South African Coal Fly Ash Research Articles

Surface and bulk characterization of an ultrafine South African coal fly ash with reference to polymer applications

South African coal-fired power stations produce about 25 million tons of fly ash per annum, of which only approximately 5% is currently reused. A growing concern about pollution and increasing landfill costs stimulates research into new ways to utilize coal fly ash for economically beneficial applications. Fly ash particles may be used as inorganic filler in polymers, an application which generally requires the modification of their surface properties. In order to design experiments that will result in controlled changes in surface chemistry and morphology, a detailed knowledge of the bulk chemical and mineralogical compositions of untreated fly ash particles, as well as their morphology and surface properties, is needed. In this paper, a combination of complementary bulk and surface techniques was explored to assess the physicochemical properties of a classified, ultrafine coal fly ash sample, and the findings were discussed in the context of polymer application as fillers. The sample was categorized as a Class F fly ash (XRF). Sixty-two percent of the sample was an amorphous glass phase, with mullite and quartz being the main identified crystalline phases (XRD, FTIR). Quantitative carbon and sulfur analysis reported a total bulk carbon and sulfur content of 0.37% and 0.16% respectively. The spatial distribution of the phases was determined by 2D mapping of Raman spectra, while TGA showed a very low weight loss for temperatures ranging between 25 and 1000°C. Individual fly ash particles were characterized by a monomodal size distribution (PSD) of spherical particles with smooth surfaces (SEM, TEM, AFM), and a mean particle size of 4.6μm (PSD). The BET active surface area of this sample was 1.52m2/g and the chemical composition of the fly ash surface (AES, XPS) was significantly different from the bulk composition and varied considerably between spheres. Many properties of the sample (e.g. spherical morphology, small particle size, thermal stability) appeared to be suitable for its applicability as filler in polymers, although the wide variation in surface composition between individual particles may challenge the development of a suitable surface modification technique. The observation that the bulk and surface compositions of the particles were so intrinsically different, strongly suggested that surface characterization is important when considering compatibility between matrices when applying fly ash as filler in polymers.

Direct synthesis of carbon nanofibers from South African coal fly ash.

Carbon nanofibers (CNFs), cylindrical nanostructures containing graphene, were synthesized directly from South African fly ash (a waste product formed during the combustion of coal). The CNFs (as well as other carbonaceous materials like carbon nanotubes (CNTs)) were produced by the catalytic chemical vapour deposition method (CCVD) in the presence of acetylene gas at temperatures ranging from 400°C to 700°C. The fly ash and its carbonaceous products were characterized by transmission electron microscopy (TEM), thermogravimetric analysis (TGA), laser Raman spectroscopy and Brunauer-Emmett-Teller (BET) surface area measurements. It was observed that as-received fly ash was capable of producing CNFs in high yield by CCVD, starting at a relatively low temperature of 400°C. Laser Raman spectra and TGA thermograms showed that the carbonaceous products which formed were mostly disordered. Small bundles of CNTs and CNFs observed by TEM and energy-dispersive spectroscopy (EDS) showed that the catalyst most likely responsible for CNF formation was iron in the form of cementite; X-ray diffraction (XRD) and Mössbauer spectroscopy confirmed these findings.

Characterization of the surface and physical properties of South African coal fly ash modified by sodium lauryl sulphate (SLS) for applications in PVC composites

The application of coal fly ash as mineral filler in polymers is hampered by the aggregation of the ash particles and a lack of interaction between the ash and polymer. Therefore surface treatment is usually performed on mineral fillers to enhance workability and compatibility between the polymer and filler. In this study, a commercially available South African coal fly ash sample was surface modified under a variety of conditions with an anionic surfactant, sodium lauryl sulphate (SLS), with the aim to alter the surface properties of the ash. The properties of the modified products were compared to those of the untreated samples by means of scanning electron microscopy (SEM), transmission electron microscopy (TEM), thermogravimetric analysis (TGA-IR), Fourier transform infrared spectroscopy (FTIR), X-ray diffraction (XRD) and X-ray fluorescence spectroscopy (XRF). A small shift of the SO stretch vibration in FTIR spectra of SLS treated fly ash is indicative of interaction between fly ash and SLS. Although the overall chemical composition of the SLS modified coal fly ash sample was not altered extensively, significant changes could be observed in its physical properties. Contact angle measurements indicated that the hydrophilic surface of untreated fly ash was rendered hydrophobic after SLS treatment. SEM and TEM results showed agglomerates on the surface of most of the fly ash spheres. Feasibility tests of using fly ash samples as filler in PVC indicated that SLS treated fly ash can successfully replace CaCO3 as filler in PVC under conditions of low filler loadings.

Distributional Fate of Elements during the Synthesis of Zeolites from South African Coal Fly Ash.

The synthesis of zeolites from South African coal fly ash has been deemed a viable solution to the growing economical strain caused by the disposal of ash in the country. Two synthesis routes have been studied thus far namely the 2-step method and the fusion assisted process. Fly ash contains several elements originating from coal which is incorporated in the ash during combustion. It is vital to determine the final destination of these elements in order to unveil optimization opportunities for scale-up purposes. The aim of this study was to perform a material balance study on both synthesis routes to determine the distributional fate of these elements during the synthesis of zeolites. Zeolites were first synthesized by means of the two synthesis routes. The composition of all raw materials and products were determined after which an overall and elemental balance were performed. Results indicated that in the 2-step method almost all elements were concentrated in the solid zeolite product while during the fusion assisted route the elements mostly report to the solid waste. Toxic elements such as Pb, Hg, Al, As and Nb were found in both the supernatant waste and washing water resulting from each synthesis route. It has also been seen that large quantities of Si and Al are wasted in the supernatant waste. It is highly recommended that the opportunity to recycle this liquid waste be investigated for scale-up purposes. Results also indicate that efficiency whereby Si and Al are extracted from fused ash is exceptionally poor and should be optimized.

Synthesis of zeolites from coal fly ash using mine waters

In this study mine waters obtained from coal mining operations in South Africa were used as a substitute for pure water during the synthesis of zeolites from South African coal fly ash. Procedures that had been optimized to produce single phase zeolite Na-P1 and X using pure water were employed independently. The use of circumneutral mine water resulted in similar quality zeolite Na-P1 and X whereas the use of acidic mine drainage led to the formation of a single phase hydroxysodalite zeolite. Since these two wastes (fly ash and mine waters) are found in close proximity to each other, this study demonstrates that they can be used to ameliorate each other and at the same time produce saleable zeolitic products that can be used to offset their costs of disposal and treatment.

Synthesis of Zeolites Na-P1 from South African Coal Fly Ash: Effect of Impeller Design and Agitation.

South African fly ash has been shown to be a useful feedstock for the synthesis of some zeolites. The present study focuses on the effect of impeller design and agitation rates on the synthesis of zeolite Na-P1 which are critical to the commercialization of this product. The effects of three impeller designs (4-flat blade, Anchor and Archimedes screw impellers) and three agitation speeds (150, 200 and 300 rpm) were investigated using a modified previously reported synthesis conditions; 48 hours of ageing at 47 °C and static hydrothermal treatment at 140 °C for 48 hours. The experimental results demonstrated that the phase purity of zeolite Na-P1 was strongly affected by the agitation rate and the type of impeller used during the ageing step of the synthesis process. Although zeolite Na-P1 was synthesized with a space time yield (STY) of 15 ± 0.4 kg d−1m−3 and a product yield of 0.98±0.05 g zeolites/g fly ash for each impeller at different agitation speeds, zeolite formation was assessed to be fairly unsuccessful in some cases due the occurrence of undissolved mullite and/or the formation of impurities such as hydroxysodalite with the zeolitic product. This study also showed that a high crystalline zeolite Na-P1 can be synthesized from South African coal fly ash using a 4-flat blade impeller at an agitation rate of 200 rpm during the ageing step at 47 °C for 48 hours followed by static hydrothermal treatment at 140 °C for 48 hours.

Thermal stability studies of zeolites A and X synthesized from South African coal fly ash

The thermal stability of zeolites A and X synthesized from coal fly ash was studied by evaluation of TGA-DTA curves obtained on increasing the tem- perature and by in-situ temperature-programmed XRD analysis. It was found that zeolites A and X were both stable up to approximately 800 C and retained their characteristic diffraction peaks up to 440 C, meaning the crystal structure was still stable. Of particular interest was that zeolite X, which has a unique hierarchical morphology, was thermally stable and was, hence, suitable for applications requiring elevated temperatures, for example catalysis and pollution control.

Waste Minimization Protocols for the Process of Synthesizing Zeolites from South African Coal Fly Ash.

Production of a high value zeolite from fly ash has been shown to be an avenue for the utilization of South African fly ash which presently constitutes a huge disposal problem. The synthesis of zeolites Na-P1 and analcime on a micro-scale has been successful and preliminary investigation shows that scale-up synthesis is promising. However, the post-synthesis supernatant waste generated contains high levels of NaOH that may constitute a secondary disposal problem. A waste minimization protocol was developed to reduce the volume of waste generated with a view to enhancing the feasibility of the scale synthesis. Series of experiments were conducted in 100 mL jacketed batch reactors. Fly ash was reacted with 5 Mol NaOH on a 1:1 mass basis during the aging step, followed by hydrothermal treatment in which ultrapure water was added to the slurry. This study shows that by re-introducing the supernatant waste into the experiments in such a way that it supplies the required reagent (NaOH) for the zeolite synthesis, zeolite Na-P1 and analcime can be synthesized. It also shows that the synthesis process can be altered to allow up to 100% re-use of the supernatant waste to yield high value zeolitic products. This study effectively constructed two protocols for the minimization of waste generated during the synthesis of zeolites from South African coal fly ash. This result could be used to establish a basis for legal and environmental aspects involved in the commission of a full-scale plant synthesizing zeolites NaP1 and analcime.

Kinetics Studies of Adsorption and Desorption of South African Fly Ash for Some Phenolic Compounds

The extent of adsorbability and desorbability of an unclassified South African coal fly ash (SACFA) from the Lethabo power plant was evaluated in the treatment of phenol, 2-nitrophenol, and 4-nitrophenol from aqueous solutions. Batch studies were performed to evaluate the effects of various experimental parameters such as adsorbent dosage, initial pH (pHo), and contact time on the removal of these three adsorbates. The adsorption isotherm indicates that the Freundlich model correctly fits the experimental data for the adsorbates better than the Langmuir model, with fly ash having the highest adsorption capacity of 6.51 × 10−2 mg/g for 4-nitrophenol, 2-nitrophenol 6.00 × 10−2 mg/g, and phenol 6.31 × 10−2 mg/g. SACFA was found to adsorb 90.2% of phenol, 88.9% of 2-nitrophenol, and 92.6% of 4-nitrophenol at an initial concentration of 20 mg/l. The desorption of the adsorbates from the surface of the fly ash was achieved using 30 ml of distilled water at 307 K. The analyses of the results obtained revealed that the desorption of 4-nitrophenol was the most difficult of the three adsorbates to be desorbed. The desorption efficiencies obtained were 17.9% for phenol, 18.8% for 2-nitrophenol, and 10.2% for 4-nitrophenol.

Adsorptive removal of various phenols from water by South African coal fly ash

South African coal fly ash (SACFA) was used to effectively remove phenol, 2-nitrophenol and 4-nitrophenol from wastewater. The rate of adsorption follows first-order kinetics before attaining equilibrium with the sorption rate (Kad) obtained being the  highest for 4-nitrophenol (p-nitrophenol) (7.0 x 10.3/h), followed by phenol (1.2 x 10.3/h) and 2-nitrophenol (o-nitrophenol) (1.0 x 10.3/h). Batch studies were performed to evaluate the adsorption process, and it was found that the Freundlich isothermeffectively fits the experimental data for the adsorbates better than the Langmuir model, with the fly ash having the highest adsorption capacity of 6.51 X 10-2 mg/g for 4-nitrophenol, 6.00 x 10-2 mg/g for 2-nitrophenol and 6.31 x10-2 mg/g for phenol. The fly ash was found to adsorb 90.2% of phenol, 88.9% of 2-nitrophenol and 92.6% of 4-nitrophenol at an initialconcentration of 20 mg/.. The desorption studies suggested that the desorption of 4-nitrophenol was the most difficult of the three adsorbates to be desorbed. The desorption efficiency was 17.9% for phenol, 18.8% for 2-nitrophenol and 10.2% for 4-nitrophenol. This work proved that SACFA can be used as an efficient adsorbent material for removal of phenol from water and wastewater.

Synthesis of Zeolite A, X and P from a South African Coal Fly Ash

Synthesis conditions for generating high quality zeolite type Na-P1, A, and X from a South African coal fly ash were identified in this study. XRF, XRD, FTIR and SEM analytical techniques were used to characterize the starting fly ash feedstock and the resulting synthesis product. Synthesis of these high quality zeolites types is expected to provide a competitive alternative for recycling the ever increasing quantity of fly ash produced in the South African coal-fired power plants. This approach will not only be environment friendly but could also be attractive from an economic point of view since the cost of disposal of fly ash could be offset by the income generated from the sale of the synthesized zeolitic materials.

Fate of sulphate removed during the treatment of circumneutral mine water and acid mine drainage with coal fly ash: Modelling and experimental approach

The treatment of acid mine drainage (AMD) and circumneutral mine water (CMW) with South African coal fly ash (FA) provides a low cost and alternative technique for treating mine wastes waters. The sulphate concentration in AMD can be reduced significantly when AMD was treated with the FA to pH 9. On the other hand an insignificant amount of sulphate was removed when CMW (containing a very low concentration of Fe and Al) was treated using FA to pH 9. The levels of Fe and Al, and the final solution pH in the AMD–fly ash mixture played a significant role on the level of sulphate removal in contrast to CMW–fly ash mixtures. In this study, a modelling approach using PHREEQC geochemical modelling software was combined with AMD–fly ash and/or CMW–fly ash neutralization experiments in order to predict the mineral phases involved in sulphate removal. The effects of solution pH and Fe and Al concentration in mine water on sulphate were also investigated. The results obtained showed that sulphate, Fe, Al, Mg and Mn removal from AMD and/or CMW with fly ash is a function of solution pH. The presence of Fe and Al in AMD exhibited buffering characteristic leading to more lime leaching from FA into mine water, hence increasing the concentration of Ca 2+. This resulted in increased removal of sulphate as CaSO 4·2H 2O. In addition the sulphate removal was enhanced through the precipitation as Fe and Al oxyhydroxysulphates (as shown by geochemical modelling) in AMD–fly ash system. The low concentration of Fe and Al in CMW resulted in sulphate removal depending mainly on CaSO 4·2H 2O. The results of this study would have implications on the design of treatment methods relevant for different mine waters.

Cobalt(II) removal from synthetic wastewater by adsorption on South African coal fly ash

Advanced wastewater-treatment techniques such as adsorption are essential in the removal of non- biodegradable toxic wastes from water. In this study, the use of South African coal fly ash, an industrial byproduct, has been investigated as a potential replacement for the current costly adsorbents used for removing heavy metals from wastewater. We utilised coal fly ash for the adsorption of cobalt(II) ions from synthetic petrochemical wastewater and characterised its performance. A two-level three-factor full-factorial design was successfully employed for experimental design and analysis of the results. The combined effects of pH, initial concentration and adsorbent dose on cobalt(II) removal were assessed using response surface methodology. Although the focus was on removal of cobalt(II), the adsorption was carried out in the presence of phenol and other heavy metal ions using the batch technique. The applicability of the Freundlich and Langmuir models to the equilibrium data was tested. Consequently, the equilibrium data was found to conform more favourably to the Freundlich isotherm than to the Langmuir isotherm; in this case, the coal fly ash had a maximum adsorption capacity of 0.401 mg/g for cobalt(II). We conclude that South African coal fly ash, as a natural, abundant and low-cost adsorbent, might be a suitable local alternative for elimination of cobalt(II) from aqueous solutions.

Study on surface morphology and physicochemical properties of raw and activated South African coal and coal fly ash

South African coal and coal fly ash were selected as the raw materials to be used for study of their morphology and physicochemical properties and their respective activated carbons for adsorption applications. Coal and fly ash were individually steam activated at a temperature range of 550–1000 °C for 1 h in a muffle furnace using cylindrical stainless steel containers. Scanning electron micrographs revealed a change in surface morphology with more mineral matter available on the surface of the coal particles due to increased devolatilization. However, in the case of fly ash, the macerals coalesced to form agglomerates and the presence of unburnt carbon constituted pores of diameter between 50 and 100 nm. The BET surface area of coal improved significantly from 5.31 to 52.12 m 2/g whereas in case of fly ash the surface area of the raw sample which was originally 0.59 m 2/g and upon activation increased only up to 2.04 m 2/g. The chemical composition of the fly ash confirmed that silica was the major component which was approximately 60% by weight fraction. The impact of this study was to highlight the importance of using raw materials such as coal and a waste product, in the form of coal ash, in order to produce affordable activated carbon that can be used in drinking water treatment. This would therefore ensure that the quality of water supplied to communities for drinking is not contaminated especially by toxic organic compounds.

Removal of heavy metals from wastewater using CFB-coal fly ash zeolitic materials

Polish bituminous (PB) and South African (SA) coal fly ash (FA) samples, derived from pilot-scale circulated fluidized bed (CFB) combustion facilities, were utilized as raw materials for the synthesis of zeolitic products. The two FAs underwent a hydrothermal activation with 1M NaOH solution. Two different FA/NaOH solution/ratios (50, 100g/L) were applied for each sample and several zeolitic materials were formed. The experimental products were characterized by means of X-ray diffraction (XRD) and energy dispersive X-ray coupled-scanning electron microscope (EDX/SEM), while X-ray fluorescence (XRF) was applied for the determination of their chemical composition. The zeolitic products were also evaluated in terms of their cation exchange capacity (CEC), specific surface area (SSA), specific gravity (SG), particle size distribution (PSD), pH and the range of their micro- and macroporosity. Afterwards the hybrid materials were tested for their ability of adsorbing Cr, Pb, Ni, Cu, Cd and Zn from contaminated liquids. Main parameters for the precipitation of the heavy metals, as it was concluded from the experimental results, are the mineralogical composition of the initial fly ashes, as well as the type and the amount of the produced zeolite and specifically the mechanism by which the metals ions are hold on the substrate.