Characterization of shredded television scrap and implications for materials recovery

Characterization of TV scrap was carried out by using a variety of methods, such as chemical analysis, particle size and shape analysis, liberation degree analysis, thermogravimetric analysis, sink-float test, and IR spectrometry. A comparison of TV scrap, personal computer scrap, and printed circuit board scrap shows that the content of non-ferrous metals and precious metals in TV scrap is much lower than that in personal computer scrap or printed circuit board scrap. It is expected that recycling of TV scrap will not be cost-effective by utilizing conventional manual disassembly. The result of particle shape analysis indicates that the non-ferrous metal particles in TV scrap formed as a variety of shapes; it is much more heterogeneous than that of plastics and printed circuit boards. Furthermore, the separability of TV scrap using density-based techniques was evaluated by the sink-float test. The result demonstrates that a high recovery of copper could be obtained by using an effective gravity separation process. Identification of plastics shows that the major plastic in TV scrap is high impact polystyrene. Gravity separation of plastics may encounter some challenges in separation of plastics from TV scrap because of specific density variations.     

Sensor-based control in eddy current separation of incinerator bottom ash

A sensor unit was placed online in the particle stream produced by an eddy current separator (ECS) to investigate its functionality in non-ferrous metals recovery. The targeted feed was the 1–6 mm size fraction bottom ash from a municipal waste incinerator. The sensor unit was attached to the ECS splitter, where it counted in real-time metal and mineral particles and accurately measured the grade of the stream in the metals product. Influence of segregation (e.g. due to particle size or density) on the metals concentrate were detected and studied using the sensor data collected at different splitter distances. Tests were performed in the laboratory and in a bottom ash processing plant with two different types of ECS and two sources of bottom ash with different moisture content. The measured metal grades matched the manual analyses with errors 0%, 1.5% and 3.1% for moist, dry and very wet feed, respectively. For very wet feed the ECS metals recovery dropped, which was observed from the strongly reduced particle counts and the large changes in cumulative particle properties. The measured sample proved representative for the whole metals concentrate if it is collected at a representative position within the metals particle trajectory fan produced by the ECS. ECS-performance proved sensitively dependent on splitter distance, since a 10 mm shift may result in 10% change in metal recovery and 18% change in grade. The main functionalities of the sensor unit are determined as online quality control and facilitation of automatic control over the ECS splitter distance. These functionalities translate in significant improvements in ECS metals recovery which in turn is linked to economic benefits, increased recycling rate of scrap metals and a further reduction of the ecological drawbacks of incinerator bottom ash.     

Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.     

Distribution of copper,silver and gold during thermal treatment with brominated flame retardants

The growing consumption of electric and electronic equipment results in creating an increasing amount of electronic waste. The most economically and environmentally advantageous methods for the treatment and recycling of waste electric and electronic equipment (WEEE) are the thermal techniques such as direct combustion, co-combustion with plastic wastes, pyrolysis and gasification. Nowadays, this kind of waste is mainly thermally treated in incinerators (e.g. rotary kilns) to decompose the plastics present, and to concentrate metals in bottom ash. The concentrated metals (e.g. copper, precious metals) can be supplied as a secondary raw material to metal smelters, while the pyrolysis of plastics allows the recovery of fuel gases, volatilising agents and, eventually, energy. Indeed, WEEE, such as a printed circuit boards (PCBs) usually contains brominated flame retardants (BFRs). From these materials, hydrobromic acid (HBr) is formed as a product of their thermal decomposition.In the present work, the bromination was studied of copper, silver and gold by HBr, originating from BFRs, such as Tetrabromobisphenol A (TBBPA) and Tetrabromobisphenol A-Tetrabromobisophenol A diglycidyl ether (TTDE) polymer; possible volatilization of the bromides formed was monitored using a thermo-gravimetric analyzer (TGA) and a laboratory-scale furnace for treating samples of metals and BFRs under an inert atmosphere and at a wide range of temperatures. The results obtained indicate that up to about 50% of copper and silver can evolve from sample residues in the form of volatile CuBr and AgBr above 600 and 1000 °C, respectively. The reactions occur in the molten resin phase simultaneously with the decomposition of the brominated resin. Gold is resistant to HBr and remains unchanged in the residue.     

Physical containment of municipal solid waste incineration bottom ash by accelerated carbonation

Accelerated carbonation of municipal solid waste incineration residues is effective for immobilizing heavy metals. In this study, the contribution of the physical containment by carbonation to immobilization of some heavy metals was examined by some leaching tests and SEM–EDS analysis of untreated, carbonated, and milled bottom ash after carbonation that was crushed with a mortar to a mean particle size of approximately 1 μm. The surface of carbonated bottom ash particles on SEM images seemed mostly coated, while there were uneven micro-spaces on the surface of the untreated bottom ash. Results of Japan Leaching Test No. 18 (JLT18) for soil pollution showed that milling carbonated bottom ash increased the pH and EC. The leaching concentration of each element tended to be high for untreated samples, and was decreased by carbonation. However, after the milling of carbonated samples, the leaching concentration became high again. The immobilization effect of each element was weakened by milling. The ratio of physical containment effect to immobilization effects by accelerated carbonation was calculated using the results of JLT18. The ratio for each element was as follows: Pb: 13.9–69.0 %, Cu: 12.0–49.1 %, Cr: 24.1–99.7 %, Zn: 20.0–33.3 %, and Ca: 28.9–63.4 %.     

A new strain for recovering precious metals from waste printed circuit boards

A new strain, Pseudomonas Chlororaphis (PC), was found for dissolving gold, silver, and copper from the metallic particles of crushed waste printed circuit boards (PCBs). The optimized conditions that greatly improved the ability of producing CN^? (for dissolving metals) were obtained. Dissolving experiments of pure gold, silver, and copper showed that the metals could be changed into Au⁺, Ag⁺, and Cu²⁺. PC cells and their secreta would adsorb metallic ions. Meanwhile, metallic ions destroyed the growth of PC. Dissolving experiments of metallic particles from crushed waste PCBs were performed by PC. The results indicated that 8.2% of the gold, 12.1% silver, and 52.3% copper were dissolved into solution. This paper contributed significance information to recovering precious metals from waste PCBs by bioleaching.     

Integrated municipal solid waste treatment using a grate furnace incinerator: the Indaver case

An integrated installation for treatment of municipal solid waste and comparable waste from industrial origin is described. It consists of three grate furnace lines with flue gas treatment by half-wet scrubbing followed by wet scrubbing, and an installation for wet treatment of bottom ash. It is demonstrated that this integrated installation combines high recovery of energy (40.8% net) with high materials recovery. The following fractions were obtained after wet treatment of the bottom ash: ferrous metals, non-ferrous metals, three granulate fractions with different particle sizes, and sludge. The ferrous and non-ferrous metal fractions can both be recycled as high quality raw materials; the two larger particle size particle fractions can be applied as secondary raw materials in building applications; the sand fraction can be used for applications on a landfill; and the sludge is landfilled. For all components of interest, emissions to air are below the limit values. The integrated grate furnace installation is characterised by zero wastewater discharge and high occupational safety. Moreover, with the considered installation, major pollutants, such as PCDD/PCDF, Hg and iodine-136 are to a large extent removed from the environment and concentrated in a small residual waste stream (flue gas cleaning residue), which can be landfilled after stabilisation.     

Fate and behavior of selected heavy metals with mercury mass distribution in a fluidized bed sewage sludge incinerator

In this paper, emission and distribution behavior of six heavy metals (As, Cd, Cr, Ni, Pb, and Hg), particulate matter and mass distribution of mercury within the different streams of a fluidized bed sewage sludge incinerator are presented. At the inlet of air pollution control devices (APCDs); Cd, Cr, Ni and Pb were mainly enriched in coarse particles; comparatively As content was higher in fine particles (<PM_2.5). The concentration of heavy metals in total particulate matter and PM_2.5, at the inlet of APCDs, were in the order of Cr > Ni > Pb > As > Cd. Mercury was almost always distributed in flue gas. Metals, other than mercury, were efficiently removed in APCDs and their concentrations in bottom ash, with fly ash being higher, whereas for that in wastewater, then waste sand was lesser. Overall mercury removal efficiency of APCDs was 98.6 %. More than 83.3 % of mercury was speciated into oxidized form at the inlet of APCDs, attributed by higher chlorine content in sludge. Mercury was mainly distributed in wastewater (78.4 %), wastewater from a spray dry reactor (16.8 %), fly ash in a hopper (3.4 %) and flue gas (1.4 %). This result is one of the first for data to be obtained; more experiments are required to control emission from such sources.     

Volatilisation and oxidation of aluminium scraps fed into incineration furnaces

Ferrous and non-ferrous metal scraps are increasingly recovered from municipal solid waste incineration bottom ash and used in the production of secondary steel and aluminium. However, during the incineration process, metal scraps contained in the waste undergo volatilisation and oxidation processes, which determine a loss of their recoverable mass. The present paper evaluates the behaviour of different types of aluminium packaging materials in a full-scale waste to energy plant during standard operation. Their partitioning and oxidation level in the residues of the incineration process are evaluated, together with the amount of potentially recoverable aluminium. About 80% of post-consumer cans, 51% of trays and 27% of foils can be recovered through an advanced treatment of bottom ash combined with a melting process in the saline furnace for the production of secondary aluminium. The residual amount of aluminium concentrates in the fly ash or in the fine fraction of the bottom ash and its recovery is virtually impossible using the current eddy current separation technology. The average oxidation levels of the aluminium in the residues of the incineration process is equal to 9.2% for cans, 17.4% for trays and 58.8% for foils. The differences between the tested packaging materials are related to their thickness, mechanical strength and to the alloy.     

Recycling of municipal solid waste incinerator fly ash by using hydrocyclone separation

The municipal solid waste incinerators (MSWIs) in Taiwan generate about 300,000 tons of fly ash annually, which is mainly composed of calcium and silicon compounds, and has the potential for recycling. However, some heavy metals are present in the MSWI fly ash, and before recycling, they need to be removed or reduced to make the fly ash non-hazardous. Accordingly, the purpose of this study was to use a hydrocyclone for the separation of the components of the MSWI fly ash in order to obtain the recyclable portion. The results show that chloride salts can be removed from the fly ash during the hydrocyclone separation process. The presence of a dense medium (quartz sand in this study) is not only helpful for the removal of the salts, but also for the separation of the fly ash particles. After the dense-medium hydrocyclone separation process, heavy metals including Pb and Zn were concentrated in the fine particles so that the rest of the fly ash contained less heavy metal and became both non-hazardous and recyclable.     

Evaluation on the applicability of dry processed bottom ash as lightweight aggregate for construction fields

Currently, wet bottom ash is not sufficiently utilized due to its content of unburned coal, chloride and moisture. In contrast, bottom ash discharged from the recently introduced dry process spends a longer time on the clinker conveyer in the lower part of the boiler and consequently contains a significantly smaller amount of unburned coal. Consequently, it has high potential for use as a lightweight aggregate for construction material because of properties such as high porosity, low unburned coal content, non-chloride, and non-moisture. However, it is not frequently used for construction because the ash particle has a flat and thin shape, coarse surface and unfavorable structural strength. Against this backdrop, this study has conducted a range of experiments to identify the shapes, structure, density, absorption, percentage of floating particles, unit volume weight, solid volume, characteristics of air bubbles and micro pores, crushing strength of bottom ash, and the following results were observed. Though the dry bottom ash has sharp and angular edges, its flat and thin shapes lead to vulnerable structures. Dry bottom ash of the size of 0.6 mm or larger has 50–60 % of the total pore rate and 30–50 % of the closed pore rate. Considering these qualities, by removing the relatively fragile surface parts and making the particles more globular, dry bottom ash can be used as a lightweight aggregate for construction field having outstanding performance in terms of light weight and insulation.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Recovery of gold from computer circuit board scrap using aqua regia.

Computer circuit board scrap was first treated with one part concentrated nitric acid and two parts water at 70 degrees C for 1 h. This step dissolved the base metals, thereby liberating the chips from the boards. After solid-liquid separation, the chips, intermixed with some metallic flakes and tin oxide precipitate, were mechanically crushed to liberate the base and precious metals contained within the protective plastic or ceramic chip cases. The base metals in this crushed product were dissolved by leaching again with the same type of nitric acid-water solution. The remaining solid constituents, crushed chips and resin, plus solid particles of gold, were leached with aqua regia at various times and temperatures. Gold was precipitated from the leachate with ferrous sulphate.     

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.     

Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste

In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.     

Effect of carbon particles on heavy metal emissions under ash-melting conditions

In Japan, incineration ash is subjected to a melting process to reduce waste volume and to stabilize hazardous heavy metals. In previous articles, we reported that large quantities of volatile metals are emitted under ash-melting conditions at temperatures higher than 1200°C and that such emissions are considerably increased under reducing conditions. However, the emission behavior in the presence of large amounts of char particles was unclear, and we suspected that emissions under these conditions might differ from emissions under the previous conditions. Therefore, we investigated heavy metal emissions and the melting characteristics of ash in the presence of carbon particles. In this experiment, a small crucible with ash and carbon was rapidly heated using a high-frequency induction-heating furnace to simulate the melting ash gasification with carbon. As a result, it was found that additive carbon can promote emissions of heavy metals such as zinc and lead and control the melt of the ash.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

Thermodynamic estimation of minor element distribution between immiscible liquids in Fe-Cu-based metal phase generated in melting treatment of municipal solid wastes

Waste electrical and electronic equipment (WEEE) has become an important target in managing material cycles from the viewpoint of not only waste management and control of environmental pollution but also resource conservation. This study investigated the distribution tendency of trace elements in municipal solid waste (MSW) or incinerator ash, including valuable non-ferrous metals (Ni, Co, Cr, Mn, Mo, Ti, V, W, Zr), precious group metals (PGMs) originated from WEEE (Ag, Au, Pd, Pt), and others (Al, B, Pb, Si), between Fe-rich and Cu-rich metal phases by means of simple thermodynamic calculations. Most of the typical alloying elements for steel (Co, Cr, Mo, Nb, Ni, Si, Ti, V, and W) and Rh were preferentially distributed into the Fe-rich phase. PGMs, such as Au, Ag, and Pd, were enriched in the Cu-rich phase, whereas Pt was almost equally distributed into both phases. Since the primary metallurgical processing of Cu is followed by an electrolysis for refining, and since PGMs in crude copper have been industrially recovered from the resulting anode slime, our results indicated that Ag, Au, and Pd could be effectively recovered from MSW if the Cu-rich phase could be selectively collected.     

Hybrid sensor for metal grade measurement of a falling stream of solid waste particles

A hybrid sensor system for accurate detection of the metal grade of a stream of falling solid waste particles is investigated and experimentally verified. The system holds an infrared and an electromagnetic unit around a central tube and counts all the particles and only the metal particles, respectively. The count ratio together with the measured average particle mass ratio (k) of non-metal and metal particles is sufficient for calculation of grade. The performance of the system is accurately verified using synthetic mixtures of sand and metal particles. Towards an application a case study is performed using municipal solid waste incineration bottom ash in size fractions 1-6mm, which presents a major challenge for nonferrous metal recovery. The particle count ratio was inherently accurate for particle feed rates up to 13 per second. The average value and spread of k for bottom ash was determined as 0.49 ± 0.07 and used to calculate grade within 2.4% from the manually analysed grade. At higher feed rates the sensors start missing particles which fall simultaneously through the central tube, but the hybrid system still counted highly repeatable. This allowed for implementation of a count correction ratio to eliminate the stationary error. In combination with averaging in measurement intervals for suppression of stochastic variations the hybrid system regained its accuracy for particle feed rates up to 143 per second. This performance and its special design, intended to render it insensitive to external interference and noise when applied in an eddy current separator, make the hybrid sensor suitable for applications such as quality control and sensor controlled separation.     

Behavior of metals in ash melting and gasification-melting of municipal solid waste (MSW)

In this study, metal behavior in ash-melting and municipal solid waste (MSW) gasification-melting facilities were investigated. Eight ash-melting and three MSW gasification-melting facilities with a variety of melting processes and feedstocks were selected. From each facility, melting furnace fly ash (MFA) and molten slag were sampled, and feedstock of the ash-melting processes was also taken. For the ash melting process, the generation rate of MFA was well correlated with the ratio of incineration fly ash (IFA) in feedstock, and this was because MFA was formed mostly by mass transfer from IFA and a limited amount from bottom ash (BA). Distribution ratios of metal elements to MFA were generally determined by volatility of the metal element, but chlorine content in feedstock had a significant effect on Cu and a marginal effect on Pb. Distribution ratio of Zn to MFA was influenced by the oxidizing atmosphere in the furnace. High MFA generation and distribution ratio of non-volatile metals to MFA in gasification-melting facilities was probably caused by carry-over of fine particles to the air pollution control system due to large gas volume. Finally, dilution effect was shown to have a significant effect on metal concentration in MFA.