Steam hydration of CFBC ash and the effect of hydration conditions on reactivation

A detailed study has been carried out on how hydration methods and conditions influence the sulphur capture potential of ash from a 165 MWe circulating fluidized bed combustion boiler firing a petroleum coke and coal blend. Both bed ash and fly ash were hydrated with saturated steam at various saturation conditions for different periods of time. Samples of the hydrated residues were then analyzed for free lime and calcium hydroxide content after the hydration process. Some size fractions of the steam-hydrated samples and those hydrated with liquid water in previous work were re-sulphated for 90 min using synthetic flue gas in a thermogravimetric analyzer at 850 °C to investigate how reactivation conditions affect the final sulphur capture behaviour of the ash. This work confirms that either hydration method is effective for reactivating the bed ash fractions tested but not fly ash, which should either be re-injected directly or reactivated in some other manner to improve its sulphur capture potential.     

Steam reactivation of 16 bed and fly ashes from industrial-scale coal-fired fluidized bed combustors

The hydration behaviour of sixteen ashes, obtained from different commercial-scale fluidized bed combustors, has been investigated. Hydration is important for both ash disposal and reactivation of excess lime present in the ashes for further use in flue gas desulphurization. The techniques used were instrumental and conventional chemical analysis, thermogravimetry and X-ray diffraction. The ashes comprised both fly ash and bottom ash, with particle size less than 2 mm. The ashes were heat treated in air to oxidize free carbon and then hydrated with pressurized steam at about 170 °C, alone and with addition of pure CaO.It has been shown that steam hydration is effective in quantitatively converting CaO to Ca(OH)₂, but in most cases the free lime content (i.e. CaO+Ca(OH)₂), expressed as CaO, decreases and added CaO enters into pozzolanic reactions with coal ash components, in part or even completely. Both the chemical evidence and X-ray phase analyses indicate that hydrated silicates and silicoaluminates are formed. The hydrated ashes are all able to take up additional SO₂ and it appears that the presence of amounts of Ca(OH)₂ detectable by phase analysis is not necessary for such capture.     

Sulphur dioxide removal using South African limestone/siliceous materials

This study presents an investigation into the desulfurization effect of sorbent derived from South African calcined limestone conditioned with fly ash. The main aim was to examine the effect of chemical composition and structural properties of the sorbent with regard to SO₂ removal in dry-type flue gas desulfurization (FGD) process. South African fly ash and CaO obtained from calcination of limestone in a laboratory kiln at a temperature of 900 °C were used to synthesize CaO/ash sorbent by atmospheric hydration process. The sorbent was prepared under different hydration conditions: CaO/fly ash weight ratio, hydration temperature (55-75 °C) and hydration period (4-10 h). Desulfurization experiments were done in the fixed bed reactor at 87 °C and relative humidity of 50%. The chemical composition of both the fly ash and calcined limestone had relatively high Fe₂O₃ and oxides of other transitional elements which provided catalytic ability during the sorbent sorption process. Generally the sorbents had higher SO₂ absorption capacity in terms of mol of SO₂ per mol of sorbent (0.1403-0.3336) compared to hydrated lime alone (maximum 0.1823). The sorbents were also found to consist of mesoporous structure with larger pore volume and BET specific surface area than both CaO and fly ash. X-ray diffraction (XRD) analysis showed the presence of complex compounds containing calcium silicate hydrate in the sorbents.     

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.     

Fire resistance of fired clay bricks-fly ash composite cement pastes

This work aims to study the effect of substitution of fly ash for homra on the hydration properties of composite cement pastes. The composite cements are composed of constant proportion of OPC (80%) with variable amounts of fly ash and homra. The addition of fly ash accelerates the initial and final sitting time, whereas the free lime and combined water contents decrease with fly ash content. The fly ash acts as nucleation sites which may accelerate the rate of formation of hydration products which fill some of the pores of the cement pastes. The fire resistance of composite cement pastes was evaluated after firing at 250, 450, 600, 800 °C with rate of firing 5 °C/min with soaking time for 2 h. The physico-mechanical properties such as bulk density and compressive strength were determined at each firing temperature. Moreover, the phase composition, free lime and microstructure for some selected samples were investigated. It can be concluded that the pozzolanic cement with 20 wt% fly ash can be used as fire resisting cement.     

Investigation on the porosity development by CO2 activation in heavy oil fly ashes

The porosity evolution in heavy oil fly ashes subjected to activation with CO₂ has been examined. The work examined four different heavy oil fly ashes that, after preliminary acid leaching, have been pyrolyzed at 900 °C and then activated with CO₂ at the same temperature for different times.A different evolution of porosity was observed according to the different reactivity of the samples during activation. The activated samples have been characterised as regards the surface area and the pore volume. The scanning electron microscope-energy dispersive spectrometer microanalysis has been used to interpret the experimental results.     

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.     

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.     

Kinetics of carbon oxidation from fly ash

Thermal gravimetric analysis (TGA) and evolved gas mass spectroscopy were used to study the kinetics of carbon oxidation from a Class-F fly ash. A multi-process ignition loss schema is presented wherein carbon combustion is modeled as a series or discrete independent reactions. These processes were studied at temperatures up to 1000 °C (1832 °F), for oxygen partial pressures between 0.05 and 0.50 and for heating rates between 5 and 40 °C/min (9-72 °F/min). The results show that carbon combustion can be modeled by a series of at least three processes; the weights (fractions) of which are a function of temperature and not a function of oxygen partial pressure. Such detailed combustion kinetics are relevant for the post processing of fly ash to produce materials suitable for use as concrete admixtures or in the manufacture of sintered artificial aggregate or similar densified structures based on fly ash. Such are low temperature, low heating rate processes relative to coal combustion power generation applications.     

Ge extraction from gasification fly ash

Water-soluble germanium species (GeS₂, GeS and hexagonal-GeO₂) are generated during coal gasification and retained in fly ash. This fact together with the high market value of this element and the relatively high contents in the fly ashes of the Puertollano Integrated Gasification in Combined Cycle (IGCC) plant directed our research towards the development of an extraction process for this element. Major objectives of this research was to find a low cost and environmentally suitable process. Several water based extraction tests were carried out using different Puertollano IGCC fly ash samples, under different temperatures, water/fly ash ratios, and extraction times. High Ge extraction yields (up to 84%) were obtained at room temperature (25 °C) but also high proportions of other trace elements (impurities) were simultaneously extracted. Increasing the extraction temperature to 50, 90 and 150 °C, Ge extraction yields were kept at similar levels, while reducing the content of impurities, the water/fly ash ratio and extraction time. The experimental data point out the influence of chloride, calcium and sulphide dissolutions on the Ge extraction.     

Carbonation of fly ash in oxy-fuel CFB combustion

Oxy-fuel combustion of fossil fuel is one of the most promising methods to produce a stream of concentrated CO₂ ready for sequestration. Oxy-fuel FBC (fluidized bed combustion) can use limestone as a sorbent for in situ capture of sulphur dioxide. Limestone will not calcine to CaO under typical oxy-fuel circulating FBC (CFBC) operating temperatures because of the high CO₂ partial pressures. However, for some fuels, such as anthracites and petroleum cokes, the typical combustion temperature is above 900 °C. At CO₂ concentrations of 80-85% (typical of oxy-fuel CFBC conditions with flue gas recycle) limestone still calcines, but when the ash cools to the calcination temperature, carbonation of fly ash deposited on cool surfaces may occur. This phenomenon has the potential to cause fouling of the heat transfer surfaces in the back end of the boiler, and to create serious operational difficulties. In this study, fly ash generated in a utility CFBC boiler was carbonated in a thermogravimetric analyzer (TGA) under conditions expected in an oxy-fuel CFBC. The temperature range investigated was from 250 to 800 °C with CO₂ concentration set at 80% and H₂O concentrations at 0%, 8% and 15%, and the rate and the extent of the carbonation reaction were determined. Both temperature and H₂O concentrations played important roles in determining the reaction rate and extent of carbonation. The results also showed that, in different temperature ranges, the carbonation of fly ash displayed different characteristics: in the range 400 °C < T ? 800 °C, the higher the temperature the higher the CaO-to-carbonate conversion ratio. The presence of H₂O in the gas phase always resulted in higher CaO conversion ratio than that obtainable without H₂O. For T ? 400 °C, no fly ash carbonation occurred without the presence of H₂O in the gas phase. However, on water vapour addition, carbonation was observed, even at 250 °C. For T ? 300 °C, small amounts of Ca(OH)₂ were found in the final product alongside CaCO₃. Here, the carbonation mechanism is discussed and the apparent activation energy for the overall reaction determined.     

Heavy metal concentrations in bottom ash and fly ash fractions from a large-sized (246 MW) fluidized bed boiler with respect to their Finnish forest fertilizer limit values

The total and size fractionated concentrations of As, Cd, Cr, Cu, Ni, Pb and Zn in bottom ash and two fly ash fractions from a large-sized (246 MW) fluidized bed boiler were compared to Finnish statutory limit values for forest fertilizers, which came into force in March 2007. Fly ashes were sampled from the different fields (i.e. electrodes) of the electrostatic precipitator (ESP) unit treating the stack gases. The bottom ash and the fly ash from the first ESP field are suitable for use a forest fertilizer. Due to the elevated As concentration (40 mg/kg; d.w.), which exceeded its Finnish limit value of 30 mg/kg (d.w.), the fly ash from the second ESP field is not suitable as a forest fertilizer alone. The results of ash sieving indicated that an As concentration of 40 mg/kg (d.w.) for particle size less than 0.125 mm for fly ash 2 from the second ESP electrode field exceeded the As limit value of 30 mg/kg (d.w.). In addition, a Pb concentration of 170 mg/kg (d.w.) for fly ash 1 from the first ESP electrode field for particle size 0.5-2.0 mm exceeded the Pb limit value of 150 mg/kg (d.w.). These two specific fractions are therefore not suitable for used as a forest fertilizer alone.     

Mechanical activation of fly ash: Effect on reaction, structure and properties of resulting geopolymer

Geopolymerisation of mechanically activated fly ash was studied at ambient (27 °C) and elevated (60 °C) temperatures by isothermal conduction calorimeter. Under both the conditions, mechanical activation enhanced the rate and decreased time of reaction. It was interesting to observe that in the samples milled for 45 min (median size ∼5 μm), a broad peak corresponding to geopolymerisation initiated at 27 °C after 32 h. The rate maxima at 60 °C, a measure of fly ash reactivity, showed a non-linear dependence on particle size and increased rapidly when the median size was reduced to less than 5-7 μm. Improvement in strength properties is correlated with median particle size, and reactivity of fly ash. The characterisation of the geopolymer samples by SEM-EDS, XRD and FTIR revealed that mechanical activation leads to microstructure and structural variations which can be invoked to explain the variation in the properties.     

Effects of three Turkish fly ashes on the heat of hydration of PC-FA pastes

Effects of the type and amount of fly ash substitution on the heat of hydration of portland cement-fly ash pastes were investigated. Three Turkish fly ashes were used. One of them was a high-calcium and the other two were low-calcium fly ashes. The specimens contained 0, 10, 20, and 40% fly ash by weight of portland cement. The tests were carried out as described in ASTM C 186 however one separate set of specimens were first subjected to an early external temperature of 67±2°C for six hours followed by the standard temperature until time of test. The results revealed that the low-calcium fly ashes, regardless of their type, reduce the heat evolution when used for partial cement replacement. The high-calcium fly ash, on the other hand, does not produce significant changes in the heat of hydration.     

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.     

Characterization of Chinese, American and Estonian oil shale semicokes and their sorptive potential

The primary byproduct of current oil shale oil extraction processes is semicoke. Its landfill deposition presents a potential threat to the environment and represents a waste of a potentially useable byproduct. Here we examine the sorptive characteristics of oil shale semicoke. Oil shale samples from Estonia, China and the United States were pyrolyzed at 500 and 1000 °C and their products analyzed for organic char content, surface area and porosity. Pyrolysis of the oil shales at temperatures of 500-1000 °C yields semicokes with organic char contents from 1.7% to 17.5% and BET surface areas of 4.4-57 m² g⁻¹, corresponding to 100-550 m² g⁻¹ of organic char. For comparison, the BET surface areas of class F coal fly ashes (combustion byproducts of bituminous coals) typically range from 2 to 5 m² g⁻¹, corresponding to 30-60 m² g⁻¹ of carbon while class C fly ash (from low rank coals) have carbon BET surface areas comparable to oil shale semicoke organic char surface areas.     

Synthesis and characteristics of fly ash and bottom ash based geopolymers–A comparative study

The research was carried out to develop geopolymers mortars and concrete from fly ash and bottom ash and compare the characteristics deriving from either of these products. The mortars were produced by mixing the ashes with sodium silicate and sodium hydroxide as activator solution. After curing and drying, the bulk density, apparent density and porosity, of geopolymer samples were evaluated. The microstructure, phase composition and thermal behavior of geopolymer samples were characterized by scanning electron microscopy, XRD and TGA-DTA analysis respectively. FTIR analysis revealed higher degree of reaction in bottom ash based geopolymer. Mechanical characterization shows, geopolymer processed from fly ash having a compressive strength 61.4 MPa and Young's modulus of 2.9 GPa, whereas bottom ash geopolymer shows a compressive strength up to 55.2 MPa and Young's modulus of 2.8 GPa. The mechanical characterization depicts that bottom ash geopolymers are almost equally viable as fly ash geopolymer. Thermal conductivity analysis reveals that fly ash geopolymer shows lower thermal conductivity of 0.58 W/mK compared to bottom ash geopolymer 0.85 W/mK.     

Effect of rice husk ash addition on CO2 capture behavior of calcium-based sorbent during calcium looping cycle

Rice husk ash/CaO was proposed as a CO₂ sorbent which was prepared by rice husk ash and CaO hydration together. The CO₂ capture behavior of rice husk ash/CaO sorbent was investigated in a twin fixed bed reactor system, and its apparent morphology, pore structure characteristics and phase variation during cyclic carbonation/calcination reactions were examined by SEM-EDX, N₂ adsorption and XRD, respectively. The optimum preparation conditions for rice husk ash/CaO sorbent are hydration temperature of 75 °C, hydration time of 8 h, and mole ratio of SiO₂ in rice husk ash to CaO of 1.0. The cyclic carbonation performances of rice husk ash/CaO at these preparation conditions were compared with those of hydrated CaO and original CaO. The temperature at 660 °C–710 °C is beneficial to CO₂ absorption of rice husk ash/CaO, and it exhibits higher carbonation conversions than hydrated CaO and original CaO during multiple cycles at the same reaction conditions. Rice husk ash/CaO possesses better anti-sintering behavior than the other sorbents. Rice husk ash exhibits better effect on improving cyclic carbonation conversion of CaO than pure SiO₂ and diatomite. Rice husk ash/CaO maintains higher surface area and more abundant pores after calcination during the multiple cycles; however, the other sorbents show a sharp decay at the same reaction conditions. Ca₂SiO₄ found by XRD detection after calcination of rice husk ash/CaO is possibly a key factor in determining the cyclic CO₂ capture behavior of rice husk ash/CaO.     

Alkali release characteristics of blended cements

This paper presents results of an experimental program conducted to investigate the capacity of hydration products of different cementing materials to retain “bound” alkalis when the alkalinity of the surrounding solution drops. The study covered paste samples containing high-alkali Portland cement and various levels of silica fume and/or fly ash. The results showed that the ability of the hydration products of cement-fly ash systems to bind alkalis is a function of the CaO content of the fly ash, the binding increasing as the calcium content decreases. High-alkali fly ashes (Na₂O_e > 5.0% and CaO in the range of 15% to 20%) showed considerable amounts of alkali contributed to the test solutions. Silica fume does not have a high capacity to retain alkalis in its hydration products; however, ternary blends containing silica fume and fly ash have excellent capacity to bind and retain alkalis.     

A study of fly ash-lime granule unfired brick

In this paper, the properties of fly ash-lime granule unfired bricks are studied. Granules were prepared from mixtures of fly ash and lime at fly ash to hydrated lime ratios of 100:0 (Ca/Si = 0.2), 95:5 (Ca/Si = 0.35) and 90:10 (Ca/Si = 0.5). After a period of moist curing, the microstructure and mineralogy of the granules were studied. Microstructure examination reveals that new phases in the form of needle-like particles are formed at the surface of granule. The granules were used to make unfired bricks using hydrothermal treatment at temperature of 130 ± 5 °C and pressure of 0.14 MPa. The microstructures, mineralogical compositions, mechanical properties and environmental impact of bricks were determined.The results reveal that the strengths of unfired bricks are dependent on the fineness of fly ash. The strength is higher with an increase in fly ash fineness. The strengths of the fly ash-lime granule unfired brick are excellent at 47.0-62.5 MPa. The high strength is due to the formation of new products consisting mainly of hibschite and Al-substituted 11 Å tobermorite. The main advantage of utilization of granule is the ability to increase the pozzolanic reaction of fly ash through moisture retained in the granule. In addition, the heavy elements, in particular Cd, Ni, Pb and Zn are efficiently retained in the fly ash-lime granule unfired brick.