Formation of Na-A and -X zeolites from waste solutions in conversion of coal fly ash to zeolites

Na-A and -X zeolites were synthesized from waste solutions in conversion of coal fly ash (Fa) to zeolite. The amorphous SiO₂ and Al₂O₃ of Fa were completely dissolved to form Po, Pt, and Pc type zeolites in NaOH solutions at 85°C. Only 24% of Si⁴⁺ eluted from Fa were converted to the zeolites and the remaining waste solutions contained high Si⁴⁺ concentrations. When molar ratio SiO₂/Al₂O₃ of the waste solutions was modified at 1.0≤SiO₂/Al₂O₃≤2.0 by addition of NaOH-NaAlO₂ solutions and the solutions were agied at 85°C, a single phase of Na-A zeolite was formed. The Na-X zeolite was formed at SiO₂/Al₂O₃≥2.5 and its crystallinity was increased with increasing the SiO₂/Al₂O₃ ratio, whereas the crystallinity of Na-A zeolite was decreased. At SiO₂/Al₂O₃=7.3, a single phase of Na-X zeolite was produced.     

Selective formation of Na-X zeolite from coal fly ash by fusion with sodium hydroxide prior to hydrothermal reaction

Hydrothermal treatment of fly ash with alkali gives various types of zeolites such as Na-Pl, Na-A and hydroxysodalite, where the zeolite zone was formed like an egg white, covering the central core of fly ash particles, as evinced in the previous paper. By fusion with sodium hydroxide, most of the fly ash particles were converted into sodium salts such as silicate and aluminate, from which hydrothermal reaction without stirring favourably resulted in the formation of Na-X zeolite. Crystallinity of Na-X zeolite as high as 62% was attained at the optimum condition of NaOH/fly ash = 1.2 and a fusion temperature of 823 K. Fly ash contains 14 wt% mullite (3Al₂O₃·2SiO₂), which was revealed to be a less-active crystalline component for zeolite formation. Aluminium-enriched fly ash gave Na-A in place of Na-X zeolite. Scanning electron microscope images of cubic and octahedral crystals characteristic of Na-A and Na-X zeolite, respectively, obtained from fly ash, are given.     

Removal of heavy metals from acid mine drainage (AMD) using coal fly ash, natural clinker and synthetic zeolites

Acid mine drainage (AMD) is a widespread environmental problem associated with both working and abandoned mining operations, resulting from the microbial oxidation of pyrite in presence of water and air, affording an acidic solution that contains toxic metal ions. The generation of AMD and release of dissolved heavy metals is an important concern facing the mining industry. The present study aimed at evaluating the use of low-cost sorbents like coal fly ash, natural clinker and synthetic zeolites to clean-up AMD generated at the Parys Mountain copper-lead-zinc deposit, Anglesey (North Wales), and to remove heavy metals and ammonium from AMD. pH played a very important role in the sorption/removal of the contaminants and a higher adsorbent ratio in the treatment of AMD promoted the increase of the pH, particularly using natural clinker-based faujasite (7.70-9.43) and the reduction of metal concentration. Na-phillipsite showed a lower efficiency as compared to that of faujasite. Selectivity of faujasite for metal removal was, in decreasing order, Fe>As>Pb>Zn>Cu>Ni>Cr. Based on these results, the use of these materials has the potential to provide improved methods for the treatment of AMD.     

Coal fly ash and synthetic coal fly ash aggregates as reactive media to remove zinc from aqueous solutions

Coal fly ash (CF) and synthetic coal fly ash aggregates (SCFAs) were evaluated as low-cost reactive media for the remediation of groundwater contaminated with Zn. The SCFAs were prepared by mixing CF, sodium silicate, and deionized (DI) water. Serial batch kinetic and static tests were conducted on both CF and SCFAs, under various conditions (i.e., pH, initial Zn concentration, reaction time, and solid dosage), using Zn(NO(3))(2).6H(2)O solutions. Serial column tests were also conducted on both CF and SCFAs. The final rather than the initial pH of the solution had a greater effect on the removal of Zn. At pH>7.0, the removal of Zn was due to precipitation, whereas at <7.0, the removal of Zn was due to adsorption onto the reactive media. The removal of Zn increased with increasing dosage of the reactive medium and decreasing initial Zn concentration. The results of the column and batch tests were comparable. Preferential flow paths were observed with CF, but not SCFA. The hydraulic conductivity of CF was more significantly decreased than that of SCFA with increasing dry density of the specimen.     

Mechanical and morphological properties of fly ash/epoxy composites using conventional thermal and microwave curing methods

Conventional thermal and microwave curing methods were utilized to cure fly ash/epoxy composites, and the mechanical and morphological properties of the composites were evaluated. The conventional thermal curing was performed at 70 °C for 80 min while microwave curing was carried out at 240 W for 18 min in order to achieve the optimum cure of the composites, determined using Differential Scanning Calorimeter. The results suggested that the tensile and flexural moduli of the composites increased with increasing fly ash content while the effect became opposite for tensile, flexural and impact strengths, and tensile strain at break. Improved mechanical properties of the composite could be obtained by addition of N-2(aminoethyl)-3-aminopropyltrimethoxysilane coupling agent, the contents of 0.5 wt% being recommended for the optimum mechanical properties. Beyond these recommended contents, the mechanical properties greatly reduced, except for the flexural modulus. The comparative results indicated that the composites by the microwave cure consumed shorter cure time and had higher ultimate strengths (especially impact strength), and strain at break than those by the conventional thermal cure. The composites with higher tensile and flexural moduli could be obtained by the conventional thermal cure.     

Separation of alumina from aluminum-rich coal fly ash using NaOH molten salt calcination and hydrochemical process

Clean Technologies and Environmental Policy - High-alumina coal fly ash (CFA) is considered as an important and cheap resource of aluminum. On account of high valence aluminum often trapped in...     

A study of physico-chemical and mineralogical properties of Talcher coal fly ash for stowing in underground coal mines

This study examines the suitability of Talcher coal fly ash for stowing in the nearby underground coal mines based on their physico-chemical and mineralogical analysis. The physical properties such as bulk density, specific gravity, particle size distribution, porosity, permeability and water holding capacity etc. have been determined. From the chemical characterization it is found that the ash samples are enriched predominantly in silica (SiO₂), alumina (Al₂O₃) and iron oxides (Fe₂O₃), along with a little amount of CaO, and fall under the Class F fly ash category. In addition, the mineral phases identified in the ash samples are quartz, mullite, magnetite, and hematite. The particle morphological analysis revealed that the ash particles are almost spherical in shape and the bulk ash porous in nature. From the particle size and permeability point of view, pond ash may be considered a better stowing material than fly ash.     

A comparative study on the use of fly ash and phosphogypsum in the brick production

Over 15 million tons of fly ash (FA) and 3 million tons of phosphogypsum (PG) are produced in Turkey every year. The utilization of these industrial by-product materials is important in terms of environmental and economical issues are concerned. The main purpose of this study is to evaluate the technical possibilities of incorporating FA and PG in production of building blocks. Various mixtures were prepared by incorporating these industrial wastes by replacing clay with seven different weight proportions (0%, 5%, 10%, 15%, 20%, 25% and 30%). All specimens were fired at 1000°C peak temperature. The physical and mechanical properties of all specimens such as; unit weight, compressive strength, flexural strength, dimensional stability and water absorption values were recorded. The effect of PG incorporation on the properties of samples seems to be more dominant than the effect of FA incorporation. The test results showed that; PG incorporation increased the unit weight and mechanical strength values while lowering the water absorption values. Utilization of these wastes additives is not only for conservation of clay resources, but also an alternative solution to a difficult and expensive waste disposal problems.     

A comparative study of the MIG welding of AI/TiC composites using direct and indirect electric arc processes

Metal inert gas welding of Al-1010/TiC/50p composites was carried out on 9 mm thick square bars by applying the electric arc directly and indirectly. Three pre-heating temperatures were used, 50, 100 and 150°C but only direct electric arc (DEA) was applied at room temperature. Welds were microstructurally examined and tested under tensile load. Complete penetration was achieved using both DEA and IEA methods. Uniform welds were obtained using indirect electric arc (IEA), meanwhile broadening was observed in the upper part in DEA welds facilitated by mixture of the base material with the filler. Microstructural observations showed good lateral fusion of the parent composites, little or no dissolution of TiC by IEA and only slight dissolution by DEA, which led to TiAl _x formation during solidification. The presence of Al₄C₃ was not detected. Microhardness weld profiles revealed that the use of IEA reduces the heat affected zone (HAZ). Mechanical failure of the samples was consistently in the weld zone. Mechanical strength in IEA welds (182–186 MPa) was consistent irrespective of the pre-heating conditions and dependant only of the consumable (Al-2024). The mechanical strength of DEA welds was affected to some extent by the incorporation of the reinforcing particles into the weld region and wettability aspects inherent to the welding conditions. The use of IEA seems to be a suitable route for joining Al-based composites even when the reinforcement content is high.     

Removal of 2,4-dichlorophenol and pentachlorophenol from waters by sorption using coal fly ash from a Portuguese thermal power plant

Chlorophenols are one of the most important groups of priority pollutants, due to their high toxicity, mutagenicity and carcinogenicity. Although activated carbon has been the preferred choice for the removal of such pollutants from wastewaters, the search for cheaper alternative sorbents became common in the last years. Fly ash, a by-product from coal burning power plants, has a surface composition that may enable the sorption of specific organic compounds. Therefore, this feasibility study presents the optimization of the operating parameters of a fixed-bed column containing fly ash particles, percolated by aqueous solutions of 2,4-dichlorophenol (2,4-DCP) and pentachlorophenol (PCP) with concentrations of 1 and 100 microg/ml. Both chlorophenols were analysed by gas chromatography with electron capture detection (GC-ECD), after solid-phase microextraction (SPME), with limits of detection (LODs) of 7.28 microg/l for 2,4-DCP and 1.76 microg/l for PCP. Removal efficiencies above 99% were obtained for an initial concentration of 10 microg/ml of chlorophenols. Column saturation was achieved after 7h of continuous operation for 2,4-DCP and 10h for the PCP for feed levels of 10 microg/ml. Fly ash exhibited more affinity towards the sorption of PCP, in comparison to 2,4-DCP.     

A study on the chemical and mineralogical characterization of MSWI fly ash using a sequential extraction procedure

The presence of heavy metals in municipal solid waste incineration (MSWI) fly ash is of environmental concern due to their leaching potential in landfill environments. Sequential chemical extraction was performed on fly ash samples from a large-scale municipal solid waste incineration plant in East China. The transformation of the mineralogical species of fly ash during the sequential extraction was studied using X-ray fluorescence (XRF) and X-ray powder diffraction (XRD). The leaching behavior of heavy metals such as zinc, lead, cadmium and copper in MSWI fly ash was considered to have a dependency relationship with the components of calcium, such as aphthitalite, calcite, anhydrite and calcium aluminate or calcium aluminosilicate.     

Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal fly ash

The removal performance and the selectivity sequence of mixed metal ions (Co(2+), Cr(3+), Cu(2+), Zn(2+) and Ni(2+)) in aqueous solution were investigated by adsorption process on pure and chamfered-edge zeolite 4A prepared from coal fly ash (CFA), commercial grade zeolite 4A and the residual products recycled from CFA. The pure zeolite 4A (prepared from CFA) was synthesized under a novel temperature step-change method with reduced synthesis time. Batch method was employed to study the influential parameters such as initial metal ions concentration, adsorbent dose, contact time and initial pH of the solution on the adsorption process. The experimental data were well fitted by the pseudo-second-order kinetics model (for Co(2+), Cr(3+), Cu(2+) and Zn(2+) ions) and the pseudo-first-order kinetics model (for Ni(2+) ions). The equilibrium data were well fitted by the Langmuir model and showed the affinity order: Cu(2+) > Cr(3+) > Zn(2+) > Co(2+) > Ni(2+) (CFA prepared and commercial grade zeolite 4A). The adsorption process was found to be pH and concentration dependent. The sorption rate and sorption capacity of metal ions could be significantly improved by increasing pH value. The removal mechanism of metal ions was by adsorption and ion exchange processes. Compared to commercial grade zeolite 4A, the CFA prepared adsorbents could be alternative materials for the treatment of wastewater.     

A comparative study on heat dissipation, morphological and magnetic properties of hyperthermia suitable nanoparticles prepared by co-precipitation and hydrothermal methods

Magnetite (Fe₃O₄) nanoparticles were prepared by co-precipitation and hydrothermal methods and their phase transfer was done successfully to compare their performances in different aspects. Synthesized nanoparticles were characterized for XRD, FE–SEM, TEM, UV-Vis absorption (reflectance) spectra, magnetic hysteresis loops and a.c. magnetic field induced hyperthermia. The magnetic nanoparticles prepared by the co-precipitation method show superior performances in respect of heat dissipation capability, saturation of magnetization values and particle size when compared to those prepared by the hydrothermal method.     

A comparative study of ZnNb2O6 nanoceramics synthesized by high energy ball milling and subsequent conventional and microwave annealing

Ball-milling and subsequent conventional and microwave assisted heating processes have been applied to synthesize ZnNb₂O₆ nanoceramic. X-ray diffraction, simultaneous thermal analysis, scanning electron microscope (SEM), transmission electron microscope (TEM) and BET techniques were utilized to characterize the as-milled and annealed samples. Characterization of synthesized powders revealed that in spite of the very short heating time in the microwave process without soaking time, the powder heated at 550 °C had all physical properties similar to powders synthesized in conventional heating at the 650 °C temperature with a heating rate of 10 °C/min and a soaking time of 1 h. In addition, SEM, TEM and BET observations of synthesized powders showed that the particle size of powders lies in the nano meter range.     

A comparative study of the hydrothermal crystallization of HfO2 using DSC/TG and XRD analysis

Hydrothermal crystallization of HfO₂ from aqueous suspensions of hydrous hafnia at different pH values and temperatures were monitored using differential scanning calorimetry/thermogravimetric (DSC/TG) analyses and powder X-ray diffraction (XRD). Both techniques showed that the hydrothermal crystallization proceeded much more slowly in a neutral pH medium than in an acidic or alkaline medium. However, the rate of this process appeared to be much slower according to XRD. The results of XRD analysis indicated the presence of a certain incubation time, whereas DSC/TG analysis indicated an almost immediate start of the crystallization process. The reasons for the obtained differences were discussed. The results of phase analysis of the products of hydrothermal treatment showed that, regardless of pH, hydrous hafnia crystallized into m-HfO₂. Stabilization of a metastable cubic or tetragonal HfO₂ occurred upon adding a sufficient amount of stabilizing Na⁺ ions. It was concluded that hydrothermal crystallization of HfO₂ proceeds via a dissolution/precipitation mechanism in the whole pH range.     

Application of methods (sequential extraction procedures and high-pressure digestion method) to fly ash particles to determine the element constituents: a case study for BCR 176

Sequential extraction procedures and the high-pressure digestion method were selected to determine the element constituents of fly ash samples. Sequential extraction is one of the most useful methods used to measure the various elements from municipal solid waste incineration ash and contaminated soils. The extract from each step is analyzed using various techniques and equipment, and the results are then evaluated. In this work, a six-step extraction procedure modified from that of Tessier et al. and Wang et al. was performed and applied to the certified reference material BCR 176 (city waste incineration ash). Analyses were carried out by various techniques such as inductively coupled plasma atomic emission spectrometry (ICP-AES), inductively coupled plasma-mass spectrometry (ICP-MS), scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM/EDX), and X-ray powder diffraction (XRPD) to evaluate the characteristics of fly ash. The extraction efficiency of many elements was higher than 80%, and the relative standard deviations (RSD) for recovery of most elements were within 10%. In addition, an H(2)O(2)+HNO(3)+HF mixed acid digestion solution processed using a low-temperature evaporation procedure was selected as the optimal process for fly ash digestion. The results of this work provide information on the chemical composition, distribution, and potential mobility of the investigated elements.     

A comparative study of dip coating and spray pyrolysis methods for synthesizing ITO nanolayers by using Ag colloidal sol

Indium tin oxide (ITO) films were deposited on glass substrates by dip-coating and thermal pyrolysis methods. Sn (IV) is often used in the spray method as a precursor salt, but in this research we have employed a new procedure that uses Sn (II) and In(NO₃)₃ for preparation of transparent conductive thin films. Then, colloidal Ag was deposited on the ITO layers in order to compare the two synthesis methods, and the structural and electrical properties of the resultant films were investigated by FESEM, XRD, and four-terminal resistometry. The obtained films are polycrystalline with a preferred orientation of (200). The XRD patterns of the films indicate that in both films, the Sn phase is crystallized separately from In₂O₃. The presence of a Sn peak and the overall low intensity of XRD peaks suggest relative crystallization of ITO structure. For this reason, Ag films were deposited by dip coating method using a colloidal sol. By analyzing the XRD patterns of Ag-ITO films after eliminating the Sn peak, the increased intensity of the peaks confirmed the relatively good crystallization of the ITO films. The results show that the films with a sheet resistance as low as 2 × 10^?2 Ω·cm, which is beneficial for solar cells, were achieved.     

A comparative study on indirect determination of degree of weathering of granites from some physical and strength parameters by two soft computing techniques

Weathering has several adverse effects on the physical, mechanical and deformation characteristics of rock. However, when determining the weathering degree of rocks, some difficulties are encountered. Ideally, the weathering degree can be determined by simple test results and reliable prediction models. Considering this situation, the purpose of the present study is to construct simple and low cost weathering degree prediction models with two soft computing techniques, artificial neural networks and fuzzy inference systems. When developing these models, model results were tested against data from specimens collected from the Harsit granitoid (NE Turkey) and data published in the literature. Model inputs are porosity, P-wave velocity and uniaxial compressive strength, and model output is weathering degree. The models developed in this study exhibited high prediction performances when checked by train and test data sets. This result shows that the models developed herein can be used for indirect determination of weathering degree. The artificial neural network model requests numerical data as the input, while the fuzzy inference system model can take numerical data and expert opinion as the input. As a conclusion, the models have a high potential when determining weathering degree of a rock for various purposes.     

A direct analytical method to extract mixed‐mode components of strain energy release rates from Irwin's integral using extended finite element method

A new analytical approach, within the extended finite element framework, is proposed to compute mixed‐mode components of strain energy release rates directly from Irwin's integral. Crack tip enrichment functions in extended FEM allow for evaluation of integral quantities in closed form (for some crack configurations studied) and therefore resulting in a simple and accurate method. Several benchmark examples on pure and mixed‐mode problems are studied. In particular, we analyze the effects of high‐order enrichments, mesh refinement, and the integration limits of Irwin's integral. The results indicate that high‐order enrichment functions have significant effect on the convergence, in particular when the integral limits are finite. When the integral limits tend to zero, simpler strain energy release rate expressions are obtained, and high‐order terms vanish. Nonetheless, these terms contribute indirectly via coefficients of first‐order terms. The numerical results show that high accuracy can be achieved with high‐order enrichment terms and mesh refinement. However, the effect of the integral limits remains an open question, with finite integration intervals chosen as h ∕ 2 tending to give more accurate results. Copyright © 2013 John Wiley & Sons, Ltd.     

Biosorption of cadmium (II) and lead (II) from aqueous solutions using mushrooms: A comparative study

Sorption capacity of oyster mushroom (Pleurotus platypus), button mushroom (Agaricus bisporus) and milky mushroom (Calocybe indica) were evaluated on biosorption of heavy metals, viz. cadmium (II) and lead (II) from aqueous solutions. The optimum sorption conditions were studied for each metal separately. The desired pH of the aqueous solution was found to be 6.0 for the removal of cadmium (II) and 5.0 for removal of lead (II) for all the mushrooms. The percent removal of both the metals was found to increase with the increase in biosorbent dosage and contact time. The fitness of the biosorption data for Langmuir and Freundlich adsorption models was investigated. It was found that biosorption of cadmium (II) and lead (II) ions onto the biomass of the three mushrooms were better suitable to Langmuir than Freundlich adsorption model. P. platypus showed the highest metal uptake potential for cadmium (q_max 34.96 mg/g) whereas A. bisporus exhibited maximum potential for lead (q_max 33.78 mg/g). Milky mushroom showed the lowest metal uptake capacity for both the metals. The present data confirms that mushrooms may be used as efficient biosorbent for the removal of cadmium (II) and lead (II) ions from aqueous solution.