The removal of cesium (Cs) from contaminated clay minerals is still a challenge due to the limited efficiency of the process. Thus, this study aimed to enhance the removal for Cs+ ions during the conventional acid washing process by incorporating a bead-type adsorbent. Polyacrylonitrile-based nickel potassium hexacyanoferrate (NiFC-PAN) was utilized as the Cs adsorbent to selectively adsorb Cs+ ions in a strongly acidic solution that contained competing ions. To enable easy separation of clay particles and protect the adsorbent from harsh environmental conditions, PAN was deliberately constructed as large beads. The synthesized adsorbent (NiFC/PAN in a 2:1 ratio) displayed high selectivity for Cs+ ions and had a maximum capacity of 162.78 mg/g for Cs+ adsorption in 0.5 M HNO3 solution. Since NiFC-PAN exhibited greater Cs selectivity than the clay mineral (hydrobiotite, HBT), adding NiFC-PAN during the acid washing substantially increased Cs desorption (73.3%) by preventing the re-adsorption for Cs+ ions on the HBT. The acid treatment in the presence of NiFCPAN also significantly decreased the radioactivity of 137Cs-HBT from 209 to 27 Bq/g, resulting in a desorption efficiency of 87.1%. Therefore, these findings suggest that the proposed technique is a potentially useful and effective method for decontaminating radioactive clay.

The behaviors of various desorption agents were investigated during the desorption of cesium (Cs) from samples of clay minerals and actual soil. Results showed that polymeric cation exchange agents (polyethyleneimine (PEI)) efficiently desorbed Cs from expandable montmorillonite, whereas acidic desorption solutions containing HCl or PEI removed considerable Cs from hydrobiotite. However, most desorption agents could desorb only 54% of Cs from illite because of Cs’s specific adsorption to selective adsorption sites. Cs desorption from an actual soil sample containing Cs-selective clay mineral illite (< 200 μm) and extracted from near South Korea’s Kori Nuclear Power Plant was also investigated. Considerable adsorbed 137Cs was expected to be located at Cs-selective sites when the 137Cs loading was much lower than the sample’s cation exchange capacity. At this low 137Cs loading, the total Cs amount desorbed by repeated washing varied by desorption agent in the order HCl > PEI > NH4+, and the highest Cs desorption amount achieved using HCl was 83%. Unlike other desorption agents with only cation exchange capabilities, HCl can attack minerals and induce dissolution of metallic elements. HCl’s ability to both alter minerals and induce H+/Cs+ ion exchange is expected to promote Cs desorption from actual soil samples.

Prussian blue is known as a superior material for selective adsorption of radioactive cesium ions; however, the separation of Prussian blue from aqueous suspension, due to particle size of around several tens of nanometers, is a hurdle that must be overcome. Therefore, this study aims to develop granule type adsorbent material containing Prussian blue in order to selectively adsorb and remove radioactive cesium in water. The surface of granular activated carbon was grafted using a covalent organic polymer (COP-19) in order to enhance Prussian blue immobilization. To maximize the degree of immobilization and minimize subsequent detachment of Prussian blue, several immobilization pathways were evaluated. As a result, the highest cesium adsorption performance was achieved when Prussian blue was synthesized in-situ without solid-liquid separation step during synthesis. The sample obtained under optimal conditions was further analyzed by scanning electron microscope-energy dispersive spectrometry, and it was confirmed that Prussian blue, which is about 9.7% of the total weight, was fixed on the surface of the activated carbon; this level of fixing represented a two-fold improvement compared to before COP-19 modification. In addition, an elution test was carried out to evaluate the stability of Prussian blue. Leaching of Prussian blue and cesium decreased by 1/2 and 1/3, respectively, compared to those levels before modification, showing increased stability due to COP-19 grafting. The Prussian blue based adsorbent material developed in this study is expected to be useful as a decontamination material to mitigate the release of radioactive materials.

본 연구에서는 고염/고방사성 폐액 내 함유된 주요 고방사성핵종인 Cs 제거를 목적으로 고효율의 복합 흡착제(potassium cobalt ferrocyanide (PCFC)-loaded chabazite (CHA)) 합성 및 이의 적용성을 평가하였다. 복합 흡착제는 Cs을 비롯한 다 른 입자를 수용할 수 있는 CHA를 지지체로 선정하였으며, CoCl2 및 K4Fe(CN)6 용액의 단계적인 함침/침전을 통해 PCFC를 CHA 세공 내에 고정화함으로써 합성하였다. 복합 흡착제의 합성 시 평균 입자크기가 10 ㎛ 이상의 CHA를 지지체로 사용할 경우, PCFC 입자는 안정적인 형태로 고정화되었다. 또한, 합성 시 복합 흡착제의 정제를 증가시키는 세척 방법을 최적화함으로써, 복합 흡착제의 물리적 안정성이 향상되었다. 최적의 합성법을 통해 얻은 복합 흡착제에 의한 Cs 흡착 시, 담수(무염 조건) 및 해수(고염 조건)에서 모두 빠른 흡착 속도를 보였으며, 염 농도와 무관하게 비교적 높은 분배계수 값(104 mL·g-1 이상)을 나타내었다. 그러므로, 본 연구에서 합성한 복합 흡착제는 CHA 및 PCFC가 각각 가지고 있는 물리적 안정성과 Cs 에 높은 선택성 등을 고려하여 촤적화한 소재이며, 고염/고방사성폐액에 함유되어 있는 Cs을 고효율로 신속하게 제거할 수 있음을 알 수 있다.

본 연구는 고방사성해수폐액에 함유되어 있는 주요 고방사성 핵종인 Cs을 제거하기 위하여 IE911 (crystalline silicotitanate) 에 의한 흡착 제거를 수행하였다. Cs의 효율적 흡착제거 및 2차 고체폐기물의 발생량을 최소화하기 위하여 IE911-Cs 흡착 은 m/V (흡착제 질량/용액 부피) 비=2.5 g/L, 흡착시간은 1 시간 정도가 효과적이었다. 이때 Cs은 약 99%, Sr은 5% 이하가 각각 흡착되었다. 또한 IE911-Cs 흡착은 Langmuir 등온식 및 유사 (pseudo) 2차 속도 식으로 표현할 수 있으며, 흡착속도상 수(k2)는 Cs의 초기농도 및 입자크기 증가에 따라 감소하는데 반하여, m/V 비, 온도 및 교반속도 증가에 따라서는 증가하고 있다. IE911-Cs 흡착의 활성화에너지는 약 79.9 kJ/mol 로, IE911-Cs 흡착이 보다 강력한 결합 형태를 이룬 화학적 흡착임 을 보여주고 있다. 그리고 음수 값의 Gibbs 자유에너지 및 엔탈피는 IE911-Cs의 흡착반응이 정반응의 발열반응이고, 저온에 서 반응이 상대적으로 활발함을 의미하며, 음수 값의 엔트로피는 흡착된 Cs이 IE911에 균일하게 정렬되어 있음을 나타낸다.

This study was evaluated the applicability of the membrane filtration process (Micro Filtration (MF), nanofiltration membranes (NF), reverse osmosis (RO)) on the major radioactive substances, iodine (I-) and cesium (Cs+) using membranes produced in Korea and domestic raw water. Iodine (I-) or cesium (Cs+) in the microfiltration membrane (MF) process could not be expected removal efficiency by eliminating marginally at the combined state with colloidal and turbidity material. At the domestic raw water (lake water, turbidity 1.2 NTU, DOC 1.3 mg/L) conditions, nanofiltration membrane (NF) and reverse osmosis (RO) showed a high removal rate of about 88 ~ 99% for iodine (I-) and cesium (Cs+) and likely to be an alternative process for the removal of radioactive material.

The removal of Sr ion and Cs ion was investigated to evaluate adsorption properties by using SAN-Zeolite beads immobilized with styrene acrylonitrile (SAN). The adsorption capacities increased with the decrease of SAN/zeolite ratio (SAR) from 2.5 to 0.83. The relationship of adsorption capacity (qe) and SAR was described by experimental equation such as qe=20.88＋137.81e-1.96SAR (r2=0.9980). The adsorption kinetics of Sr ion and Cs ion with SAN-Zeolite beads were fitted well by the pseudo-second-order model. The maximum adsorption capacities of Sr ion and Cs ion calculated from Langmuir isotherm model were 66.97 mg/g and 81.97 mg/g, respectively.

PVC-Zeolite composite was prepared by immobilizing zeolite with polyvinyl chloride (PVC). The prepared PVC-Zeolite beads were characterized by using X-ray diffractometer (XRD), fourier transform infrared spectrometer (FTIR), thermo gravimetric analyzer (TGA), and scanning electron microscopy (SEM). The removal properties of Sr and Cs ions from aqueous solution were investigated in batch experiment. The removal efficiencies of Sr and Cs ions by the PVC-Zeolite beads were dependent on the initial pH of solution. The removal efficiencies sharply increased at below pH 4 and was kept constant at pH 4 or more. The adsorption kinetics of Sr and Cs ions by the PVC-Zeolite beads were fitted well by the pseudosecond- order model (r2>0.99) more than pseudo-first-order model. The maximum adsorption capacities of Sr and Cs ions calculated from Langmuir isotherm model were 39.37 mg/g and 55.87 mg/g, respectively.

The three natural zeolites collected in Yungil-gun, Kyungsangbuk-do, Korea, were analyzed by means of chemical wet methods and X-ray diffraction. The results indicated that the primary species of those zeolites were clinoptilolite mixed with heulandite, feldspar, montmorillonite, and quartz. These zeolites were chemically treated with NaOH, Ca(OH)_2, and HCl solution and their differences were also studied with X-ray diffraction method. The capabilities of removing Cs^+ and Sr^2+ ions with chemically untreated zeolites, chemically treated zeolites, and also with synthetic zeolites were compared. The effect of other cations in removing Sr^2+ ions was also studied. The experimental results showed that Cs+ and Sr^2+ ions could be removed up to 98% and 95% respectively out of 5 ppm with chemically untrearted natural zeolites. The treatment of 0.02N-Ca(OH)_2 and that of 2N-NaOH were most effective in removing Cs^+ and Sr^2+ ions, respectively. It was found that the mountaintop of Sangjung 1-dong natural zeolite treated with 2N-NaOH was most efficient in removing Sr^2+ ions mixed with other cations, compared with any other chemically treated and untreated natural zeolites in this work.