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.     

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.     

Cathode ray tube glass recycling: an example of clean technology.

In this study the use of 'cleaned' end of life (EOL) cathode ray tube (CRT) glass as a raw material in ceramic glazes is described. At present, the recycling and industrial utilization of CRT, a glass material from TV and computer sets, is a subject of intense research with particular regard to the so-called open-loop recycling, namely cycles different from that of the origin. However, the use of CRT glass as a secondary raw material is strictly related to the demand of high-quality raw material. The good preliminary results reached by introducing clean TV and PC monitor panel and cone glass into ceramic glaze formulations pushed research toward the setting-up of a base glaze that is exploitable for the production of pigmented, silk-screened and flame-hardened glazes (products used industrially for coating floor tiles). The aesthetic and chemical characterization of the tiles glazed by this product showed an extremely similar behaviour to originals that did not contain CRT glass. The good technical results achieved have been supported by the life cycle assessment analysis, which has demonstrated a reduction of the environmental impact of the CRT glass-containing ceramic glaze with respect to the standard one.     

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.     

Eco-efficient waste glass recycling: Integrated waste management and green product development through LCA

As part of the EU Life + NOVEDI project, a new eco-efficient recycling route has been implemented to maximise resources and energy recovery from post-consumer waste glass, through integrated waste management and industrial production. Life cycle assessment (LCA) has been used to identify engineering solutions to sustainability during the development of green building products. The new process and the related LCA are framed within a meaningful case of industrial symbiosis, where multiple waste streams are utilised in a multi-output industrial process. The input is a mix of rejected waste glass from conventional container glass recycling and waste special glass such as monitor glass, bulbs and glass fibres. The green building product is a recycled foam glass (RFG) to be used in high efficiency thermally insulating and lightweight concrete. The environmental gains have been contrasted against induced impacts and improvements have been proposed. Recovered co-products, such as glass fragments/powders, plastics and metals, correspond to environmental gains that are higher than those related to landfill avoidance, whereas the latter is cancelled due to increased transportation distances. In accordance to an eco-efficiency principle, it has been highlighted that recourse to highly energy intensive recycling should be limited to waste that cannot be closed-loop recycled.     

Inertization of hazardous dredging spoils

Vitrification and production of ceramics materials starting from sediment excavated from Venice lagoon is described. This sediment is classified as toxic waste because contains several heavy metal ions and organic pollutants and was successfully vitrified at 1200-1350 degrees C. Twenty weight percentage of glass cullet, coming from a community glass recycling program, was added to the raw materials, previously calcined at 900 degrees C, as a way of adjusting the variations of composition of the individual sediment batches. Chemical durability (leaching) tests showed that the optimized glass compositions are inert, and thus not only volume reduction but also inertization of the waste was obtained by this process. Moreover, the economics of the entire process was analysed. The valorization of the waste was accomplished by the subsequent processing of the glass derived from the inertization. Glass ceramic materials were produced by viscous phase sintering of pressed glass powders which crystallized during the densification process. Sintered glass ceramic products had good mechanical characteristics (HV = 7.5 GPa, bending strength 150 +/- 8 MPa), making them suitable for applications in the building industry.     

Energy-efficient modification of reduction-melting for lead recovery from cathode ray tube funnel glass

Lead can be recovered from funnel glass of waste cathode ray tubes via reduction melting. While low-temperature melting is necessary for reduced energy consumption, previously proposed methods required high melting temperatures (1400 °C) for the reduction melting. In this study, the reduction melting of the funnel glass was performed at 900–1000 °C using a lab-scale reactor with varying concentrations of Na₂CO₃ at different melting temperatures and melting times. The optimum Na₂CO₃ dosage and melting temperature for efficient lead recovery was 0.5 g per 1 g of the funnel glass and 1000 °C respectively. By the reduction melting with the mentioned conditions, 92% of the lead in the funnel glass was recovered in 60 min. However, further lead recovery was difficult because the rate of the lead recovery decreased as with the recovery of increasing quantity of the lead from the glass. Thus, the lead remaining in the glass after the reduction melting was extracted with 1 M HCl, and the lead recovery improved to 98%.     

Metallurgical use of glass fractions from waste electric and electronic equipment (WEEE)

Within the European Union, it is estimated that between 8 and 9 million tonnes of waste electric and electronic equipment (WEEE) arises annually, of which television sets and computers account for an important part. Traditionally, Cathode Ray Tubes (CRT) have been used for TVs and computer monitors, but are rapidly being replaced by flat-screen technology. Only part of the discarded CRT glass is being recycled. Primary smelters use large amounts of silica flux to form iron-silicate slag, and can, in most cases, tolerate lead input. Use of discarded CRT glass in copper smelting is a potential alternative for utilization of the glass.The mineralogical composition of a slag sampled during ordinary slag praxis has been compared with that of a mixture of slag and CRT glass when re-melted and slowly cooled. Slag (iron-silicate slag) from Boliden Mineral AB, Sweden, was used for the experiments. Slag and glass have been mixed in various proportions: pure slag, pure glass, 90% slag-10% glass and 65% slag-35% glass, and heated in an inert atmosphere up to 1400 °C in a Netzsch Thermal Analysis (TA) instrument. The re-melted material has been analyzed using X-ray diffraction (XRD) and scanning electron microscopy (SEM) to determine changes in mineralogical composition after mixing with glass.The results show that the main mineralogical component of the slag is fayalite; the CRT glass is amorphous. The main crystalline phases of the slag do not change with addition of glass. An amorphous phase appears when the addition of glass is increased, which gives the sample a different structure.     

Characterization of post-consumer polyolefin wastes by hyperspectral imaging for quality control in recycling processes

In this paper new analytical inspection strategies, based on hyperspectral imaging (HSI) in the VIS–NIR and NIR wavelength ranges (400–1000 and 1000–1700 nm, respectively), have been investigated and set up in order to define quality control logics that could be applied at industrial plant level for polyolefins recycling. The research was developed inside the European FP7 Project W2Plastics “Magnetic Sorting and Ultrasound Sensor Technologies for Production of High Purity Secondary Polyolefins from Waste”. The main aim of the project is the separation of pure polyethylene and polypropylene adopting an innovative process, the magnetic density separation (MDS). Spectra of plastic particles and contaminants resulting from post-consumer complex wastes and of virgin polyolefins have been acquired by HSI and by Raman spectroscopy. The classification results obtained applying principal component analysis (PCA) on HSI data have been compared with those obtained by Raman spectroscopy, in order to validate the proposed innovative methodology. Results showed that HSI sensing techniques allow to identify both polyolefins and contaminants. Results also demonstrated that HSI has a great potentiality as a tool for quality control of feed (identification of contaminants in the plastic waste) and of the two different pure polypropylene and polyethylene flow streams resulting from the MDS-based recycling process.     

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.     

Plasma treatment of air pollution control residues

Air pollution control (APC) residues from waste incineration have been blended with silica and alumina and the mix melted using DC plasma arc technology. The chemical composition of the fully amorphous homogeneous glass formed has been determined. Waste acceptance criteria compliance leach testing demonstrates that the APC residue derived glass releases only trace levels of heavy metals (Pb (<0.007mg/kg) and Zn (0.02mg/kg)) and Cl(-) (0.2mg/kg). These are significantly below the limit values for disposal to inert landfill. It is concluded that plasma treatment of APC residues can produce an inert glass that may have potential to be used either in bulk civil engineering applications or in the production of higher value glass-ceramic products.     

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.     

The characterization of waste cathode-ray tube glass

New re-use applications are needed to address the relatively large quantity of waste electronic products generated in the world. Cathode-ray tubes (CRTs) from computer monitors and TV sets are a large component of such waste. The three glass components of CRTs are the funnel, panel and neck, which are produced by various manufacturers and are now collected by asset-recovery centres. In this paper, we characterize waste funnel and panel glass from dismantled cathode-ray tubes with a view to assisting the development of new re-use applications. The heavy metal (lead, barium, and strontium) content of such glass represents an acute risk to the environment. Our results of the chemical composition for different kinds of waste CRT glass including black & white and color CRTs show that CRT glass from different producers have generally similar chemical compositions. In particular, the compositions of funnel and panel black & white CRT glass are similar, but are different to those of panel and funnel color CRT glass. We also measured the following specific properties of each type of CRT glass: density, glass transition temperature, and linear coefficient of thermal expansion. It was found that the coefficients of thermal expansion of CRT glass do not vary with their composition. In contrast, the measured densities and glass transition temperatures do vary with composition. On the basis of our experimental data and data found in the literature, we outline the main properties of several waste CRT glass currently in circulation. The aim of this study was to provide the data required to determine if this kind of waste could be entirely (or partially) re-used and to aid the search for promising methods of treatment.     

Recycling of steel slag and glass cullet from energy saving lamps by fast firing production of ceramics

The paper reports on some experimental results obtained from the production of ceramics containing steel slag and glass cullet from exhaust energy saving lamps mixed in different proportions. Blending of components was done by attrition milling. Pressed powders were fast fired (50 min, cold to cold) in air up to several temperatures in the range 1000–1140 °C. The sintering behaviour was studied by shrinkage and water absorption measurements. Density, strength and hardness of the fired bodies were determined and XRD were examined. The fired samples were finally tested in acidic environment in order to evaluate their elution behaviour and consequently their possible environmental compatibility. It is observed that the composition containing 60 wt.% of steel slag and 40 wt.% of glass cullet displayed the best overall behaviour.     

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.     

Characterization of residue from leached cathode ray tube funnel glass: reutilization as white carbon black

Cathode ray tube (CRT) funnel glass remains an urgent environmental problem and is composed mainly of lead oxide and silicon oxide. In this research, the residue could be obtained from 2 h to 500 rpm activated CRT funnel glass after extracting lead via acid leaching under the conditions of HNO₃ concentration 1.0 mol/L, leaching temperature 95 °C and leaching time 1 h. In order to reutilize the residue, its physico-chemical properties were characterized by scanning electron microscopy, Brunauer–Emmett–Teller, thermogravimetric analysis, X-ray diffraction and Fourier transform infrared spectroscopy. The results indicated that the residue was an amorphous superfine powder with approximately 93 wt% silica oxide and specific surface area of more than 170 m²/g. It can be reutilized as white carbon black.     

Recycling of calcium fluoride sludge as ceramic material using low temperature sintering technology

The Chinese integrated circuit industry has been transformed from a small state-owned sector into a global competitor, but chip manufacturing produces large amounts of calcium fluoride sludge (CFS). The current treating method is landfill in China. In order to solve the problem of unavailable landfill sites and the dissolved CFS polluting water sources, CFS was tested as a component for a ceramic product made with sodium borate, sodium phosphate, and waste alumina using a low temperature sintering technology. The ceramic was characterized by X-ray diffraction (XRD), microstructure, compressive strength. XRD and microstructure analyses verified that CFS was transformed into Na₂Ca(PO₄)F as an inert crystalline phase in ceramic, which is enclosed by the borophosphate glass liquid phase. Toxicity characteristic leaching procedure and corrosion resistance tests verified that fluorine from CFS was solidified in the inert crystalline phase, which did not release to cause secondary pollution. This novel technology produces high-performance ceramic as a construction material, in accordance with the concept of sustainable development.     

Fast firing of tiles containing paper mill sludge, glass cullet and clay

The paper describes results obtained in the development of a previous research. We study here, in fast firing, the sintering behaviour and measure some properties of tiles containing a mixture of 60 wt% of paper mill sludge and 40 wt% of glass cullet. The behaviour of this material is compared to those displayed by materials obtained by the same mixture added with 10, 20 and 30 wt% of a natural red clay. In parallel, the same properties are measured also on a reference blend, which is presently used to produce commercial tiles. We show that powders containing 60 wt% of paper sludge and 40 wt% of glass cullet to which 30 wt% of clay is added give rise to materials that display a stable sintering process and have good hardness and strength and therefore could be used for the industrial production of tiles.     

Reuse of ground waste glass as aggregate for mortars

This work was aimed at studying the possibility of reusing waste glass from crushed containers and building demolition as aggregate for preparing mortars and concrete. At present, this kind of reuse is still not common due to the risk of alkali-silica reaction between the alkalis of cement and silica of the waste glass. This expansive reaction can cause great problems of cracking and, consequently, it can be extremely deleterious for the durability of mortar and concrete. However, data reported in the literature show that if the waste glass is finely ground, under 75mum, this effect does not occur and mortar durability is guaranteed. Therefore, in this work the possible reactivity of waste glass with the cement paste in mortars was verified, by varying the particle size of the finely ground waste glass. No reaction has been detected with particle size up to 100mum thus indicating the feasibility of the waste glass reuse as fine aggregate in mortars and concrete. In addition, waste glass seems to positively contribute to the mortar micro-structural properties resulting in an evident improvement of its mechanical performance.