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.     

Recycling of iron foundry sand and glass waste as raw material for production of whiteware.

The purpose of this study was to evaluate the production feasibility of triaxial whiteware using sand from cast iron moulds as a raw material instead of silica, and recycled glass in place of feldspar. Formulations were prepared using sand, glass waste, and white-firing clay such that only 50% of the composition was virgin material (clay). The ceramic bodies were formed by pressing and fired at different temperatures (between 1100 and 1300 degrees C). Specimens were characterized in terms of green density prior to firing; and their flexural strength, linear shrinkage, and water absorption were measured after firing. The microstructure was determined by scanning electron microscopy. Possible environmental impacts of this recycling process were also evaluated, through solubility and leaching tests, according to Brazilian standards. Gaseous emissions during the firing process were also analysed. The results showed that it is possible to produce triaxial ceramics by using such alternative raw materials.     

Spectral cullet classification in the mid-infrared field for ceramic glass contaminants detection.

The presence of glass-like contaminants inside waste glass products, usually resulting from both industrial and differentiated urban waste collection, has greatly increased in recent years, due to the introduction to the market of a large amount of goods manufactured from ceramic glass. The presence of contaminants in the glass recycling streams reduces product quality and increases production costs. The detection of ceramic glass detection is an unresolved problem, as such material looks like normal glass and can only be detected by trained personnel. In this study an innovative approach to ceramic glass recognition, based on the spectral signature in the mid-infrared (MIR) field, was proposed and investigated. The study specifically addressed the spectral characterization of glass and ceramic glass fragments collected in a real recycling plant from two different production lines: coloured container glass and white container glass. To define suitable inspection strategies to separate the useful (glass) from the polluting (ceramic glass) materials at the recycling plants, fragments presenting different colour, thickness, size, shape and manufacturing were selected. Both dirty and clean cullet was considered. The analyses, carried out in the MIR spectral field (2280-4480 nm), show that ceramic glass and glass fragments can be recognized according to their different spectral signature. In particular, by selecting a specific wavelength ratio the two classes of materials can be rapidly recognized, suggesting the possibility of developing an integrated hardware and software sorting system for 'on-line' ceramic glass separation.     

Non-parametric analysis of infrared spectra for recognition of glass and glass ceramic fragments in recycling plants

Glass ceramic detection in glass recycling plants represents a still unsolved problem, as glass ceramic material looks like normal glass and is usually detected only by specialized personnel. The presence of glass-like contaminants inside waste glass products, resulting from both industrial and differentiated urban waste collection, increases process production costs and reduces final product quality. In this paper an innovative approach for glass ceramic recognition, based on the non-parametric analysis of infrared spectra, is proposed and investigated. The work was specifically addressed to the spectral classification of glass and glass ceramic fragments collected in an actual recycling plant from three different production lines: flat glass, colored container-glass and white container-glass. The analyses, carried out in the near and mid-infrared (NIR-MIR) spectral field (1280-4480 nm), show that glass ceramic and glass fragments can be recognized by applying a wavelet transform, with a small classification error. Moreover, a method for selecting only a small subset of relevant wavelength ratios is suggested, allowing the conduct of a fast recognition of the two classes of materials. The results show how the proposed approach can be utilized to develop a classification engine to be integrated inside a hardware and software sorting architecture for fast "on-line" ceramic glass recognition and separation.     

Evaluation of thermally treated asbestos based on fiber number concentration determined by transmission electron microscopy

Appropriate treatment of asbestos waste is a significant problem. In Japan, inertization of asbestos-containing waste by novel techniques approved by the Ministry of the Environment is now promoted. A quantitative method of testing with high sensitivity to the asbestos levels present in the inertization products is required for the approval process, but many testing methods are only qualitative. Thus, we have developed an evaluation method for asbestos in inertized products, consisting of the extraction of fibers from inertized products and determination of fiber number concentration by transmission electron microscopy. We adopted this testing method to evaluate thermally treated asbestos. It was found that fiber number concentrations of thermally treated asbestos decreased with increased treatment temperature, and were below the environmental level (10² Mf/g) at more than 1000 °C for chrysotile and crocidolite and more than 1400 °C for amosite and other amphibole forms of asbestos.     

Treatment of copper industry waste and production of sintered glass-ceramic.

Copper waste is iron-rich hazardous waste containing heavy metals such as Cu, Zn, Co, Pb. The results of leaching tests show that the concentration of these elements exceeds the Turkish and EPA regulatory limits. Consequently, this waste cannot be disposed of in its present form and therefore requires treatment to stabilize it or make it inert prior to disposal. Vitrification was selected as the technology for the treatment of the toxic waste under investigation. During the vitrification process significant amounts of the toxic organic and inorganic chemical compounds could be destroyed, and at the same time, the metal species are immobilized as they become an integral part of the glass matrix. The copper flotation waste samples used in this research were obtained from the Black Sea Copper Works of Samsun, Turkey. The samples were vitrified after being mixed with other inorganic waste and materials. The copper flotation waste and their glass-ceramic products were characterized by X-ray analysis (XRD), scanning electron microscopy and by the toxicity characteristic leaching procedure test. The products showed very good chemical durability. The glass-ceramics fabricated at 850 degrees C/2 h have a large application potential especially as construction and building materials.     

Inertization of pyrite cinders and co-inertization with electric arc furnace flue dusts by pyroconsolidation at solid state

The viability of a pyroconsolidation process to render pyrite cinders inert and to co-inert pyrite cinders with a hazardous polymetallic residue such as electric arc furnace flue dusts (EAF) containing Pb, Cu, Zn, As, Cr, Ni and Mo were investigated. The effects of pyroconsolidation temperature (800-1200 degrees C), milling pyrite cinders and additions of both CaO and EAF on the resulting microstructure of the pellets were determined. The microstructural changes were then compared with the results of the standard leaching tests. Full inertization of pyrite cinders was achieved after milling to < 100 micron followed by a pelletization and pyroconsolidation process at a temperature of 1200 degrees C. This process also allows co-inertization of pyrite cinders with controlled additions of EAF (up to approximately to 10%). Following pyroconsolidation at 1200 degrees C, the metallic elements were inert components in the four main phases: traces of Cr in hematite; Cr, Cu, Zn and Ni in spinel-phase; traces of Cr and Zn in calcium ferrites; and Pb and traces of Cu, Zn and Ba in K-Ca-Al-Fe glassy silicate.     

The applicability of different waste materials for the production of lightweight aggregates

The applicability of different waste materials for the production of lightweight aggregates has been studied. The following waste materials were investigated: silica sludge, superfluous clay in the quarry, waste glass, and residue from the polishing process of different types of stone. SiC and MnO₂ were selected as foaming agents. Feldspar containing minerals and scrap glass were added in order to lower the softening point of the waste materials. The granules were prepared by mixing together finely ground waste with one or both of the selected foaming agents. The granules were then fired at different temperatures above the softening point of the glassy phase within the temperature range from 1150 to 1220 °C, where the foaming agent degasses, and the resulting gasses remain trapped in the glassy structure. The foaming process was observed by hot-stage microscopy. The properties of the so-obtained granules, such as their apparent density and compressive strength, were determined, and their microstructures were evaluating using SEM and polarizing microscopy.With the addition to clay of polishing residue from granite-like rocks, after firing at 1220 °C homogeneously porous granules with a density down to 0.42 g/cm³ were obtained, whereas with the addition to waste silica sludge of polishing residue from granite-like rocks and waste glass with a foaming agent, after firing at 1220 °C densities from 0.57 to 0.82 g/cm³ were obtained.     

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.     

Digestion of frozen/thawed food waste in the hybrid anaerobic solid-liquid system

The hybrid anaerobic solid-liquid (HASL) system, which is a modified two-phase anaerobic digester, is to be used in an industrial scale operation to minimize disposal of food waste at incineration plants in Singapore. The aim of the present research was to evaluate freezing/thawing of food waste as a pre-treatment for its anaerobic digestion in the HASL system. The hydrolytic and fermentation processes in the acidogenic reactor were enhanced when food waste was frozen for 24h at -20 degrees C and then thawed for 12h at 25 degrees C (experiment) in comparison with fresh food waste (control). The highest dissolved COD concentrations in the leachate from the acidogenic reactors were 16.9g/l on day 3 in the control and 18.9g/l on day 1 in the experiment. The highest VFA concentrations in the leachate from the acidogenic reactors were 11.7g/l on day 3 in the control and 17.0g/l on day 1 in the experiment. The same volume of methane was produced during 12 days in the control and 7 days in the experiment. It gave the opportunity to diminish operational time of batch process by 42%. The effect of freezing/thawing of food waste as pre-treatment for its anaerobic digestion in the HASL system was comparable with that of thermal pre-treatment of food waste at 150 degrees C for 1h. However, estimation of energy required either to heat the suspended food waste to 150 degrees C or to freeze the same quantity of food waste to -20 degrees C showed that freezing pre-treatment consumes about 3 times less energy than thermal pre-treatment.     

Imaging spectroscopy based strategies for ceramic glass contaminants removal in glass recycling

The presence of ceramic glass contaminants in glass recycling plants reduces production quality and increases production costs. The problem of ceramic glass inspection is related to the fact that its detectable physical and pictorial properties are quite similar to those of glass. As a consequence, at the sorting plant scale, ceramic glass looks like normal glass and is detectable only by specialized personnel. In this paper an innovative approach for ceramic glass recognition, based on imaging spectroscopy, is proposed and investigated. In order to define suitable inspection strategies for the separation between useful (glass) and polluting (ceramic glass) materials, reference samples of glass and ceramic glass presenting different colors, thicknesses, shapes and manufacturing processes have been selected. Reflectance spectra have been obtained using two equipment covering the visible and near infrared wavelength ranges (400-1000 and 1000-1700 nm). Results showed as recognition of glass and ceramic glass is possible using selected wavelength ratios, in both visible and near infrared fields.     

Petrogenetic characteristics of molten slag from the pyrolysis/melting treatment of MSW

MSW slag materials derived from four pyrolysis melting plants in Japan were studied from the viewpoint of petrology in order to discriminate the glass and mineral phases and to propose a petrogenetic model for the formation process of molten slag. Slag material is composed of two major components: melt and refractory products. The melt products that formed during the melting process comprise silicate glass, and a suite of minerals as major constituents. The silicate glass is essentially composed of low and high silica glass members (typically 30% and 50% of SiO(2), respectively), from which minerals such as spinels, melilite, pseudowollastonite, and metallic inclusions have been precipitated. The refractory products consist mainly of pieces of metals, minerals and lithic fragments that survived through the melting process. Investigations demonstrated that the low silica melts (higher Ca and Al contents) were produced at upper levels of high temperature combustion chamber HTCC, at narrower temperature ranges (1250-1350 degrees C), while the high silica melts formed at broader temperature ranges (1250-1450 degrees C), at the lower levels of HTCC. The recent temperature ranges were estimated by using CaOAl(2)O(3)SiO(2) (CAS) ternary liquidus diagram that are reasonably consistent with those reported for a typical combustor. It was also understood that the samples with a higher CaO/SiO(2) ratio (>0.74-0.75) have undergone improved melting, incipient crystallization of minerals, and extensive homogenization. The combined mineralogical and geochemical examinations provided evidence to accept the concept of stepwise generation of different melt phases within the HTCC. The petrogenesis of the melt products may therefore be described as a two-phase melt system with immiscible characteristics that have been successively generated during the melting process of MSW.     

Utilization of municipal solid waste incineration (MSWI) fly ash in ceramic brick: product characterization and environmental toxicity

In this study, municipal solid waste incineration (MSWI) fly ash was used as a blending in making ceramic brick based on its characterization and an orthogonal test was performed to determine the optimal mixture ratio of the materials. Besides, the fired bricks made in accordance with the optimal mixture ratio were characterized for performance, phase transformation, microstructure, leaching toxicity of the heavy metals in accordance with GB/T 2542-92 (Detection methods for bricks analysis, China) and by means of XRD, SEM and leaching toxicity analysis. It was found that the optimal mixture ratio of materials (MSWI fly ash:red ceramic clay:feldspar:gang sand) was 20:60:10:10 by mass, and the optimal sintering temperature was 950 °C. Leaching results of heavy metals from sintered bricks were reduced considerably in comparison with those from green bricks prior to sintering process. The results as a whole suggested that utilization of MSWI fly ash in ceramic brick constituted a potential means of adding value.     

Sinterability study of ceramic bodies made from a mixture of mineral coal bottom ash and soda-lime glass cullet.

The aim of this study was to investigate the sinterability to improve the technical properties of ceramic bodies made from coal bottom ash and soda-lime glass cullet. Different mixtures of bottom ash and glass cullet were formulated. The amount of bottom ash was 100, 70, 50 and 30 wt.%. The particle size distribution was the same for all formulations. The mixture containing 50 wt.% bottom ash also had its particle size distribution changed. Samples were formed by dry pressing and then fired at 950, 1050 and 1150 degrees C. Samples were evaluated for linear shrinkage, water absorption, flexural mechanical resistance, scanning electronic microscopy, pyroplastic deformation and thermodilatometric analysis. The higher firing temperature led to a decrease in water absorption and increased linear shrinkage, mechanical resistance and pyroplastic deformation. This effect was also observed for addition of glass up to 50 wt.%. The effect of smaller particles of bottom ash was more significant for linear shrinkage and mechanical resistance of ceramic bodies fired at 1150 degrees C. The use of a finer powder contributed to increase these properties. The influence of finer particles on water absorption and mechanical resistance of ceramic bodies fired at 950 and 1050 degrees C was not significant.     

Solid Waste Recycling And Reuse In Bangkok

Materials recovered from solid waste in Bangkok are mainly glass bottles, paper and paper products, plastic products and metals. Materials are separated at three different stages of the collection process: at the source, prior to collection; by the crews of the collection vehicle; and by the scavengers at the dump site. The total daily tonnage of recyclable garbage collected at the source by the waste pickers is estimated at 286 tonnes, about 5% of the garbage collected by the city. There are small scale recycling shops (SSR) located around the main disposal sites where collected materials are sold by the collection crews and the scavengers. The quantity of materials delivered to the SSR shops by the collection crew vary between 1-6 tonnes per day. The amount of materials recovered by the scavengers (at the dump site) varies between 50-150 kg person^-1 day^-1. Therefore around 7.5% of the solid waste is recycled. In Bangkok both formal and informal sectors manufacture paper pulp, cardboard boxes and magazines from the recyclable paper. Paper products which account for 55% of the total waste stream are considered as the largest "product group" in the municipal solid waste. Recyclable glass (1-3% of the total waste stream) or cullet is used to manufacture plain glasses or cups. Plastics constitute about 10-15% of the waste stream. The benefit/cost ratios of production of most of these industries were reported to be higher than 1.5. In order to enhance recycling, legislative measures need to be introduced and enforced. In Thailand, there is, however, no law concerning recycling. There is no incentive for the consumer to separate solid waste for recycling, as the prices of waste in Bangkok are low and inconsistent. Therefore the pricing system should be more organized for recycling to be more effective.     

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.     

Use of mix of clay/solid waste from steel works for civil construction materials.

The present study focuses on the use of solid waste generated by the steel works in Brazil for manufacturing clay-based structural products. The waste sample was characterized regarding chemical composition, X-ray diffraction, particle size, morphology, specific surface and plastic properties. The waste was added in gradual proportions to a kaolinitic clay from zero up to 3 wt.%. Ceramic bodies were formed by vacuum extrusion and fired at 950 degrees C. The physical-mechanical properties (linear shrinkage, water absorption, apparent density and flexural strength) of the resulting clay/solid waste mixtures were determined. In addition, leaching tests were performed according Brazilian Standards as well as a preliminary analysis of gases evolved during the thermal process. It was found that the solid waste is formed by irregular particles, ranging in size from 1 to 500 microm. The test results indicate that solid wastes generated by steel works can be used as filler in construction materials, thereby increasing reuse in an environmentally safe manner.     

Thermal pyrolysis of fresh and waste fishing nets

Kinetic tests on the pyrolysis of nylon-6 taken from fresh (new) fishing nets and waste fishing nets were conducted using thermogravimetric analysis at heating rates of 0.5, 1.0 and 2.0 degrees C/min. The main region of decomposition of both materials was between 340 and 440 degrees C at each heating rate. The region of decomposition for the nylon-6 from the waste fishing nets was slightly lower than that of the fresh fishing nets. The result shows that the value of activation energies increased from 128 to 433 kJ mol(-1) as the conversion of the pyrolysis reaction increased from 5% to 95%. Nylon-6 from the fresh fishing nets was pyrolyzed in a micro-scale tubing bomb reactor for 60, 80 and 100 min at 440 degrees C. The yield of pyrolyzed gases increased from 3.94 to 5.50 wt% with reaction time. The selectivity to specific hydrocarbons was not detected from the pyrolyzed oil and the carbon number distribution of the pyrolyzed oil was random.     

Treatment of waste printed circuit board by green solvent using ionic liquid

Recycling of waste printed circuit boards (WPCBs) is an important subject not only for the protection of environment but also for the recovery of valuable materials. A feasibility study was conducted to dissolve bromine epoxy resins of WPCBs using ionic liquid (IL) of 1-ethyl-3-methylimizadolium tetrafluoroborate [EMIM(+)][BF(4)(-)] (nonaqueous green solvent) for recovering copper foils and glass fibers. Experimental results indicated that the initial delamination had seen from the cross-section of the WPCBs by mean of metallographic microscope and digital camera when WPCBs were heated in [EMIM(+)][BF(4)(-)] at 240°C for a duration of 30min. When temperature was increased to 260°C for a duration of 10min, the bromine epoxy resins of WPCBs were throughout dissolved into [EMIM(+)][BF(4)(-)] and the separations of copper foils and glass fibers from WPCBs were completed. This clean and non-polluting technology offers a new way to recycle valuable materials from WPCBs and prevent the environmental pollution of WPCBs effectively.