Reduction of metal leaching in brown coal fly ash using geopolymers

Current regulations classify fly ash as a prescribed waste and prohibit its disposal in regular landfill. Treatment of the fly ash can reduce the leach rate of metals, and allow it to be disposed in less prescribed landfill. A geopolymer matrix was investigated as a potential stabilisation method for brown coal fly ash. Precipitator fly ash was obtained from electrostatic precipitators and leached fly ash was collected from ash disposal ponds, and leaching tests were conducted on both types of geopolymer stabilised fly ashes. The ratio of fly ash to geopolymer was varied to determine the effects of different compositions on leaching rates. Fourteen metals and heavy metals were targeted during the leaching tests and the results indicate that a geopolymer is effective at reducing the leach rates of many metals from the fly ash, such as calcium, arsenic, selenium, strontium and barium. The major element leachate concentrations obtained from leached fly ash were in general lower than that of precipitator fly ash. Conversely, heavy metal leachate concentrations were lower in precipitator fly ash than leached pond fly ash. The maximum addition of fly ash to this geopolymer was found to be 60wt% for fly ash obtained from the electrostatic precipitators and 70wt% for fly ash obtained from ash disposal ponds. The formation of geopolymer in the presence of fly ash was studied using 29Si MAS-NMR and showed that a geopolymer matrix was formed. X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) imaging showed the interaction of the fly ash with the geopolymer, which was related to the leachate data and also the maximum percentage fly ash addition.     

Evaluation of engineering properties for the use of leached brown coal ash in soil covers

The need to engineer cover systems for the successful rehabilitation or remediation of a wide variety of solid wastes is increasing. Some common applications include landfills, hazardous waste repositories, or mine tailings dams and waste rock/overburden dumps. The brown coal industry of the Latrobe Valley region of Victoria, Australia, produces significant quantities of coal ash and overburden annually. There are some site-specific acid mine drainage (AMD) issues associated with overburden material. This needs to be addressed both during the operational phase of a project and during rehabilitation. An innovative approach was taken to investigate the potential to use leached brown coal ash in engineered soil covers on this overburden dump. The basis for this is two-fold: first, the ash has favourable physical characteristics for use in cover systems (such as high storage capacity/porosity, moderately low permeability, and an ability to act as a capillary break layer generating minimal leachate or seepage); and second, the leachate from the ash is mildly alkaline (which can help to mitigate and reduce the risk of AMD). This paper will review the engineering issues involved in using leached brown coal ash in designing soil covers for potentially acid-forming overburden dumps. It presents the results of laboratory work investigating the technical feasibility of using leached brown coal ash in engineered solid waste cover systems.     

MSW fly ash stabilized with coal ash for geotechnical application

The solidification and stabilization of municipal solid waste (MSW) fly ash for the purpose of minimizing the geo-environmental impact caused by toxic heavy metals as well as ensuring engineering safety (strength and soaking durability) are experimentally evaluated. The mixtures of MSW fly ash stabilized with cement and fluidized bed combustion coal fly ash (FCA) were used for unconfined compressive strength tests, leachate tests, and soaking tests. The behavior of soluble salts contained in the MSW fly ash significantly affects strength development, soaking durability, and the hardening reaction of the stabilized MSW fly ash mixtures. The cement stabilization of the MSW fly ash does not have enough effect on strength development and soaking durability. The addition of cement only contributes to the containment of heavy metals due to the high level of alkalinity. When using FCA as a stabilizing agent for MSW fly ash, the mixture exhibits high strength and durability. However, the Cd leachate cannot be prevented in the early stages of curing. Using a combination of cement and FCA as a MSW fly ash stabilizer can attain high strength, high soaking durability, and the containment of heavy metals. The stabilized MSW fly ash with cement and FCA can be practically applied to embankments.     

Utilization of coal fly ash in the glass-ceramic production

Manufacturing the glass-ceramic has been proposed as a useful choice to recycle coal fly ash from power plants. In this work, a glass-ceramic of SiO2-Al2O3-Fe2O3-CaO family was synthesized by mixing 90 wt% of coal fly ash, from a power plant in west of China, with Na2O, and then melted at 1350 degrees C. The ceramization of the obtained glass was carried out at 770 degrees C for 2h. Esseneite and nepheline were found present as major crystal phases. The produced glass-ceramic exhibited good chemical durability as well as good mechanical properties. The toxicity characteristic leaching procedure (TCLP) method found that the glass-ceramic was non-hazardous.     

Grain characteristics and engineering properties of coal ash

Ash produced by the coal fired thermal plants is often used as a geo-material where its characteristics and mechanical behavior is important. The present study describes an investigation into the grain characteristics and the engineering properties of coal ash. The results of x-ray diffraction, micrographic observation and grain size distribution are analyzed in relation to maximum and minimum void ratio, permeability, compressibility and frictional properties. The grain size is found to be a significant grain characteristic that may be used for classification of ash as well as interpretation of primary, secondary and index properties. The compressibility and frictional characteristics depend on stress environment and packing with respect to a critical state uniquely identified by material characteristics. The fitting parameters for the selected sets of samples have been evaluated for the Ropar coal ash. This study presents the data and the correlations that are pertinent to a wider community of geo-technical and geo-environmental engineers interested in the utilization of coal ash as a structural fill.     

Ultimate bearing capacity of footings on coal ash

Coal ash is recognized as an alternative fill material to the conventional natural soils near a coal fired thermal power station where its large deposits are available. This paper presents experimental investigations on footings on coal ash subjected to loads. A series of laboratory model tests on varying sizes of footings were conducted. The conventional bearing capacity evaluation methods applied for natural soils do not consider progressive failure. These effects are explained based on the non-linear strength behavior of the granular soil and occurrence of progressive failure. The classical bearing capacity theory was applied in relation to the relative dilatancy of coal ash to describe this phenomenon. Few novel observations presented here show that the extent of progressive failure of ash fills is a compressed function of material characteristics of the ash, size and depth of footing and the settlement ratio.     

The surface chemistry of leaching coal fly ash

The utilization of coal fly ash in the construction and non-construction areas has seen a rapid growth in the last decade. As production outweighs the utilization of fly ash, its disposal as a dilute or dense slurry is still practiced in coal fired power stations. In this review the surface chemistry of leaching coal fly ash is presented to highlight the role of mass transfer in providing resistance and consequently delayed leaching of elements, when fly ash is disposed or used for value addition.     

Assessment of the multi-scale leaching behaviour of compacted coal fly ash

Peer experimental-modelling tools were developed and applied in the case of coal fly ashes with the aim to assess the leaching behaviour of ash compacted layers in a use scenario. Laboratory-scale (dissolution kinetics, ANC test, column percolation) and field pilot experimental studies (release monitoring during 18 month, hydrodynamic study, ANC on 44 month leached waste) were performed in order to identify and quantify the main transport phenomena and chemical processes. A quantitative geochemical model was developed taking into account equilibrium chemical reactions as well as kinetic processes for silicate phases like albite, K-feldspar and Ca-olivine. Phases like BaHAsO(4) and a solid solution Ba(x)Sr(1-x)(SO(4))(y)(CrO(4))(1-y) were proposed to explain the complex leaching behaviour of As, Cr, Ba, S; the soluble CaMoO(4) seems to control the Mo concentration. At neutral and acid pH, the model of surface complexation on ferric hydroxides was added for describing the behaviour of As, Cr, and Mo. At each scale the dynamic processes were identified and quantified by modelling. During the first contact with water an equilibration time of about 10 days was identified and then considered in all other laboratory experiments (ANC, column percolation). The hydrodynamic properties of compacted fly ashes were identified: a high water retention capacity (97% of the pores are still filled after draining under normal pressure), a flow regime close to plug type, a low fraction of stagnant zones (<0.03%). The scenario factors like carbonation and rainfall play an important role on the leaching behaviour at field scale. The carbonation diminishes the leachate pH from 11 to 8.5. The alternation of rain periods determines an apparent batch behaviour which slows down the outflow of the initial soluble fraction in pore water, if compared with the laboratory percolation column. The coupled geochemical-transport model was validated by comparison of the simulation results on ANC data obtained on the waste after 44 months of leaching under natural conditions.     

Deposition characteristics of coal ash slurries at higher concentrations

High concentration slurry disposal system (HCSD) for transportation of coal ash to ash ponds from coal fired thermal power plants using pipelines has emerged as an economical and environmental friendly method. Coal Ash in slurry form is deposited in the ash pond and hence the deposition characteristics at higher concentrations (C_w >60% by weight) are very important. The settled solid profile in the ash pond at high concentrations is of great interest to the ash pond designers. The present study is an attempt to establish the relationship between the settled solid profile and the physical/rheological properties of coal ash slurry at high concentrations. The settled solid profile is experimentally measured in terms of cone angle for slurries of fly ash as well as mixture of fly ash (FA) and bottom ash (BA) in the ratio of 4:1 at high concentrations. The values of cone angle if the slurries are poured on either a pervious or impervious bed have also been measured. The results obtained from the experiments show that the cone angle depends on rheological properties like yield stress and Bingham plastic viscosity which in turn depend on various properties like solid concentration, particle size distribution etc. Also, cone angle for fly ash slurry is higher than that for the mixture of FA and BA slurry at any given concentration. Further, it was also observed from the experiments that cone angle is higher for pervious bed as compared to impervious bed for both types of slurries.     

Formation process of Na-X zeolites from coal fly ash

In order to synthesize Na-X zeolite from coal fly ash (Fa), Fa was pretreated under stirring condition at various temperatures of 20–50°C for 72 h and then aged at 85°C for a given period with NaOH solutions. The resulting materials were characterized by various means. When Fa was aged for 72 h without pretreatment, species P were formed. As the pretreating temperature raised from 20 to 50°C, the degree of crystallinity of faujasite increased, while that of species P decreased. The faujasite species formed was identified as Na-X zeolite with molar ratio SiO₂/Al₂O₃ = 2.4. When Fa was pretreated at 50°C and aged for 60 h, the only species formed was Na-X zeolite. Increasing the pretreating temperature up to 50°C results in the increase of Si⁴⁺ and Al³⁺ concentrations in the treating solution by dissolution of amorphous material in Fa. With the conditions used, the crystalline phase, such as -quartz and mullite, was poorly dissolved during the treatment. Hence, the higher pretreating temperature would give the uniform nucleation and crystal growth of Na-X zeolite during the aging.     

Solidification of coal fly ash using hydrothermal processing method

Solidification of Coal Fly-ash (CFA) has been carried out using a hydrothermal processing method. In the hydrothermal processing, the CFA was first compacted in a mold at 20 - 50 MPa, and then hydrothermally cured in an autoclave. The hydrothermal curing was performed at 150 – 250°C for 15 – 60 h. The experimental results showed that NaOH solution, Ca(OH)₂ content, compaction pressure, autoclave curing temperature and time significantly affected the strength of solidified bodies. The most important strength-producing constituent in the solidified bodies produced with CFA was tobermorite, or tobermorite-like calcium silicate hydrate. When the CaO/SiO₂ ratio of the starting material was close to 0.83, tobermorite readily formed and the formed tobermorite enhanced the strength of solidified bodies. The tensile strength determined by the Brazilian test reached more than 10 MPa under the hydrothermal processing. As such, the hydrothermal processing method may provide a high potential for recycling CFA on a large scale.     

In situ high-temperature powder diffraction studies of solid oxide electrolyte direct carbon fuel cell materials in the presence of brown coal

Direct carbon fuel cells are an attractive alternative for conventional power generation; however, there is almost no information on the stability of conventional fuel cell materials in direct carbon fuel cell environments, in particular when exposed to realistic fuels and the contaminants contained within these fuels. Similarly, there is little information on the structure and phase assemblage of solid fuels exposed to typical environments found in direct carbon fuel cells. In this paper, we use in situ high-resolution synchrotron powder diffraction on conventional high-temperature fuel cell materials and untreated brown coal to assess the stability and reactivity of these materials at various temperatures up to 850 °C. Materials investigated include nickel metal (Ni), gadolinium-doped ceria (GDC) and yttria-stabilised zirconia (YSZ). The phase stability, crystallite size, lattice parameters and associated linear coefficient of thermal expansion were determined. The phase stability of all fuel cell materials was found to be good with no additional phase formation noted either during heating or after prolonged periods at temperature. An increase in the crystallite size was observed for both GDC and Ni. Non-linear thermal expansion observed in these materials was related to partial reduction of cerium ions (GDC) and due to a Curie point transition (Ni). A wide range of mineral phases were observed in the coal samples and these phases were found to change significantly with temperature. Mineral phases consistent with the ash composition and existing literature on Victorian brown coal were assigned to phases observed.     

Mechanochemical activation of iron ore-based catalysts for the hydrogenation of brown coal

Genesis of pyrrhotite catalysts from different iron ore concentrates and pure iron oxides was investigated using the method of mechanochemical treatment in a planetary mill. The dispersion and fine crystalline structure of oxide and pyrrhotite particles were studied as the function of mechanical load, sulfiding temperature and mode of preparation. Methods for the preparation of high performance iron ore-based catalysts for brown coal hydrogenation have been developed. Received 16 May 2000 / Reviewed and accepted: 8 June 2000     

Sintered coal ash/flux materials for building materials

An Illinois coal ash, which has metals and a large amount of iron, is considered to be an especially difficult waster for disposal. In the process described in this paper, the high iron and metal content is used to create a building material with special properties. The metals are sequestered. The metals allow a process that creates valueadded products, building materials. The products are inexpensively prepared colored, strong, lightweight insulative structural panels. By either sintering in an oven at 725°C or by adding a flux and sintering at 525°C, panels are produced which will not leach metals from the ash. The use of an acid with the fly ash as a flux was investigated in comparison with fly ash control samples. The effects of sintering samples at different temperatures and with or without vacuum were also observed. Properties of the samples, including values for strength, water absorption, insulation, and color, are presented from this study.

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Résumé Une cendre de charbon de l'Illinois, qui a des métaux et une grande quantité de fer, est considérée comme un déchet particulièrement difficile à éliminer. Dans le processus décrit par cette étude, la teneur élevée en fer et en métal est utilisée pour créer un matériau de construction avec des propriétés spéciales. Les métaux sont isolés. Les métaux permettent un processus qui crée de la valeur ajoutée. Les produits sont des panneaux structuraux isolés, colorés, forts et légers qui sont préparés à peu de frais. On produit des panneaux qui ne lixivieront pas les métaux de la cendre par une concrétion dans un four à 725 degrés Celsius, ou bien par une concrétion à 525 degrés Celsius, en ajoutant un flux. L'utilisation d'un acide avec la cendre en l'air comme flux a été étudiée en comparaison avec des échantillons témoins de cendres flottantes dans l'air. On a également observé les effets de concrétionnement des échantillons à différentes températures avec ou sans vide. Les propriétés des échantillons, y compris les indices pour la solidité, l'absorption de l'eau, l'isolation, et la couleur, sont présentées dans cette étude.

     

Adsorption of herbicides on coal fly ash from aqueous solutions

Development of low cost adsorbent for pesticide retention is an important area of research in environmental sciences. The present study reports the sorption potential of coal fly ash, a waste from power stations, for removal of metribuzin, metolachlor and atrazine from water. Batch sorption method was used to study the sorption of herbicides from water. The amount of herbicides sorbed increased with increase in the amount of fly ash in the suspension. The maximum capacity of the fly ash to adsorb metribuzin, metolachlor and atrazine was found to be 0.20, 0.28 and 0.38 mg/g by Freundlich equation and 0.56, 1.0 and 3.33 mg/g by Langmuir equation. Freundlich adsorption equation better explained the results of herbicides sorption in fly ash as regression coefficient (R²) values were higher from Freundlich equation than the Langmuir equation. Adsorption isotherms were L-type suggesting that the herbicide sorption efficiency of fly ash depend on the initial concentration of herbicide in the solution and maximum removal of herbicide was observed at concentrations less than 10 μg/ml. The results of this study have implications in using the fly ash for removal of these herbicides from industrial and agricultural waste water and can find use as a material in the preparation of biobeds to minimize environmental contamination from pesticide use.     

Mechanical characteristics of clay structural ceramics containing coal fly ash

In this work, the mechanical characterization of ceramic products processed from red clay with different amounts of added coal fly ash was investigated. Coal fly ash produced by power plants is a waste material that constitutes an alternative source of minerals for the production of traditional building ceramics, as it is a complex mixture of several oxides such as SiO₂, Al₂O₃, CaO, Fe₂O₃, Na₂O, TiO₂, which are usually present in the composition of such ceramics. A powder technology and firing route was followed for the processing of the clay and coal fly ash based ceramics. Different proportions of waste (10, 25 and 50%, by weight) were added to red clay, and then the mixed powders were pressed to form compacts that were fired at a selected temperature in the range 850–1,150°C. The effects of waste content and of heating conditions on the microstructure and mechanical characteristics of the obtained materials were investigated. The density, porosity, water absorption, flexural strength, hardness and fracture toughness of the produced materials were evaluated. A comparison was made between the properties of the produced ceramics with those of traditional ceramic materials used in construction, e.g. floor or wall tiles, and it was observed that the clay based products with coal fly ash additions may be used in similar applications.     

Retention of cobalt on a humin derived from brown coal

In this work, the retention of cobalt on a humin (HU) derived from a brown coal is studied. Through a systematic and coordinated investigation of the behavior of the metal ions in solution (speciation diagrams as a function of pH) and their adsorption and precipitation processes with reactive functional groups of the solid (sorption isotherms), the interactions of different Co(II) species with HU are probed. To further confirm the nature of these interactions, the complementary spectroscopic techniques of FTIR, Raman microspectroscopy, UV-visible absorption and XRD are employed. Molecular modeling techniques are used to gain information about the stability of different Co(II) species as a function of pH, as well as the stability of Co(II) species complexed with benzoic acid, a common surface component of humic substances. It is found that the selectivity that humin has for different Co(II) species, as well as the amount of Co(II) that it can retain, are both highly dependent on pH. Through Raman microspectroscopy measurements, the presence and location of Co(OH)(2) precipitates on the surface of HU is confirmed.