During an eight day trial automotive shredder residue (ASR) was added to the usual waste feed of a Fluidized Bed Combustor (FBC) for waste-to-energy conversion; the input waste mix consisted of 25% ASR, 25% refuse-derived fuel (RDF) and 50% wastewater treatment (WWT) sludge. All inputs and outputs were sampled and the concentration of the 17 PCDD/Fs with TEF-values was determined in order to obtain "PCDD/F fingerprints". The ASR contained approximately 9000 ng PCDD/Fs/kg(DW), six times more than the RDF and 10 times more than the WWT sludge. The fingerprint of ASR and RDF was dominated by HpCDD and OCDD, which accounted for 90% of the total PDDD/F content, whereas the WWT sludge contained relatively more HpCDFs and OCDF (together 70%). The flue gas cleaning residue (FGCR) and fly and boiler ash contained approximately 30,000 and 2500 ng PCDD/Fs/kg(DW), respectively. The fingerprints of these outputs were also dominated by HpCDFs and OCDF. The bottom ash contained only OCDD and OCDF, in total 8 ng PCDD/Fs/kg (DW). From the comparison of the bottom ash fingerprints with the fingerprints of the other output fractions and of the inputs, it could be concluded that the PCDD/Fs in the waste were destroyed and new PCDD/Fs were formed in the post combustion process by de novo synthesis. During the ASR-co-incineration, the PCDD/F congener concentrations in the fly and boiler ash, FGCR and flue gas were 1.25-10 times higher compared to the same output fractions generated during incineration of the usual waste mix (70% RDF and 30% WWT sludge). The concentration of the higher chlorinated PCDD/Fs increased most. As these congeners have the lowest TEF-factors, the total PCDD/F output, expressed in kg TEQ/year, of the FBC did not increase significantly when ASR was co-incinerated. Due to the relatively high copper levels in the ASR, the copper concentrations in the FBCs outputs increased. As copper catalysis the de novo syntheses, this could explain the increase in PCDD/F concentrations in these outputs.
The European directive 2000/53/EC implies a "reuse and recovery" rate for end-of-life vehicles (ELVs) of 95% to be reached by the year 2015. One of the options to increase the actual average European "reuse and recovery" rate of approximately 78% (EU 15, 2008) is incineration of automotive shredder residue (ASR) with energy-recovery. The mass balance and the congener fingerprints for PCDD/Fs, dioxin-like PCBs, PCBs and PAHs in a real scale fluidized bed combustor (FBC) incinerating 25% ASR with 25% refuse derived fuel (RDF) and 50% waste water treatment sludge (WWT sludge) were investigated. The PCDD/F, dioxin-like PCB, PCB and PAH concentrations in this input waste mix were more than hundred times higher than in the usual waste feed of the incinerator (30% RFD and 70% WWT sludge). In the outputs of the FBC, however, the concentrations of these POP groups were comparable or only slightly higher than in the outputs generated during the incineration of the usual waste feed. The considered POPs in the waste were destroyed efficiently and the formation of new POPs during cooling of the flue gas appeared to a large extent independent of the POP concentrations in the incinerated waste.
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.
The flue gas cleaning system of a MSW incinerator with a capacity of 350 kt/year was changed to improve the HCl elimination efficiency. Instead of the semi-wet operating spray reactor and subsequent baghouse, a two-step wet flue gas cleaning was added behind the baghouse. Elemental composition, X-ray powder diffraction patterns and TGA measurements showed that the resulting APC residue was totally different from the former residue. As a consequence, leaching characteristics of both residues also differed and another treatment was required prior to disposal. For the former residue, mainly leaching of Pb (>100 mg/l), necessitated treatment prior to landfilling. The lower alkalinity of the new residue resulted in a leachate pH of 9.7 and a Pb concentration of 0.8 mg/l. The leachate pH of the former residue was 12.4. The leaching of Pb and Zn increased above 100 mg/l when immobilising the new residue with cement. Better results were obtained when immobilising with micro silica. The high CaCl2 x 2H2O content of the new residue brought along clogging of the bag filter system. Adding 1.4% of CaO (or 1.9% of Ca(OH)2) to the residue already improved these inconveniences but again significantly changed the leaching behaviour of the residue.
This paper covers the Flemish legislative tools concerning the management of bottom ash, fly ash and APC residue from municipal waste incinerators, with respect to their contamination with heavy metals. The situation in Flanders is compared to the one in the Walloon region, The Netherlands, Germany and France. Waste management in the countries considered differs on the level of available management options, of leaching tests and of limit values. To make an indicative comparison of leaching tests and limit values in the different countries, leaching tests were carried out on bottom ash and fly ash, and the results are compared to the relevant limit values for recycling and landfilling of the different countries. The comparison of legislations as well as the leaching results show that discrepancies in waste management between the different regions and countries exist. Recently, European limit values for landfilling became available. European legislation on recycling, however, has not been developed and urgently needs to be considered and drafted as the market for recycling can be expanding rapidly.
The 0.1–2 mm fraction of a MSWI-bottom ash cannot be used as granular construction material because leaching of Cu exceeds Flemish limit values. In addition, leaching of Ba, Mo and Sb exceeds informal limit values. Leaching characteristics thus need to be improved. Carbonation was the chosen treatment method and this was performed by placing samples in a CO2 chamber. The CO2 percentage and the temperature of the chamber atmosphere, as well as the initial humidity of the samples, were varied to optimize carbonation parameters. Metal leaching was tested with the EN 12457 extraction test. Carbonation decreased Cu leaching from 3.3 to 1.0 mg/kg, but not yet to below the official limit value of 0.5 mg/kg. Leaching of Mo and Sb remained fairly constant or even increased after carbonation, but their limit values are only informal. Ba leaching decreased to below the informal limit value. Carbonation also caused Cr leaching to increase, in some cases to above the official limit value. Of the tested parameters, a CO2 percentage of 10% and a carbonation temperature of 50 °C in the atmosphere, together with ash humidity between 13% and 25% appeared to give the best leaching results. The main carbonation reactions took place within the first 24 h.
MSWI-bottom ash often may not be recycled as construction material in Flanders, because leaching of Cu exceeds the limit value of 0.5 mg/kg. Leaching of other components such as Mo and Sb is critical as well, but limit values for these elements are to date only informal. Three treatment techniques were investigated to lower Cu leaching: thermal treatment destroying organic matter still present in the incinerator residue and ligands that may form complexes with Cu and enhance leaching, washing with solutions of organic complexants to extract Cu and accelerated carbonation. Carbonation decreases pH and causes metal hydroxides to react to carbonates. Heating the bottom ash to 400°C decreases Cu leaching to 0.1 mg/kg. Washing was performed with six solutions, of which washing with citric acid and ammoniumcitrate decreases Cu leaching to below the limit value. Carbonation decreased Cu leaching from 3.3 mg/kg to 1.0 mg/kg, but further improvement should be possible. Although heating and washing gave better results in the laboratory, accelerated carbonation seems to be the most promising technique.
Cement as agent for immobilising Pb from air pollution control residues is compared with the use of different silica-containing materials. The DIN 38414-S4 leaching test was used to control Pb leachability and to compare obtained Pb leachate concentrations with the landfill limit of 2 mg/l for Pb. Firstly, one scrubber residues was treated with cement and micro-silica. With cement, the Pb leachability could be reduced with a factor ranging from 3 to 50 depending on the type and amount of cement used and depending on the curing time. The landfill limit of 2 mg/l was, however, never attained. From all tested silica-containing additives, aerosil could reduce the initial Pb leaching (101.3mg/l) to below the detection limit at a dosage of 0.13 g aerosil/g residue. Second best and an economically preferable silica-containing additive was micro-silica: a reduction from 101.3 to 0.7 mg/l was observed at a dosage of 0.4 g micro-silica/g residue. The formation of Ca-silicates was found to be responsible for the decreased Pb leachability. To generalise the findings, the Pb leachability of five cement-treated and five micro-silica-treated air pollution control residues were compared. For three scrubber residues, 2-20 times lower Pb leachate concentrations were measured for micro-silica-treated samples (cured for 5 weeks) than cement-treated samples. For a fly ash and a boiler ash the difference was, respectively, 48 and 17 times. pH-dependent leaching tests showed that at pH=2.5, Pb leaching is 250 times lower for the micro-silica-treated residue than for the cement-treated residue and almost seven times lower at pH 12.4.
The immobilization of MSWI-scrubber residues with soluble PO43− was studied and compared to the immobilization using cement. The DIN 38414-S4 leaching protocol and pH dependent leaching were used to evaluate the leaching of Pb and Zn. Four different scrubber residues from MSW combustion (Pb concentration: 2.8–4.8 mg/g; Zn concentration: 3.0–12.3 mg/g) were mixed with water and cement or Na2HPO4 as source of soluble PO43− at dosages of at least 0, 0.1, 0.2, 0.3 and 0.4 g per g residue. With cement as well as with PO43− a reduction in Pb and Zn leaching was observed. With 0.4 g cement per g residue, the Pb leaching was reduced by a factor ranging from 70 to 100, but still exceeded the Pb landfill limit of 2 mg/l. With PO43− the Pb leaching was reduced with a factor of 100–300 to below 2 mg/l. The Zn landfill limit (10 mg/l) was only exceeded by one untreated residue. Adding 0.2 g cement or 0.1 g PO43− per g of that residue was enough to reduce leaching below 10 mg/l. However, when 0.6 g Na2HPO4 per g residue was added to a lime based scrubber residue, an increase in Zn leaching up to 12.5 mg/l was observed due to an increase in pH of up to 13.0. When using NaH2PO4 and H3PO4 no such increase in Zn leaching was observed. pH dependent leaching performed on one of the four residues showed that in the pH range of 2.5–6, Pb leaching was 100–50 times lower with Na2HPO4 treatment than with cement. In the pH range from 7–11, almost equal results were obtained for cement treated and Na2HPO4 treated residue. Above a pH of 12, Pb leaching was three times lower for the PO43−-treated residue than for the cement treated residue. With soluble PO43−, Pb leaching below 2 mg/l could be attained at a dosage of 0.27 g PO43−/g residue. With cement, Pb leaching was never below 2 mg/l.