Preparation and characterization of ceramic products by thermal treatment of sewage sludge ashes mixed with different additives

The study of the ceramic characteristics of sludge ashes, alone or mixed with additives (kaolin, montmorillonite, illitic clay, powdered flat glass) includes characterization of additives, preparation of probes (dry or wet mixed), thermal treatment (up to 1200 degrees C, except melting or deformation) and control (densities, compressive strengths and water absorption). Thermal treatment increases the density and compressive strength of probes (both parameters go through maxima, with later decreases) and decreases the absorption of water. The densification is also revealed by the evolution of the ratio of decrease of volume/loss of mass. The maximum values of compressive strengths were obtained for 25% of illitic clay, montmorillonite and glass powder. Densification concerning probes with sludge ashes alone does not occur with kaolin. Experimental data were adjusted to exponential relationships between compressive strengths and densities for every composition, and also to a general equation for all probes. The apparent density obtained was adjusted to a non-linear dependence with temperature, leading to a maximum in density and permitting calculating the temperature of occurrence of this maximum. The adjustment was not possible for probes containing kaolin, requiring presumably higher temperatures to densify. Water absorption has low values for ashes or kaolin probes, intermediate values for illite and powdered flat glass probes and high values for montmorillonite probes. Excepting with kaolin, ceramic materials with better characteristics than sludge ashes without additives were obtained at lower treatment temperatures.     

Improving the adsorption capacity and solid structure of natural volcanic soil using a foaming-sintering process based on recycled polyethylene terephthalate (PET).

The volcanic soils of southern Chile have demonstrated a high capacity to adsorb environmental pollutants, but for an industrial application, a stable solid material is necessary. The objective of this work was to produce a stable ceramic material through a process involving volcanic soil-polyurethane foam produced with recycled polyethylene terephthalate (PET)-polyols, and further thermal treatment. The selected foam formulation with 35.4% volcanic soil (< 63 microm) seems to be the most suitable for thermal treatment, with temperature steps at 700, 850, 1000 and 1200 degrees C. The porous ceramic material obtained has a stable solid form and an improved chlorophenols adsorption capacity (comparable to natural zeolites) that makes it suitable for advanced wastewater treatment and landfill leachate depuration.     

Treatment and recycling of incinerated ash using thermal plasma technology

To treat incinerated ash is an important issue in Taiwan. Incinerated ashes contain a considerable amount of hazardous materials such as dioxins and heavy metals. If these hazardous materials are improperly treated or disposed of, they shall cause detrimental secondary contamination. Thermal plasma vitrification is a robust technology to treat and recycle the ash residues. Under the high temperature plasma environment, incinerated ashes are vitrified into benign slag with large volume reduction and extreme detoxification. Several one-step heat treatment processes are carried out at four temperatures (i.e. 850, 950, 1,050 and 1,150 degrees C) to obtain various "microstructure materials". The major phase to form these materials is a solid solution of gehlenite (Ca2Al2SiO7) and ?kermanite (Ca2MgSi2O7) belonging to the melilite group. The physical and mechanical properties of the microstructure materials are improved by using one-step post-heat treatment process after plasma vitrification. These microstructure materials with good quality have great potential to serve as a viable alternative for construction applications.     

Characterization of MSWI bottom ashes towards utilization as glass raw material

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO(2), a network glass former oxide, was present in a relatively high content (52-58wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na(2)O and K(2)O, which act as fluxing agents, were present in various amounts (2-17wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO(2)) and calcite (CaCO(3)) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 degrees C and that total weight loss was <10wt%. Heating both bottom ashes at 1400 degrees C for 2h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction.     

Use of vitrified MSWI bottom ashes for concrete production

Bottom ashes from a north Italian municipal solid waste incinerator (MSWI) were vitrified at 1450 degrees C without adding any vitrifying agent, then ground and sieved to different granulometry (ranging from 50 microm to 20mm), and used as filler, sand, or aggregate for concrete. Samples were characterized via slump tests (UNI 9418), alkali-silica reactivity (UNI 8520/22 and ASTM C 298), and compression strength tests (UNI 6132, 6132/72, 6686/72), and compared to reference samples obtained without vitrified bottom ashes (VBA). Our results show that vitrified bottom ashes are unsuitable as a sand substitute; however, concrete containing up to 20 wt.% of VBA filler used as a substitute for cement and up to 75 vol.% of VBA as a substitute for natural aggregate retains the same mechanical properties as reference samples. Alkali-silica or other detrimental reactions were not observed in VBA-containing concrete samples after a period of two years. The results of this work demonstrate that vitrified bottom ashes from MSWI can be used instead of natural aggregates in mortar and concrete production.     

Glass-ceramics obtained by the recycling of end of life cathode ray tubes glasses

This work is concerned with open-loop recycling of end of life Cathode Ray Tubes glass (an unsolved problem when considering that in Europe almost 90% of EOL electronic goods is disposed of in landfills), focusing on the development of glass-ceramics from panel or funnel glass with dolomite and alumina, and the evaluation of the tendency towards crystallisation with particular attention on composition and thermal treatment. Glasses were melted at a temperature of about 1500 degrees C and transformed into glass-ceramics by different thermal treatments (900 degrees C to approximately 1100 degrees C temperature range and 0.5 to approximately 8h soaking time). By using the evaluation of thermal, mineralogical and microstructural data it has been pointed out that a good degree of crystallisation is reached at about 1000 degrees C and with a high proportion of waste glass (50-75%) if 40-45% of CaO and MgO bearer (dolomite) is introduced. In this way alkaline and alkaline-earth silicate and aluminosilicate mainly develop probably with a surface mechanism.     

Leachability of automotive shredder residues burned in a fluidized bed system

This paper presents the results of the study of a combustible fraction of automotive shredder residues (CASRs) and the corresponding ashes generated by combustion on a fluidized bed pilot with the aim to understand the influence of thermal treatment regarding properties for final disposal, such as landfilling. The chemical composition was evaluated and the leachability behaviour of ashes and CASR was investigated using the three more commonly used tests: the European Standard EN 12457, the US TCLP-EPA 1311 and the Dutch availability test EA NEN 7371. Different results were obtained depending on the specific conditions of the methods employed. It was found that both the CASR and the ashes contained large amounts of toxic metals and other undesirable elements, such as Cl and S. For the CASR, in addition to the leachability of organic matter above the limit set for hazardous materials, the release of heavy metals, either under alkaline and acidic conditions was significant, revealing the serious risks associated to the landfilling practices still being undertaken worldwide. Release of organic matter from ashes was insignificant, but solubility of sulphates increased and chlorides exceed the hazardous limits in the case of fly ashes. Toxic metals were found to leach from the ashes only under acidic conditions, except Pb and Cu which also leached from finer ashes at alkaline pH. Cr also leached from ashes at alkaline pH values. Both the Dutch availability and TCLP revealed much higher leaching intensities than the European Standard due to the acidity of leachants. However, it was found that ashes may be more resistant to acidification because they exhibit much higher acid neutralization capacity (ANC) than the untreated CASR. The study undertaken shows that thermal valorisation of the combustible fraction of ASR may avoid the risks associated with their landfilling; however, care has to be taken with the ashes because they also behave as hazardous residues. Although, the mass reduction provided by thermal treatment may make landfilling less expensive, a more profitable reutilization of the ashes should be developed.     

Residues characterisation from the fluidised bed combustion of East London’s solid recovered fuel

Waste thermal treatment in Europe is moving towards the utilisation of the combustible output of mechanical, biological treatment (MBT) plants. The standardisation of solid recovered fuels (SRF) is expected to support this trend and increase the amount of the generated combustion residues. In this work, the residues and especially the fly ashes from the fluidised bed combustion (FBC) of East London’s NCV 3, Cl 2, and Hg 1 class SRF, are characterised. The following toxicity indicators have been studied: leachable chlorine, organochlorides expressed as pentachlorobenzene and hexachlorobenzene, and the heavy metals Cu, Cr, Cd, Zn, Ni, and Pb. Furthermore the mineralogical pattern of the ashes has been studied by means of XRD and SEM–EDS. The results suggest that these SRF derived ashes have significantly lower quantities of Cu, Cd, Pb, Zn, leachable Cl, and organochlorides when compared to other literature values from traditional waste thermal treatment applications. This fact highlights the importance of modern separation technologies employed in MBT plants for the removal of components rich in metals and chlorine from the combustible output fraction of SRF resulting to less hazardous residues.     

Effect of fly ash addition on the removal of hydrogen sulfide from biogas and air on sewage sludge-based composite adsorbents

Desulfurization adsorbents were prepared from the mixtures of various compositions of New York City sewage sludge and fly ashes from SASOL, South Africa, by pyrolysis at 950 degrees C. The resulting materials were used as adsorbents of hydrogen sulfide from simulated dry digester gas mixture or moist air. The adsorbents before and after H(2)S removal were characterized using adsorption of nitrogen, elemental analysis, pH measurements, XRF, XRD, and thermal analysis. It was found that the addition of fly ash decreases the desulfurization capacity in comparison with the sewage sludge-based materials. The extent of this decrease depends on the type of ash, its content and the composition of challenging gas. Although the presence of CO(2) deactivates some adsorption sites to various degrees depending on the sample composition, the addition of ashes has a more detrimental effect when the adsorbents are used to remove hydrogen sulfide from air. This is likely the result of hydrophobicity of ashes since the H(2)S removal capacity was found to be strongly dependent on the reactivity towards water/water adsorption. On the other hand, the addition of ashes strongly decreases the porosity of materials where sulfur, as a product of hydrogen sulfide oxidation, can be stored.     

High temperature co-treatment of bottom ash and stabilized fly ashes from waste incineration

Bottom ashes from two Danish municipal solid waste incineration plants were heated at 900 degrees C with iron oxide stabilized air pollution control residues at actual mass flow ratios (9:1), simulating a treating method for the residues. The two residues were co-treated, producing one combined stream that may be utilized as a secondary road construction material. Scanning electron microscope analysis and grain size distribution analysis indicated that sintering of the particles did not occur. Batch leaching tests at liquid/solid 10 l/kg at a range of pH-values (6-10) quantified with respect to Cd, Cr and Pb revealed significant positive effects of co-heating the ashes, although Pb showed slightly increased leaching. At a liquid/solid ratio of 10 l/kg the leachate concentrations were still low at pH 7-10 and the release of Pb was, thus, not expected to limit the utilization of the mixed ashes. The process, thus, fixates the metals in the solid residues without altering the leaching properties of the bottom ash too significantly.     

Study of fine sediments for making lightweight aggregate.

The objective of this study was to investigate the recycling of the fine sediments of Shih-Men Reservoir to manufacture lightweight aggregate. By qualitative and quantitative analysis of the fine sediment and sintered aggregate through soil test, X-ray fluorescence, X-ray diffraction and scanning electron microscopy, a strategy of recycling fine sediment as aggregate for other similar material is proposed. The test results indicate that such fine sediment can be classified as low plastic clay, and clay of such chemical composition is located in the Riley's 'area of bloating'. The particle density of sintered lightweight aggregate decreases when the sintering temperature increases especially above 1200 degrees C due to phase transformation and formation of a vitrified layer on the surface through subsequent dehydration, bloating and collapsing stages. Our findings show that the fine sediment of Shin-Men Reservoir could be a suitable raw material for making expanded lightweight aggregate sintered at 1200 to 1300 degrees C for 10 to 12 min by a programmable furnace and a diffusion process.     

Treatment and use of air pollution control residues from MSW incineration: an overview

This work reviews strategies for the management of municipal solid waste incineration (MSWI) residues, particularly solid particles collected from flue gases. These tiny particles may be retained by different equipment, with or without additives (lime, activated carbon, etc.), and depending on the different possible combinations, their properties may vary. In industrial plants, the most commonly used equipment for heat recovery and the cleaning of gas emissions are: heat recovery devices (boiler, superheater and economiser); dry, semidry or wet scrubbers; electrostatic precipitators; bag filters; fabric filters, and cyclones. In accordance with the stringent regulations in force in developed countries, these residues are considered hazardous, and therefore must be treated before being disposed of in landfills. Nowadays, research is being conducted into specific applications for these residues in order to prevent landfill practices. There are basically two possible ways of handling these residues: landfill after adequate treatment or recycling as a secondary material. The different types of treatment may be grouped into three categories: separation processes, solidification/stabilization, and thermal methods. These residues generally have limited applications, mainly due to the fact that they tend to contain large quantities of soluble salts (NaCl, KCl, calcium compounds), significant amounts of toxic heavy metals (Pb, Zn, Cr, Cu, Ni, Cd) in forms that may easily leach out, and trace quantities of very toxic organic compounds (dioxin, furans). The most promising materials for recycling this residue are ceramics and glass-ceramic materials. The main purpose of the present paper is to review the published literature in this field. A range of studies have been summarized in a series of tables focusing upon management strategies used in various countries, waste composition, treatment processes and possible applications.     

Utilization of gold tailings as an additive in Portland cement.

Mine tailings are formed as an industrial waste during coal and ore mining and processing. In the investigated process, following the extraction of gold from the ore, the remaining tailings are subjected to a two-stage chemical treatment in order to destroy the free cyanide and to stabilize and coagulate heavy metals prior to discharge into the tailings pond. The aim of this study was the investigation of the feasibility of utilization of the tailings as an additive material in Portland cement production. For this purpose, the effects of the tailings on the compressive strength properties of the ordinary Portland cement were investigated. Chemical and physical properties, mineralogical composition, particle size distribution and microstructure of the tailings were determined by Fourier transform infrared spectroscopy (FTIR), X-ray diffractometry (XRD), particle size analyzer (Mastersizer) and scanning electron microscope (SEM). Following the characterization of the tailings, cement mortars were prepared by intergrinding Portland cement with dried tailings. Composition of the cement clinkers were adjusted to contain 5, 15, 25% (wt/wt) dried tailings and also silica fume and fly ash samples (C and F type) were added to clinker in different ratios. The mortars produced with different amounts of tailings, silica fume, fly ashes and also mixtures of them were tested for compressive strength values after 2, 7, 28 and 56 days according to the European Standard (EN 196-1). The results indicated that gold tailings up to 25% in clinker could be beneficially used as an additive in Portland cement production. It is suggested that the gold tailings used in the cement are blended with silica fume and C-type fly ash to obtain higher compressive strength values.     

Sewage sludge ash to phosphorus fertiliser (II): Influences of ash and granulate type on heavy metal removal

Ashes from monoincineration of sewage sludge suggest themselves as an ideal base for inorganic fertiliser production due to their relatively high phosphorus (P)-content. However, previously they need to be detoxified by reducing their heavy metal content. The core process considered in this paper consists of three steps: mixing of the ashes with suitable chlorine-containing additives, granulation of the mixture and thermochemical treatment in a rotary kiln. Here relevant heavy metal compounds are first transformed into volatile species with the help of the additives and then evaporated from the granules.In this study two chemically different ashes and their mixture were agglomerated to two different granulate types, briquettes and rolled pellets. The resulting six different materials were subjected to thermal treatment at different temperatures. The heavy metals examined were Cu and Zn due to their strong dependence on treatment conditions and their relevance concerning thermal treatment of sewage sludge ashes. Besides, the behaviour of Cl and K was monitored and evaluated.The experiments showed that ash type and temperature are more influential on Cl and heavy metal chemistry than granulate type. Temperature is a primary variable for controlling removal in both cases. Cu removal was less dependent on both ash and granulate type than Zn. The Cl utilization was more effective for Cu than for Zn. Depending on the treatment conditions some K could be retained, whereas always all P remained in the treated material. This satisfies the requirement for complete P recycling.     

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.     

A study of disposed fly ash from landfill to replace Portland cement

The landfills of fly ash are the problem of all power plants because this disposed fly ash is not used in any work. This research studies the potential of using disposed fly ashes which have disposal time of 6-24 months from the landfill of Mae Moh power plants in Thailand to replace Portland cement type I. Median particle sizes of disposed fly ashes between 55.4 and 99.3 microm were ground to reduce the sizes to about 7.1-8.4 microm. Both original and ground disposed fly ashes were investigated on physical and chemical properties. Compressive strengths of disposed fly ash mortars were determined when Portland cement type I was replaced by disposed fly ashes at the rate of 10%, 20%, and 30% by weight of cementitious material (Portland cement type I and disposed fly ash). The results presented that most particles of original disposed fly ashes were solid and sphere with some irregular shape while those of ground disposed fly ashes were solid and irregular shape. CaO and LOI contents of disposed fly ashes with different disposal times had high variation. The compressive strengths of original disposed fly ash mortars were low but those of ground disposed fly ash mortars at the age of 7 days were higher than 75% of the standard mortar and increased to be higher than 100% after 60 days. From the results, it could be concluded that ground disposed fly ashes were excellent pozzolanic materials and could be used as a partial replacement of cement in concrete, even though they were exposed to the weather for 24 months.     

Coal fly ash as raw material for the manufacture of geopolymer-based products

In this work coal fly ash has been employed for the synthesis of geopolymers. Two different systems with silica/alumina ratios stoichiometric for the formation of polysialatesiloxo (PSS, SiO2/Al2O3=4) and polysialatedisiloxo (PSDS, SiO2/Al2O3=6) have been prepared. The alkali metal hydroxide (NaOH or KOH) necessary to start polycondensation has been added in the right amount as concentrated aqueous solution to each of the two systems. The concentration of each alkali metal solution has been adjusted in order to have the right liquid volume to ensure constant workability. The systems have been cured at four different temperatures (25, 40, 60, and 85 degrees C) for several different times depending on the temperature (16-672 h at 25 degrees C; 72-336 h at 40 degrees C; 16-120 h at 60 degrees C and 1-6h at 85 degrees C). The products obtained in the different experimental conditions have been submitted to the quantitative determination of the extent of polycondensation through mass increase and loss on ignition, as well as to qualitative characterization by means of FT-IR spectroscopy. Furthermore, physico-structural and mechanical characterization has been carried out through microscopic observations and the determination of unconfined compressive strength, elasticity modulus, apparent density, porosity and specific surface area. The results have indicated that the systems under investigation are suited for the manufacture of pre-formed building blocks at room temperature.     

A novel way to upgrade the coarse part of a high calcium fly ash for reuse into cement systems

Reject fly ash (rFA) represents a significant portion of the fly ashes produced from coal-fired power plants. Due to the high carbon content and large particle mean diameter, rFA is not utilized in the construction sector (for example, as supplementary cementing material) and is currently dumped into landfills, thus representing an additional environmental burden. Recently, the feasibility of using rFA in a relatively small number of applications, like solidification/stabilization of other wastes, has been investigated by different researchers. However, as the overall amount of fly ash utilized in such applications is still limited, there is a need to investigate other possibilities for rFA utilization starting from a deeper understanding of its properties. In the work presented herein, mechanical and hydration properties of cementitious materials prepared by blending the coarse fraction of a lignite high-calcium fly ash with ordinary cement were monitored and compared with the respective ones of a good quality fly ash-cement mixture. The results of this work reveal that a relatively cheap, bilateral classification-grinding method is able to promote the pozzolanic behavior of the rFAs, so that the overall performances of rFA containing cements are drastically improved. The evaluation of these results supports the belief that appropriate utilization of non-standardized materials may lead to new environmental-friendly products of superior quality.     

Physical-mechanical and environmental properties of sintered municipal incinerator fly ash

A step-wise treatment of Municipal Solid Waste (MSW) incinerator fly ash including washing, milling and sintering was investigated in order to manufacture ceramic materials with improved physical, mechanical and environmental properties and, possibly, to reduce the power input of the sintering process. An interpretation of the test results based on the microstructure of sintered products and sintering kinetic modeling was also attempted to identify the densification mechanisms. It was found that milling of washed fly ash represents a basic step for manufacturing high-density ceramic materials with very high compressive strengths (up to 500 N/mm2). A significant reduction in the power input of the sintering process (reduction of firing temperature from 1210 degrees C for washed fly ash to 1140 degrees C for milled-washed fly ash) is also achieved. A dense, well-sintered microstructure is formed through an intermediate-stage, liquid-phase sintering mechanism controlled by liquid-phase diffusion and grain shape accommodation. Such a microstructure is able to strongly immobilise heavy metals, thus giving good environmental properties to sintered product.