경북 감포지역에서 산출되는 천연 벤토나이트를 이용하여 제올라이트를 합성하였으며 세제용 builder로서 가능성을 연구하였다. 최적의 합성조건은 기질의 몰비가 SiO2/Al2O3=2, Na2O3/Al2O3=1, H2O/A12O3=30이고 90˚C에서 3시간 반응시킬 경우였고, 이 조건에서는 A형 제올라이트가 합성되는 것을 XRD를 통하여 확인하였다. 최적 조건에서 합성된 제올라이트의 이온교환능을 측정하기 위하여 경도 40˚Dh의 CaCl2용액과 30˚C에서 IS분 접촉시킨 결과 264.9mg CaO/g-zeolite 정도로 우수한 값을 나타내었다. 이 시료의 백색도는 89%이었고, 평균 입자크기는 9.95μm이었다.

경북 감포지역에서 산출되는 천연 벤토나이트를 이용하여 제올라이트 A를 합성하기 위해 반응기질의 몰비, 반응온도, 반응시간 등에 따른 최적의 합성조건을 조사하였다. 실리카원은 40%-황산용액으로 처리한 천연 벤토나이트를 사용하였고, 알루미늄원은 NaA1O₂를 합성하여 사용하였다. 반응기질의 몰비는 SiO₂ : A1₂O₃ : NaO₂ : H₂O=2 : 1 : 1 : 25와 2 : 1 : 1 : 30이었고, 60℃에서 1시간 묵힘과정을 거친 후 90, 100, 120℃에서 1, 3, 5hr반응시켰다 제올라이트 A의 최적의 합성조건은 SiO₂: Al₂O₃ : Na₂O = H₂O=2 : 1 : 1 : 30이고, 90℃에서 3hr 반응시키는 경우였고, 이 조건에서 합성된 제올라이트의 열적 성질은 79.2℃에서 층간수가 증발하였고, 503.0℃에서 결정수가 탈리되었다. 수분의 감소량은 제올라이트 중량비의 5.9%이었다.

A zeolite material (ZCH) was synthesized from coal fly ash in an HD thermal power plant using a fusion/hydrothermal method. ZCH with high crystallinity could be synthesized at the NaOH/CFA ratio of 0.9. Ion-exchanged ZCH adsorbents for ammonia removal were prepared by ion-exchanging various cation (Cu2+, Co2+, Fe3+, and Mn2+) on the ZCH. They were used to evaluate the ammonia adsorption breakthrough curves and adsorption capacities. The ammonia adsorption capacities of the ZCH and ion-exchanged ZCHs were high in the order of Mn-ZCH > Cu-ZCH ≅ Co-ZCH > Fe-ZCH > ZCH according to NH3-TPD measurements. Mn-ZCH ion-exchanged with Mn has more Brønsted acid sites than other adsorbents. The ion-exchanged Cu2+, Co2+, Fe3+, or Mn2+ ions uniformly distributed on the surface or in the pores of the ZCH, and the number of acidic sites increased on the alumina sites to form the crystal structure of zeolite material. Therefore, when the ion-exchanged ZCH was used, the adsorption capacity for ammonia gas increased.

Tl+ 이온으로 교환된 제올라이트 A (|Tl12|[Si12Al12O48]-LTA, Tl12-A) 단결정을 진공 탈수시킨 후, 623 K 에서 72시간 동안 ZrI4 (g, 6.0 × 103 Pa) 와 반응시켜, Zr,I,Tl-A (|Zr0.25I1.5Tl12|[Si12Al12O48]-LTA)를 제조하였다. 제조된 단결정의 구조는 294 K에서 단결정 X-선 회절 기술을 이용하여 Pm3m (a = 12.337(2) Å) 입방 공간군에 속함을 확인 하였고, Fo> 4σ(Fo)를 사용하여 최종 오차 인자를 R1/wR2= 0.055/0.189로 정밀화 하였다. 이 구 조에서 Tl+ 이온은 6-ring 맞은편의 3-fold 축상의 서로 다른 3개의 결정학적 위치에서 단위세포당 7.5개가 발 견되었고, 모든 8-ring 근처(단위세포당 3개)에서 3개의 결정학적 위치로 채워졌다. 그리고 단위세포당 1.5개의 Tl+ 이온은 ZrI4(g)와 반응 후 sodalite cavity 안에서 3-fold 축상을 벗어난 자리에서 골격산소 O2 및 O3와 결 합하면서 발견되었다. Zr4+ 이온은 6개의 I- 이온과 함께 8면체의 ZrI6 2- 형태로 large cavity 정중앙에 존재하 였고, 이들은 8-ring 및 6-ring 근처에 존재하고 있던 Tl+ 양이온과 3차원적으로 연결하면서 ZrI6Tl11 9+ cationic cluster을 형성하였다. 이러한 cationic cluster은 Zr,I,Tl-A의 large cavity 중에서 약 25%에만 존재하였다.

A zeolite material with a Si/Al molar ratio of 1.2 was synthesized by changing the NaOH/CFA ratio of coal fly ash (CFA) via a fusion/hydrothermal reaction in the HD thermal power plant. The change in the crystal structure of the zeolite was confirmed using XRD and SEM, and the ammonia adsorption capacities of the synthesized zeolitic materials and a commercial zeolite (Na-A zeolite) were analyzed via an ammonia temperature-programmed desorption (NH3-TPD) process. The SEM and XRD results revealed out the zeolitic materials from the coal fly ash maintained a hexagonal Linde-type crystal structure similar to that of Na-A zeolite, but the crystallinity of the synthesized zeolitic material was reduced due to impurities. The NH3 adsorption capacity, determined from the NH3-TPD analysis of was 1.122 mmol/g of the synthesized zeolitic material, which was lower than the NH3 adsorption capacity of the Na-A zeolite.

Zeolitic material, Z-Y3, was synthesized from coal fly ash (CFA) under low-alkaline conditions (NaOH/CFA ratio = 0.3 and NaOH solution concentrations of 0.0, 0.5, and 1.0 M) using a fusion/hydrothermal method. The adsorption capacities of the fabricated Z-Y3 samples for Cs and Sr ions and the desorption capacity of Na ions were evaluated. The XRD patterns of the Z-Y3 sample fabricated using a 1.0 M NaOH solution (Z-Y3 (1.0 M)) indicated the successful synthesis of a zeolitic material, because the diffraction peaks of Z-Y3 coincided with those of the Na-A zeolite in the 2θ range of 7.18-34.18. Moreover, the SEM images revealed that morphology of the Z-Y3 (1.0 M) sample, which presented zeolitic materials characteristics, consisted of sharp-edged cubes. The adsorption isotherms of Cs and Sr ions on all the fabricated Z-Y3 samples were described using the Langmuir model, and the maximum adsorption capacities of Cs and Sr were calculated to be 0.14-0.94 mmol/g and 0.19-0.78 mmol/g, respectively. The desorption of Na ions from the Cs and Sr ions adsorbed Z-Y3 samples followed the Langmuir desorption model. The maximum desorption capacities of Na ions from the Cs and Sr ions adsorbed Z-Y3 (1.0 M) samples were 1.28 and 1.49 mmol/g, respectively.

In this study, zeolitic materials were synthesized from Jeju Volcanic Rocks (JVR) using a fusion/hydrothermal method at NaOH/JVR ratios of 0.6 and 1.2. The crystallinities of the zeolitic materials at NaOH/JVR ratios of 0.6 and 1.2 were 25.5% and 59.0%, respectively. It was confirmed through the SEM image that the zeolitic materials covered the zeolite particle with a cube-shaped crystals. The Co ions adsorption by the zeolitic materials were to reach the adsorption equilibrium at 120 min. It could be better simulated in the pseudo-second order adsorption kinetic equation than in the pseudo-first order adsorption kinetic equation. The adsorption capacities (qm) of Co ions could be to estimate Langmuir isotherm better than Freundlich isotherm. The maximum adsorption capacities (qm) at NaOH/JVR ratios of 0.6 and 1.2 were 55.3 mg/g and 68.7 mg/g, respectively. It was found that there was a high correlation between the crystallinity of zeolitic materials and the adsorption capacity of Co ions adsorption.

The characteristics of ammonia-nitrogen (NH4 +-N) adsorption by a zeolitic material synthesized from Jeju scoria using the fusion and hydrothermal method was studied. The synthetic zeolitic material (Z-SA) was identified as a Na-A zeolite by X-ray diffraction, X-ray fluorescence analysis and scanning electron microscopy images. The adsorption of NH4 +-N using Jeju scoria and different types of zeolite such as the Z-SA, natural zeolite, and commercial pure zeolite (Na-A zeolite, Z-CS) was compared. The equilibrium of NH4 +-N adsorption was reached within 30 min for Z-SA and Z-CS, and after 60 min for Jeju scoria and natural zeolite. The adsorption capacity of NH4 +-N increased with approaching to neutral when pH was in the range of 3-7, but decreased above 7. The removal efficiency of NH4 +-N increased with increasing Z-SA dosage, however, its adsorption capacity decreased. For initial NH4 +-N concentrations of 10-200 mg/L at pH 7, the adsorption rate of NH4 +-N was well described by the pseudo second-order kinetic model than the pseudo first-order kinetic model. The adsorption isotherm was well fitted by the Langmuir model. The maximum uptake of NH4 +-N obtained from the Langmuir model decreased in the order of Z-CS (46.8 mg/g) > Z-SA (31.3 mg/g) > natural zeolite (5.6 mg/g) > Jeju scoria (0.2 mg/g).

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.

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.

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.

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.