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.     

THE RECYCLING OF LINZ–DONAWITZ (LD) CONVERTER SLAG BY USE AS A LIMING AGENT ON PASTURE LAND

Slag is a major by-product of the basic oxygen steelmaking converter process (BOS). Methods are being developed to make use of this by-product and large quantities are now employed in agriculture and in the production of aggregates in several European Community (EC) countries. However, a great deal of slag is still either simply discarded or discharged in landfills. This paper reports the effects over a 3-year period on both soil and crops, of the application of Linz–Donawitz (LD) converter slag on pasture land. Comparative studies were performed using different quantities of low phosphorus LD converter slag and fertilizer on land sown withDactylis glomerata,Trifolium repensandLolium perenne. The results showed an increase in soil pH and in the availability of Ca and Mg in the soil exchange complex. Aluminium content was reduced. When LD converter slag and fertilizer were applied together, plants were seen to contain the greatest concentrations of nutrients and greater yields were obtained.     

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.     

Direction of CRT waste glass processing: electronics recycling industry communication

Cathode Ray Tube, CRT, waste glass recycling has plagued glass manufacturers, electronics recyclers and electronics waste policy makers for decades because the total supply of waste glass exceeds demand, and the formulations of CRT glass are ill suited for most reuse options. The solutions are to separate the undesirable components (e.g. lead oxide) in the waste and create demand for new products. Achieving this is no simple feat, however, as there are many obstacles: limited knowledge of waste glass composition; limited automation in the recycling process; transportation of recycled material; and a weak and underdeveloped market. Thus one of the main goals of this paper is to advise electronic glass recyclers on how to best manage a diverse supply of glass waste and successfully market to end users. Further, this paper offers future directions for academic and industry research. To develop the recommendations offered here, a combination of approaches were used: (1) a thorough study of historic trends in CRT glass chemistry; (2) bulk glass collection and analysis of cullet from a large-scale glass recycler; (3) conversations with industry members and a review of potential applications; and (4) evaluation of the economic viability of specific uses for recycled CRT glass. If academia and industry can solve these problems (for example by creating a database of composition organized by manufacturer and glass source) then the reuse of CRT glass can be increased.     

Cathode ray tube (CRT) recycling: current capabilities in China and research progress

It is estimated that approximately 6,000,000 scrap TVs and 10,000,000 personal computers are generated each year in China. Cathode ray tubes (CRTs) from these machines consist of 85% glass (65% panel, 30% funnel and 5% neck glass). The leaded glass (funnel-24%, neck-30%) may seriously pollute the environment if it is not properly disposed of. In this paper, the past, current and future status of CRT dismantling technologies as well as the CRT glass recycling situation in China are presented and discussed. Recycling technology for waste CRTs in China is still immature. While the conventional CRT dismantling technologies have disadvantages from both economic and environmental viewpoints, some of the new and emerging treatments such as automatic optical sorting facilities that have been applied in developed countries offer advantages, and therefore should be transferred to China in the next few years to solve the CRT pre-processing problem. Meanwhile, because the demand for CRT glass closed-loop recycling is extremely limited, the authorities should take effective measures to improve CRT glass recycling rates and to facilitate a match to local conditions. Moreover, we also provide a broad review of the research developments in recycling techniques for CRT cullet. The challenge for the future is to transfer these environmentally friendly and energy-saving technologies into practice.     

Chemical and mineralogical evaluation of slag products derived from the pyrolysis/melting treatment of MSW

This paper provides the results of studies on the characteristics of novel material derived from pyrolysis/melting treatment of municipal solid waste in Japan. Slag products from pyrolysis/melting plants were sampled for the purpose of detailed phase analysis and characterization of heavy metal-containing phases using optical microscopy, electron probe microanalysis (EPMA), XRF and XRD. The study revealed that the slag material contains glass (over 95%), oxide and silicate minerals (spinel, melilite, pseudowollastonite), as well as individual metallic inclusions as the major constituents. A distinct chemical diversity was discovered in the interstitial glass in terms of silica content defined as low and high silica glass end members. Elevated concentrations of Zn, Cr, Cu, Pb and Ba were recorded in the bulk composition. Cu, Pb and Ba behave as incompatible elements since they have been markedly characterized as part of polymetallic alloys and insignificantly sulfides in the form of spherical metallic inclusions associated with tracer amounts of other elements such as Sb, Sn, Ni, Zn, Al, P and Si. In contrast, an appreciable amount of Zn is retained by zinc-rich end members of spinel and partially by melilite and silica glass. Chromium exhibits similar behavior, and is considerably held by Cr-rich spinel. The intense incorporation of Zn and Cr into spinel indicates the very effective enrichment of these two elements into phases more environmentally resistant than glass. There was no evidence, however, that Cu and Pb enter into the structure of the crystalline silicates or oxides that may lead to their easier leachability upon exposure to the environment.     

Characterisation of major component leaching and buffering capacity of RDF incineration and gasification bottom ash in relation to reuse or disposal scenarios

Thermal treatment of refuse derived fuel (RDF) in waste-to-energy (WtE) plants is considered a promising solution to reduce waste volumes for disposal, while improving material and energy recovery from waste. Incineration is commonly applied for the energetic valorisation of RDF, although RDF gasification has also gained acceptance in recent years. In this study we focused on the environmental properties of bottom ash (BA) from an RDF incineration (RDF-I, operating temperature 850-1000 °C) and a RDF gasification plant (RDF-G, operating temperature 1200-1400 °C), by evaluating the total composition, mineralogy, buffering capacity, leaching behaviour (both at the material’s own pH and as a function of pH) of both types of slag. In addition, buffering capacity results and pH-dependence leaching concentrations of major components obtained for both types of BA were analysed by geochemical modelling. Experimental results showed that the total content of major components for the two types of BA was fairly similar and possibly related to the characteristics of the RDF feedstock. However, significant differences in the contents of trace metals and salts were observed for the two BA samples as a result of the different operating conditions (i.e. temperature) adopted by the two RDF thermal treatment plants. Mineralogy analysis showed in fact that the RDF-I slag consisted of an assemblage of several crystalline phases while the RDF-G slag was mainly made up by amorphous glassy phases. The leached concentrations of major components (e.g. Ca, Si) at the natural pH of each type of slag did not reflect their total contents as a result of the partial solubility of the minerals in which these components were chemically bound. In addition, comparison of total contents with leached concentrations of minor elements (e.g. Pb, Cu) showed no obvious relationship for the two types of BA. According to the compliance leaching test results, the RDF-G BA would meet the limits of the Italian legislation for reuse and the European acceptance criteria for inert waste landfilling. RDF-I BA instead would meet the European acceptance criteria for non hazardous waste landfilling. A new geochemical modelling approach was followed in order to predict the leaching behaviour of major components and the pH buffering capacity of the two types of slags on the basis of independent mineralogical information obtained by XRD analysis and the bulk composition of the slag. It was found that the combined use of data regarding the mineralogical characterization and the buffering capacity of the slag material can provide an independent estimate of both the identity and the amount of minerals that contribute to the leaching process. This new modelling approach suggests that only a limited amount of the mineral phases that control the pH, buffering capacity and major component leaching from the solid samples is available for leaching, at least on the time scale of the applied standard leaching tests. As such, the presented approach can contribute to gain insights for the identification of the types and amounts of minerals that control the leaching properties and pH buffering capacity of solid residues such as RDF incineration and gasification bottom ash.     

Understanding the chemical and mineralogical properties of the inorganic portion of MSWI bottom ash

This paper investigates the changes of mineralogical composition of bottom ash in the environment. The chemical and mineralogical bulk composition was determined by X-ray fluorescence (XRF) and X-ray powder diffraction (XRPD) Rietveld method. Single bottom ash particles were investigated by optical microscopy, scanning electron microscopy with quantitative energy-dispersive X-ray microanalysis (SEM/EDX) and electron probe micro analysis (EPMA). SEM/EDX and EPMA are valuable complement to bulk analysis and provide means for rapid and sensitive multi-elemental analysis of ash particles. The fresh bottom ash consists of amorphous (>30 wt.%) and major crystalline phases (>1 wt.%) such as silicates, oxides and carbonates. The mineral assemblage of the fresh bottom ash is clearly unstable and an aging process occurs by reaction towards an equilibrium mineral phase composition in the environmental conditions. The significant decrease of anhydrite and amorphous contents was observed in the aged bottom ash, leading to the formation of ettringite, hydrocalumite and rosenhahnite under atmospheric conditions. In the water-treated sample, the calcite contents increased significantly, but ettringite was altered by the dissolution and precipitation processes in part, to produce gypsum, while the remaining part reacted with chloride to form hydrocalumite. Gypsum and other Ca based minerals may take up substantial amounts of heavy metals and subsequently control leaching behaviour of bottom ash.     

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 cathode ray tube panel glasses as aggregates of concrete blocks and clay bricks

While the cathode ray tube (CRT) funnel containing lead could be transported to a smelting facility to recover lead, which could be an available option in domestic, a proper technology to recycle a CRT panel must be developed. Thus, it was suggested that CRT panel glass be used as aggregates of concrete blocks and clay bricks. Samples of blocks and bricks were fabricated with CRT powders and tested to measure their strength and absorption rate to determine their qualities, and environmental soundness was determined by measuring the leaching rate of hazardous metals. For concrete blocks, CRT panel glass powders incorporated as aggregates up to 40 % replacing stone powder was proposed as the proper condition for manufacturing blocks. Around 2 % of CRT panel incorporated into clay brick to substitute Kaoline was suggested to fabricate the best quality of clay brick. Results of leaching test met the criteria with much less concentration of hazardous metals, even lead compound containing in the CRT funnel. To conclude, the use of CRT panel powder after crushing it to the proper size as an aggregate of concrete blocks or clay bricks could be one of the appropriate alternatives to recycle for CRT glass waste being generated drastically in a short term.     

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.     

Characteristics of bricks made from waste steel slag

The characteristics of bricks made from steel slag were investigated in this research. Slag addition was shown to reduce the required firing temperature. When the firing temperature was greater than 1050 degrees C and the slag addition less than 10%, the bricks met ROC national standard CNS 3319 third-class brick for builders. The percentage of slag increased as the quartz and kaolin decreased in the sintered samples while the magnesium aluminum silicate and calcium silicate increased. There were no new crystal phases observed in these samples.     

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.     

Use of slag for dye removal

Adsorption techniques employing activated carbon have been found to be reasonably effective in the removal of some of the ionic impurities in water. However, economic considerations may require the use of inexpensive sorbents which are either naturally available or available as waste products from manufacturing processes. Slag is one such waste product obtained during the manufacture of steel, and the present study investigates dye removal characteristics of slag from colored waters. Aqueous solutions prepared from commercial grade acid, basic, and disperse dyes were used in this study, and batch pH, kinetic, and isotherm studies were undertaken on a laboratory scale. The data were evaluated for applicability to the Langmuir, Freundlich, and BET isotherm models, and the removal capacity of slag was compared with that of granular activated carbon. Results indicated approximately 94% removal of the disperse dye by slag, compared with a removal of approximately 49% achieved by activated carbon. Removal of acid dyes (dyes containing anionic groups) was reasonably good (approximately 47 and 74%), though not as good as obtained using activated carbon (approximately 100%). Column studies were conducted with a disperse dye (nonionic, slightly soluble in water), and analysis of data showed a sorption capacity of 1.3 mg of disperse dye per gram of slag. However, effluent dye concentrations were found to be higher than the permissible levels for discharge to receiving waters.     

Kinetics of steel slag leaching: Batch tests and modeling

Reusing steel slag as an aggregate for road construction requires to characterize the leaching kinetics and metal releases. In this study, basic oxygen furnace (BOF) steel slag were subjected to batch leaching tests at liquid to solid ratios (L/S) of 10 and 100 over 30 days; the leachate chemistry being regularly sampled in time. A geochemical model of the steel slag is developed and validated from experimental data, particularly the evolution with leaching of mineralogical composition of the slag and trace element speciation. Kinetics is necessary for modeling the primary phase leaching, whereas a simple thermodynamic equilibrium approach can be used for secondary phase precipitation. The proposed model simulates the kinetically-controlled dissolution (hydrolysis) of primary phases, the precipitation of secondary phases (C-S-H, hydroxide and spinel), the pH and redox conditions, and the progressive release of major elements as well as the metals Cr and V. Modeling indicates that the dilution effect of the L/S ratio is often coupled to solubility-controlled processes, which are sensitive to both the pH and the redox potential. A sensitivity analysis of kinetic uncertainties on the modeling of element releases is performed.     

Assessment of toxic metals in waste personal computers

Considering the enormous production of waste personal computers nowadays, it is obvious that the study of their composition is necessary in order to regulate their management and prevent any environmental contamination caused by their inappropriate disposal. This study aimed at determining the toxic metals content of motherboards (printed circuit boards), monitor glass and monitor plastic housing of two Cathode Ray Tube (CRT) monitors, three Liquid Crystal Display (LCD) monitors, one LCD touch screen monitor and six motherboards, all of which were discarded. In addition, concentrations of chromium (Cr), cadmium (Cd), lead (Pb) and mercury (Hg) were compared with the respective limits set by the RoHS 2002/95/EC Directive, that was recently renewed by the 2012/19/EU recast, in order to verify manufacturers’ compliance with the regulation. The research included disassembly, pulverization, digestion and chemical analyses of all the aforementioned devices. The toxic metals content of all samples was determined using Inductively Coupled Plasma-Mass Spectrometry (ICP-MS). The results demonstrated that concentrations of Pb in motherboards and funnel glass of devices with release dates before 2006, that is when the RoHS Directive came into force, exceeded the permissible limit. In general, except from Pb, higher metal concentrations were detected in motherboards in comparison with plastic housing and glass samples. Finally, the results of this work were encouraging, since concentrations of metals referred in the RoHS Directive were found in lower levels than the legislative limits.     

Characteristics of steel slag under different cooling conditions

Four types of steel slags, a ladle slag, a BOF (basic oxygen furnace) slag and two different EAF (electric arc furnace) slags, were characterized and modified by semi-rapid cooling in crucibles and rapid cooling by water granulation. The aim of this work was to investigate the effect of different cooling conditions on the properties of glassy slags with respect to their leaching and volume stability. Optical microscopy, X-ray diffraction, scanning electron microscope and a standard test leaching (prEN 12457-2/3) have been used for the investigation. The results show that the disintegrated ladle slag was made volume stable by water granulation, which consisted of 98% glass. However EAF slag 1, EAF slag 2 and the BOF slag formed 17%, 1% and 1% glass, respectively. The leaching test showed that the glass-containing matrix did not prevent leaching of minor elements from the modified slags. The solubility of chromium, molybdenum and vanadium varied in the different modifications, probably due to their presence in different minerals and their different distributions.     

Study on the mechanical and environmental properties of concrete containing cathode ray tube glass aggregate

Cathode ray tube (CRT) glass is considered a hazardous material due to its lead toxicity. In addition, current disposal practices are being phased out due to their adverse environmental impacts. In this project, CRT glass was used as a fine aggregate replacement in concrete. Life-cycle material characterization was conducted by evaluating the durability and strength of the CRT-Concrete. Leaching tests were also conducted to investigate whether the material meets drinking water limits for Pb. Test results show that the plastic state of the CRT-Concrete was affected by the angularity of the glass particles. Moreover, the compressive strength of CRT-Concrete met and exceeded that of the control specimen. However, CRT-Concrete was susceptible to expansive alkali-silica reactions when more than 10% CRT replacement was used. Environmental leaching results show that lead concentrations from CRT-Concrete are below the drinking water limits depending on the CRT volume replacement and if biopolymers are used.     

Physicochemical properties of slags produced at various amounts of iron addition in lead smelting

In the process of lead production from lead-bearing materials generated in copper metallurgy, a large amount of hazardous waste in the form of slag is produced. To assess the effect of the slag on the environment, its physicochemical properties were determined. In this study, the following methods were used: wavelength dispersive X-ray fluorescence (WD XRF), X-ray diffraction (XRD), and Bunte-Baum-Reerink method to determine softening and melting points, as well as viscosity examination and leaching tests. The measurements were performed on the slag produced with two different amounts of iron addition to the lead smelting process. The resulting slags, an oxide rich phase slag and a sulfide rich phase slag have different compositions and physicochemical properties. It was found that the increase in iron addition causes an increase in the softening melting point of the oxide rich phase slag by about 100 °C, and a twofold increase in the viscosity of both slag phases. The increase in iron addition also results in the decrease in As leachability and increase in Zn, Fe, and Cu leachability from the slags. Slag produced with increased iron addition has a greater impact on the environment.

     

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.