Mineralogy of combustion wastes from coal-fired power stations

A combination of methods, including separation procedures, light microscopy, SEM, TEM, XRD and DTA-TGA methods, were used to characterize the phase-mineralogical and chemical composition, microstructural and some genetic phase peculiarities of solid waste products from coal burning. Fly ashes, bottom ashes and lagooned ashes from eleven Bulgarian thermoelectric power stations were studied. These products comprise inorganic and organic constituents. The inorganic part consists mainly of non-crystalline (amorphous) components and lesser amounts of crystalline components represented by various major, minor and accessory mineral phases. The organic constituent contains unburnt coal components represented by slightly changed, semicoked and coked coal particles. The origin of solid phases could be: primary — minerals and phases contained in coal and having undergone no phase transition (silicates, oxides, volcanic glass, coal particles); secondary — phases formed during burning (magnetite, hematite, metakaolinite, mullite, anhydrite, lime, periclase, CaMg silicates, glass, semicoke, coke); or tertiary — minerals and phases formed during the transport and storage of fly ashes and bottom ashes (sulphates, carbonates and oxyhydroxides).     

固硫灰渣的基本特性及其作水泥混合材的关键问题研究进展

固硫灰渣是循环流化床燃煤技术的主要副产物,如何高效、清洁地利用这一类固体废弃物是一个亟待解决的问题。本文根据近年来国内外对固硫灰渣的研究成果,从化学组成、矿物组成、微观结构、典型特性等方面综述了固硫灰渣的主要特征。相较于粉煤灰等其他燃煤副产物,固硫灰渣中存在游离氧化钙、硫酸钙和无定形铝硅酸盐物质,且颗粒疏松多孔,这导致其具有明显的火山灰活性、自硬性和水化膨胀性等特性。同时本文分析了固硫灰渣作为水泥混合材使用时需要注意的几个关键问题。结果表明,固硫灰渣特殊的组成、微结构和性质导致其作为水泥混合材使用时,必须考虑使用合适的激发剂提高灰渣活性,调整养护工艺、用水量等条件提高制品的安定性,并以添加减水剂等方式控制水泥制浆中的需水量,提高水泥石强度。这为有效实现固硫灰渣的建材资源化利用提供一定指导。     

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.     

Variation in fly ash properties with milling and acid leaching

Coal-burning power plants that consume pulverized solid fuels produce large amounts of fly ash as a residue. Fly ashes have been used in construction, agriculture, metal recovery and water pollution control. This paper considers the variation in properties of fly ashes to be used in the field of construction.The fly ashes produced in two coal-burning power plants in Asturias (Spain) were physically and chemically characterized in order to determine their pozzolanic activity and reactivity. Fly ashes are used as hydraulically active additives as they are a finely divided inorganic material. They were examined to determine whether they could be used as special preservatives in cements and concretes. To improve their properties, they are mechanically activated by wet milling as well as chemically activated by leaching with 30% by weight sulfuric acid at different temperatures and times.     

The chemistry and mineralogy of the Negev oil shale ashes

The characteristic feature of the oil shale ashes produced by fluidized bed combustion (700-800 °C) in PAMA's demonstration power plant is the large amount of amorphous phases, Ca-Al-silicates and Al-silicates, together with anhydrite and lime. Practically all the S and heavy metals in the oil shales are retained in the ash, which, from an ecological point of view, is important. Two kinds of ashes were examined: industrial ashes produced at PAMA's demonstration plant and ashes produced in laboratory experiments. Three different types of ash are produced at the demonstration plant. Ash Cooler (AC), which is comparable to bottom ash in coal power plants. This ash is produced from oil shale subjected to the lowest temperatures and is the most coarse-grained. It contains relatively larger quantities of unaltered minerals (calcite, clays, apatite, etc.) than the other two. The two other ashes Boiler Bank (BB) and Fly Ash (FAS) are not much different from each other and both may be compared to fly ash in coal power plants. Both BB and FAS ashes contain more authigenic (formed in the boiler) phases than AC. The results of the laboratory experiments show that the main factor in the raw material controlling the mineralogy and chemistry of the oil shale ashes is the Al₂O₃ concentration (clay content), and not the organic matter concentration.     

Comparison of calculated mercury emissions from three Alberta power plants over a 33 week period - Influence of geological environment

Feed coals and fly ashes from two coal-fired power plants burning Alberta subbituminous coal were analyzed for C, Cl, Hg, and S and calorific values (for feed coal only), every week for a period of 33 weeks. The feed coals used in this study were deposited in brackish water and are compared to the coals deposited in a freshwater environment. The Hg and char (unburnt carbon) content of the fly ash was monitored to determine the variation of Hg and its possible relationship to the char types in the fly ash. The feed coals have Hg content of 0.026-0.089 mg/kg and their fly ash contains 0.02-0.243 mg/kg of Hg. The C content of the fly ashes ranges from 0.15% to 0.51%. The carbon/char was separated from the fly ash using HF and HCl. Reactive vitrinitic (formed from woody part of plants) and less reactive inertinitic (natural char) chars were separated by density separations of various specific gravities using ZnBr₂.The char is mostly reactive vitrinitic (67-80 vol.%). Both stations have similar range of C content for their respective fly ashes. However, station 2 shows a much wider range of Hg in fly ash compared to station 1. In general, the fly ash from coal deposited under brackish water environment (stations 1 and 2) appears to have same or higher Hg content for lower C content compared to the fly ash from coal deposited under fresh water environment.The calculated emitted Hg for the period of 33 weeks for station 1 is estimated to be 64-90% of the total input of Hg with an average of 74%. The calculated emitted Hg shows a more complex pattern for station 2 and falls into two groups; with group (a) showing higher enrichment index for both Hg and S. The calculated emitted Hg for this group is 43-74% with an average of 57%, indicative of more Hg being captured by fly ash, possibly due to interaction between Hg and S. In the second group (b) the emitted Hg is calculated to be 74-95% with an average of 85%. The relative enrichment of both Hg and S in group (b) is low compared to group (a), indicative of possible slight paleo-weathering of the feed coal.The present study indicates that geological parameters such as paleo weathering and also depositional environment of the feed coal may influence the Hg content of fly ash.     

Physico-chemical characteristics of European pulverized coal combustion fly ashes

Fly ashes sourced from European pulverised coal burning power plants (from Spain, The Netherlands, Italy and Greece) were characterised in terms of their chemical composition, mineralogy and physical properties. The amount and composition of the glass present in the ashes were also determined. The materials analysed have very different compositions and were selected with a view to determining their suitability for different applications and for further studies on applications. The results were compared to the literature to determine their similarities to UK coal fly ashes. Chemical analysis has enabled the categorisation of the ashes based on their oxide contents. Devitrification of the glass phase has been effected using suitable heat treatments and crystal phases formed are used as an indicator of glass reactivity. Based on leaching tests, certain ashes were identified as having limitations for some further uses due to the relatively high levels of leachable trace elements. A wide range of physical properties such as density were observed and these are related to factors such as mineralogical content and particle morphology.     

Neapolitan Yellow Tuff as raw material for lightweight aggregates in lightweight structural concrete production

The possibility of using Italian zeolitized volcanoclastites for the production of lightweight aggregates in the building industry has been tested.The present paper definitely demonstrates the good attitude of the Neapolitan Yellow Tuff (NYT) for the production of lightweight expanded aggregates (LEA) with bulk densities ranging between 0.9 and 1.1 g/cm³. LEAs showing these features, usually manufactured with clays, are mainly used in the production of lightweight structural concretes (LSC). The physical characterization of LEAs was carried out by means of: grain size analysis, loose weight, mean density of the single grain, water absorption after 30 min and 24 h, and strength of particles (UNI-7549). Afterwards, LEAs were mixed with sand, cement and water to prepare cubic concrete blocks following the UNI specifications (UNI-7549-12). On these specimens, the unit weight and uniaxial compressive strength after 28 days were determined.The investigated parameters measured both on LEAs and concretes, are comparable with those measured on materials commonly traded in Italy.The obtained results foresee interesting potential applications of a raw material characterized by a low exploitation cost and a widespread availability on the Italian territory.     

Behaviour of elements and minerals during preparation and combustion of the Pernik coal,Bulgaria

The chemical and mineral composition, including major (Al, Ca, Fe, K, Mg, S, Si, Ti), minor (Na, P) and trace (Br, Cl, Co, Cr, Cu, Li, Mn, Ni, Pb, Rb, Sr, Zn) elements and different minerals, of the Pernik subbituminous coals and their preparation and combustion solid waste products were studied. Feed coals, upgraded coals (high-grade and low-grade coals) and their waste products, namely coal slimes and host rocks generated from the Pernik coal preparation plant, as well as combustion waste products such as bottom ashes, fly ashes and lagooned ashes resulted from the Republica coal-fired thermoelectric power station were characterized. The occurrence and behaviour (partitioning, volatilization, condensation, capture and retention) of the above-mentioned elements and various minerals during coal preparation and combustion are described. The results indicate some technological problems and possible environmental pollution of the air, water, soil and vegetation with certain elements in the areas surrounding both thermoelectric power station and coal preparation plant.     

Use of mineral coal ashes in insulating refractory brick

Coal ash from Candiota thermoelectric power plant in southern Brazil is a waste generated in great amount. Current estimates indicate that coal ash production is likely to reach 2.000.000 tons per year. Of this total, only 10% are commercialized, so the price of this material is very low. In this work, it was investigated the use of coal ashes in a composition of refractory insulating brick. In coal combustion process, fly ashes and bottom ashes are generated. Bottom ashes are formed by partially fused ashes that precipitate to the bottom of the boiler, due to their coarser particle size. Therefore, it was analyzed fly ash addition in a refractory body and the addition of bottom ashes, partially replacing chamote (calcinated clay). The results showed that the effect of the ash is small in the fired materials. In terms of technological characterization, the bricks formulates with coal ash were considered suitable to commercial brick standards. Density and thermal conductivity of the refractory bricks with coal ashes had revealed to be similar the commercial products. Then, the use of ash is economical attractive and technical feasible. Translated from Novye Ogneupory, No. 6, pp. 60–63, June 2008.     

Lightweight geopolymer concrete: A critical review on the feasibility,mixture design,durability properties,and microstructure

Lightweight geopolymer concretes have gained attention because of their superior durability, lower environmental impact and sustainable characteristics. They are the product of natural or artificial aggregates with low specific gravities mixed with aluminosilicate binders, and an alkaline solution. In this study, different aspects of lightweight geopolymer concretes and mortars such as environmental and economic considerations, materials and mixture, durability-related properties like permeability, chloride attacks and performance at high temperatures, thermal conductivity, and the microstructure are reviewed. This study also discusses the effect of different geopolymer binders and various alkaline activators and additives with focus on lightweight geopolymer concrete made with different lightweight aggregates. The key results from previous studies in literature pertaining mix proportions, chemical composition and properties of lightweight geopolymers are summarized and presented. The main aim is to provide an informed outlook on the advantages and drawbacks of lightweight geopolymer concretes and present a comprehensive review of the studies performed in this area.     

Biomass fly ash in concrete: Mixture proportioning and mechanical properties

ASTM C 618 prohibits use of biomass fly ashes in concrete. This document compares the properties of biomass fly ashes from cofired (herbaceous with coal), pure wood combustion and blended (pure wood fly ash blended with coal fly ash) to those of coal fly ash in concrete. The results illustrate that with 25% replacement (wt%) of cement by fly ash, the compressive strength (one day to one year) and the flexure strength (at 56th day curing) of cofired and blended biomass fly ash concrete is statistically equal to that of two coal fly ash concrete in this investigation (at 95% confidence interval). This implies that biomass fly ash with co-firing concentration within the concentration interest to commercial coal-biomass co-firing operations at power plants and blended biomass fly ash within a certain blending ratio should be considered in concrete.     

Use of zeolite-rich rocks and waste materials for the production of structural lightweight concretes

This paper aims at testing the use of mixtures constituted by natural zeolitized products and SiC-bearing industrial wastes (sludge deriving from polishing of porcelain stoneware tiles, hereafter DPM) for the production of lightweight expanded aggregates as constituents of structural and/or thermo-insulating lightweight concretes. Two commercial products have been used as zeolite natural source: Cab70 (Yellow facies of Campanian Ignimbrite) and IZclino (Turkish clinoptilolite-rich epiclastite). Different amounts of a calcareous material (Pozzano limestones — hereafter CP) from the Sorrento peninsula (Naples — Italy) were also added to a Cab70–DPM mixture. All raw materials were characterized by means of mineralogical (XRPD) and chemical (XRF) analyses. All the products and mixtures were tested from a technological point of view by means of fusibility and firing tests in order to evaluate the expanding properties. It was evidenced that the expansion of the mixture was deeply depending on the occurrence of SiC in the industrial waste. The addition of CP (10 wt.%) to the mixtures accounts for an even increased expansion, though this is accompanied by a worsening of the mechanical features of the material.These results along with literature data allowed to select 3 mixtures (70% Cab70–30% DPM, 70% IZclino–30% DPM, 60% Cab70–30% DPM–10% CP) and each of them was used for the preparation of 5 l of lightweight aggregates afterward employed for the manufacture of lightweight concretes. It was remarked that natural zeolitized materials mixed with DPM (30 wt.%) can provide lightweight aggregates with densities ranging between 0.8 and 1.0 g/cm³ suitable for the preparation of structural lightweight concretes. The addition to the mixture of CP (10 wt.%) produces less dense aggregates (0.6–0.7 g/cm³) potentially useful for the manufacture of thermo insulating lightweight concretes.     

Leaching characteristics of selected Korean fly ashes and its implications for the groundwater composition near the ash disposal mound

Currently only 20% of the fly ash produced in Korea is utilised for industry, and the remainder is disposed as waste in landfill sites. Both anthracite and sub-bituminous coals are burnt in Korea. Fly ash and coal samples were collected from five different coal-fired power stations in Korea and analysed for their chemistry and mineralogy. Batch leaching tests were also carried out to investigate the leaching behaviour of selected fly ashes. The fly ash leachate chemistry was compared with the groundwater taken directly from the monitoring well installed in one of the power stations. The anthracite coals contain illite, pyrophyllite and kaolinite whereas kaolinite is the representative clay mineral for the sub-bituminous coals. Anthracite coals were higher in Si, Al and K than the sub-bituminous coals, reflecting higher mineral matter contents in the anthracite coals. Mullite and quartz are the main mineral phases for two different types of the fly ashes, with some iron oxides. The chemical compositions of the anthracite and sub-bituminous fly ashes are comparable with each other, except for extraordinary high concentrations of Cr for one anthracite fly ash. Most of the trace elements in the ash were enriched in the finer fraction, indicating surface associations. Although, some elements including Na, K, Ca and Cu were released rapidly in the initial stage of leaching, measurable amounts of metals were still detectable in the fly ash leachate treated several times with distilled water. Such leaching behaviour indicates slow and long-term leaching of elements associated with the glass fractions of the ash particle. This was confirmed by leaching of weathered fly ash, which had been disposed of for several years. Comparison of the ash leachate, treated with 0.1N-HCl, fly ash slurry in the ash pond and the groundwater indicate the influence of the ash leachate from the ash disposal mound on the groundwater composition.     

Phase-mineral and chemical composition of coal fly ashes as a basis for their multicomponent utilization. 1. Characterization of feed coals and fly ashes

The phase-mineral and chemical composition of feed coals and their fly ashes (FAs) produced in four large Spanish thermo-electric power stations was characterized as a basis for multicomponent FA utilization. The feed fuels used are bituminous coals, semi-anthracites and anthracites with high detrital mineral abundance and mixed carbonate and sulphide-sulphate authigenic mineral tendency. Their mineral composition includes quartz, kaolinite, illite-muscovite, pyrite, chlorite, plagioclase, K-feldspar, gypsum, siderite, calcite, dolomite, marcasite, montmorillonite, jarosite, and ankerite. The FAs studied have aluminosilicate composition with higher concentrations of alkaline and alkaline-earth oxides than Fe oxide. Elements such as Ag, As, Ba, Cr, Cs, Li, P, Sb, Sc, Sn, Sr, Ti, V, Zn, and Zr are relatively enriched in these FAs in comparison with the respective mean values for bituminous coal ashes worldwide. The FAs consist basically of aluminosilicate glass, to a lesser extent of mineral matter (with high silicate abundance and dominant oxide tendency) and moderate char occurrence. The phase-mineral composition (in decreasing order of significance) of these FAs is normally glass, mullite, quartz, char, kaolinite-metakaolinite, hematite, cristobalite, plagioclase, K-feldspar, melilite, anhydrite, wollastonite, magnetite and corundum plus 42 important accessory minerals or phases. A scheme of conventional separation procedures was applied to recover sequentially six initial and potentially useful and/or hazardous products from FAs, namely: (1) a ceramic cenosphere concentrate; (2) a water-soluble salt concentrate; (3) a magnetic concentrate; (4) a char concentrate; (5) a heavy concentrate; and finally (6) an improved FA residue.     

Composition and morphology of char particles of fly ashes from industrial burning of high-ash coals with different reactivity

A comparative investigation of the composition and the morphology of char particles was conducted: char particles were recovered from fly ashes of two power stations in Russia from burning of high- and low-reactivity high-ash coals; the known results of studies of char particles generated in laboratory conditions from coals characterized according to the ASTM D388-98a standard were also used. The composition of organic and mineral components of different fraction char particles was studied. An inverse correlation between the content of the organic substance and the iron content in char particles was identified. The morphology of the char particles for the three main types (Cenospheric, Network and Solid) and the influence of coal reactivity and temperature on char morphology were investigated. The morphology of the mineral component of char particles of the two varieties of coals was also studied. It was shown that the high-temperature of industrial burning of Ekibastuz coal results in melting of the mineral substance and forming of micron-scale microspheres located in the lamellar porous structure of the carbon matrix.     

The fate of trace elements and bulk minerals in pulverized coal combustion in a power station

The behaviour of 15 trace elements (As, Ba, Cr, Cu, Mn, Mo, Nb, Ni, Pb, Rb, Sr, V, Y, Zn and Zr) and 10 major and minor elements (Al, Ca, Fe, K, Mg, Na, P, S, Si and Ti) in coal during combustion in a power station has been studied. Synchronized sampling of pulverized coal, bottom ash and fly ash was undertaken over a limited time period. Fly ash morphology was studied by SEM and the mineral composition was studied by EDX and XRD. Major, minor and trace elements were determined by XRF and AAS. Differences between the composition of the ashes of pulverized coal, bottom ashes and fly ashes have been observed. As, Cu, Mo, Pb and Zn were concentrated in the fly ash. The relationship between the composition of the fly ashes and their particle size was studied. Enrichment factors were calculated for each element in different size fractions. As the particle sizes of fly ash decrease, the concentrations of As, Cu, Mo, Pb and Zn increase. From the different composition of bottom ashes and fly ashes (and relying on the results of the characterization of the feed coal carried out in previous work), it can be assumed that pyrite and carbonates make a greater contribution to the furnace bottom ashes. Quartz carries through into the fly ash. This mineral is almost absent in the finest fractions, reflecting the absence of small quartz particles in the feed coal.     

Utilization of solid wastes from the gasification of coal-water slurries

It was found that only fly and bottom ashes are the solid wastes of water-coal slurry gasification in a direct-flow gasifier. The yields and chemical compositions of fly and bottom ashes obtained after the gasification of water-coal slurries prepared using brown (B) and long-flame (D) coals from the Berezovskii and Mokhovskii strip mines (Kansk-Achinsk and Kuznetsk Basins, respectively) were characterized. Based on an analysis of currently available information, the areas of utilization of fly and bottom ashes after water-coal slurry gasification with dry ash removal were summarized. The use of these wastes in the construction of high-ways and earthwork structures (for the parent coals of B and D grades) and in the manufacture of ash concrete (for the parent coal of D grade) is most promising.     

Bond strength evaluation of palm oil fuel ash-based geopolymer normal weight and lightweight concretes with steel reinforcement

This article presents a comparison of the bond behaviour between palm oil fuel ash (POFA)-derived geopolymer and conventional cement-based normal weight and lightweight concretes. A total of 16 variables were tested, which includes concrete cover (50 and 100 mm), bar diameter (12 and 16 mm) and types of concrete (POFA-based geopolymer normal/ lightweight concrete and cement-based normal/lightweight concrete). Results showed that the bond strength of cement-based concretes had higher critical bond stress and ultimate bond strength as well as lower slip at the ultimate bond strength compared to the corresponding POFA-based geopolymer concretes. The cement-based and geopolymer lightweight concrete specimens also exhibited greater bond strength than the normal weight concrete specimens. All of the concrete specimens generally exhibited similar bond stress-slip curves. Besides that, bond strength models proposed in the past predicted satisfactory match (difference of up to 35%) to the experimental ultimate bond strength values in the case of cement-based normal weight concrete and geopolymer concrete whereas a difference in the range of 16–138% was found for the case of lightweight concrete.     

Mercury and selenium retention in fly ashes: Influence of unburned particle content

Mercury and selenium are present as trace elements in coal and may be emitted to the environment in gas phase during coal conversion processes or be partially retained on the fly ashes. The present work explores the possibility that selenium may contribute to mercury capture in fly ashes in two different situations: firstly the power station itself, in order to evaluate the influence of typical working conditions, and secondly in a fixed bed of fly ashes enriched with Se, in order to study the capture of mercury in more severe conditions. It was found that the presence of selenium in fly ashes may improve their capacity to capture mercury. However, in the four fly ashes of different origin studied, selenium is not the most important component for mercury retention. In fact, the presence of selenium in fly ash samples enriched in unburned carbon does not have any significant effect on mercury retention.