Recovery of zinc and lead from fly ash from ash-melting and gasification-melting processes of MSW--comparison and applicability of chemical leaching methods

Fly ash generated from MSW ash-melting and gasification-melting plants, known as Melting Furnace Fly Ash (MFA), contains considerable amounts of heavy metals such as Pb and Zn. These metals can be recovered using a smelting furnace after "pre-treatment" for removal of unnecessary elements such as Cl, Sn and Si. Chemical methods have been studied for pretreatment in the past. However, they have been discussed only with regard to treatment cost and the concentration of Pb and Zn recovered, but neither applicability to various types of MFA nor the environmental impact have been considered. In this study, acid, alkaline and ammonia/chloride leaching methods were compared from the standpoints of: (1) applicability to MFA, (2) concentration of Pb and Zn recovered, (3) treatment cost, and (4) environmental impact. Twenty-three samples of MFAs were collected and classified into 4 types based on element contents. A Pb and Zn recovery experiment was conducted for the representative MFA of those types. The results showed: (1) MFA from gasification-melting plants cannot be treated by chemical methods; (2) the other MFA can be treated to an acceptable quality by existing smelting furnaces; (3) only MFA from electric resistance ash-melting plants can be treated easily by the water washing method; and (4) alkaline and ammonia/chloride leaching methods were more effective than acid leaching.     

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.     

Characteristics of element distributions in an MSW ash melting treatment system

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

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.     

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

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

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.     

Water extraction with CO2 bubbling as pretreatment of melting-furnace fly ash for metal recovery

In Japan, melting-furnace fly ash (MFA) generated from ash melting and gasification/melting plants is considered an “urban mine” due to its high metal content. This study aimed to develop a novel approach to pretreating MFA for metal recovery. Water extraction with CO₂ bubbling was investigated because MFA mainly consists of water-soluble salts containing elements such as Cl, Ca, Na, and K. Instead of acid addition, CO₂ bubbling was applied to maintain the optimal pH for minimizing the release of target metal elements and maximizing the removal of undesirable elements during water extraction. The results revealed that CO₂ bubbling effectively decreased the release of Pb, Zn, and Cd into the treatment water. This was mainly due to coprecipitation with CaCO₃, which was primarily formed by the reaction of Ca²⁺ from the MFA with CO₃ ²⁻ from the CO₂ gas. The bubbling process also helped accelerate the removal of Cl from MFA. Furthermore, the study showed that it is possible to lower the water-to-solid ratio to 5 with only a slight reduction in water extraction effect. Finally, approximately four times the concentration of target metals (rare metals and Cu, Pb, and Zn) was achieved by removing 90% of Cl, 70%–90% of Na and K, and 30%–40% of Ca through water extraction with CO₂ bubbling, resulting in a concentration of target metals that was nearly equal to that of ore.     

Evaluating waste disposal systems

Waste disposal systems conventionally exhibit many problems, such as difficulties in finding final disposal sites for incinerator residues and the issue of how to recycle waste materials. Some new technologies have been developed to solve such problems, including ash melting and gasification melting. Furthermore, to improve the power generation efficiency of waste treatment facilities so that their energy is used more efficiently, combined stoker/gas turbine power generation (super waste power generation) technology has been developed. Through examination of two cases in this study, environmental impacts and costs were determined using lifecycle assessment (LCA) and lifecycle cost (LCC) methods in a model city. In case 1, a stoker furnace was compared to a combined stoker/gas turbine system. In case 2, a stoker furnace plus ash melting system was compared to a gasification melting system. The results demonstrate that the stoker furnace has a lower environmental impact than the combined stoker/gas turbine system in case 1, and that the stoker plus ash melting system costs less than the gasification melting system in case 2, but both systems had strong impacts on the environment.     

Toxicity mitigation and solidification of municipal solid waste incinerator fly ash using alkaline activated coal ash

Municipal solid waste (MSW) incineration is a common and effective practice to reduce the volume of solid waste in urban areas. However, the byproduct of this process is a fly ash (IFA), which contains large quantities of toxic contaminants. The purpose of this research study was to analyze the chemical, physical and mechanical behaviors resulting from the gradual introduction of IFA to an alkaline activated coal fly ash (CFA) matrix, as a mean of stabilizing the incinerator ash for use in industrial construction applications, where human exposure potential is limited. IFA and CFA were analyzed via X-ray fluorescence (XRF), X-ray diffraction (XRD) and Inductive coupled plasma (ICP) to obtain a full chemical analysis of the samples, its crystallographic characteristics and a detailed count of the eight heavy metals contemplated in US Title 40 of the Code of Federal Regulations (40 CFR). The particle size distribution of IFA and CFA was also recorded. EPA's Toxicity Characteristic Leaching Procedure (TCLP) was followed to monitor the leachability of the contaminants before and after the activation. Also images obtained via Scanning Electron Microscopy (SEM), before and after the activation, are presented. Concrete made from IFA, CFA and IFA-CFA mixes was subjected to a full mechanical characterization; tests include compressive strength, flexural strength, elastic modulus, Poisson's ratio and setting time. The leachable heavy metal contents (except for Se) were below the maximum allowable limits and in many cases even below the reporting limit. The leachable Chromium was reduced from 0.153 down to 0.0045 mg/L, Arsenic from 0.256 down to 0.132 mg/L, Selenium from 1.05 down to 0.29 mg/L, Silver from 0.011 down to .001 mg/L, Barium from 2.06 down to 0.314 mg/L and Mercury from 0.007 down to 0.001 mg/L. Although the leachable Cd exhibited an increase from 0.49 up to 0.805 mg/L and Pd from 0.002 up to 0.029 mg/L, these were well below the maximum limits of 1.00 and 5.00 mg/L, respectively.     

Removal of unburned carbon from municipal solid waste fly ash by column flotation

Unburned carbon (UC) is the major source of organic contaminants in municipal solid waste (MSW) fly ash. So most organic contaminants can be removed by the removal of the UC from the MSW fly ash. In this paper, we first used a technique of column flotation to remove UC from MSW fly ash. The influences of column flotation parameters on the recovery efficiency of UC were systematically studied. It was found that the UC recovery efficiency was greatly influenced by the gas flow rate, pH value, collector kerosene's concentration and the types of fly ash. By optimizing the above parameters, we have successfully removed 61.2% of the UC from MSW fly ash having 5.24% UC content. The removal mechanism was well accounted for the kinetic theory of column flotation and surface-chemistry theory. The results indicate that the column flotation technique is effective in removing the UC from MSW fly ash, and show that there is a strong possibility for practical application of this technique in removing the organic contaminants from MSW fly ash.     

Leachability of municipal solid waste ashes in simulated landfill conditions

In Japan the volume of municipal solid waste is reduced by incineration, with fly ash and bottom ash disposed in controlled landfills. The leachability of anions and heavy metal cations, Zn, Cu and Pb, from MSW fly ash and bottom ash at different pHs was examined using batch- and column-leaching tests. The MSW ashes had a high capacity for neutralizing acids. Behaviour during leaching depended on the pH of the solution. For the volumes applied, the leachabilities of MSW fly ash were very similar at pHs from 3 to 6. Due to its amphoteric nature, Pb is leachable at pHs of approximately 10 or more, with leachate concentrations of about 3 and 3-10mg/L for the fly ash and bottom ash, respectively, much higher than for Zn and Cu. Pb concentrations for most leaching solutions were 1 and 3mg/L for the fly ash and bottom ash, respectively. Zn, and Cu leached at low concentrations for solutions of pH 3-6. Na and K ions leached at high concentrations of approximately 5000 mg/L in the first batch leaching test, decreasing to 10mg/L by the fourth leach. Ca and Mg ions leached more gradually than Na and K. Cl(-) and SO(4)(2+) ions were the major anions in the MSW ash. The high pH and cation leaching are expected to have negative impacts on the performance of clay liners.     

Diopside-based glass-ceramics from MSW fly ash and bottom ash

By utilising MSW fly ash from the Shanghai Yuqiao municipal solid waste (MSW) incineration plant as the main raw material, diopside-based glass-ceramics were successfully synthesized in the laboratory by combining SiO(2), MgO and Al(2)O(3) or bottom ash as conditioner of the chemical compositions and TiO(2) as the nucleation agent. The optimum procedure for the glass-ceramics is as follows: melting at 1500 degrees C for 30 min, nucleating at 730 degrees C for 90 min, and crystallization at 880 degrees C for 10h. It has been shown that the diopside-based glass-ceramics made from MSW fly ash have a strong fixing capacity for heavy metals such as lead (Pb), chromium (Cr), cadmium (Cd) etc.     

Behaviour of Cd,Cr, Mn,Ni, Pb,and Zn in sewage sludge incineration by fluidised bed furnace

Cd, Cr, Mn, Ni, Pb, and Zn behaviour during sewage sludge incineration was investigated in seven pilot tests using a circulating fluidised bed furnace. Dewatered sludge at a solids concentration of 15-18% was fed to the furnace either alone (two tests) or spiked with chlorinated organic compounds (five tests). The behaviour of metals in the fluidised bed furnace was studied by comparing metal concentrations in the two main ash streams: ash separated from the cyclone immediately following the fluidised bed furnace, and fly ash recovered in the final bag filter. A metal enrichment factor was defined as the ratio of metal concentration between filter ash and cyclone ash. Only Cd and Pb showed any significant enrichment. Their enrichment factors were mainly affected by chlorine concentration in the feed sludge. To check whether simple equilibrium models may explain and predict metal behaviour, experimental data were compared with percentage of the metal vaporisation in the combustion chamber predicted using a thermodynamic model. Discrepancies between model predictions and experimental results are accounted for by considering that kinetics may be a limiting factor in the formation of metal chloride gaseous species. Due to the very short sludge residence time in the fluidised bed furnace, the gaseous compounds have little chance to evolve completely.     

Corrosion behavior of glass and glass-ceramics made of municipal solid waste incinerator fly ash

Glasses and glass-ceramics were prepared by melting municipal solid waste (MSW) incinerator fly ash and their corrosion properties were evaluated. Corrosion of both materials proceeded in two different steps. At the initial stage, the corrosion process is a diffusion-controlled process. After approximately 10 h at the initial stage, weight losses increased linearly with time due to the total dissolution of glasses or glass-ceramics. Leaching of heavy metals from glasses and glass-ceramics were well within international environmental regulations. Corrosion proceeded uniformly in fly ash glass while Na2CaSiO4 crystalline phase was preferentially dissolved in the glass-ceramics.     

Classification and categorization of treatment methods for ash generated by municipal solid waste incineration: A case for the 2 greater metropolitan regions of greece

The primary goal of managing MSW incineration residues is to avoid any impact on human health or the environment. Incineration residues consist of bottom ash, which is generally considered as rather harmless and fly ash which usually contains compounds which are potentially harmful for public health. Small quantities of ash (both bottom and fly) are produced currently in Greece, mainly from the healthcare waste incineration facility in Attica region. Once incineration plants for MSW (currently under planning) are constructed in Greece, the produced ash quantities will increase highly. Thus, it is necessary to organize, already at this stage, a roadmap towards disposal/recovery methods of these ash quantities expected.Certain methods, related to the treatment of the future generated ash which are more appropriate to be implemented in Greece are highlighted in the present paper. The performed analysis offers a waste management approach, having 2016 as a reference year for two different incineration rates; 30% and 100% of the remaining MSW after recycling process. The results focus on the two greater regions of Greece: Attica and Central Macedonia. The quantity of potential future ash generation ranges from 137 to 459 kt for Attica region and from 62 to 207 kt for central Macedonia region depending on the incineration rate applied. Three alternative scenarios for the treatment of each kind of ash are compiled and analysed. Metal recovery and reuse as an aggregate in concrete construction proved to be the most advantageous -in terms of economy-bottom ash management scenario. Concerning management of the fly ash, chemical treatment with phosphoric solution addition results to be the lowest total treatment cost and is considered as the most profitable solution. The proposed methodology constitutes a safe calculation model for operators of MSW incineration plants regardless of the region or country they are located in.     

Reduction of hazardous elements contained in sewage sludge incineration ash

Research and experimental studies were carried out in relation to reduction of hazardous elements contained in sewage sludge incineration ash. A questionnaire survey was conducted in 69 Japanese municipalities with sewage sludge incineration facilities. Selenium content in bag filter ash and ceramic filter ash was relatively higher than that in ash of cyclone and electrostatic precipitators. It was assumed that selenium vaporized in the furnace was due to adsorb in the fly ash on filter when passing through the low-temperature filter. To reduce high boiling point heavy metals in the ash, sewage sludge and incineration ash were heated up using a small muffle furnace. As the result, the chrome and nickel contents were reduced. A decrease in the surface area of ash and the reduction of elements occurred at the same time in sewage sludge and incineration ashes tested in this study.     

Occurrence of phenols in leachates from municipal solid waste landfill sites in Japan

The concentrations of 41 phenols in leachates from 38 municipal solid waste (MSW) landfill sites in Japan were measured. The main phenols detected in leachates were phenol, three cresols, 4-tert-butylphenol, 4-tertoctylphenol, 4-nonylphenol, bisphenol A, and some chlorophenols. The concentration levels of phenols were affected by the pH values of the leachates and the different types of landfill waste. The origins of phenol and p-cresol were considered to be incineration residues, and the major origin of 4-tert-butylphenol, bisphenol A, and 2,4,6-trichlorophenol was considered to be solidified fly ash. In contrast, the major origins of 4-tert-octylphenol and 4-nonylphenol were considered to be incombustibles. The discharge of leachates to the environment around MSW landfill sites without water treatment facilities can cause environmental pollution by phenols. In particular, the disposal of incineration residues including solidified fly ash and the codisposal of solidified fly ash and incombustibles might raise the possibility of environmental pollution. Moreover, the discharge of leachates at pH values of 9.8 or more could pollute the water environment with phenol. However, phenol, 4-nonylphenol, and bisphenol A can be removed to below the con centration levels that impact the environment around landfill sites by a series of conventional water treatment processes.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

Chloride extraction for quality improvement of municipal solid waste incinerator ash for the concrete industry.

Coal ash from power stations has long been used successfully in the cement industry as binders in several Portland formulations. This is not the case for municipal solid waste (MSW) ash as chloride concentrations, ranging from 10 to 200 g kg(-1) dry weight in the bottom and fly ash, respectively, exceed the maximum allowable concentration in most cement mixtures. To reduce chloride content in MSW bottom ash, a laboratory investigation was carried out based on the exhaustive washing in tap water. The influence of operative parameters such as temperature, granulometric properties and solid/liquid ratio of extraction was evaluated. In addition to optimization of the mentioned operative parameters for full-scale application, the paper gives preliminary indications on mechanistic aspects of the washing operation.     

Properties of alkali-activated systems with stone powder sludge

This article investigates the effects of stone powder sludge on the microstructure and strength development of alkali-activated fly ash and blast furnace slag mixes. Stone powder sludge produced from a crushed aggregate factory was used to replace fly ash and granulated blast furnace slag at replacement ratios of 0%, 10%, 20%, and 30% by mass. The unit weight and compressive strength of the samples were measured, and scanning electron microscopy/energy dispersive spectroscopy and X-ray diffraction (XRD) analyses were performed. The test results indicated that the compressive strength of alkali-activated blast furnace slag mixes using stone powder sludge was higher than that of the alkali-activated blast furnace slag control mix, but the compressive strength of alkali-activated fly ash mixes decreased with increasing replacement ratio of stone powder sludge. Microscopy results indicated that for alkaliactivated blast furnace slag samples, broken surfaces were more evident than for the alkali-activated fly ash samples. For all XRD diagrams, broad and diffuse peaks were observed around 2θ = 35° (d = 2.96–3.03 Å), implying amorphous or short-ordering structure phases.