본 연구에서는 Na2SO4 폐수 처리를 위한 바이폴라막 전기투석(bipolar membrane electrodialysis, BPED)에 적용하 기 위한 sulfonated poly(phenylence oxide) (SPPO) 기반 강화 양이온교환막(cation-exchange membrane, CEM)을 제조하고 그 성능을 평가하였다. 특히, 다양한 open area, opening size, 두께를 가지는 직조형 지지체를 사용하여, 지지체가 강화막의 물리 적 및 전기화학적 특성에 미치는 영향을 분석하였다. 실험 결과, open area와 opening size가 증가할수록 이오노머의 충진율 이 증가하고 이온 전도 경로가 개선되어 막의 전기적 저항이 감소하고 함수율은 증가하는 경향성을 나타내었다. 한편, OH- 이온은 함수율이 높은 조건에서 막을 통해 더 쉽게 투과하였으며, SO4 2‒ 이온은 지지체의 특성과는 상관없이 전반적으로 낮 은 투과도를 나타내었다. 또한 제조막의 특성과 산/알칼리 조건에서의 내화학성을 종합적으로 고려한 결과, polypropylene (PP)이 가장 적합한 보강재 소재로 판단되었으며, 이를 활용하여 제조한 강화막은 상용막 대비 우수한 인장강도와 구조적 안 정성을 나타내었다. 개발된 강화 CEM을 BPED에 적용한 결과, 상용막 대비 막을 통한 SO4 2‒ 누출이 현저히 억제되어 산/염 기 순도, 전류 효율, 및 에너지 효율이 향상됨을 확인할 수 있었다.

본 연구에서는 산 폐수에서 효율적인 산-금속이온 분리를 위한 전기투석 공정에 적용할 수 있는 1가 이온에 대한 높은 선택성을 가진 양이온 교환막의 제조에 관한 연구를 수행하였다. 설폰산기를 가진 sodium 4-vinylbenzenesulfonate (NaSS), 포스폰산기를 가진 vinylphosphonic acid (VPA) 단량체 및 가교제를 비대칭 구조의 다공성 지지체에 충진하고 in-situ 광중합을 통해 세공충진 양이온 교환막을 제조하였다. 제조된 세공충진 양이온 교환막은 상용막 대비 이온교환용량이 다소 낮았으나 실제 응용에 적합한 수준의 전기적 저항 및 기계적 물성을 나타내었다. 다양한 NaSS:VPA 몰 비율로 제조된 세공충진 양이온 교환막과 상용막(CSE, Astom, Japan)의 H+/Fe2+ 혼합용액에서의 선택투과도를 측정한 결과 NaSS:VPA = 25:75 조건에서 가장 우수한 선택투과도를 확인하였으며 이는 상용막 대비 10 이상 높은 값이었다. 또한 최적 조건의 제조막 을 이용한 H+/Fe2+ 혼합용액의 전기투석 결과 상용막 대비 우수한 산-금속 이온 분리 성능을 확인할 수 있었다. 이온전도성이 우수한 설폰산기와 금속이온에 대한 결합력이 강한 포스폰산을 함께 도입한 양이온 교환막은 Fe2+ 이외에도 산 폐액으로부터 다양한 유가 금속이온을 분리하는 데 효과적일 것으로 기대된다.

During the initial cooling period of spent nuclear fuel, Cs-137 and Sr-90 constitute a large portion of the total decay heat. Therefore, separating cesium and strontium from spent nuclear fuel can significantly decrease decay heat and facilitate disposition. This study presents analytical technique based on the gas pressurized extraction chromatography (GPEC) system with cation exchange resin for the separation of Sr, Cs, and Ba. GPEC is a micro-scaled column chromatography system that allows for faster separation and reduction volume of elution solvent compared to conventional column chromatography by utilizing pressurized nitrogen gas. Here, we demonstrate the comparative study of the conventional column chromatography and the GPEC method. Cation exchange resin AG 50W-X12 (200~400 mesh size) was used. The sample was prepared at a 0.8 M hydrochloric acid solution and gradient elution was applied. In this case, we used the natural isotopes 88Sr, 133Cs, and 138Ba instead of radioactive isotopes for the preliminary test. Usually, cesium is difficult to measure with ICP-OES, because its wavelengths (455.531 nm and 459.320 nm) are less sensitive. So, we used ICP-MS to determine the identification and the recovery of eluate. In this study, optimized experimental conditions and analytical result including reproducibility of the recovery, total analysis time and volume of eluents will be discussed by comparing GPEC and conventional column chromatography.

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.

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.