Copper leaching of MSWI bottom ash co-disposed with refuse: Effect of short-term accelerated weathering

Co-disposal of refuse with municipal solid waste incinerator (MSWI) bottom ash (IBA) either multi-layered as landfill cover or mixed with refuse could pose additional risk to the environment because of enhanced leaching of heavy metals, especially Cu. This study applied short-term accelerated weathering to IBA, and monitored the mineralogical and chemical properties of IBA during the weathering process. Cu extractability of the weathered IBA was then evaluated using standard leaching protocols (i.e. SPLP and TCLP) and co-disposal leaching procedure. The results showed that weathering had little or no beneficial effect on Cu leaching in SPLP and TCLP, which can be explained by the adsorption and complexation of Cu with DOM. However, the Cu leaching of weathered IBA was reduced significantly when situated in fresh simulated landfill leachate. This was attributed to weakening Cu complexation with fulvic acid or hydrophilic fractions and/or intensifying Cu absorption to neoformed hydr(oxide) minerals in weathered IBA. The amount of total leaching Cu and Cu in free or labile complex fraction (the fraction with the highest mobility and bio-toxicity) of the 408-h weathered IBA were remarkably decreased by 86.3% and 97.6% in the 15-day co-disposal leaching test. Accelerated weathering of IBA may be an effective pretreatment method to decrease Cu leaching prior to its co-disposal with refuse.     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

Solidification/stabilization of ash from medical waste incineration into geopolymers

In the present work, bottom and fly ash, generated from incinerated medical waste, was used as a raw material for the production of geopolymers. The stabilization (S/S) process studied in this paper has been evaluated by means of the leaching and mechanical properties of the S/S solids obtained. Hospital waste ash, sodium hydroxide, sodium silicate solution and metakaolin were mixed. Geopolymers were cured at 50 °C for 24 h. After a certain aging time of 7 and 28 days, the strength of the geopolymer specimens, the leachability of heavy metals and the mineralogical phase of the produced geopolymers were studied. The effects of the additions of fly ash and calcium compounds were also investigated. The results showed that hospital waste ash can be utilized as source material for the production of geopolymers. The addition of fly ash and calcium compounds considerably improves the strength of the geopolymer specimens (2–8 MPa). Finally, the solidified matrices indicated that geopolymerization process is able to reduce the amount of the heavy metals found in the leachate of the hospital waste ash.     

Effect of natural ageing on volume stability of MSW and wood waste incineration residues

This paper presents the results of a study on the effect of natural weathering on volume stability of bottom ash (BA) from municipal solid waste (MSW) and wood waste incineration. BA samples were taken at different steps of treatment (fresh, 4 weeks and 12 weeks aged) and then characterised for their chemical and mineralogical composition and for volume stability by means of the mineralogical test method (M HMVA-StB), which is part of the German quality control system for using aggregates in road construction (TL Gestein-StB 04). Changes of mineralogical composition with the proceeding of the weathering treatment were also monitored by leaching tests. At the end of the 12 weeks of treatment, almost all the considered samples resulted to be usable without restrictions in road construction with reference to the test parameter volume stability.     

The effects of accelerated carbonation on CO2 uptake and metal release from incineration APC residues

This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO₂ at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO₂ uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO₂, owing to the abundance of calcium hydroxides phases, with a maximum CO₂ uptake of ～250 g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour.     

Process development for recovery of copper and precious metals from waste printed circuit boards with emphasize on palladium and gold leaching and precipitation

A novel hydrometallurgical process was proposed for selective recovery of Cu, Ag, Au and Pd from waste printed circuit boards (PCBs). More than 99% of copper content was dissolved by using two consecutive sulfuric acid leaching steps in the presence of H₂O₂ as oxidizing agents. The solid residue of 2nd leaching step was treated by acidic thiourea in the presence of ferric iron as oxidizing agent and 85.76% Au and 71.36% Ag dissolution was achieved. The precipitation of Au and Ag from acidic thiourea leachate was investigated by using different amounts of sodium borohydride (SBH) as a reducing agent. The leaching of Pd and remained gold from the solid reside of 3rd leaching step was performed in NaClO-HCl-H₂O₂ leaching system and the effect of different parameters was investigated. The leaching of Pd and specially Au increased by increasing the NaClO concentration up to 10 V% and any further increasing the NaClO concentration has a negligible effect. The leaching of Pd and Au increased by increasing the HCl concentration from 2.5 to 5 M. The leaching of Pd and Au were endothermic and raising the temperature had a positive effect on leaching efficiency. The kinetics of Pd leaching was quite fast and after 30 min complete leaching of Pd was achieved, while the leaching of Au need a longer contact time. The best conditions for leaching of Pd and Au in NaClO-HCl-H₂O₂ leaching system were determined to be 5 M HCl, 1 V% H₂O₂, 10 V% NaClO at 336 K for 3 h with a solid/liquid ratio of 1/10. 100% of Pd and Au of what was in the chloride leachate were precipitated by using 2 g/L SBH. Finally, a process flow sheet for the recovery of Cu, Ag, Au and Pd from PCB was proposed.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

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

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

Influence of leaching conditions for ecotoxicological classification of ash

The Waste Framework Directive (WFD; 2008/98/EC) states that classification of hazardous ecotoxicological properties of wastes (i.e. criteria H-14), should be based on the Community legislation on chemicals (i.e. CLP Regulation 1272/2008). However, harmonizing the waste and chemical classification may involve drastic changes related to choice of leaching tests as compared to e.g. the current European standard for ecotoxic characterization of waste (CEN 14735). The primary aim of the present study was therefore to evaluate the influence of leaching conditions, i.e. pH (inherent pH (～10), and 7), liquid to solid (L/S) ratio (10 and 1000 L/kg) and particle size (<4 mm, <1 mm, and <0.125 mm), for subsequent chemical analysis and ecotoxicity testing in relation to classification of municipal waste incineration bottom ash. The hazard potential, based on either comparisons between element levels in leachate and literature toxicity data or ecotoxicity testing of the leachates, was overall significantly higher at low particle size (<0.125 mm) as compared to particle fractions <1 mm and <4 mm, at pH 10 as compared to pH 7, and at L/S 10 as compared to L/S 1000. These results show that the choice of leaching conditions is crucial for H-14 classification of ash and must be carefully considered in deciding on future guidance procedures in Europe.     

The weathering of municipal solid waste incineration bottom ash evaluated by some weathering indices for natural rock

The weathering of municipal solid waste incineration (MSWI) residues consists of complicated phenomena. This makes it difficult to describe leaching behaviors of major and trace elements in fresh/weathered MSWI bottom ash, which was relevant interactively to pH neutralization and formation of secondary minerals. In this study, mineralogical weathering indices for natural rock profiles were applied to fresh/landfilled MSWI bottom ash to investigate the relation of these weathering indices to landfill time and leaching concentrations of component elements. Tested mineralogical weathering indices were Weathering Potential Index (WPI), Ruxton ratio (R), Weathering Index of Parker (WIP), Vogt’s Residual Index (V), Chemical Index of Alternation (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alternation (PIA), Silica–Titania Index (STI), Weathering Index of Miura (Wm), and Weatherability index of Hodder (Ks). Welch’s t-test accepted at 0.2% of significance level that all weathering indices could distinguish fresh and landfilled MSWI bottom ash. However, R and STI showed contrasted results for landfilled bottom ash to theoretical expectation. WPI, WIP, Wm, and Ks had good linearity with reclamation time of landfilled MSWI bottom ash. Therefore, these four indices might be applicable as an indicator to indentify fresh/weathered MSWI bottom ash and to estimate weathering time. Although WPI had weak correlation with leachate pH, other weathering indices had no significant correlation. In addition, all weathering indices could not explain leaching concentration of Al, Ca, Cu, and Zn quantitatively. Large difficulty to modify weathering indices correctly suggests that geochemical simulation including surface sorption, complexation with DOM, and other mechanisms seems to be the only way to describe leaching behaviors of major and trace elements in fresh/weathered MSWI bottom ash.     

Chemical stabilization of medical waste fly ash using chelating agent and phosphates: Heavy metals and ecotoxicity evaluation

Chemical stabilization of heavy metals in medical waste fly ash has been carried out using the following compounds: a chelating agent (Ashnite S803), a commercial acidic phosphoric acid solution (Ashnite R303) as well as basic one (Ashnite R201). In order to predict the leachability of heavy metals, Japanese Leaching Test (JLT-13) procedure was applied to the stabilized fly ash products. An ecotoxicity assessment of the stabilized fly ash products leachate and the unstabilized fly ash leachate was conducted using a battery of bioassays based on lettuce root elongation inhibition, Daphnia magna mortality and Vibrio fischeri photoinhibition. The results showed that the three stabilizing agents were able to significantly decrease (ANOVA, P < 0.05) the concentration of heavy metals in the leachates. Although the leachate from both stabilized and unstabilized fly ash were very toxic to lettuce and daphnids, the incorporation of these stabilizing agents diminished significantly (ANOVA, P < 0.05) the toxicity of the leachates towards the three tested organisms. Pearson correlation analysis was used to analyze the strength of the relationship between chemical elements concentration in the leachate and bioassays results. Most of the heavy metals in the leachate were significantly correlated (ANOVA, P < 0.05) with the toxicity values of the bioassays. However, the correlation was not found between the concentration of dissolved organic carbon (DOC) and the toxicity effect of the leachate to the tested organisms.     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

Alkali activation processes for incinerator residues management

Incinerator bottom ash (BA) is produced in large amount worldwide and in Italy, where 5.1 millions tons of municipal solid residues have been incinerated in 2010, corresponding to 1.2–1.5 millions tons of produced bottom ash. This residue has been used in the present study for producing dense geopolymers containing high percentage (50–70 wt%) of ash. The amount of potentially reactive aluminosilicate fraction in the ash has been determined by means of test in NaOH. The final properties of geopolymers prepared with or without taking into account this reactive fraction have been compared. The results showed that due to the presence of both amorphous and crystalline fractions with a different degree of reactivity, the incinerator BA geopolymers exhibit significant differences in terms of Si/Al ratio and microstructure when reactive fraction is considered.     

Glass–ceramic from mixtures of bottom ash and fly ash

Along with the gradually increasing yield of the residues, appropriate management and treatment of the residues have become an urgent environmental protection problem. This work investigated the preparation of a glass–ceramic from a mixture of bottom ash and fly ash by petrurgic method. The nucleation and crystallization kinetics of the new glass–ceramic can be obtained by melting the mixture of 80% bottom ash and 20% fly ash at 950 °C, which was then cooled in the furnace for 1 h. Major minerals forming in the glass–ceramics mainly are gehlenite (Ca₂Al₂SiO₇) & akermanite (Ca₂MgSiO₇) and wollastonite (CaSiO₃). In addition, regarding chemical/mechanical properties, the chemical resistance showing durability, and the leaching concentration of heavy metals confirmed the possibility of engineering and construction applications of the most superior glass–ceramic product. Finally, petrurgic method of a mixture of bottom ash and fly ash at 950 °C represents a simple, inexpensive, and energy saving method compared with the conventional heat treatment.     

Assessing the environmental impact of ashes used in a landfill cover construction

Large amounts of construction materials will be needed in Europe in anticipation for capping landfills that will be closed due to the tightening up of landfill legislation. This study was conducted to assess the potential environmental impacts of using refuse derived fuel (RDF) and municipal solid waste incineration (MSWI) ashes as substitutes for natural materials in landfill cover designs. The leaching of substances from a full-scale landfill cover test area built with different fly and bottom ashes was evaluated based on laboratory tests and field monitoring. The water that drained off above the liner (drainage) and the water that percolated through the liner into the landfill (leachate) were contaminated with Cl^?, nitrogen and several trace elements (e.g., As, Cu, Mo, Ni and Se). The drainage from layers containing ash will probably require pre-treatment before discharge. The leachate quality from the ash cover is expected to have a minor influence on overall landfill leachate quality because the amounts generated from the ash covers were low, <3–30 l (m² yr)^?1. Geochemical modelling indicated that precipitation of clay minerals and other secondary compounds in the ash liner was possible within 3 years after construction, which could contribute to the retention of trace elements in the liner in the long term. Hence, from an environmental view point, the placement of ashes in layers above the liner is more critical than within the liner.     

Study on the influence of various factors in the hydrometallurgical processing of waste printed circuit boards for copper and gold recovery

The present lab-scale experimental study presents the process of leaching waste printed circuit boards (WPCBs) in order to recover gold by thioureation. Preliminary tests have shown that copper adversely affects gold extraction; therefore an oxidative leaching pre-treatment was performed in order to remove base metals. The effects of sulfuric acid concentration, hydrogen peroxide volume and temperature on the metal extraction yield were studied by analysis of variance (ANOVA). The highest copper extraction yields were 76.12% for sample A and 18.29% for sample D, after leaching with 2 M H₂SO₄, 20 ml of 30% H₂O₂ at 30 °C for 3 h. In order to improve Cu removal, a second leaching was performed only on sample A, resulting in a Cu extraction yield of 90%. Other experiments have shown the negative effect of the stirring rate on copper dissolution. The conditions used for the process of gold extraction by thiourea were: 20 g/L thiourea, 6 g/L ferric ion, 10 g/L sulfuric acid, 600 rpm stirring rate. To study the influence of temperature and particle size, this process was tested on pins manually removed from computer central processing units (CPUs) and on waste CPU for 3½ h. A gold extraction yield of 69% was obtained after 75% of Cu was removed by a double oxidative leaching treatment of WPCBs with particle sizes smaller than 2 mm.     

Pilot scale evaluation of the BABIU process – Upgrading of landfill gas or biogas with the use of MSWI bottom ash

Biogas or landfill gas can be converted to a high-grade gas rich in methane with the use of municipal solid waste incineration bottom ash as a reactant for fixation of CO₂ and H₂S. In order to verify results previously obtained at a laboratory scale with 65–90 kg of bottom ash (BA), several test runs were performed at a pilot scale, using 500–1000 kg of bottom ash and up to 9.2 N m³/h real landfill gas from a landfill in the Tuscany region (Italy). The input flow rate was altered. The best process performance was observed at a input flow rate of 3.7 N m³/(h t_BA). At this flow rate, the removal efficiencies for H₂S were approximately 99.5–99%.     

Aluminium recovery vs. hydrogen production as resource recovery options for fine MSWI bottom ash fraction

Waste incineration bottom ash fine fraction contains a significant amount of aluminium, but previous works have shown that current recovery options based on standard on-step Eddy Current Separation (ECS) have limited efficiency. In this paper, we evaluated the improvement in the efficiency of ECS by using an additional step of crushing and sieving. The efficiency of metallic Al recovery was quantified by measuring hydrogen gas production. The ash samples were also tested for total aluminium content with X-ray fluorescence spectroscopy (XRF). As an alternative to material recovery, we also investigated the possibility to convert residual metallic Al into useful energy, promoting H₂ gas production by reacting metallic Al with water at high pH. The results show that the total aluminium concentration in the <4 mm bottom ash fraction is on average 8% of the weight of the dry ash, with less than 15% of it being present in the metallic form. Of this latter, only 21% can be potentially recovered with ECS combined with crushing and sieving stages and subsequently recycled. For hydrogen production, using 10 M NaOH at 1 L/S ratio results in the release of 6–11 l of H₂ gas for each kilogram of fine dry ash, equivalent to an energy potential of 118 kJ.     

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 %.     

Thermodynamic analysis on heavy metals partitioning impacted by moisture during the MSW incineration

A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 °C, 950 °C, and 1150 °C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 °C and 1150 °C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700–1000 °C, the impact of temperature on Pb and Cd was little and the moisture was the main factor; while at the temperature of 1000–1200 °C, the impact of increase in moisture and decrease in temperature on Pb and Cd was almost equal and reversed.