotube 분산성이 건식 공정을 사용 하였을 때 보다 더욱 증가된 결과를 확인 할 수 있었다

최근 자원과 에너지를 절약하고 효과적으로 사용하여 환경 훼손을 줄이고 청정에너지를 이용할 수 있는 기술의 연구가 활발하게 진행되고 있다. 이와 관련 하여, 친환경적이고 경제적이며 독성이 거의 없는 초임계 유체가 물질의 합성과 프로세스에 많이 응용되고 있다. 이산화탄소는 낮은 임계온도와 압력, 가격 경쟁력 그리고 무독성 등의 장점을 가짐으로써 초임계 공정에 많이 사용되고 있는 용매 중에 하나이다. 그러나 분자량이 높은 고분자들에게는 낮은 용해력이 단점으로 있어서 사용에 제한적이다. 따라서, 분자량이 높은 고분자를 용해하기 위해선 하이드로카본 계열의 용매를 사용하여야 한다. 본 연구에서는, 초임계 유체를 이용하여 Poly (methyl methacrylate)/클레이 나노 복합체 제조에 관한 연구를 진행 하였다. 또한, 초임계 유체 내에서 분산성을 극대화 할 수 있도록 Na+-MMT 클레이 표면을 플로린 계열의 surfactant로 개질 시키어 복합체 제조에 응용 하였다. 개질된 클레이를 이용하여 제조 된 복합체는 neat Poly (methyl methacrylate)보다 향상된 기계적, 열적 특성을 보였으며, 제조 된 복합체는 X-ray 회절 방법, 열적 안정성 그리고 TEM 으로 나노 클레이의 분산성을 분석 하였다.

최근 낮은 표면장력, 높은 확산계수, 가스와 같은 낮은 점도, 그리고 액체와 유사한 밀도를 갖는 초임계 유체의 장점을 이용하여 여러 가지 물질의 합성이나 응용 공정에 초임계 유체를 이용하고 있다. 초임계 유체를 이용하여 복합체 제조 시 기존의 용융공정에 비해서 분자들의 움직임이 활발하게 이루어 질 수 있어서 물성의 향상을 기대할 수 있다. 또한 클레이가 고농도로 함유된 마스터 배치를 쉽게 제조할 수 있으며, 기존의 유기 용매를 사용하여 복합체를 제조할 때보다 잔존 용매를 쉽게 제거할 수 있다는 장점을 가지고 있다. 따라서 본 연구에서는 이러한 초임계 이산화탄소를 이용하여 폴리에틸렌옥사이드/클레이 나노복합체를 제조하였다. 또한 본 연구의 목적은 초임계 상태에서 분자들의 활발한 움직임을 기대할 수 있으므로 고분자가 용해되고 클레이 층상으로 효과적으로 삽입되어 복합체의 열적 특성 및 다른 여러 가지 물성을 증가시키는 데 있다. 복합체 제조 후 XRD, TGA, 그리고 DSC를 이용하여 복합체의 특성을 분석 했다. 그 결과 용융방법으로 제조한 복합체보다 열 안정성이 향상되었으며, 클레이 층상 거리도 더 많이 벌어짐을 확인할 수 있었다.

본 연구에서는 초임계 CO2 추출법을 이용하여 공정변수가 대두유의 수율에 미치는 영향과 초고압 처리가 초임계 추출에 미치는 영향에 대하여 분석하였다. RSM 실험법을 통한 최적화 실험에서 468.18 bar, 80.23oC, 46.82 g/min의 조건에서 최대값 25.88%를 나타내었다. 초임계 추출법의 최적추출조건에서 초고압 전처리 후 추출 수율은 17.15-23.66%로 전처리 전보다 감소하는 경향을 나타내었다. 462.13MPa, 1분의 추출조건에서 정상점은 최대값으로 24.91%가 예측되었다. 초고압 전처리 후 초임계 추출에서 수율이 증가하지 않은 이유는 초고압 전처리시 입자의 뭉침현상이 일어나 평균입자크기가 증가하여 나타난 현상으로 추론하였다. 결과적으로 초고압 전처리는 초임계 추출 수율 증가에 영향을 미치지 못하는 것을 알 수 있었다. 초임계 CO2 추출법을 이용하여 대두유를 추출할 경우 추출 압력, 유량이 높을수록 추출온도가 낮을수록 더 많은 양의 대두유를 추출할 수 있다.

유기용매와 초임계유체를 사용하여 대두분말에서 지방성분을 추출하는 공정에서 분말화공정(분쇄)의 시간의 변화에 따른 입자도와 초고압처리에 의한 추출속도를 측정하였다. 대두분말의 입자가 작을수록 추출속도가 향상되었으면 이는 입자의 크기가 작아짐에 따라 전체적인 표면적이 증가하여 고-액추출에서 중요한 반응기작인 물질전달속도를 증가시켰기 때문이라 판단된다. 초고압공정을 적용 시 동일한 입자크기에서 추출속도가 현저히 향상되었으며 이는 대두분말 내부에서 발생하는 확산현상에 대한 저항이 초고압상태에서의 변화로 감소되었기 때문이라 사료된다. 초임계유출에 의한 추출은 수율이 낮은 단점이 있으나 입자의 크기가 큰 상태에서는 초고압처리를 전처리로 사용할 경우 시간당 추출량을 상당부분 증가시킬 수 있음을 보여주었으나, 입자크기가 작을 경우 초고압처리가 영향을 미치지 못함을 보여주었다.

초임계 유체 추출 공정을 이용하여 참깨에서 hydrocarbon류를 검출하여 참깨의 방사선 조사 여부 검지 전처리 기술에 활용하고자 하였다. 참깨를 2 kGy의 감마선을 조사하여 hexane으로 지방을 추출한 용매 추출과 초임계 유체 추출을 이용하여 추출한 지방을 Florisil column으로 분리한 후 hydrocarbon류를 GC-MS로 분석하였다. 용매 추출에서와 같이 초임계 유체 추출 공정을 이용하여 검출된 hydrocarbon류은 동일하게 검지되었으며 그 marker로써 활용 가능한 hydrocarbon류인 16:3, 17:2, 16:2, 17:1은 비조사 참깨에서는 검출되지 않았다. 보조 용매를 사용한 초임계 추출 공정에서 각 보조용매에서 추출된 지방량은 용매 추출보다 많았으며 보조용매를 사용하여 검출된 hydrocarbon류의 검출량은 methanol을 제외하고 전반적으로 많이 검출되었다. 특히 acetone의 경우 marker로 사용가능한 hydrocarbon류는 용매 추출에서보다 3-4배 정도, CO2만을 사용한 초임계 유체 추출 공정에서 보다 거의 2배의 검출 특성을 보여주었다. 이러한 결과는 초임계 유체 추출 공정이 방사선 조사 여부 검지 기술에 있어서 기존의 용매 추출에 비해 지방 추출시 용매 소모량의 감소, hydrocarbon류의 검출량 증가 등의 이유로 hydrocarbon류의 검지 기술에 있어 전처리 기술로 활용 가능하리라 사료된다.

The purpose of the present study is to investigate the method decreasing debinding time as well as lowering operation condition than pure supercritical debinding by using cosolvent or binary mixture of propane + . First method is to add cosolvent, such as n-hexane, DCM, methanol, 1-butanol, in supercritical . In case of adding cosolvent, we were found the addition of non-polar cosolvent (n-hexane) improves dramatically the binder removal rate (more than 2 times) compared with pure supercritical debinding, second method is to use mixture of supercritical propane + , as solvent. In case of using mixture of supercritical propane + , the rate of debinding speeded up with increasing of pressure and concentration of propane at 348.15 K. It was found that addition of cosolvent (e.g., n-hexane, DCM) and binary mixture propane + for supercritical solvent remarkably improved binder removal rate for the paraffin wax-based binder system, in comparison with using pure supercritical .

본 연구에서는 resorcinol과 formaldehyde를 이요하여 수상에서 축중합시켜 겔을 만든 후 저온 초임계 건조 공정을 이용하여 겔 구조의 변형없이 용매를 제거하여 내무 표면적과 같은 에어로겔의 최종 물성에 미치는 영향을 알아보기 위하여 고형분의 농도(2-5%)를 변화시켜 실험한 결과 초기 반응조건이 반응시간 및 최종물성에 변수가 됨을 알 수 있었다. 또한 제조된 에어로겔에 100-300˚C까지 온도를 가하며 표면 특성을 분석한 결과 열을 가함에 따라 기공의 크기가 커지고 표면적이 감소됨을 관찰할 수 있었다.

Recently biodiesel has drawn much attraction as renewable enegy due to its environmental benefits and the fact that it is made from renewable resources. However, the production cost of biodiesel is one of the main hurdle to commercialize it. One of the way to reduce the biodiesel production cost is to use the waste cooking oil as feedstock. In the conventional transesterification process of waste cooking oils for biodiesel production, the presence of free fatty acids and water causes severe problems such as formation of soap and decreasing of catalyst yield. Much effort has been devoted to solve the above problems and one of the promising way is the supercritical methanol treatment which is performed at the methanol supercritical environment (>239.45℃, >8.10 Mpa)one of the serious problems of the application of SCM process for the biodiesel production is the tough operation condition(high pressure, high temperature. In this study, we have studied about the supercritical methanol treatment for the biodiesel production with the soybean waste cooking oil as a feedstock in the present of various heterogeneous solid catalysts such as mesoporous silica and acid-doped mesorpous silica. Biodiesel conversion was increased at more mild opreation condition to the previous studies by using the catalysts. The conversion was more enhanced by modifying the catalysts.

An experimental study on the preparation of monolithic porous polymers by environmentally friend process in supercritical carbon dioxide has been carried out. Polymerization mixture composed of a cross-linking monomer, initiator and functional co-polymer was charged in the reactor with sapphire window. After the system was purged with a flow of CO2 for 15 min, the reactor was pressurized with liquid CO2 up to 100 bars. The reactor was isolated from and placed back to the system via quick connector for shaking until the mixture had become fully homogeneous. The reactor was then heated and pressurized to the required reaction conditions and left overnight. After cooling and CO2 evacuation, the polymer was removed from the reactor as dry, white, continuous monoliths. The effect of experimental conditions on the physical properties of porous polymer was systematically examined, and it was found that monomer content had a major effect on the physical properties of the polymers.