In order to fabricate porous mullite ceramics with controlled pore structure and improved mechanical strength, a freeze casting route has been processed using camphene mixed with tertiary-butyl alcohol (TBA) and coal fly ash/alumina as the solvent and the ceramic material, respectively. After sintering, the solidification characteristics of camphene and TBA solvent were evident in the pore morphology, i.e., dendritic and straight pore channels formed along the solidification directions of camphene and TBA ice, respectively, after sublimation. Also, the presence of microcracks was observed in the bodies sintered at 1500 oC, mainly due to the difference in solidification volume change between camphene and TBA. The compressive strength of the sintered bodies was found generally to be dependent, in an inverse manner, on the porosity, which was mainly determined by the processing conditions. After sintering at 1300~1500 oC with 30~50 wt% solid loading, the resulting mullite ceramics showed porosity and compressive strength values in ranges of 83.8~43.1% and 3.7~206.8 MPa, respectively.

석탄회를 NaOH로 용융시킨 후 수열 처리에 의하여 제올라이트 A를 합성하였다. NaOH/석탄회의 비, 용융 온도, NaAlO2의 첨가량, 수열 처리 온도 및 시간이 생성된 제올라이트의 종류와 결정도에 미치는 영향에 대하여 연구하였다. 결정도가 높은 제올라이트의 생성에 필요한 최적의 NaOH/석탄회의 중량비는 1.2, 최적의 용융 온도는 550℃이었다. 용융된 석탄회로부터 Si4+ 와 Al3+의 용출은 교반 시간의 영향을 받지 않았다. 생성된 제올라이트의 형태는 첨가한 NaAlO2의 영향을 받는 것으로 나타났다. 적은 양의 NaAlO2를 첨가하면 제올라이트 X가 생성되나 NaAlO2의 양이 증가하면 단일상의 제올라이트 A가 생성되었다. 수열처리 시간과 온도가 증가하면 제올라이트 A는 hydroxysodalite로 변화하였다. 승온 속도를 낮춰 반응 온도까지의 도달시간을 증가시키면 결정도가 좋은 제올라이트 A를 얻을 수 있었다.

석탄회는 독특한 화학조성과 광물학적 특징을 가지고 있다. 본 연구는 해안가에 위치한 영동화력발전소의 매립 호수에서 배출되는 석탄회와 주변 해수와의 반응에서 토착 미생물이 중금속 용출에 어떤 영향을 미치는지를 알아보았다. 매립 호수의 pH는 6.3-8.5로 나타났다. 본 연구를 위해 매립 호수의 세 지점을 선정하여 각 지점에서 석탄회(0.4 L)와 해수(1.6 L)가 혼합된 세 개의 시료를 채취하였다. 채취한 시료는 각각 120˚C, 2.5기압 환경하에서 멸균 처리하고, 미생물의 활동을 촉진하기 위해 글루코스를 첨가하여 배양하였으며, 나머지 하나는 자연 상태로 60일 동안 보관하면서 박테리아의 활동에 따른 지화학적 변화과정을 살펴보았다. 다른 시료와 비교하여 글루코스를 첨가한 시료에서 15일 후에 알카리도가 크게 증가하였으며, Mg, Ca, K와 같은 양이온은 글루코스를 넣은 시료에서 초기에 증가하다가 15일 이후 감소하였다. SO42-는 글루코스를 첨가한 시료에서 크게 감소하였다. 이러한 지화학적 결과는 매립 호수에 서식하는 박테리아의 활동성과 관련이 있다. 이러한 결과는 석탄회 내에 서식하는 박테리아의 특성을 이해하기 위한 기초자료로서 활용될 수 있을 것으로 판단된다.

석탄회는 독특한 화학조성과 광물학적 특성을 나타내는 것으로 알려져 있다. 석탄회의 철산화광물에는 중금속원소들이 다량 농집되어 있어서 침출이 일어나는 환경에서는 토양과 지하수 및 해양오염의 가능성이 높다. 본 연구에서는 해안가에 위치한 당진화력 발전소에서 배출하고 있는 석탄회와 주변 해수와의 반응과정에서 토착 미생물이 어떤 역할을 하는지를 알아보고자 하였다. 이를 위해 해수와 석탄회를 혼합하여 배양기에 60일 동안 보관하면서 물시료와 석탄회 시료를 분석함으로써 박테리아의 활동에 따른 광물의 상변화 및 해수의 지화학적 변화 정도를 살펴보았다. 매립호수에서 해수의 평균 pH는 8.97이다. 지화학적 변화 결과에 비추어 볼 때, 박테리아의 활동은 실험 시작 7일 이후부터 급격하게 활성화되었다. SO42-는 글루코스를 첨가한 시료에서 다른 처리방식에 비해 현저하게 감소하는 경향을 나타낸다. 매립호수에 서식하는 박테리아는 주로 Mn, Fe, Zn와 반응하여 매립호수로부터 금속이온을 제거시킬 수 있을 뿐 아니라 탄산염 광물을 형성하는 과정에서 이산화탄소를 고정시킬 수 있는 역할도 할 수 있을 것으로 기대된다.

Recycling industrial wastes such as fly ash from a coal burning heat power plant and shell from an oyster farming were investigated to prevent environment contamination as well as to enhance the value of recycling materials. In this study, the lightweight aggregates and the red bricks were fabricated from fly ashes with other inorganic materials and wastes. The starting materials of the lightweight aggregate were fly ash powder and water glass, and the compacts of these materials were heat treated at . The fabricated lightweight aggregates had low bulk density, , hence floated on the water and had the strength of 7.0-11.0 MPa and the modulus of 2900-3300 MPa which indicates it has enough strength as the aggregate. Another type of the light weight aggregate was prepared from fly ashes, shell powders and clays. The bulk density, porosity, and compressive strength of these aggregates were and 5-12 MPa, respectively. The addition of a small amount of fly ash powder prevented hydration of the light weight aggregates. The red brick was also fabricated from the fly ash containing materials. It is suitable for the brick facing of a building as it has moderate strength and low water absorption rate.

저가형 TiO2 광촉매의 개발과 광촉매의 활용범위를 확대하고자, 석탄회를 지지체로 이용하여 TiO2 광촉매를 제조하였다. 석탄회 표면에 TiO2 입자의 피복은 침전법에 의해서 수행되었다. TiO2의 공급원으로는 TiCl4수용액과 침전제로는 NH4HCO3가 사용되었다. 이들의 중화반응에 의해 석탄회 표면에 생성되는 Ti(OH)44는 300~700˚C의 열처리 과정에서 산화되었다. 여기서 생성된 TiO2의 결정구조는 anatase형을 나타내었다. 피복 TiO2의 결정립 크기는 열처리 온도의 상승에 따라 증가하였으나, NO가스의 제거능은 감소하는 경향을 보였다. TiO2피복 석탄회를 300~400˚C의 온도 범위에서 2시간 동안 열처리할 경우, TiO2의 결정립 크기는 약 9nm이었고, 질소산화물 제거율은 85~92%이었다. 또한, TiO2피복 석탄회의 백색도는 TiO2의 피복량이 증가할수록 열처리 온도가 증가할수록 상승하는 경향을 나타내었다.

Ash ball 배지의 이화학적특성과 사용배지의 염류집적 및 제거효과를 펄라이트 및 입상암면과 비교하였다. ash ball의 가비중, 진비중, 공극율은 각각 0.93 g.cm-3, 2.29 g.cm-3, 40.6%, 59.4%로서 그중 가비중은 펄라이트 및 입상암면에 비해 현저히 높았고 가공율은 낮았다. 배지의 포화수분함량(saturation moisture capacity)은 ash ball이 52%, 펄라이트가 71%, 입상암면이 90%로 나타났고, 배수 1시간 후 수분율은 ahs ball이가 21%, 펄라이트가 27%, 입상암면이 80%로 낮아졌다. Ash ball의 입도별 수분율은 소립(3~5 mm)이 대립 (7~15mm)에 비해 5% 정도 높았다. Ash ball의 배드내 수분율은 수직 및 수평방향의 분포가 균일하여 수분확산성이 좋은 것으로 나타났다. ash ball의 pH는 7.6으로 약염기성을 나타내었다. 배지를 침지한 배양액의 pH는 7.6으로 약염기성을 나타내었다. 배지를 침지한 배양액의 pH는 다소 증가하는 경향을 보였으며 EC는 거의 변호가 없었으며, 배지내 무기이온의 흡착은 ash ball과 입상암면은 인산의 흡착이 비교적 많았다. 토마토 재배에 사용된 ash ball의 염류집적은 펄라이트와 비슷하였고 8회 정도의 침수처리로 배지표면에 흡착된 무기염을 대부분 제거할 수 있었다. 위의 결과로부터, ash ball 배지는 보수력은 다소 낮지만 통기성 및 수분확산성이 우수하여 배지내의 수분조절이 용이한 배지임을 알 수 있었다.

This study was carried out to synthesis the zeolite using the bituminous coal fly ash emitted from power plant that occurs several environmental problems. In spite of fly ash has contained high content of SiO2 and Al2O3, it disposed mainly landfill. If the effective methods to recover the SiO2 and Al2O3 were developed, the fly ash could be utilized valuable raw materials. In this study, fly ash was used as raw material to synthesize the zeolite by pressurized hydrothermal reaction. Also, experimental parameters included temperature(70~110℃, and pressure(140~200 psi) of crystallization were investigated. The more crystallization pressure was increased, the more Zeolite 4A was synthesized at 70 and 90℃. Zeolite 4A of metastable phase tend to be transformed into sodalite of stable phase at 110℃.

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.

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.

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.

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.

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.

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.