Chemical durability of glasses obtained by vitrification of industrial wastes

The vitrification of zinc-hydrometallurgy wastes, electric arc furnace dust (EAFD), drainage mud, and granite mud was shown to immobilize the hazardous components in these wastes. Batch compositions were prepared by mixing the wastes with glass-cullet and sand to force the final glass composition into the glass forming region of the SiO2-Fe2O3-(CaO, MgO) system. The vitrification was carried out in the 1400-1450 degrees C temperature range followed by quenching in water or on stainless steel mold. The United States (US) Environmental Protection Agency (EPA) toxic characterization leaching procedure (TCLP) test was used as a standard method for evaluating the leachability of the elements in the glasses and glass-ceramics samples made with different percentages of wastes. The results for EAFD glasses highlighted that the chemical stability is influenced by the glass structure formed, which, in turn, depends on the Si/O ratio in the glass. The chemical durability of jarosite glasses and glass-ceramics was evaluated by 24 h contact in NaOH, HCl and Na2CO3, at 95 degrees C. Jarosite glass-ceramics containing pyroxene (J40) are more durable than the parent glass in HCl. Jarosite glass-ceramics containing magnetite type spinels (J50) have a durability similar to the parent glass and even lower in HCl because the magnetite is soluble in HCl.     

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.     

Solidification/stabilization Process For Steel Foundry Dust Using Cement Based Binders: Influence Of Processing Variables

The influence of processing variables: mixing time, waste/binder ratio and water/solid ratio on the solidification/stabilization process of steel foundry dust has been studied. The characterization of the final product was based on the Toxic Characterization Leaching Procedure (TCLP) followed by the biotoxicity (bioluminescence assay) and concentration of the metals, Cr, Cd, Pb and Zn in the leachates. The final product characteristics depend mainly on the waste/binder ratio, as a function of the metal hydroxide solubilities. The results of this work allow one to establish the optimization of a solidification/stabilization process for steel foundry dust.     

Vitrification as an alternative to landfilling of tannery sewage sludge

Due to high content of heavy metals such as chromium, tannery sewage sludge is a material which is difficult to be biologically treated as it is in the case of organic waste. Consequently, a common practice in managing tannery sewage sludge is landfilling. This poses a potential threat to both soil and water environments and it additionally generates costs of construction of landfills that meet specific environment protection requirements. Vitrification of this kind of sewage sludge with the addition of mineral wastes can represent an alternative to landfilling.The aim of this study was to investigate the possibility of obtaining an environmentally safe product by means of vitrification of tannery sewage sludge from a flotation wastewater treatment process and chemical precipitation in order to address the upcoming issue of dealing with sewage sludge from the tannery industry which will be prohibited to be landfilled in Poland after 2016. The focus was set on determining mixtures of tannery sewage sludge with additives which would result in the lowest possible heavy metal leaching levels and highest hardness rating of the products obtained from their vitrification.The plasma vitrification process was carried out for mixtures with various amounts of additives depending on the type of sewage sludge used. Only the materials of waste character were used as additives.One finding of the study was an optimum content of mineral additives in vitrified mixture of 30% v/v waste molding sands with 20% v/v carbonate flotation waste from the zinc and lead industry for the formulations with flotation sewage sludge, and 45% v/v and 5% v/v, respectively, for precipitation sewage sludge. These combinations allowed for obtaining products with negligible heavy metal leaching levels and hardness similar to commercial glass, which suggests they could be potentially used as construction aggregate substitutes. Incineration of sewage sludge before the vitrification process lead to increased hardness of the vitrificates and reduced leaching of some heavy metals.     

Characteristics of element distributions in an MSW ash melting treatment system

Thermal treatment of municipal solid waste (MSW) has become a common practice in waste volume reduction and resource recovery. For the utilization of molten slag for construction materials and metal recovery, it is important to understand the behavior of heavy metals in the melting process. In this study, the correlation between the contents of elements in feed materials and MSW molten slag and their distributions in the ash melting process, including metal residues, are investigated. The hazardous metal contents in the molten slag were significantly related to the contents of metals in the feed materials. Therefore, the separation of products containing these metals in waste materials could be an effective means of producing environmentally safe molten slag with a low hazardous metals content. The distribution ratios of elements in the ash melting process were also determined. The elements Zn and Pb were found to have a distribution ratio of over 60% in fly ash from the melting furnace and the contents of these metals were also high; therefore, Zn and Pb could be potential target metals for recycling from fly ash from the melting furnace. Meanwhile, Cu, Ni, Mo, Sn, and Sb were found to have distribution ratios of over 60% in the metal residue. Therefore, metal residue could be a good resource for these metals, as the contents of Cu, Ni, Mo, Sn, and Sb in metal residue are higher than those in other output materials.     

Characterization and phosphate stabilization of dusts from the vitrification of MSW combustion residues

The use of soluble PO₄³⁻ as a heavy metal chemical stabilization agent was evaluated for a dust generated from melting or vitrification of municipal solid waste combustion residues. Vitrification dusts contain high concentrations of volatile elements such as Cl, Na, K, S, Pb, and Zn. These elements are present in the dusts largely as simple salts (e.g. PbCl₂, ZnSO₄) which are highly leachable. At an experimental dose of 0.4 moles of soluble PO₄³⁻ per kg of residue, the pH-dependent leaching (pH 5,7,9) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 100 for many metals; particularly Cd, Cu, Pb and Zn. Bulk and surface spectroscopies showed that the insoluble reaction products are tertiary metal phosphate [e.g. Zn₃(PO₄)₂] and apatite [e.g. Pb₅(PO₄)₃Cl] family minerals. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca²⁺, Zn²⁺, Pb²⁺, Cu²⁺, and Cd²⁺ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids. Soluble phosphate effectively converted soluble metal salts into insoluble metal phosphate phases despite the relatively low doses and dry mixing conditions that were used. Soluble phosphate is an effective stabilization agent for divalent heavy metals in melting dusts where leachable metals are present in high concentrations.     

Glass-ceramics from vitrified sewage sludge pyrolysis residues and recycled glasses

Pyrolysis of urban plant sewage sludge has been demonstrated to be an effective way to produce fuel gas. However, a complete disposal of this particular waste is not achieved if the solid residues from the treatment are not considered. In this paper we discuss the feasibility an integrated pyrolysis/vitrification/sintering approach, aimed at a “full” disposal: the pyrolysis residues are first converted into a glass, then transformed into glass–ceramics, by simple viscous flow sintering treatments, with or without additions of inexpensive recycled glasses and kaolin clay. The obtained products were demonstrated to constitute an alternative to natural stones, in terms of both mechanical strength and chemical stability.     

Vitrification for reclaiming spent alkaline batteries

The object of this study is to stabilize spent alkaline batteries and to recover useful metals. A blend of dolomite, limestone, and cullet was added to act as a reductant and a glass matrix former in vitrification. Specimens were vitrified using an electrical heating furnace at 1400 °C and the output products included slag, ingot, flue gas, and fly ash. The major constituents of the slag were Ca, Mn, and Si, and the results of the toxicity leaching characteristics met the standards in Taiwan. The ingot was a good material for use in production of stainless steel, due to being mainly composed of Fe and Mn. For the fly ash, the high level of Zn makes it economical to recover. The distribution of metals indicated that most of Co, Cr, Cu, Fe, Mn, and Ni moved to the ingot, while Al, Ca, Mg, and Si stayed in the slag; Hg vaporized as gas phase into the flue gas; and Cd, Pb, and Zn were predominately in the fly ash. Recovery efficiency for Fe and Zn was >90% and the results show that vitrification is a promising technology for reclaiming spent alkaline batteries.     

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.     

Thermodynamic and experimental studies on condensation behavior of low-boiling-point elements volatilized in the melting process

To study the volatilization and condensation behaviors of low-boiling-point elements in the waste melting process, experiments were conducted to collect the dust from a coke-type incineration residue melting furnace. Then, a comparison was made between the experimental results and the calculated values obtained from a thermodynamic equilibrium model in terms of the chemical composition of the dust. The composition of the dust collected from a cylindrical filter in the exhaust gas duct was determined by chemical methods, scanning electron microscopy/energy-dispersive X-ray spectroscopy, and X-ray analysis. As a result, the sampled dust was classified into two different types: fine particles mainly containing Na, K, Pb, and Zn collected from the side face of the cylindrical filter, and large particles containing Ca, Si, and Al collected from the bottom face of the cylindrical filter. From X-ray analysis of the sampled dust, NaCl, KCl, PbS, and ZnS were identified in the fine-particle dust, while CaO, SiO₂, Al₂O₃ were detected in the large-particle dust. From the results of the thermodynamic equilibrium calculation in the gas cooling process from 2000 to 600 K, it was found that Na, K, Pb, and Zn volatilized as metals in the melting furnace were condensed as alkali chlorides such as NaCl and KCl and heavy metal sulfides such as PbS and ZnS. These computational results were in good agreement with the X-ray diffraction results of the sampled dust at a gas temperature of 823 K for the formation of NaCl, KCl, PbS, and ZnS.     

Development of Mn recovery process from waste dry cell batteries

High-purity Mn is necessary for high strength steel production. However, the availability of metal Mn is limited to a few countries. Therefore, as an alternative to direct purchasing of metal Mn, a process for Mn recovery was investigated. Waste dry cell batteries are considered to be one of the most feasible Mn sources. We have developed a high efficiency chemical separation system. This system consists of a three-phase chemical treatment. In the first phase, the metal components of the waste dry cell batteries were dissolved by acid, along with a reducing agent. Afterward, the undissolved carbon particles were separated by filtration. In the second phase, the dissolved Mn was selectively precipitated as manganese oxide by O₃ oxidation. Then, the precipitated manganese oxide was separated from the other metal components by filtration. Finally, in the third phase, the manganese oxide was reduced to high-purity Mn using an electric furnace.     

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.     

Contribution to closing the loop on waste materials: valorization of bottom ash from waste-to-energy plants under a life cycle approach

Incineration has undergone several technology improvements, reducing air emissions and increasing the efficiency of energy and material recovery; however, there is still a long way to go. To analyze the environmental impacts of waste incineration, this study assessed 15 waste fractions that compose municipal waste in Spain, which are grouped as non-inert materials (plastics, paper, cardboard and organic matter), unburned materials (glass and Al) and ferrous materials. Additionally, this paper evaluates the valorization of bottom ash (BA) to produce steel, aluminum and cement in these recycled/recoverable waste fractions. The results depend on the input waste composition and the heating value (HHV) and showed that ferrous and unburned materials had the worst environmental performance due to the null HHV. The valorization of BA in steel, Al and cement production significantly reduced the environmental impact and the consumption of resources. BA recycling for secondary steel and Al production would improve the environmental performance of the combustion of unburned materials and ferrous materials, whereas the use of BA in cement production diminished the consumption of NR for non-inert materials. This is of great interest for organic matter and PC, waste with a low energy production and high heavy metal and sulfur content.     

Physical separation,mechanical enrichment and recycling-oriented characterization of spent NiMH batteries

Nickel–metal hydride (NiMH) batteries contain high amount of industrial metals, especially iron, nickel, cobalt and rare earth elements. Although the battery waste is a considerable secondary source for metal and chemical industries, a recycling process requires a suitable pretreatment method before proceeding with recovery step to reclaim all valuable elements. In this study, AA- and AAA-type spent NiMH batteries were ground and then sieved for size measurement and classification. Chemical composition of the ground battery black mass and sorted six different size fractions were determined by an analytical technique. Crystal structures of the samples were analyzed by X-ray diffraction. Results show that after mechanical treatment, almost 87 wt% of the spent NiMH batteries are suitable for further recycling steps. Size classification by sieving enriched the iron content of the samples in the coarse fraction which is bigger than 0.25 mm. On the other hand, the amounts of nickel and rare earth elements increased by decreasing sample size, and concentrated in the finer fractions. Anode and cathode active materials that are hydrogen storage alloy and nickel hydroxide were mainly collected in finer size fraction of the battery black mass.     

Material and energy recovery from Automotive Shredded Residues (ASR) via sequential gasification and combustion

Shredding is the common end-of-life treatment in Europe for dismantled car wrecks. It produces the so-called Automotive Shredded Residue (ASR), usually disposed of in landfill. This paper summarizes the outcome of a study carried out by Politecnico di Milano and LEAP with the support of Actelios SpA on the prospects of a technology based on sequential gasification and combustion of this specific waste stream. Its application to the treatment of ASR allows the recovery of large fractions of metals as non-oxidized, easily marketable secondary raw materials, the vitrification of most of the ash content and the production of power via a steam cycle. Results show that despite the unfavourable characteristics of ASR, the proposed technology can reach appealing energy performances. Three of four environmental impact indicators and the cumulative energy demand index are favourable, the main positive contributes being electricity production and metal recovery (mainly aluminium and copper). The only unfavourable indicator is the global warming index because, since most of the carbon in ASR comes from fossil sources, the carbon dioxide emissions at the stack of the thermal treatment plant are mainly non-renewable and, at the same time, the avoided biogas production from the alternative disposal route of landfilling is minor.     

Analysis of energy recovery potential using innovative technologies of waste gasification

In this paper, two alternative thermo-chemical processes for waste treatment were analysed: high temperature gasification and gasification associated to plasma process. The two processes were analysed from the thermodynamic point of view, trying to reconstruct two simplified models, using appropriate simulation tools and some support data from existing/planned plants, able to predict the energy recovery performances by process application. In order to carry out a comparative analysis, the same waste stream input was considered as input to the two models and the generated results were compared. The performances were compared with those that can be obtained from conventional combustion with energy recovery process by means of steam turbine cycle. Results are reported in terms of energy recovery performance indicators as overall energy efficiency, specific energy production per unit of mass of entering waste, primary energy source savings, specific carbon dioxide production.     

Leaching characteristics of rare metal elements and chlorine in fly ash from ash melting plants for metal recovery

In terms of resource recovery and environmental impact, melting furnace fly ash (MFA) is attracting much attention in Japan due to its high metal content. The study aims to obtain fundamental information on using a water extraction method not only to concentrate valuable rare metals but also to remove undesirable substances such as chlorine for their recovery from MFA. The composition and leaching characteristics of MFA was investigated. The results revealed that the metal content in MFA is nearly equal to raw ore quality. The content of Ag, In, Pd, Pb, and Zn is, in fact, higher than the content of raw ore. As for leaching behavior, Ag, Bi, In, Ga, Ge, Sb, Sn, and Te showed the lowest release at a neutral pH range. Pd was leached constantly regardless of pH, but its concentration was quite low. On the other hand, most of the Tl was easily leached, revealing that water extraction is not appropriate for Tl recovery from MFA. Major elements Cl, Ca, Na, and K, occupying about 70% of MFA, were mostly leached regardless of pH. Base metal elements Cu, Pb, and Zn showed minimum solubility at a neutral pH. The leaching ratio of target rare metal elements and base metal elements suggests that the optimal pH for water extraction is 8-10, at which the leaching concentration is minimized. The water extraction process removed most of the Cl, Ca, Na, and K, and the concentration of rare metals and base metals increased by four or five times.     

Evaluation of leaching characteristics and environmental compatibility of solidified/stabilized industrial waste

An attempt was made to judge the environmental compatibility, the governing leaching mechanism, and mobility patterns in a waste–cement solidified/stabilized matrix after 21 days of curing. The mixed sludge from a steel pickling facility was stabilized by ordinary Portland cement. Iron was the major leachable metal, along with Pb, Zn, and Mn. To characterize the leaching behavior, the mobility and mechanism of leaching were determined by diffusion leaching tests. In the solidified/stabilized matrix, the mobility of all the elements studied was reduced, and average to low mobility was observed. Values for the negative log of the effective diffusion coefficient of more than 12.5 were obtained for the metals. The dominant leaching mechanisms were surface wash off in the initial stage, followed by diffusion. The environmental performance of the solidified/stabilized product when considered in terms of mass leached over 64 days was found to be satisfactory for consideration for the safe disposal and reuse of waste.     

Waste stabilization mechanism by a recirculatory semi-aerobic landfill with the aeration system

The main purpose of this research is to clarify and compare the mechanism of waste stabilization by a recirculatory semi-aerobic landfill with the aeration system. Our research is proposing the semi-aerobic landfill system for developing countries because of the simple and low-cost technology for the final disposal. Moreover, this system with leachate recirculation can be a more effective system for waste stabilization because of the improvement of leachate quality as an organic pollutant and, also, nitrogen removal. In this research, five different systems of landfill (Ae: aerobic, An: anaerobic, Se: semi-aerobic, SeR: recirculatory semi-aerobic landfill, and SeRA: recirculatory semi-aerobic landfill with aeration system) are compared with lysimeters which are 1 m high with a diameter of 0.3 m. The results of the leachate quality shows that the leachate treatment effect of the SeRA system can be observed to be as high as the Ae system. To determine the mechanism of this process, all lysimeters are dismantled after 1,100 days in the experimental period and the waste composition, the dissolution test, the mass balance of carbon and nitrogen, the determination of bacterial counts, etc., were analyzed. In this research, it was proven that the SeRA system has an optimal leachate treatment effect that is the same as the Ae system. And, from the results of the mass balance of carbon and nitrogen, the SeR and SeRA systems show higher waste stabilization effectiveness and nitrogen removal than the other systems. Moreover, the number of the aerobic bacteria can be observed to be higher in the SeR and SeRA systems. To determine these results, the waste stabilization mechanism is considered by the results of leachate quality, the mass balance of carbon and nitrogen, and, also, the bacterial numbers.     

Valorization of titanium metal wastes as tanning agent used in leather industry

The development of new tanning agents and new technologies in the leather sector is required to cope with the increasingly higher environmental pressure on the current tanning materials and processes such as tanning with chromium salts. In this paper, the use of titanium wastes (cuttings) resulting from the process of obtaining highly pure titanium (ingots), for the synthesis of new tanning agent and tanning bovine hides with new tanning agent, as alternative to tanning with chromium salts are investigated. For this purpose, Ti waste and Ti-based tanning agent were characterized for metal content by inductively coupled plasma mass spectrometry (ICP-MS) and chemical analysis; the tanned leather (wet white leather) was characterized by Scanning Electron Microscope/Energy Dispersive Using X-ray (Analysis). SEM/EDX analysis for metal content; Differential scanning calorimetric (DSC), Micro-Hot-Table and standard shrinkage temperature showing a hydrothermal stability (ranged from 75.3 to 77 °C) and chemical analysis showing the leather is tanned and can be processed through the subsequent mechanical operations (splitting, shaving). On the other hand, an analysis of major minor trace substances from Ti-end waste (especially vanadium content) in new tanning agent and wet white leather (not detected) and residue stream was performed and showed that leachability of vanadium is acceptable. The results obtained show that new tanning agent obtained from Ti end waste can be used for tanning bovine hides, as eco-friendly alternative for chrome tanning.