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.     

Gasification of biomass wastes in an entrained flow gasifier: Effect of the particle size and the residence time

Experimental tests in an entrained flow gasifier have been carried out in order to evaluate the effect of the biomass particle size and the space residence time on the gasifier performance and the producer gas quality. Three types of biomass fuels (grapevine pruning and sawdust wastes, and marc of grape) and a fossil fuel (a coal-coke blend) have been tested. The results obtained show that a reduction in the fuel particle size leads to a significant improvement in the gasification parameters. The thermochemical characterisation of the resulting char-ash residue shows a sharp increase in the fuel conversion for particles below 1 mm diameter, which could be adequate to be used in conventional entrained flow gasifiers. Significant differences in the thermochemical behaviour of the biomass fuels and the coal-coke blend have been found, especially in the evolution of the H₂/CO ratio with the space time, mainly due to the catalytic effect of the coal-coke ash. The reaction temperature and the space time have a significant effect on the H₂/CO ratio (the relative importance of each of these parameters depending on the temperature), this value being independent of the fuel particle size.     

Mineralogical and elemental composition of fly ash from pilot scale fluidised bed combustion of lignite, bituminous coal, wood chips and their blends

The chemical and mineralogical composition of fly ash samples collected from different parts of a laboratory and a pilot scale CFB facility has been investigated. The fabric filter and the second cyclone of the two facilities were chosen as sampling points. The fuels used were Greek lignite (from the Florina basin), Polish coal and wood chips. Characterization of the fly ash samples was conducted by means of X-ray fluorescence (XRF), inductive coupled plasma-optical emission spectrometry (ICP-OES), thermogravimetric analysis (TGA), particle size distribution (PSD) and X-ray diffraction (XRD). According to the chemical analyses the produced fly ashes are rich in CaO. Moreover, SiO₂ is the dominant oxide in fly ash with Al₂O₃ and Fe₂O₃ found in considerable quantities. Results obtained by XRD showed that the major mineral phase of fly ash is quartz, while other mineral phases that are occurred are maghemite, hematite, periclase, rutile, gehlenite and anhydrite. The ICP-OES analysis showed rather low levels of trace elements, especially for As and Cr, in many of the ashes included in this study compared to coal ash from fluidised bed combustion in general.     

Characterisation of fly ashes. Potential reactivity as alkaline cements

A representative group of Spanish fly ashes has been characterised in order to determine its capacity for being alkali activated and give place to a material with cementitious properties. The characterisation studies have been carried out through chemical analysis, laser granulometry, Blaine, BET, particle size distribution, XRD and ²⁹Si MAS NMR. Compressive mechanical strength test was used to determine the reactivity of the fly ashes as alkaline binders. The results obtained have demonstrated that all investigated fly ashes are suitable to be alkali activated. Additionally it has also been demonstrated that the key factors of their potential reactivity are: the reactive silica content, the vitreous phase content and the particle size distribution.     

Determination of glass content and estimation of glass composition in fly ash using quantitative X-ray diffractometry

The proportion of amorphous or glassy material in a series of fly ashes has been evaluated by X-ray powder diffraction (XRD) using the Rietveld-based SIROQUANT software package. Several different sample preparation and processing methods were investigated, including XRD analysis of samples spiked with known masses of synthetic corundum and zinc oxide as well as techniques based on analysing the raw or unspiked fly ash directly using the SIROQUANT process. In the latter case, two different poorly crystallised silicate mineral patterns, metakaolin and tridymite, were used in the SIROQUANT processing of the raw ash XRD data to represent the amorphous constituents. The results of the different methods based on XRD of spiked samples were found to be mutually consistent, and also consistent with other published data for an international reference fly ash sample. SIROQUANT analysis of the unspiked fly ashes gave similar results, although different poorly crystallised silicate reference patterns seem to be more suited for ashes from Australian and North American sources.The mineralogy of the ashes, including the proportions of quartz, iron oxide and glassy constituents, appears to be related to the nature of the mineral matter in the relevant feed coals. Calculations based on subtracting the inferred chemistry of the crystalline minerals in the fly ashes from the total fly ash chemistry were also used to estimate the overall chemical composition of the glass fraction in each ash. The results indicate that ashes derived from lower-rank coals in the samples studied have different glass compositions to those derived from higher-rank (bituminous) materials. These different glass compositions appear to be related to several other ash properties, including particle density and particle surface area. Evaluation of glass content and composition may be significant in different aspects of ash utilisation, and also in evaluating interactions with water at ash disposal sites.     

Particle size distribution profile of some Indian fly ash—a comparative study to assess their possible uses

Fly ash collected from three different thermal power plants in Eastern India were critically examined in respect to their particle size distribution. The objective of the investigation was to obtain proper distribution profiles of such ashes with the nature of combustors vis-à-vis their efficiency and to point out the possible areas of application/utilisation. For this purpose, particle size distribution profiles of the as received fly ash, the size fractionated ones as well as the magnetic and non-magnetic components, were determined. Distribution profiles reveal that fly ash obtained from Super Thermal Power Plants have better profiles than the fly ash obtained from captive power plants. It is observed that, in general, the finer fractions have a better profile in the sense that a considerable amount of the particles fall below 45 μm range; this is important in respect to utility in the construction industry. The magnetic particles are larger and rounder than the non-magnetic ones, and can probably be used for coal flotation. An important observation is that the fly ash collected from Stoker-fired thermal power plants possesses very poor distribution profile (AMD for as received fly ash ≥200 μm).     

Cd speciation in biomass fly ash particles after size separation by centrifugal SPLITT

The finest particle size fractions (≤25 μm) in four fly ash samples from fluidised bed combustion of three biomass based fuels and a municipal solid waste fuel were size separated using a centrifugal SPLITT fractionation cell. The ashes were separated into different size fractions and the cadmium concentration, partition and speciation in each separated fraction were then investigated in relation to their possible leaching.The fractionation was evaluated by environmental scanning electron microscopy, which also provided indications of the associations between Cd and other main elements on the particles through the use of X-ray fluorescence mapping. The total concentration of Cd in each fraction was determined by AAS analysis which showed different dependences on the ash particle size in the case of biomass or waste fuels. In addition, the speciation of Cd in each fraction, investigated by sequential chemical extractions and X-ray powder diffraction analysis, showed Cd to be present mainly as non-easy leachable forms, i.e. oxide and silicates. A readily leachable fraction was found only in the municipal solid waste fly ashes.     

The characteristics of inorganic elements in ashes from a 1 MW CFB biomass gasification power generation plant

This paper investigated the characteristics of inorganic elements in ashes from biomass gasification power generation (BGPG) plant. The ash samples of the gasifier ash, separator ash and wet scrubber ash were collected in a 1 MW circulating fluidized bed (CFB) wood gasification power generation plant. Particle size distribution of ashes was determined by gravimetric measurement and super probe analyzer. The concentrations of trace elements and major ash-forming elements, such as As, Al, Ca, Cd, Cr, Cu, K, Mg, Na, Ni, Pb, Ti in different ashes as a function of particle size were determined by Inductive Coupled Plasma Spectrometer. The concentrations and distribution coefficient and enrichment factors of the inorganic elements in ashes were studied. X-ray fluorescence spectrometer and X-ray powder diffraction were used to provide information on the characteristics of the ashes. The results showed that most of the trace elements had an enrichment tendency in the finer size particles. A considerable amount of the ashes was residual carbon. Most of the volatile e.g. halogen elements and alkali elements existed mainly in wet scrubber ash and enriched in fly ash. Most of the Si, Ni, Pb, Zn, Cr, Cd were found in separator ash, indicating an enrichment of heavy metal elements in separator ash. K, S, Mn, Cu mainly existed in gasifier ash.     

57Fe Mössbauer spectroscopic studies of fly ash from coal-fired power plants and bottom ash from lignite-natural gas combustion

A series of four fly ashes, representing a variety of geological origins, and a bottom ash sample derived from the combustion of lignite-natural gas mixtures have been studied by ⁵⁷Fe Mössbauer spectroscopy. The ashes are separated into magnetic and non-magnetic fractions to facilitate a study of the chemical state of the iron contained in the ash. The bottom ash contains no magnetic fraction whereas the magnetic fractions of the fly ashes range from 1.1 to 7.3%. The magnetic fractions contained iron in the form of magnetite, Fe₃O₄. Iron in the non-magnetic fly ash fractions occur as Fe⁺¹ and Fe⁺² mullites, and Fe⁺³ and Fe⁺² silicates. Only Fe⁺³ silicates are found in the bottom ash.     

A comprehensive characterisation of fly ash from a thermal power plant in Eastern India

A comprehensive characterisation of fly ash from Bokaro Thermal Power Plant, Jharkhand, India has been carried out for creating utilisation potential of the ash. As received fly ash, was size fractionated and the fractions were characterised. The non-magnetic and magnetic fractions of ash have been analysed in terms of their morphological, mineralogical features and physico-chemical properties. The results of such analysis reveal that there is a striking difference in the features and properties of the coarser and finer particles. The coarser fractions of the non-magnetic component seem to contain high percentage of char and semicoked/coked carbonaceous particles. The percentage of char albeit the carbon content decreases with decrease in size of the particles. The particles of the finer fractions have more spheroidal character than the coarser ones. The non-magnetic components essentially contain quartz and mullite as the main mineral phases. The magnetic component differs from the non-magnetic ones in respect of shape, mineralogical composition and carbon content. These are much more spheroidal than the non-magnetic ones. The ferrospheres present in these components bear crystallites with different geometrical patterns clearly indicating a definite degree of variation in the crystallisation process. Such comprehensive characterisation leads to not only a definite direction about the uses of the various fractions of the ash, but also gives useful informations regarding the prevailing combustion process.     

Ash behaviour of lignocellulosic biomass in bubbling fluidised bed combustion

The purpose of this work is to characterise biomass ash behaviour in a bubbling fluidised bed (BFB) combustion pilot plant (1 MWth) with silica as the bed material and using a woody biomass, poplar, and a herbaceous biomass, Brassica carinata. Ash characterisation and mass balances of the inorganic elements with relevance for bed agglomeration, fouling and emissions were performed in the BFB combustion pilot plant.The agglomerates formed in the silica bed material have not been found to be associated with chemical reaction sintering related to gas-solid reaction such as the formation of CaSO₄ and CaCO₃. Therefore this chemical reaction mechanism is neglected when it is compared to the bed agglomeration based on the partial melting of the alkaline compounds contained in the biomass ash. Similarities of crystalline phases and elemental content between ash deposited on the tubes and biomass ash obtained in laboratory at 550 °C enable to the laboratory tests of ash melting behaviour to predict the sintering in the ash deposited on the heat exchangers of the thermal plants.     

Characterisation of the glass fraction of a selection of European coal fly ashes

Fly ash largely consists of the inorganic content of coal that remains after combustion. The crystalline phases present in fly ash may form upon cooling of a molten alumino‐silicate glass. This view is supported by the spherical shape of many fly ash particles, inferring that they have gone through a viscous fluid state. The amorphous content in fly ash is believed to dominate reactivity behaviour, under both alkaline and acid conditions, because glasses have a higher potential energy than the equivalent crystal structure and the variation of bond angles and distances in a glass makes the bond breakage easier. It is the degradation behaviour under alkaline conditions, and the subsequent release of silica from the glass phase, that is important in the use of fly ash for conversion to zeolites and for pozzolanic applications in cement. This research comprehensively studies the composition, quantity and stability of the glass phase in a series of nine fly ashes sourced from Spanish and Italian power plants. The quantitative elemental composition of the glass phase in each fly ash was determined. Samples of the ashes then underwent a series of tests to determine the internal structure of the ash particles. Heat treatment of most of the ashes results in mullite crystallising from the glass phase; this is the crystalline phase that is predicated to form by both the relevant phase diagrams and also by NMR spectroscopy. In the ashes, mullite is present as a spherical shell, tracing the outline of the particle but in some specific cases the mullite skeleton is made up of coarse crystals reach also the internal parts of the particles. The morphology and density of the mullite crystals in these shells varies greatly. This work has supported the view that some crystalline phases present in fly ashes, such as mullite, form upon cooling of the amorphous glass melt as opposed to direct conversion from existing mineral phases in the coal during the combustion process. Copyright © 2004 Society of Chemical Industry     

Catalytic effect of biomass ash on CO, CH4 and HCN oxidation under fluidised bed combustor conditions

In fluidised bed combustion heterogeneous reactions catalysed by the bed material, CaO, and char are significant for the emission levels for instance of NO, N₂O, and CO. The catalysts present in the bed affect significantly the selectivity of HCN and NH₃ oxidation, which are known as precursors of NO_x (i.e. NO and NO₂) and N₂O emissions from solid fuel combustion. Thus the catalytic activity of biomass ashes may also be responsible for the negligible N₂O emissions from biomass combustion due to the presence of a large amount of solids in fluidised bed combustion, homogeneous oxidation may be suppressed within the bed by the quenching of the radicals. For this reason the catalytic oxidation of hydrocarbons and CO on the bed material may be of significance for the total burnout within the fluidised bed combustor.Within this study the effect of different ashes from spruce wood, peat, and for comparison bituminous coal on the oxidation of CH₄, CO, and HCN was studied. The different ashes were shown to have a strong catalytic activity for the oxidation of CH₄, CO, and HCN. In HCN oxidation the selectivity towards NO is high, whereas very little N₂O is formed. The activity of the ashes is strongly dependent on the fuel, which may be explained by their composition.The kinetics of the oxidation of CO and HCN in the temperature range relevant for fluidised bed combustion, i.e. 800-900 °C, has been evaluated for spruce wood ash.     

Mineralogy of western fly ash

Twenty-six fly ash specimens from North Dakota, Wyoming and Montana lignite and sub-bituminous source coals have been studied in detail by X-ray diffraction. Chemically, these western fly ashes are characterized by higher CaO+MgO+SO₃ contents and lower Al₂O₃+SiO₂ contents than eastern bituminous fly ashes. These western fly ashes have greater proportions of crystalline material. The characteristic phases are quartz, lime, periclase, anhydrite, ferrite spinel, tricalcium aluminate, merwinite and melilite. Alkali sulfates, a sodalite structure phase and hematite also occur in some fly ashes.     

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.     

High temperature elemental losses and mineralogical changes in common biomass ashes

The elemental losses from ashes of common biomass fuels (rice straw, wheat straw, and wood) were determined as a function of temperature from 525 °C to below 1525 °C, within the respective melting intervals. The experimental procedure was chosen to approach equilibrium conditions in an oxidizing atmosphere for the specific ash and temperature conditions. All experiments were conducted in air and used the ashes produced initially at temperatures of 525 °C as reactants. Losses during the initial ashing at 525 °C were negligible, except for a K₂O loss of 26% for wood and a Cl loss of 20% for wheat straw. Potassium losses are positively correlated with temperature for all fuel ashes. The K₂O loss for wood ash commences at 900–1000 °C. Carbonate is detected in the wood ashes to about 700–800 °C and thus cannot explain the retention of K₂O in the ashes to 1000 °C. Other crystalline phases detected in the wood ashes (pericline and larnite) contain little or no potassium. Petrographic examinations of high temperature, wood ash products have failed to reveal potassium bearing carbonates, sulfates, or silicates. The release of potassium, thus, appears to be unrelated to the breakdown of potassium-bearing crystalline phases. The straw ashes show restricted potassium loss compared to wood ash. The potassium content declines for both straw ashes from about 750 °C. Cristobalite appears in the straw ashes at about 700–750 °C and is replaced by tridymite in the rice straw ash from about 1100 °C. Sylvite (KCl) disappears completely above 1000 °C. The Cl content starts to decline at about 700 °C, approximately at the same temperature as potassium, suggesting that the breakdown of sylvite is responsible for the losses. The K–Cl relations demonstrate that about 50% of K (atomic basis) released from breakdown of sylvite is retained in the ash. The presence of chlorine in the ash is, therefore, best attributed to the presence of sylvite. Potassium is easily accommodated in the silicate melt formed at temperatures perhaps as low as 700–800 °C from dehydration, recrystallization, and partial melting of amorphous components. Loss of potassium persists for ashes without remaining sylvite and points to the importance of release of potassium from partial melt at temperatures within the melting interval for the fuel ashes.     

Characteristics and composition of fly ash from Canadian coal-fired power plants

Fly ashes were collected from the electrostatic precipitator (ESPs) and/or the baghouse of seven coal-fired power plants. The fly ashes were sampled from power plants that use pulverized subbituminous and bituminous feed coals. Fly ash from bituminous coals and limestone feed coals from fluidized-bed power plant were also sampled. The fly ashes were examined for their mineralogies and elemental compositions. The fly ashes from pulverized low sulfur coals are ferrocalsialic, those from high sulfur coals are ferrosialic and the fly ashes from the fluidized bed coals are ferrocalcic. The concentrations of As, Cd, Hg, Mo, Ni, and Pb in fly ash are related to the S content of the coal. Generally, those feed coals with a high S content contain higher concentrations of these elements. The concentrations of these elements are also greater for baghouse fly ash compared to ESP fly ash for the same station. The S content of fly ash from high S coal is 0.1% for pulverized ESP fly ash and 7% for baghouse fly ash from the fluidized bed, indicating that most of the S is captured by fly ash in the fluidized bed. The baghouse fly ash from the fluidized bed has the highest content of Cd, Hg, Mo, Pb, and Se, indicating that CaO, for the most part, captures them. Arsenic is captured by calcium-bearing minerals and hematite, and forms a stable complex of calcium or a transition metal of iron hydroxy arsenate hydrate [(M²⁺)₂Fe₃(AsO₄)₃(OH)₄·10H₂O] in the fly ash. Most elements in fly ash have enrichment indices of greater than 0.7 indicating that they are more enriched in the fly ash than in the feed coal, except for Hg in all ESP ashes. Mercury is an exception; it is more enriched in baghouse fly ash compared to ESP. Fly ash collected from a station equipped with hot side ESP has a lower concentration of Hg compared to stations equipped with cold side ESP using feed coals of similar rank and mercury content. Fly ash particles from fluidized bed coal are angular and subangular with cores of quartz and calcite. The quartz core is encased in layer(s) of calcium-rich aluminosilicates, and/or calcium/iron oxides. The calcite core is usually encased in an anhydrite shell.     

The roles of lime and iron oxide on the formation of ash and deposits in PF combustion

This paper presents the results of a study to assess the slagging propensities of a suite of UK, Spanish and South African coals, ranging from lignites to anthracites. Laboratory deposits were collected on ceramic deposition probes at gas temperatures of ∼1250°C, using an entrained flow reactor that simulates the time-temperature conditions experienced by pulverised coal particles in a large utility boiler. The degree of sintering and consolidation of the deposits would not have been predicted from bulk ash chemistry, indicating the importance of mineral matter distributions in the pulverised coal. Deposits with similar base to acid ratios and Fe₂O₃ contents displayed a range of slagging propensities on CCSEM analysis, consistent with the visual ranking. CCSEM analysis of the fly ashes collected from the combustion gases revealed a similar chemical composition to the coal ash and ash collected at the base of the EFR. CaO was observed to have readily assimilated into the aluminosilicate fly ash particles. On deposition, the CaO distribution largely remained unchanged. Fe₂O₃ was redistributed on forming a deposit possibly aided by CaO already dissolved in the aluminosilicates. The study provides an insight into the observations made by boiler operators burning coals with high CaO and Fe₂O₃ ashes.     

Agglomeration and strength development of deposits in CFBC boilers firing high-sulfur fuels

Fluidized bed combustor (FBC) ashes from high-sulfur, low-ash fuels, can agglomerate if subjected to sulfating conditions for long enough (days to weeks). The degree of sulphation increases with both temperature and time under these conditions, and at a conversion equivalent to the production of 50–60% or more of CaSO₄ in the deposit the ashes agglomerate. Fly ash agglomerates less readily than does bed and loop seal ash and produces weaker deposits, although all of these materials will agglomerate if sufficient time is allowed. The potential for agglomeration increases if the temperature is increased from 850 to 950°C. Agglomeration also occurs at lower temperatures (down to at least 750°C), but the mechanism may be via carbonation and then sulphation of the ash. Although experiments reported here suggest that if pure CaSO₄ is compressed to the 140 kPa range it does show some tendency to agglomerate, the agglomeration of FBC ash is not produced simply by the formation of CaSO₄. Finally, the agglomeration process is only weakly influenced by the partial pressure of SO₂ in the flue gas. Attempts to identify physical parameters to differentiate the tendency of various bed materials to agglomerate have been only partially successful. Two bed materials with strong and weak agglomerating tendencies were studied. These were shown to have very similar particle shapes and only slightly different angles of repose, but quite different bulk densities. Residues with a greater bulk density appear to have a stronger tendency to agglomerate, and this may provide a method of ranking the agglomeration potential of different bed materials.     

Effect of particle size distribution of fly ash-cement system on the fluidity of cement pastes

This paper investigates the effect of particle size distribution of fly ash-cement system on the fluidity of the cement pastes using class F fly ash collected from the hopper attached to an electrostatic precipitator when the burning conditions and types of coal are changed at a coal-fired power plant. The unburned carbon content of fly ashes used in the experiment is less than 1.5%. To prevent the unburned carbon in fly ashes from affecting the fluidity of the pastes, polycarboxylic acid plasticizer with more saturation amount is added into the pastes for experimentation. The particle size distribution of fly ash-cement system is analyzed using n value of Rosin-Rammler function and the n value is derived with a nonlinear least squares fitting method. As the result, it is shown that the fluidity increases as the particle size distribution becomes wider, i.e., as n value gets smaller.