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.
Abstract Recently, the circular economy aiming at elimination of waste and the continual use of resources has attracted a lot of attentions. In the circular system, the resource recovery uses the recycled wastes as the raw material to manufacture new valuable products. This work focuses on a low-cost process, in which an activated carbon (AC) adsorbent was prepared from waste cation exchange resin by calcination and HNO3 activation hydrothermal method. Surface structure and chemistry of AC were characterized by SEM, XRD, FTIR and Boehm titration. It was found that the acid treatment could increase the number of pores and the content of oxygen-containing functional groups on AC surface. In the adsorption experiment, Methylene blue (MB) was used to assess the adsorption capacity of AC. Experimental results showed that the highest efficiency of MB removal was achieved by AC with modification of 4M HNO3, showing the acidification effect on the adsorption capacity of AC. Adsorption isotherms of Langmuir and Freundlich were employed to fit the experimental data. It was shown that MB adsorption on AC is more consistent with Langmuir model that assumes a homogeneous adsorption. In the adsorption kinetic analysis, the adsorption was found to follow the pseudo-second-order model, indicating that adsorption of MB on acidified AC is dominated by chemical adsorption. The study revealed that the waste ion-exchange resin is a proper precursor of carbon adsorbent for MB dye. This low-cost method would specifically reduce the environmental cost of waste disposal.