Ca2+ 이온으로 부분적으로 치환된 제올라이트 A (|Ca4Na4|[Si12Al12O48]-LTA) 단결정과 Se을 가는 모세관에 넣은 후 523 K 에서 5일동안 반응을 시켜 Se이 흡착된 제올라이트 A 단결정을 합성 하였다. 이 결정의 구조는 294 K 에서 단결정 X-선 회절 기술을 이용하여 Pm3m (a = 12.2787(13) Å) 입방 공간군에 속함을 확인 하였고, Fo> 4s(Fo)를 사용하여 최종 오차 인자를 R1/wR2= 0.0960/0.3483로 정밀화 하였다. 이 구조에서는 4개의 Na+와 4개의 Ca2+ 이온이 모든 6-ring 자리에 채워져 있었으며, 이들 이온들은 모두 6-ring 맞 은편의 3-fold 축상의 결정학적 위치에서 발견되었다. Se 원자들은 뚜렷하게 서로 다른 3개의 결정학적 위 치에서 발견되었다. 단위 세포당 2개의 Se(1) 원자는 sodalite cavity 내 6-ring 맞은편 (Se(1)-Na(1) = 2.53(5) Å), 1개의 Se(2) 원자는 4-ring 맞은편 (Se(2)-O(1) = 2.76(10) Å), 그리고 1개의 Se(3) 원자는 large cavity 내 6-ring 맞은편 (Se(3)-Na(1) = 2.48(5) Å)에 각각 위치하고 있었다. 2가지 형태의 Se2 분자 (Se(1)-Se(1) = 2.37(7) or 2.90(8) Å and Se(2)-Se(3) = 2.91(5)) Å)가 sodalite cavity와 large cavity 내에서 발견되었으며, Se4와 Se8 과 같은 형태의 클러스터가 large cavity 내에 존재할 수 있었다. 이들 클러스터내 Se 원자들 사이의 거리는 기체상태의 Se2 분자내 Se 원자 사이의 거리보다 더 길게 나타났다.

Zeolite material having XRD peaks of Na-A zeolite in the 2θ range of 7.18 to 34.18 can be synthesized from the waste catalyst using a fusion/hydrothermal method. The adsorption rate of Mn ions by a commercial Na-A zeolite and the synthesized zeolitic material increased as the adsorption temperature increased in the range of 10 ~ 40℃. The adsorption of Mn ion were very rapid in the first 30 min and then reached to the equilibrium state after approximately 60 min. The adsorption kinetics of Mn ions by the commercial Na-A zeolite and the zeolitic material were found to be well fitted to the pseudo-2nd order kinetic model. Equilibrium data by the commercial Na-A zeolite and the zeolitic material fit the Langmuir, Koble-Corrigan, and Redlich-Peterson isotherm models well rather than Freundlich isotherm model. The removal capacity of the Mn ions by the commercial Na-A zeolite and the zeolitic material obtained from the Langmuir model was 135.2 mg/g and 128.9 mg/g at 30℃, respectively. The adsorption capacity of Mn ions by the synthesized zeolitic material was almost similar to that of commercial Na-A zeolite. The synthesized zeolitic material could be applied as an economically feasible commercial adsorbent.

The characteristics of heavy metal ion (Ni2+, Zn2+, and Cr3+) adsorption by zeolite synthesized from Jeju scoria using the fusion and hydrothermal method, were studied. The synthetic zeolite was identified as a Na-A zeolite by X-ray diffraction analysis and scanning electron microscopy images. The equilibrium of heavy metal ion adsorption by synthetic zeolite was reached within 60 min for Ni2+ and Zn2+, and 90 min for Cr3+. The uptake of heavy metal ions increased with increasing pH in the range of pH 3-6 and the uptake decreased in the order of Cr3+ > Zn2+ > Ni2+. For initial heavy metal concentrations of 20-250 mg/L at nonadjusted pH, the adsoption of heavy metal ions was well described by the pseudo second-order kinetic model and was well fitted by the Langmuir isotherm model. The maximum uptake of heavy metal ions obtained from the Langmuir model, decreased in the order of Zn2+ > Ni2+ > Cr3+, differing from the effect of pH on the uptake, which was mainly based on the different pH of the solutions.

콘크리트는 외부로부터 침투하는 열화 인자들의 침투에 의해 철근이 부식하고 구조재료로써의 성능이 저하된다. 발수제를 직접 도포하거나 혼입하는 방법이 연구되고 있고, 본 연구에서는 발수제의 뭉침 및 떠오름을 방지하기 위하여 다공성 재료인 제올라이트를 혼입한 발수콘크리트 개발을 위한 기초연구를 수행하였다. 제올라이트 치환율에 따른 시험체를 제작하였으며, 접촉각 측정결과 치환량과 접촉각의 크기는 비례하여 증가하는 것을 확인하였다.

A zeolitic material (Z-Y2) was synthesized from Coal Fly Ash (CFA) using a fusion/hydrothermal method under low-alkali condition (NaOH/CFA = 0.6). The adsorption performance of the prepared zeolite was evaluated by monitoring its removal efficiencies for Sr and Cs ions, which are well-known as significant radionuclides in liquid radioactive waste. The XRD (X-ray diffraction) patterns of the synthesized Z-Y2 indicated that a Na-A type zeolite was formed from raw coal fly ash. The SEM (scanning electron microscope) images also showed that a cubic crystal structure of size 1~3㎼ was formed on its surface. In the adsorption kinetic analysis, the adsorption of Sr and Cs ions on Z-Y2 fitted the pseudo-second-order kinetic model well, instead of the pseudo-first-order kinetic model. The second-order kinetic rate constant (k2) was determined to be 0.0614 g/mmol·min for Sr and 1.8172 g/mmol·min for Cs. The adsorption equilibria of Sr and Cs ions on Z-Y2 were fitted successfully by Langmuir model. The maximum adsorption capacity (qm) of Sr and Cs was calculated as 1.6846 mmol/g and 1.2055 mmol/g, respectively. The maximum desorption capacity (qdm) of the Na ions estimated via the Langmuir desorption model was 2.4196 mmol/g for Sr and 2.1870 mmol/g for Cs. The molar ratio of the desorption/adsorption capacity (qdm/qm) was determined to be 1.44 for Na/Sr and 1.81 for Na/Cs, indicating that the amounts of desorbed Na ions and adsorbed Sr and Cs ions did not yield an equimolar ratio when using Z-Y2.

In this study, zeolitic materials at Na2CO3/CFA ratio of 0.6 1.8 were synthesized from coal fly ash from a thermal power plant using a fusion/hydrothermal method. The zeolitic materials were found to have cubic crystals structure and X-ray diffraction (XRD) peaks of Na-A zeolite by XRD and SEM analysis. When the zeolitic materials were synthesized from the coal fly ash, the XRD peaks of the zeolitic materials at Na2CO3/CFA ratios of 0.9-1.8 had the same location as the XRD peaks of commercial Na-A zeolite. The XRD peaks of the Na-A zeolite (Na12Al12Si12O4827.4H2O) were confirmed in the 2θ in the range of 7.18-34.18. However, it was also confirmed that peaks of CaCO3, an impurity inhibiting synthesis of Na-A zeolite from CaO and Na2CO3 in the coal fly ash, occurred in the XRD peaks of the zeolitic materials at Na2CO3/CFA ratio of 1.5-1.8. The crystallinities of the zeolitic materials tended to increase gradually within the Na2CO3/CFA ratio range of 0.6-1.8.

This research and development analysis provides numerical analysis techniques that can be used conveniently to determining the safety of the current state and to predict the stability in the future. It also seeks to present algorithms of back analysis to develop unified management system for control, prediction, coordination, and information modeling that can reasonably handle appropriate responses to structural behavior at project sites and design changes.

The adsorption properties of Cs+ and Cu2+ ions were evaluated by using a polysulfone scoria zeolite (PSf-SZ) composite with synthetic zeolite synthesized from Jeju volcanic rocks (scoria). In order to investigate the adsorption properties, various parameters, such as pH, contact time, reaction rate, concentration, and temperature in aqueous solutions, were evaluated by tests carried out in batch experiments. The adsorption capacities of Cs+ and Cu2+ ions increased between pH 2 but achieved equilibrium at pH 4 and above. The adsorption rate increased rapidly up to the initial 24 h, after which it plateaued ; the adsorption rate then sustained at equilibrium from 48 h. The adsorption kinetics of Cs+ and Cu2+ ions were described better by the pseudo-second-order kinetic model than the pseudo-first-order kinetic model. The Langmuir model fitted the adsorption isotherm data better than the Freundlich model. The maximum adsorption capacities of Cs+ and Cu2+ ions obtained from the Langmuir model were 53.8 mg/g and 84.7 mg/g, respectively. The calculated thermodynamic parameters showed that the adsorption of Cs+ and Cu2+ ions on PSf-SZ was feasible, spontaneous and endothermic reaction.

In this study, PAN-SZ (polyacrylonitrile scoria zeolite) beads were prepared by immobilizing Na-A zeolite (SZ-A) synthesized from Jeju volcanic rocks (scoria) on the polymer PAN. FT-IR and TGA analysis results confirmed that the SZ-A was immobilized in the PAN-SZ beads. SEM images showed that the PAN-SZ beads are a spherical shape with 2 mm diameter and exhibit a porous inner structure inside the bead. The most suitable mixing ratio of PAN to SZ-A as the adsorbent for removing Sr ions was PAN/SZ-A = 0.2 g/0.3 g. The adsorption kinetic data for Cu and Sr ions were fitted well with the pseudo-second-order model. The Cu and Sr ion uptakes followed a Langmuir isotherm model and the maximum adsorption capacities at 20℃ were 84.03 mg/g and 75.19 mg/g, respectively. The amount of Sr ion adsorbed by SZ-A on the PAN-SZ beads was about 160 mg/g, which was similar to that adsorbed by SZ-A powder. Thus, the PAN-SZ beads prepared in this study are considered to be effective adsorbents for removing metal ions in aqueous solutions.

본 연구는 제올라이트 Y (Si/Al = 1.56)에서 Cs+ 이온 교환에 Ca2+ 이온의 경쟁 양이온 효과를 연구하기 위해 수행되었다. 완전히 탈수되고 부분적으로 Cs+ 이온으로 교환된 3개의 제올라이트 Y(Si/Al = 1.56)의 단결정은 혼합이온교환 용액을 사용하여 흐름법으로 제조되었으며, 전체 농도가 0.05 M인 이온교환용액의 CsNO3 : Ca(NO3)2 몰비는 1 : 1 (Crystal 1), 1 : 100 (Crystal 2) 및 1 : 250 (Crystal 3)이다. 이온교환된 단결정을 723 K에서 2일 동안 1 × 10-4 Pa로 진공 탈수시켰으며, 결정구조는 100(1) K에서 입방공간군 Fd3̅m을 사용하여 단결정 싱크트론 X선 회절법으로 해석하고 구조를 정밀화하였다. Crystal 1, 2 및 3의 단위세포당 화학식은 |Cs21Ca27|[Si117Al75O384]-FAU, |Cs2Ca36.5|[Si117Al75O384]-FAU 및 |Cs1Ca37|[Si117Al75O384]-FAU이다. 3개의 결정 모두에서, Ca2+ 이온은 D6Rs 내의 site I을 우선적으로 점유하고 있으며 나머지는 site I’, II’ 및 II를 점유하고 있다. 한편 주어진 이온교환용액의 초기 Cs+ 이온의 농도에 따라 Cs+ 이온의 분포에 중요한 차이가 관찰되었다. Crystal 1에서는 Cs+ 이온이 site II’, II, III와 III’에 위치하고 있으며, Crystal 2에서는 site II, IIIa, IIIb에 위치하고 있다. Crystal 3에서는 Cs+ 이온은 site IIIa 및 IIIb에만 위치하고 있다. 초기 Ca2+ 이온의 농도가 증가하고 Cs+ 이온의 농도가 감소에 따라 Cs+ 이온의 교환정도는 28.0에서 2.7과 1.3 %로 급격히 감소하였다.

In this study, zeolite (Z-C1) was synthesized using a fusion/hydrothermal method from coal fly ash. The morphological structures of Z-C1 were confirmed to be highly crystalline with a cubic crystal structure. Exchange capacities of Ca2+ and Mg2+ ions in a single and a mixed solution reached equilibrium within 120 min. The exchange kinetics of these ions were well predicted by the pseudo-second-order rate equation. The exchange isotherms of the Ca2+ and Mg2+ ions matched the Langmuir isotherm better than the Freundlich isotherm. The maximum cation exchange capacities (qm) obtained by the Langmuir isotherm model were 2.11 mmol/g (84.52 mg/L) and 1.13 mmol/g (27.39 mg/L) for the Ca2+ and Mg2+ ions, respectively.

The adsorption characteristics of Cu ions were studied using the zeolite Na-A synthesized from Jeju volcanic rocks. The effects of various operating parameters such as initial concentration of Cu ions, contact time, solution pH, and solution temperature were investigated in batch experiments. The adsorption of Cu ions by Na-A zeolite was fitted well by pseudo-second-order kinetics and the Langmuir isotherm model. The maximum adsorption capacity determined using the Langmuir isotherm model was 152.95 mg/g. In addition, the adsorption of Cu ions by zeolite Na-A was primarily controlled by particle diffusion model in comparison with the film diffusion model. As the temperature increased from 303 K to 323 K, ΔG˚ decreased from -2.22 kJ/mol to –3.41 kJ/mol, indicating that the adsorption of Cu ions by Na-A zeolite is spontaneous process.

기후변화에 따른 신재생에너지 사용에 대한 사회적 요구가 증가되고 있지만, 아직까지 우리나라는 전력생산의 약 40%를 석탄화력발전에 의존하고 있는 실정이다. 이에 따른 석탄재 발생량은 지난 10년간 약 2배 정도 증가하여 2015년 한해에만 약 900만톤의 석탄재가 발생하였다. 이렇게 발생된 석탄재 중 비산재는 주요성분이 Al2O3, SiO2, Fe2O3의 광물 (>95%)로 구성되어 있어, 양회용 건설재료로 많이 쓰이고 있다. 하지만, 아직까지 연간 약 200만톤의 석탄재가 매립되고 있는 실정이여서 이와관련된 여러 가지 환경오염문제들이 발생하고 있다. 본 연구에서는 국내화력발전소에서 수집한 석탄재를 이용하여 주요성분인 Al와 Si를 추출하여, 기존의 보고된 제올라이트 합성방법을 수정하여 새롭고 다양한 제올라이트로 합성하는 기술을 개발하였다. 또한, 합성된 제올라이트를 서포터로 하는 촉매를 개발하여 수내에 환경오염물질의 효과적인 제거가 가능한지 여부를 평가하였다. 본 연구의 결과들은 향후 지속적으로 발생되는 석탄재의 환경정화소재화 기술을 통해서 다양한 오염물질 분해에 적용할 수 있는 가능성을 보여준다.

In this study, zeolite (Z-C2) was synthesized using a fusion/hydrothermal method on coal fly ash (FA) discharged from a thermal power plant in the Ulsan area and then analyzed via scanning electron microscopy (SEM) and X-ray diffraction (XRD). The Z-C2 was characterized in terms of mineralogical composition and morphological analysis. The XRD results showed that its peaks had the characteristics of Na-A zeolite in the range of 2θ of 7.18~34.18. The SEM images confirmed that the Na-A zeolite crystals had a chamfered-edge crystal structure almost identical to that of the commercial zeolite. The adsorption kinetics of Cu, Co, Mn and Zn ions by Z-C2 were described better by the pseudo-second-order kinetic model more than by the pseudo-first-order kinetic model. The Langmuir model fitted the adsorption isotherm data better than the Freundlich model did. The maximum adsorption capacities of Cu, Co, Mn and Zn ions obtained from the Langmuir model were in the following order : Cu (94.7 mg/g) > Co (77.7 mg/g) > Mn (57.6 mg/g) > Zn (51.1 mg/g). These adsorption capacities are regarded as excellent compared to those of commercial zeolite.

In order to investigate the adsorption characteristics for Sr ion using the Na-X zeolite synthesized from coal fly ash, batch tests and response surface analyses were carried out. The adsorption kinetic data for Sr ions, using Na-X zeolite, fitted well with the pseudo-second-order model. The uptake of Sr ions followed the Langmuir isotherm model, with a maximum adsorption capacity of 196.46 mg/g. Thermodynamic studies were conducted at different reaction temperatures, with the results indicating that Sr ion adsorption by Na-X zeolite was an endothermic (ΔHo>0) and spontaneous (ΔGo<0) process. Using the response surface methodology of the Box-Behnken method, initial Sr ion concentration (X1), initial temperature (X2), and initial pH (X3) were selected as the independent variables, while the adsorption of Sr ions by Na-X zeolite was selected as the dependent variable. The experimental data fitted well with a second-order polynomial equation by multiple regression analysis. The value of the determination coefficient (R2=0.9937) and the adjusted determination coefficient (adjusted R2=0.9823) was close to 1, indicating high significance of the model. Statistical results showed the order of Sr removal based on experimental factors to be initial pH > initial concentration > temperature.

Cd2+ 이온으로 교환된 제올라이트 Y 단결정은 294 K에서 |Na75|[Si117Al75O384]-FAU(Na75-Y, Si/Al = 1.56)에 0.05 M인 Cd(NO3)2(pH = 3.65)수용액으로 교환하여 723 K에서 진공 탈수를 통해 준 비하였고(crystal 1) 두 번째 결정은 첫 번째 결정과 같이 준비한 뒤 294 K에서 건조된 벤젠을 72시간 동안 노출시켜 준비했다(crystal 2). 이들의 구조는 싱크로트론 X-선을 이용하여 결정학적으로 확인하 였고 Fo > 4σ(Fo)를 사용하여 최종 오차 인자를 각각 R1/wR2 = 0.040/0.121 그리고 0.052/0.168로 정 밀화하였다. Crystal 1(|Cd36H3|[Si117Al75O384]-FAU)에서 Cd2+이온은 주로 site I과 site IIa에 점유되어 있었고, 이와 더불어 site I’, II’ 그리고 site IIb에도 Cd2+ 이온이 점유되어졌다. Crystal 2(|Cd35(C6H6)24H5|[Si117Al75O384]-FAU)에서 Cd2+ 이온은 다섯 개의 결정학적 자리에 점유되었다. 24개 의 벤젠분자는 supercage 내부에서 두 개의 뚜렷한 자리에서 발견 되었다. 17개의 벤젠분자는 site IIa 에 있는 Cd2+ 이온과 면상에서 서로 상호작용하였고 supercage 안에서 3회 회전축 상에서 발견되었다. 나머지 7개의 벤젠분자는 12-ring 면상에서 골격(framework)산소들과 함께 약한 다수의 정전기적인 작용과 van der Waals 상호작용으로 안정화되어 있었다.

최근 전 세계적으로 자원 고갈의 문제에 대비한 신재생에너지 개발 및 자원순환에 대한 관심이 커지고 있다. 특히 수자원은 인간과 생태계에 밀접한 관련이 있는 자원중 하나로 수자원 순환에 대한 다양한 정책이 시행되고 있다. 그중 하수 재이용 정책으로 인해 다양한 처리법이 연구되고 있고, 전기응집 공법 또한 연구가 활발히 진행되고 있다. 전기응집은 전극에 일정전압이 가해지면 금속이 용해되어 수산화물을 생성하고 이것이 폐수 중콜로이드성 물질과 응집하여 침전되면서 오염물질을 제거한다. 전기응집은 시스템의 구성이 간단하여 조작이 쉽고, 온도나 pH에 거의 영향을 받지 않아 경제적인 장점이 있다. 하지만 전기응집 공법은 응집으로 인한 플럭을 제거해야 하며, 이는 여과로 빠르게 분리가 가능해 간단하게 처리할 수 있다. 이에 본 연구에서는 전기응집 처리수에서 발생된 플럭을 제올라이트 여과를 이용해 처리하고자 하였다. 제올라이트를 이용하여 전기응집 플럭이 제거 가능한지 알아보기 위해 탁도를 측정하여 확인한 후, 오염물질 제거에 큰 영향을 미치는 여과유량을 설정하기 위해 EBCT 변화에 따른 실험을 진행하였다. 이때 탁도 뿐만 아니라 CODcr농도와 총인농도, pH를 측정하여 최적 EBCT를 판단하고 재이용수의 수질기준에 만족하는지에 대해 알아보고자 하였다.

This study evaluates the adsorption properties of Sr ions in an aqueous solution of the synthetic zeolite (Z-Y1) prepared using coal fly ash generated from a thermal power plant. In order to investigate the adsorption characteristics, the effects of various parameters such as the initial concentrations of Sr ion, contact time, and solution pH were investigated in a batch mode. The Langmuir and Redlich-Peterson model fitted the adsorption isotherm data better than the Freundlich model. The maximum adsorption capacity of Sr ions, as determined the Langmuir model, was 181.68 mg/g. It was found that by varying the Sr ion concentration, pH, and temperature, the pseudo-second-order kinetic model describes the adsorption kinetics of the Sr ion better than the pseudo-first-order kinetic model. The calculated thermodynamic parameters of ΔH0 and ΔG0 showed that the adsorption of Sr ions on Z-Y1 was occurred through a spontaneous and an endothermic reaction. We found that the adsorption of Sr ions by Z-Y1 was more affected by pH than by temperature and Sr ion concentration.

Zeolite (FZ) prepared using coal fly ash from an Ulsan industrial complex was immobilized with polysulfone (PS) to fabricate PS-FZ beads. The prepared PS-FZ beads were characterized by scanning electron microscopy and Fourier transform infrared spectroscopy. The optimum ratio for preparing PS-FZ beads was 1 g of PS to 2 g of FZ. The removal efficiencies of Sr and Cu ions by the PS-FZ beads increased as the solution pH increased and nearly reached a plateau at pH 4. A pseudo-second-order model morel fit the adsorption kinetics of both ions by the PS-FZ beads better than a pseudo-first-order model. The Langmuir isotherm model fit the equilibrium data well. The maximum adsorption capacities calculated from the Langmuir isotherm model were 46.73 mg/g and 62.54 mg/g for the Sr and Cu ions, respectively. Additionally, the values of thermodynamic parameters such as free energy (ΔG˚), enthalpy (ΔH˚) and entropy (ΔS˚) were determined. The results implied that the prepared PS-FZ beads could be interesting an alternative material for Sr and Cu ion removal.

Zeolite (FZ), prepared from fly ash, was immobilized with polyacrylonitrile (PAN) to fabricate PAN/FZ beads. The prepared PAN/FZ beads were characterized by scanning electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The optimum ratio to prepare PAN/FZ beads was 0.3 g of PAN to 0.3 g of FZ. The diameter of the prepared PAN/FZ beads was about 3 mm. Sr and Cu ion adsorption experiments were conducted with PAN/FZ beads. A pseudo-second-order model fit the kinetic data for Sr and Cu ion adsorption by PAN/FZ beads well. The equilibrium data fitted well with the Langmuir isotherm model, and the maximum adsorption capacities were 96.5 mg/g and 74.6 mg/g for the Sr and Cu ions, respectively. Additionally, the values of thermodynamic parameters such as Gibbs free energy (ΔGo), enthalpy (ΔHo) and entropy (ΔSo) were determined. The positive values of ΔHo revealed the endothermic nature of the adsorption process and the negative values of ΔGo were indicative of the spontaneity of the adsorption process.