Mineralogy and microstructure of sintered lignite coal fly ash☆

Lignite coal fly ash from the ‘Nikola Tesla’ power plant in Yugoslavia has been characterised, milled, compacted and sintered to form monolithic ceramic materials. The effect of firing at temperatures between 1130 and 1190 °C on the density, water accessible porosity, mineralogy and microstructure of sintered samples is reported. This class C fly ash has an initial average particle size of 82 μm and contains siliceous glass together with the crystalline phases quartz, anorthite, gehlenite, hematite and mullite. Milling the ash to an average particle size of 5.6 μm, compacting and firing at 1170 °C for 1 h produces materials with densities similar to clay-based ceramics that exhibit low water absorption. Sintering reduces the amount of glass, quartz, gehlenite and anhydrite, but increases formation of anorthite, mullite, hematite and cristobalite. SEM confirms the formation of a dense ceramic at 1170 °C and indicates that pyroplastic effects cause pore formation and bloating at 1190 °C.     

Synthesis and characterization of novel solid base catalyst from fly ash

A new type of solid base catalyst was synthesized by chemical and thermal activation of fly ash, collected from Thermal Super Power Station situated in Kota, Rajasthan, India. The chemical activation was carried out by 50 wt.% NaOH followed by thermal activation at 450 °C. The modified physiochemical property of solid base fly ash (SBFA) was determined by X-ray diffraction, FT-IR spectroscopy, Scanning Electron Microscopy, N₂ adsorption-desorption studies and Flame Atomic Absorption Spectrophotometry. The results reveal that the catalyst is nano-crystalline in nature with crystallite size 11 nm and particle size in the range 840 nm to 6.95 μm. The surface basicity and therefore, catalytic activity in SBFA was originated by increased hydroxyl content as compared to fly ash, suggesting that the catalyst possess higher surface active sites. The basicity of the catalyst was measured by liquid phase, solvent free, single step condensation of benzaldehyde with cyclohexanone giving higher conversion (>70%) and selectivity (>80%) of desired product α,α′-dibenzylidenecyclohexanone. This excellent conversion shows that the catalyst has sufficient basic sites both on the surface and in the bulk, responsible for the catalytic activity. Furthermore, this catalyst may replace conventional environmentally hazardous homogeneous liquid bases making an ecofriendly; solvent free, solid base catalyzed process. The application of fly ash to synthesize a solid base catalyst finds a noble way to utilize this abundant waste material.     

Assessing the catalytic effect of coal ash constituents on the CO2 gasification rate of high ash, South African coal

The catalytic effect of inorganic species, within the ash, on the CO₂ gasification of three South African coals containing similar carbon-structural properties (elemental, structural and petrographical properties) was assessed. The reactivity of the coals with a particle size between 150 and 250 μm was determined in a thermo gravimetric analyser. The reactivity was measured at temperatures between 900 and 1000 °C, pressures between 1 and 10 bar, and fractions of CO₂ between 10 and 30%. For the selected coals, the reactivity decreased with ash content, and was found to be dependent on the composition of the ash. Specifically, the reactivity increased with calcium and magnesium content and alkali index.     

Burning and physico-chemical characteristics of carbon in ash from a coal fired power plant

The paper addresses the relationship between the chemico-physical properties and the residual combustion reactivity of fly ashes from a full-scale front fired PF coal boiler. Ashes collected at different rows of electrostatic precipitators (EP) have been characterized for their particle size distribution, morphology, chemical composition and combustion reactivity. The combustion time of carbon in ash has been estimated for a wide range of temperatures using a thermobalance and a heated strip reactor.Results showed the existence of marked differences in the content of both carbon and inorganic elements according to the row of EP and the granulometric size of the samples. In contrast with this, the combustion reactivity of all ash samples was similar regardless of their collection point and particle size. Ash reactivity resulted to be approximately 100 times lower than that of the parent coal.The role of thermal annealing on the low reactivity of fly ashes and their propensity to undergo additional thermodeactivation upon further heat treatment has also been investigated. To this end coal and fly ashes have been heated under inert conditions up to 2000 °C and then characterised for their residual combustion reactivity. These tests showed that heat treatment does reduce the reactivity of coal but does not reduce any further the already low reactivity of fly ashes.     

NaOH-activated ground fly ash geopolymer cured at ambient temperature

NaOH-activated ground fly ash geopolymers, cured at room temperature, were studied in this paper. Ground fly ash (GFA), with a median particle size of 10.5 μm, was used as source material. NaOH concentrations of 4.5-16.5 M (M) were used as an alkali activator. Compressive strength tests and microstructure observations using SEM, EDX, XRD and FTIR were performed. Results indicated that GFA gave higher strength geopolymer paste compared to original fly ash. Ground fly ash could be used as a source material for making geopolymers cured at room temperature. An increase in NaOH concentration from 4.5 to 14.0 M increased the strength of GFA geopolymer pastes. Microstructure studies indicated that NaOH concentrations of 12.0-14.0 M created new crystalline products of sodium aluminosilicate. The compressive strengths at 28 days of 20.0-23.0 MPa were obtained with the NaOH concentrations of 9.5-14.0 M. Increasing the NaOH concentration beyond this point resulted in a decrease in the strength of the paste due to early precipitation of aluminosilicate products.     

The effect of BaCO3 addition on the sintering behavior of lignite coal fly ash

The effect of BaCO₃ (witherite) addition on the sintering behavior of lignite coal fly ash taken from the Seyitömer power plant of Kütahya/Turkey was examined at temperatures of 1100, 1150 and 1200 °C in air atmosphere. Bloating of the fly ash samples sintered at 1150 °C was prevented, that is, the decomposition temperature of CaSO₄ in the fly ash is shifted to a higher temperature, and their physico-mechanical properties (porosity, water absorption, bulk density and bending strength) were improved with BaCO₃ addition. Positive effects of BaCO₃, however, were not seen on the fly ash samples sintered at 1100 °C. All the fly ash samples sintered at 1200 °C were bloated due to the gas evolving and also they melted. During the thermal treatment at 1150 °C a phase transformation from CaSO₄ (anhydrite) to BaSO₄ (Barite) occurred in the fly ash with BaCO₃ addition as seen from the X-ray diffraction (XRD) patterns and the bar shaped fly ash samples with BaCO₃ saved their structural integrity up to 1150 °C.     

Carbonation of FBC ash by sonochemical treatment

This work explores the sonochemical-enhanced carbonation of FBC ash for direct disposal in landfills. Tests have been conducted using four ashes originating from three commercial CFBC boilers. Experiments with additives such as NaCl and seawater have also been carried out. Tests were performed at low (20°, 40 °C) and high (60°, 80 °C) temperatures. Sonicated samples were analyzed using TGA, TGA-FTIR and XRD techniques to determine the influence of other calcium compounds (OCC). The particle size reduction brought about by sonication was quantified using wet sieving. The ash reactivity displays a strong temperature dependency with almost complete carbonation achieved in minutes at higher temperatures. Additives were found to increase the level of hydration of the ashes, in line with previous work; however, carbonation levels were unaffected. TGA, TGA-FTIR and XRD analysis of the samples indicated participation of OCC, which were also formed during hydration.     

Processing of dense nanostructured HAP ceramics by sintering and hot pressing

A nanosized HAP powder was sintered and hot pressed, in order to obtain dense HAP ceramics. In a first series of experiments, the powder was isostatically pressed into uniform green compacts and sintered at temperatures ranging from 1000 °C to 1200 °C in air atmosphere for different times. In a second series, the isostatically pressed green compacts were hot pressed in argon atmosphere at 900 °C, 950 °C and 1000 °C. The SEM micrograph of the sample sintered at 1200 °C for 2 h showed a uniform 3 μm mean grain size dense microstructure. In the case of hot pressed HAP compacts, full dense, translucent nanostructures were obtained having mean grain size below 100 nm and improved mechanical properties. With the grain size decreasing from 3 μm to 50 nm, the fracture toughness of pure HAP ceramics increased from 0.28 MPa m^1/2 to 1.52 MPa m^1/2.     

Sintering studies of nano-crystalline zinc oxide

Sintering and grain growth of nano-crystalline undoped ZnO has been studied in detail over a wide range of temperature and holding time. Below 800 °C, sintering of over 70% theoretical density is not observed, irrespective of particle size. At 900 °C for 6 h, the nano-crystalline sample sinters to 99% of theoretical density whereas the density for as received sample is 93% of theoretical density. However, at 1300 °C or higher, the densification is found to be much faster and after a few hours becomes independent of holding time. Grain growth studies reveal a similar feature of attaining saturation over holding time. The average saturated grain size is found to be ∼1.5 and ∼2.2 μm at 800 and 900 °C, respectively, while at 1300 °C or higher, it is in between 12 and 13 μm.     

Studies on ionic conductivity of stabilized zirconia ceramics (8YSZ) densified through conventional and non-conventional sintering methodologies

Densification studies of 8 mol% yttria stabilized zirconia ceramics were carried out by employing the sintering techniques of conventional ramp and hold (CRH), spark plasma sintering (SPS), microwave sintering (MWS) and two-stage sintering (TSS). Sintering parameters were optimized for the above techniques to achieve a sintered density of >99% TD. Microstructure evaluation and grain size analysis indicated substantial variation in grain sizes, ranging from 4.67 μm to 1.16 μm, based on the sintering methodologies employed. Further, sample was also sintered by SPS technique at 1425 °C and grains were intentionally grown to 8.8 μm in order to elucidate the effect of grain size on the ionic conductivity. Impedance spectroscopy was used to determine the grain and grain boundary conductivities of the above specimens in the temperature range of RT to 800 °C. Highest conductivity of 0.134 S/cm was exhibited by SPS sample having an average grain size of 1.16 μm and a decrease in conductivity to 0.104 S/cm was observed for SPS sample with a grain size of 8.8 μm. Ionic conductivity of all other samples sintered vide the techniques of TSS, CRH and MWS samples was found to be ∼0.09 S/cm. Highest conductivity irrespective of the grain size of SPS sintered samples, can be attributed to the low densification temperature of 1325 °C as compared to other sintering techniques which necessitated high temperatures of ∼1500 °C. The exposure to high temperatures while sintering with TSS, CRH and MWS resulted into yttria segregation leading to the depletion of yttria content in fully stabilized zirconia stoichiometry as evidenced by Energy Dispersive Spectroscopy (EDS) studies.     

Role of active sites in the steam activation of high unburned carbon fly ashes

Previous studies on carbon gasification have not included high unburned carbon content fly ashes, and therefore it remains unclear why not all fly ash carbon samples are equally suitable for activation. The concentration of active sites is well known to influence carbon gasification reactions. Therefore, the objective of this work was to investigate the effect of the concentration of active sites on the behavior of fly ash carbon samples upon steam activation. Six fly ash carbons were selected to produce activated carbons using steam at 850 °C. The concentration of active sites was determined by non-dispersive infrared analysis (NDIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS). XRD analyses were also conducted to determine the crystallite size. It was observed that the concentration of active sites played a more significant effect on the surface areas of activated carbons in the carbon burn-off zone of >60%. Statistical analysis was used to relate the surface areas of activated carbon variances with carbon burn-off levels.     

Significance of surface moisture removal on triboelectrostatic beneficiation of fly ash

The gas transport, triboelectrostatic beneficiation of coal combustion fly ash into carbon-rich and ash-rich products was studied relative to the effect of ash surface moisture. Increasing the humidity to which the ashes from American and Italian coal-fired utilities were exposed under process and ambient conditions affected carbon and ash separability. The effect of humidity and particle surface moisture became more important as particle size decreased: particles greater than 75 μm in diameter were nearly unaffected whereas particles smaller than 45 μm experienced up to a four-fold change in their separability upon changing their surface moisture contents. Although particle size influences the moisture adsorption, which in turn affects tribocharging, the decrease in adhesive forces between carbon and ash from otherwise intractable clusters during drying also may be a factor influencing triboelectrostatic beneficiation performance.     

The sintering kinetics of porcelain bodies made from waste glass and fly ash

Porcelain is a material produced from kaoline, quartz and potassium-feldspar. Recently, research of new materials, for example non-hazardous wastes, that are able to replace traditional fluxing agents without changing the process or quality of the final products has been realized. The aim of this work is to study the possibility of the use of glass powder waste and fly ash together for manufacturing porcelain. Instead of quartz, fly ash was used at the selected porcelain composition. The waste glass was added partially and fully in replacement of potassium-feldspar. Samples were fired in an electric furnace with a heating rate of 10 °C/min at 1100, 1150 and 1200 °C for a period of 1, 2, 3 and 5 h. The sintered samples were characterised by XRD (X-ray diffraction) and SEM (scanning electron microscopy). Sintering activation energies were determined based on the bulk density result. At 10, 15, 20 and 25 wt.% glass waste addition, the apparent activation energies were calculated to be 145, 113.5, 70.4 and 53.74 kJ/mol, respectively. It was found that the sintering activation energy decreased with increasing waste glass addition.     

Preparation of a new ceramic microfiltration membrane from mineral coal fly ash: Application to the treatment of the textile dying effluents

New microfiltration membranes from mineral coal fly-ash material are obtained using ceramic method. Paste from mineral coal fly ash (obtained by calcinations at 800 °C of non-grinded mineral coal) is extruded to elaborate a porous tubular configuration used as supports. The support heated at 1125 °C, shows an average pore diameter and porosity of about 4.5 μm and 51%, respectively. The properties in terms of mechanical and corrosion resistances are very interesting. The elaboration of the layer based on fly-ash powder (obtained by sintering at 700 °C of a finely grinded mineral coal) is performed by slip-casting method. The heating treatment at 800 °C leads to an average pore size of 0.25 μm. The water permeability determined of this membrane is 475 L/h m² bar. This membrane can be used for crossflow microfiltration. The application to the treatment of the dying effluents generated by the washing baths in the textile industry shows an important decrease of turbidity (inferior to 1 NTU), of chemical oxygen demand (COD) values (retention rate of about 75%) and a total color removal. The performances in term of permeate flux and efficiency were determined and compared to those obtained using a commercial alumina microfiltration membrane. Almost the same stabilised permeate flux was obtained (about 100 L h⁻¹ m⁻²). So, it seems that the prepared membrane is suitable for such wastewater treatment.     

Injection and stabilization of mesophase pitch in the fabrication of carbon-carbon composites: Part II. Stabilization process

In the fabrication of carbon-carbon composites by mesophase injection through a fiber preform, it is essential to stabilize the flow-induced microstructure in the flow channels and to prevent relaxation and exudation of the mesophase. Oxidation stabilization studies were conducted on preforms injected with the naphthalene-based AR mesophase pitch. Oxidation mass gain (OMG) curves at 170, 222, and 270 °C were generated for 60°-wedges cut from full size composite disks. The rates of OMG at 170 °C of first- and second-cycle injection wedges and full-size disks were comparable to those using as-spun filaments 30 μm in diameter, and particles sieved to 200 to 340 μm. The results suggest that oxygen is accessible deep into a mesophase matrix and the transport is facilitated by connected array of shrinkage cracks. Oxidation at 170 °C has strong advantage over higher oxidation temperatures by having a higher carbon yield and lower OMG threshold and thus oxidation time required for stabilization. The 60°-wedges could be stabilized at 170 °C after a 25 h oxidation with a 7.2% OMG and attaining a carbon yield above 85%.     

Ultra-fast densification of boron carbide ceramics under high heating rate and high pressure

Boron carbide ceramics were obtained in 2 min by a method based on self-propagating high-temperature synthesis plus quick pressing (SHS/QP). The samples were densified to 98% of theoretical density under a large mechanical pressure (120 MPa) and a fast heating rate (2300 °C/min). The microstructure and mechanical properties were studied. The sample obtained at this heating rate presents an average grain size of 3 μm and a hardness of 34 ± 0.2 GPa.     

Mechanochemical synthesis of MgTa2O6 ceramic

MgTa₂O₆ powders were prepared by mechanochemical synthesis from MgO and Ta₂O₅ in a planetary ball mill in air atmosphere using steel vial and steel balls. High-energy ball milling gave nearly single-phase MgTa₂O₆ after 8 h of milling time. Annealing of high-energy milled powder at various temperatures (700–1200 °C) indicated that high-energy milling speed up the formation and crystallization of MgTa₂O₆ from the amorphous mixture. The powder derived from 8 h of mechanical activation gave a particle size of around 28 nm. Although at low-annealing temperatures the grain size was almost the same as-milled powder, the grain size increased with annealing temperature reaching to around 1–2 μm after annealing at 1200 °C for 8 h.     

Steam hydration-reactivation of FBC ashes for enhanced in situ desulphurization

Bed and fly ashes originating from industrial-scale fluidized bed combustors (FBCs) were steam hydrated to produce sorbents suitable for further in situ desulphurization. Samples of the hydrated ash were characterized by X-ray diffraction analysis, scanning electron microscopy and porosimetry. Bed ashes were hydrated in a pressure bomb for 30 and 60 min at 200 °C and 250 °C. Fly ash was hydrated in an electrically heated tubular reactor for 10 and 60 min at 200 °C and 300 °C. The results were interpreted by considering the hydration process and the related development of accessible porosity suitable for resulphation. The performance of the reactivated bed ash as sulphur sorbent improved with a decrease of both the hydration temperature and time. For reactivated fly ash, more favourable porosimetric features were observed at longer treatment times and lower hydration temperatures. Finally, it was shown that an ashing treatment (at 850 °C for 20 min) promoted a speeding up of the hydration process and an increase in the accessible porosity.     

Effects of fly ash and bottom ash on the frictional behavior of composites

Immense quantities of coal combustion by-products are produced every year, and only a small fraction of them are currently utilized. Our recent work has focused on developing value-added products especially from fly ash, bottom ash, and flue gas desulfurization (FGD) scrubber sludge. We explored the potential utilization of fly ash, bottom ash, and sulfate-rich scrubber sludge as frictional modifiers and additives for automotive frictional composites. The surfaces of the frictional composites, fabricated from scrubber sludge and fly ash or bottom ash, were characterized with the help of scanning electron microscopy (SEM). The mechanical properties of by-products containing composites were evaluated using a dynamic mechanical analyzer (DMA). The frictional behavior of the composites was probed with the help of friction assessment and screening test (FAST). The frictional results suggested that fly ash or bottom ash had a profoundly different effect on the frictional coefficient (μ) and wear of the composite than those observed for scrubber sludge particles. It appeared that fly ash or bottom ash particles had abrasive characteristics and gave frictional composites a higher μ-value. The FAST test also revealed that the fluctuations in the μ-value were a minimum for composites that contained 20 vol% fly ash or bottom ash among the ash-derived composites. The composites that contained 30 vol% fly ash or bottom ash showed fade after approximately 60 min of continuous FAST test. We compared the frictional and wear performance of our composites with a commercial automotive brake, and it appeared that frictional composites could be formed which contained up to 20 vol% fly ash or bottom ash and 25 vol% scrubber sludge.     

Characterisation of the properties of size fractions from ten world coals and their chars produced in a drop-tube furnace

A range of coals from different parts of the world was studied to determine if there were any common relationships that could be determined to gain a clearer understanding of the distribution of coal properties within different particle-sizes. The properties examined were proximate analysis, maceral analysis and %Unreactives from image analysis. Each fraction was also pyrolysed in a drop-tube furnace at 1300°C, 1 vol% oxygen and a residence time of 200 ms and the resulting chars analysed for morphology using image analysis. There were substantial variations between the particle-size distributions of the different coal samples even though they were ground to the same specification for trials on a combustion rig. Ash distributions showed in all cases that the smallest particle size (−38 μm) had either the highest ash level or was very close to it. However, the trends in ash level for increasing particle size showed variations between coals with some coals showing increases in ash towards the larger particles. Fusinite content did not necessarily concentrate in the smallest size fraction, however, liptinite content did increase with particle size. %Unreactives generally increases with particle size and is related to char morphology through an empirical parameter, the ACA [5]. In addition the ACA [5] parameter showed the effect of both particle size and %Unreactives on char morphology and clearly showed the significant influence of particle size on burnout. A parameter such as this could, therefore, be used in burn-out models and further correlated with %Unreactives and particle size.