Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

Fate of metals contained in waste electrical and electronic equipment in a municipal waste treatment process

In Japan, waste electrical and electronic equipment (WEEE) that is not covered by the recycling laws are treated as municipal solid waste. A part of common metals are recovered during the treatment; however, other metals are rarely recovered and their destinations are not clear. This study investigated the distribution ratios and substance flows of 55 metals contained in WEEE during municipal waste treatment using shredding and separation techniques at a Japanese municipal waste treatment plant. The results revealed that more than half of Cu and most of Al contained in WEEE end up in landfills or dissipate under the current municipal waste treatment system. Among the other metals contained in WEEE, at least 70% of the mass was distributed to the small-grain fraction through the shredding and separation and is to be landfilled. Most kinds of metals were concentrated several fold in the small-grain fraction through the process and therefore the small-grain fraction may be a next target for recovery of metals in terms of both metal content and amount. Separate collection and pre-sorting of small digital products can work as effective way for reducing precious metals and less common metals to be landfilled to some extent; however, much of the total masses of those metals would still end up in landfills and it is also important to consider how to recover and utilize metals contained in other WEEE such as audio/video equipment.     

Automotive shredder residue (ASR) characterization for a valuable management

Car fluff is the waste produced after end-of-life-vehicles (ELVs) shredding and metal recovery. It is made of plastics, rubber, glass, textiles and residual metals and it accounts for almost one-third of a vehicle mass. Due to the approaching of Directive 2000/53/EC recycling targets, 85% recycling rate and 95% recovery rate in 2015, the implementation of automotive shredder residue (ASR) sorting and recycling technologies appears strategic. The present work deals with the characterization of the shredder residue coming from an industrial plant, representative of the Italian situation, as for annual fluxes and technologies involved. The aim of this study is to characterize ASR in order to study and develop a cost effective and environmentally sustainable recycling system. Results show that almost half of the residue is made of fines and the remaining part is mainly composed of polymers. Fine fraction is the most contaminated by mineral oils and heavy metals. This fraction produces also up to 40% ashes and its LHV is lower than the plastic-rich one. Foam rubber represents around half of the polymers share in car fluff. Moreover, some chemical–physical parameters exceed the limits of some parameters fixed by law to be considered refuse derived fuel (RDF). As a consequence, ASR needs to be pre-treated in order to follow the energy recovery route.     

Thermal valorisation of automobile shredder residue: injection in blast furnace

Wastes with residual heating value, according to the trend of the world legislation, could be thermally reused. The present study is conducted to verify the possibility of thermal valorisation of a waste, denominated fluff, by injection in blast furnace. The fluff, arising from the automobile shredder operations, is a waste characterised by a high organic matrix and is potentially dangerous due to the heavy metals, oils filter and halogenated plastics content. The first step of the work is the chemical, physical and toxicological characterisation of this material. Then the fluff injection in a blast furnace tuyere is theoretically analysed with a mathematical model. Finally, experimental trials are conducted in a pilot plant, simulating the most important part of the blast furnace: the raceway, in order to analyse process and industrial aspects. In view of an industrial application a first economical evaluation is carried out on the basis of model and experimental results.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Metals, non-metals and PCB in electrical and electronic waste--actual levels in Switzerland

The chemical composition of waste of small electrical and electronic equipment (s-WEEE), a rapidly growing waste stream, was determined for selected metals (Cu, Sb, Hg etc.) and non-metals (Cl, Br, P) and PCBs. During a 3-day experiment, all output products and the s-WEEE input mass flows in a WEEE recycling plant were measured. Only output products were sampled and analyzed. Material balances were established, applying substance flow analysis (SFA). Transfer coefficients for the selected substances were also determined. The results demonstrate the capability of SFA to determine the composition of the highly heterogeneous WEEE for most substances with rather low uncertainty (2 sigma +/- 30%). The results confirm the growing importance of s-WEEE regarding secondary resource metals and potential toxic substances. Nowadays, the thirty times smaller s-WEEE turns over larger flows for many substances, compared to municipal solid waste. Transfer coefficient results serve to evaluate the separation efficiency of the recycling process and confirm--with the exception of PCB and Hg--the limitation of hand-sorting and mechanical processing to separate pollutants (Cd, Pb, etc.) out of reusable fractions. Regularly applied SFA would serve to assess the efficacy of legislative, organizational and technical measures on the WEEE.     

Recycling of WEEE plastics: a review

Electric and electronic equipment (EEE) is swiftly growing in volume, level of sophistication, and diversity. Also, it evolves briskly, moved by innovation and technical change, and draws on numerous and at times rare resources. Waste EEE (WEEE) has evolved into an important societal problem. Recycling and treating WEEE implies occupational as well as environmental hazards that are still incompletely documented. Still, second hand EEE has been exported and treated in Africa, China, and India in a precarious informal context. In developed countries, EEE recycling has been sustained by a wide range of initiatives and motives, such as sustainability, creating jobs, and the value of precious or rare metals. Current EU Directives require a steep reduction of WEEE plastics (WEEP) going to landfill. Mechanical, thermal, and feedstock recycling of WEEP are analysed and some options confronted. Plastics recycling should be weighed against the eventual risks related to their hazardous ingredients, mainly legacy brominated fire retardants and heavy metals. Another paper is related to a somewhat similar problem, yet involving a different mix of plastics: recycling plastics from automotive shredder residue.     

Flow analysis of metals in a municipal solid waste management system

This study aimed to identify the metal flow in a municipal solid waste (MSW) management system. Outputs of a resource recovery facility, refuse derived fuel (RDF) production facility, carbonization facility, plastics liquefaction facility, composting facility, and bio-gasification facility were analyzed for metal content and leaching concentration. In terms of metal content, bulky and incombustible waste had the highest values. Char from a carbonization facility, which treats household waste, had a higher metal content than MSW incinerator bottom ash. A leaching test revealed that Cd and Pb in char and Pb in RDF production residue exceeded the Japanese regulatory criteria for landfilling, so special attention should be paid to final disposal of these substances. By multiplying metal content and the generation rate of outputs, the metal content of input waste to each facility was estimated. For most metals except Cr, the total contribution ratio of paper/textile/plastics, bulky waste, and incombustible waste was over 80%. Approximately 30% of Cr originated from plastic packaging. Finally, several MSW management scenarios showed that most metals are transferred to landfills and the leaching potential of metals to the environment is quite small.     

Sustainable alkali-activated binders with municipal solid waste incineration ashes as sand or fly ash replacement

The present study investigates the feasibility of using two types of municipality solid wastes incineration ashes, namely, fly ash and bottom ash in the production of sustainable alkali-activated binder. The ashes are collected from the incineration plant and characterized to determine their particle size distribution, specific gravity, chemical composition, and heavy metals content. The ashes are then used as either fly ash or sand replacement with five replacement ratios 0%, 5%, 10%, 15%, and 20% to produce the binder. The produced binder are characterized in terms of strength, workability, density, water absorption, thermal conductivity and stability, chemical composition, and heavy metals content. The results reflect the ability of producing sustainable alkali-activated binder with small dosage of MSWI ashes as either fly ash or sand replacement without negatively affecting its strength, workability, density, and water absorption. The ashes enhance the thermal insulation capability of the binder.

     

Comparative studies of waste incineration bottom ashes from various grate and firing systems,conducted with respect to mineralogical and geochemical methods of examination

Mineralogical and geochemical techniques can be used successfully to characterize and evaluate bottom ashes produced in waste incineration. At the present time, it is not quite clear to what extent the mineral phase compositions and the content of main elements and heavy metal concentrations of bottom ashes are influenced by the conditions of combustion. Once the location of heavy metals in or with specific minerals is known, it may be considered, in the light of technical possibilities, whether a change in temperature or in the residence time of waste in the combustion chamber could be sufficient to remove these components from their mineral phases.     

End-of-Life Vehicles management: Italian material and energy recovery efficiency

Each European Member State must comply with Directive 2000/53/EC recycling and recovery targets by 2015, set to 85% and 95%, respectively. This paper reports a shredder campaign trial developed and performed in Italy at the beginning of 2008. It turns out to be the first assessment about the critical aspects belonging to the Italian End-of-Life Vehicles (ELVs) reverse supply chain involving 18 dismantling plants, a shredder plant and 630 ELV representatives of different categories of vehicles treated in Italy during 2006. This trial aims at improving the experimental knowledge related to ELVs added waste, pre-treatment, part reuse, recycling and final metal separation and car fluff disposal. Finally, the study also focuses on the calculation of the effective Italian ELV recycling rate, which results equal to 80.8%, and auto shredder residue (ASR) characterization. According to the results obtained in this work, ASR still contains up to 8% of metals and 40% of polymers that could be recovered. Moreover, physical-chemical analysis showed a Lower Heat Value of almost 20,000 kJ/kg and revealed the presence of pollutants such as heavy metals, mineral oils, PCBs and hydrocarbons.     

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.     

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.     

The behaviour of ashes and heavy metals during the co-combustion of sewage sludges in a fluidised bed

Co-combustion tests of dry sewage sludges with coal were performed in a pilot bubbling FBC aiming at the characterization of ashes and determining the behaviour of heavy metals in the process. The tests showed compliance with the regulatory levels as far as heavy metal emissions were concerned. The bottom ashes, which accounted for about 70% of the total ash production, were obtained in a granular form, with diameters ranging from 0.5 to 4 mm. The heavy metals were distributed in ashes obtained from different locations of the installation and their concentrations were found to vary depending on the location of capture. The increase in heavy metals content in bottom ashes was not found to lead to higher leachability and ecotoxicity compared to sewage sludges, suggesting that there could be opportunities for their further use. Mercury suffered vaporisation inside the reactor, thus leaving bottom ashes free of contamination by it. However, there was observed a strong retention of mercury in cyclone ashes due to the presence of unburned carbon which probably acted as an adsorbent. The effluent mercury was also found to be mostly associated with the particulate fraction, being less than 20% emitted in gaseous forms. The results suggested that the combustion of the sewage sludge could successfully be carried out and the amount of unburned carbon leaving the combustor but captured in cyclone was large enough to ensure substantial retention of mercury at low temperatures, hence could contribute to an improvement of the mercury release which still remains an issue of great concern to resolve during combustion of waste materials.     

Enrichment of elements in industrial waste incineration bottom ashes obtained from three different types of incinerators,as studied by ICP-AES and ICP-MS

The elemental composition of the industrial waste incineration bottom ash (IWIBA) samples collected from three different types of incinerator with different kinds of wastes were compared. The major-to-ultratrace elements in the IWIBA samples were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES) and inductively coupled plasma mass spectrometry (ICP-MS). As a result, ca. 40 elements in the concentration range from milligrams per gram to submicrograms per gram could be determined with relative standard deviations of less than 5%. The IWIBA sample from petrochemical wastes contained lower concentrations of the elements, because fewer mineral constituents were contained in the input waste materials. On the contrary, the elemental concentrations in the IWIBA sample from industrial solid wastes provided the highest values for most elements, while the elemental compositions of the IWIBA sample from food wastes were similar to those of municipal solid waste incineration bottom ash. In addition, it was found from the analytical results that the levels of various heavy metals such as Cr, Mn, Fe, Ni, Cu, As, Zr, Mo, Sb, Ba, and Pb were higher in the IWIBA samples than in municipal solid waste incineration bottom ash. The enrichment factors of the elements in the IWIBA samples were estimated from the analytical results to compare the elemental distributions in incineration bottom ashes in relation to their mining influence factors, which are the indices for human use of the elements.     

Recycling of non-metallic fractions from waste electrical and electronic equipment (WEEE): A review

The world’s waste electrical and electronic equipment (WEEE) consumption has increased incredibly in recent decades, which have drawn much attention from the public. However, the major economic driving force for recycling of WEEE is the value of the metallic fractions (MFs). The non-metallic fractions (NMFs), which take up a large proportion of E-wastes, were treated by incineration or landfill in the past. NMFs from WEEE contain heavy metals, brominated flame retardant (BFRs) and other toxic and hazardous substances. Combustion as well as landfill may cause serious environmental problems. Therefore, research on resource reutilization and safe disposal of the NMFs from WEEE has a great significance from the viewpoint of environmental protection. Among the enormous variety of NMFs from WEEE, some of them are quite easy to recycle while others are difficult, such as plastics, glass and NMFs from waste printed circuit boards (WPCBs). In this paper, we mainly focus on the intractable NMFs from WEEE. Methods and technologies of recycling the two types of NMFs from WEEE, plastics, glass are reviewed in this paper. For WEEE plastics, the pyrolysis technology has the lowest energy consumption and the pyrolysis oil could be obtained, but the containing of BFRs makes the pyrolysis recycling process problematic. Supercritical fluids (SCF) and gasification technology have a potentially smaller environmental impact than pyrolysis process, but the energy consumption is higher. With regard to WEEE glass, lead removing is requisite before the reutilization of the cathode ray tube (CRT) funnel glass, and the recycling of liquid crystal display (LCD) glass is economically viable for the containing of precious metals (indium and tin). However, the environmental assessment of the recycling process is essential and important before the industrialized production stage. For example, noise and dust should be evaluated during the glass cutting process. This study could contribute significantly to understanding the recycling methods of NMFs from WEEE and serve as guidance for the future technology research and development.     

Thermal process of fluff: Preliminary tests on a full-scale treatment plant

Until only recently fluff has been largely disposed of in controlled landfill sites. However, in Europe environmental regulations, including the EU Landfill Directive 1999/31/EC and ELV (End of Life Vehicle) Directive 2000/53/EC, have dramatically increased the pressure on all stakeholders to develop alternative solutions. As increasingly stringent legislation forces Shredder Residues (SR) to be diverted from landfilling, newly developed technologies will be in a position to compete for the market value of disposing of the waste.However, the fluff waste stream is so variable that it cannot be automatically assumed that processes developed for one type of fluff will prove to be suitable for other fluff streams. This situation has contributed towards convincing stakeholders to withhold investment funds or delay taking decisions as to how best to proceed; as a consequence, very few technologies have been fully developed on a commercial basis. It is of particular interest therefore that commercial alternatives to be used in dealing with this complex waste stream should be identified.The present paper illustrates the findings of a full-scale thermal treatment performed on SR samples obtained from various shredding plants. The outcome of the study provides an important contribution towards assessing the feasibility and reliability of the process, thus constituting a basic prerequisite for process performance evaluation. The full-scale plant, designed for the thermo-valorization of tyres, was purpose-modified to allow for fluff combustion. Three different fluff compositions (car fluff with different percentage of shredding, whites and 100% car fluff) were taken into consideration. Both the raw samples and solid products were thoroughly characterized. Combustion emissions were continuously analyzed during the test period, alternatively operating for tyre and fluff combustion. Classification of combustion residues for landfill disposal was carried out indicating only 2% (ashes) as hazardous waste. Preliminary results, obtained from a unsophisticated thermodynamic analysis of the process, indicated a value of 0.61 for energy efficiency parameter calculated in accordance with the Directive 2008/98/EC.To conclude, the thermal treatment investigated may be deemed an appropriate technique for use in managing fluff. Indeed, values obtained for all organic and inorganic contaminants released into the atmosphere were lower than legal limits prescribed, and a significant energy content was recovered from waste fractions.     

Biodegradable municipal solid waste: characterization and potential use as animal feedstuffs

Five different fractions of the biodegradable municipal solid waste (BMSW) were evaluated as potential animal feedstuffs. For each source of waste (meat waste (MW), fish waste (FW), fruit and vegetables waste (FVW), restaurant waste (RW), household waste (HW)), samples were obtained from small shops (butchers, fishmongers, fruit and vegetable shops), restaurants and a MSW treatment plant (household waste). The chemical composition, microbiological characterization, dioxins, furans, PCB's and mineral content were determined for every type of waste fraction. The analysed biodegradable waste presented high moisture content (from 60% to 90%). Some fractions were dense in one nutrient: meat waste in ether extract, fish waste in crude protein, fruit and vegetable waste in nitrogen free extract. The other studied fractions (restaurant fraction and household fraction) presented a more balanced composition, but the presence of toxic concentrations of contaminants such as metals was higher than European legislation permitted values in animal feeding. From a microbiological standpoint, a heat treatment at 65 degrees C for 20 min was sufficient to ensure microbiological quality of the samples. This treatment was also advisable to reduce the moisture content: a lower moisture content facilitates the waste handling and processing and, therefore, the inclusion of these waste fractions in commercial animal diets. This paper presents a potential alternative for the recovery of organic matter content in municipal solid waste. The results obtained in this research and the feedstuffs legislation in force related to animal feed, indicated that some of the studied biodegradable waste fractions (meat waste, fruit and vegetable waste and fish waste) could be considered as alternatives to typical raw materials used in animal feeds.     

Physical and mechanical properties of cement-based products containing incineration bottom ash

This paper presents the results of a wider experimental programme conducted in the framework of the NNAPICS ("Neural Network Analysis for Prediction of Interactions in Cement/Waste Systems") project funded by the European Commission and a number of industrial partners under Brite-EuRamIII. Based on the fact that bottom ashes from waste incineration are classified as non-hazardous wastes according to the European Waste Catalogue, the aim of the present work was to investigate the feasibility of addressing the potential use of such residues in cement-based mixtures. This issue was suggested by the analysis of the properties of different bottom ashes coming from Italian municipal and hospital solid waste incinerators, which showed a chemical composition potentially suitable for such applications. Different mixes were prepared by blending bottom ash with ordinary Portland cement in different proportions and at different water dosages. The solidified products were tested for setting time and bulk density, unconfined compressive strength and evaporable water content at different curing times. The results of the experimental campaign were analysed through a statistical procedure (analysis of variance), in order to investigate the effect of mixture composition (waste replacement level and water dosage) on the product properties.     

Household hazardous waste: composition of paint waste.

'Paint waste', a part of the 'household hazardous waste', amounting to approximately 5 tonnes was collected from recycling stations in two Danish cities. Sorting and analyses of the waste showed paint waste comprised approximately 65% of the mass, paint-like waste (cleaners, fillers, etc.) comprised 15-25% and foreign items comprised 10-20%.Water-based paint was the dominant part of the paint waste. The chemical composition of the paint waste and the paint-like waste was characterized by an analysis of 27 substances in seven waste fractions. The content of critical substances was low and the paint waste was less contaminated with heavy metals than was the ordinary household waste. This may suggest that households no longer need to source-segregate their paint if the household waste is incinerated, since the presence of a small quantity of solvent-based paint will not be harmful when incinerated. Allowing household paint waste to be collected with ordinary household waste is expected to reduce the cost of handling household hazardous waste, since paint waste in Denmark comprises the major fraction of household hazardous waste.