Chemical stability of geopolymers containing municipal solid waste incinerator fly ash

Municipal solid waste incinerators every year produce tons of fly ashes which, differently from coal fly ashes, contain large amounts of toxic substances (heavy metals, dioxins, furans). The stabilization/solidification (S/S) technology known as geopolymerization is proposed with the purpose to bond physically and chemically incinerator fly ashes (IFA) in a solid matrix, in order to reduce pollutant mobility. The chemical stability of geopolymers with Si/Al ratio of 1.8–1.9 and Na/Al ratio of 1.0, synthesized by alkali activation of metakaolin and the addition of 20 wt% of two different kinds of IFA, is presented. The concentration of the alkaline solution, water to solid ratio and curing process have been optimized. The room temperature consolidation of IFA containing geopolymers has been tested for leachability in water for 1 day, accordingly to EN 12457 regulation and extended to 7 days to increase the water attack on solid granules. Leachable metals in the test solution, determined by ICP_AES, fall within limit values set by regulation for non-dangerous waste landfill disposal. Geopolymeric matrix evolution with leaching time has been also evaluated in terms of pH and electrical conductivity increase in solution.     

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

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

Carbon speciation in municipal solid waste incinerator (MSWI) bottom ash in relation to facilitated metal leaching

The release of inorganic and organic contaminants from municipal solid waste incinerator (MSWI) bottom ash is controlled to a large extent by the release of dissolved organic carbon (DOC), and in particular by the reactive humic (HA) and fulvic acids (FA) subfractions of DOC. The properties of organic matter contributing to the release of DOC, HA and FA are, therefore, important for environmental risk assessment. In this study we have quantitatively measured the carbon speciation, and its relation with the leaching of Cu, in three fresh and carbonated MSWI bottom ash samples. Results show that up to only 25% of loss on ignition (LOI) consists of organic carbon (OC), while about 17% of OC in the three samples consists of HA and FA. Up to 50% of DOC in MSWI bottom ash leachates was identified as fulvic acid (FA). This value is substantially higher than previously estimated for these MSWI bottom ash samples and is consistent with the higher recovery of the new method that was applied. The results of this study imply that methods focusing on specific carbon fractions are more appropriate for assessment of environmentally relevant organic carbon species than the measurement of LOI.     

Vitrification of bottom ash from a municipal solid waste incinerator

During incineration of municipal solid waste (MSW), various environmentally harmful elements and heavy metals are liberated either into bottom ash, or carried away with the off-gases and subsequently trapped in fly-ash. If these minor but harmful elements are not properly isolated and immobilized, it can lead to secondary environmental pollution to the air, soil and water. The stricter environmental regulations to be implemented in the near future in The Netherlands require a higher immobilization efficiency of the bottom ash treatment. In the present study, MSW incinerator bottom ash was vitrified at higher temperatures and the slag formed and metal recovered were examined. The behaviour of soluble elements that remain in the slag is evaluated by standard leaching test. The results obtained can provide a valuable route to treat the ashes from incinerators, and to make recycling and more efficient utilization of the bottom ash possible.     

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.     

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.     

Chemical speciation of carbon in municipal solid waste incinerator residues

Incinerators do not achieve a complete mineralization of organic constituents of municipal solid waste. The solid residues (bottom ash, boiler ash and air pollution control residues) contain carbon which can be determined as total organic carbon (TOC). This work focuses on the TOC composition and its significance to the genesis and diagenesis of the solid residues. An analytical procedure is presented to characterize carbon species by different chemical and microscopic analytical methods. The procedure is based on two steps. In the first step a quantitative classification of TOC into four different carbon species (elemental carbon, water extractable organic carbon, dichloromethane extractable organic carbon and non extractable organic carbon) is performed to obtain a first survey of the TOC composition. Based on this survey a further characterization of individual carbon species is performed. The results of the qualitative and quantitative characterization of carbon species allow to postulate hypotheses on the influence of organic carbon on the long-term behavior of the solid residues.     

Phosphorus recovery from municipal solid waste incineration fly ash

The potential of phosphorus (P) recycling from municipal solid waste incineration (MSWI) residue is investigated. Vast and ever increasing amounts of incineration residues are produced worldwide; these are an environmental burden, but also a resource, as they are a major sink for the material flows of society. Due to strict environmental regulations, in combination with decreasing landfilling space, the disposal of the MSWI residues is problematic. At the same time, resource scarcity is recognized as a global challenge for the modern world, and even more so for future generations.This paper reports on the methods and efficiency of P extraction from MSWI fly ash by acid and base leaching and precipitation procedures. Phosphorus extracted from the MSWI residues generated each year could meet 30% of the annual demand for mineral phosphorus fertiliser in Sweden, given a recovery rate of 70% achieved in this initial test.The phosphorus content of the obtained product is slightly higher than in sewage sludge, but due to the trace metal content it is not acceptable for application to agricultural land in Sweden, whereas application in the rest of the EU would be possible. However, it would be preferable to use the product as a raw material to replace rock phosphate in fertilizer production. Further development is currently underway in relation to procedure optimization, purification of the phosphorus product, and the simultaneous recovery of other resources.     

Speciation of the radioactive nuclides in incinerator fly ash of municipal solid waste using sequential extractions

Journal of Material Cycles and Waste Management - The radioactive nuclides in the incinerator fly ashes from municipal solid waste sampled in June 2006 were analyzed with γ-ray spectrometry....     

Leaching behavior of polychlorinated dibenzo-p-dioxins and furans from the fly ash and bottom ash of a municipal solid waste incinerator

The leaching behavior of dioxins from landfill containing bottom ash and fly ash from municipal solid waste incineration has been investigated by leaching tests with pure water, non-ionic surfactant solutions, ethanol solutions, or acetic acid solutions as elution solvents for a large-scale cylindrical column packed with ash. Larger amounts of dioxins were eluted from both bottom ash and fly ash with ethanol solution and acetic acid solution than with pure water. Large quantities of dioxins were leached from fly ash but not bottom ash by non-ionic surfactant solutions. The patterns of distribution of the dioxin congeners in the leachates were very similar to those in the bottom ash or fly ash from which they were derived.     

Synthesis of mesoporous silica materials from municipal solid waste incinerator bottom ash

Incinerator bottom ash contains a large amount of silica and can hence be used as a silica source for the synthesis of mesoporous silica materials. In this study, the conditions for alkaline fusion to extract silica from incinerator bottom ash were investigated, and the resulting supernatant solution was used as the silica source for synthesizing mesoporous silica materials. The physical and chemical characteristics of the mesoporous silica materials were analyzed using BET, XRD, FTIR, SEM, and solid-state NMR. The results indicated that the BET surface area and pore size distribution of the synthesized silica materials were 992 m²/g and 2–3.8 nm, respectively. The XRD patterns showed that the synthesized materials exhibited a hexagonal pore structure with a smaller order. The NMR spectra of the synthesized materials exhibited three peaks, corresponding to Q² [Si(OSi)₂(OH)₂], Q³ [Si(OSi)₃(OH)], and Q⁴ [Si(OSi)₄]. The FTIR spectra confirmed the existence of a surface hydroxyl group and the occurrence of symmetric Si–O stretching. Thus, mesoporous silica was successfully synthesized from incinerator bottom ash. Finally, the effectiveness of the synthesized silica in removing heavy metals (Pb²⁺, Cu²⁺, Cd²⁺, and Cr²⁺) from aqueous solutions was also determined. The results showed that the silica materials synthesized from incinerator bottom ash have potential for use as an adsorbent for the removal of heavy metals from aqueous solutions.     

Chemical behaviour of municipal solid waste incinerator bottom ash in monofills

A method is presented to predict the short-term (months to years) and long-term (> 30 years) chemical behaviour of bottom ash from municipal solid waste incinerators in monofills. It is based on bottom ash composition and laboratory kinetic studies of bottom ash with water. Bottom ash after the quench tank is a reactive mixture in which slow and fast acid/base reactions occur. These intrinsic acid/base reactions continue for at least several months, and the end point is not yet known. The heavy metal concentrations observed in the aqueous extracts reflect primarily the advance of these reactions. Consequently leaching tests based solely on short-term (hours to months) extraction procedures cannot predict the chemical behaviour of bottom ash in monofills. However, laboratory experiments with samples of bottom ash, in which the intrinsic acid/base reactions have proceeded differently, provide useful information on the nature of chemical reactions significant in the short- and long-term.     

Investigation of hydrogen generation from municipal solid waste incineration fly ash

Hydrogen generation from municipal solid waste incineration fly ash was investigated to understand the influences of contacting method, kinds of contact solution, liquid to solid ratio, and particle size distribution of materials. Redox properties of materials and hydrogen generation were also studied. The largest quantity of gas generated in contact with water was 29.1 ml/g-ash, most of which was hydrogen. Fluidized bed fly ash generated more gas than stoker fly ash. In order to calculate the hydrogen generation potential (the maximum quantity of gas generated in contact with water), a novel system using a Y-shaped test tube and NaOH was utilized. This method gives values which are related to the quantity of generated gas in contact with water. A relationship between the aluminum content and hydrogen generation potential was observed, especially for fluidized bed fly ash. The reducing potential of fluidized bed fly ash was higher than that of stoker fly ash. Only fluidized bed fly ash showed a positive correlation between aluminum content and reducing potential, and between reducing potential and hydrogen generation potential. These results suggest that fluidized bed fly ash contains more Al⁰ than stoker fly ash. Received: September 11, 1998 / Accepted: March 19, 1999     

Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Comparison of two types of municipal solid waste incinerator fly ashes with different alkaline reagents in washing experiments

In this study, we propose a "washing-calcination-conversion of washed fly ash into cement material with bottom ash" (WCCB) system to reduce the amount of fly ash that must be specially treated so it can be used as raw cement material. Calcium hydroxide (Ca(OH)2) is widely used in air-pollution control devices of incinerators while sodium bicarbonate (NaHCO3) is not. We conducted single-, double-, and triple-washing experiments to compare the washing characteristics of two types of fly ash. Unlike NaHCO3 fly ash, Ca(OH)2 fly ash has almost twice as much washed residue and almost 2.5 times more chlorine after the same washing procedure. After washing once, the washing frequency is also important for NaHCO3 fly ash, while the mixing time and liquid/solid ratio are more critical for Ca(OH)2 fly ash. The use of NaHCO3 is more suitable for the WCCB system.     

Effect of the milling solution on lead stabilization in municipal solid waste incinerator fly ash during the milling processes

The wet milling process had been found to effectively stabilize lead in fly ash. This study adopts this method and looks at the effect of different milling solutions to improve the efficiency of lead stabilization. Different milling solutions (water, phosphoric acid and ethanol) and different milling times (1, 24, 48 and 96 h) were selected as parameters. Since lead oxide can be identified by XRD in this experiment’s samples, 5% lead oxide was added to the extracted mixed fly ash to make instrumental analysis easier. The experimental results indicate that the effect of stabilization of lead after milling could exceed 96%. During milling with water, considerable lead leached into the water in the initial stage (1 h) of the process, but a stable level was reached as the milling time increased. After milling with ethanol and 0.2 M phosphoric acids, the efficiency could exceed 93% after 1 h of milling time. The results of the sequential extraction procedure (SEP) results show that the residual fraction could be increased from 8.93% to 56.16% when a 0.2 M phosphoric acid solution was used. Clearly the choice of an appropriate milling solution can enhance lead stabilization in the fly ash.     

The potential of recycling and reusing municipal solid waste incinerator ash in Taiwan

By 2004, there were 19 municipal solid waste incinerators (MSWI) with a total yearly treatment capacity of 7.72 million tons in service in Taiwan. All 19 incinerators operated daily to generate about 1.05 million tons of incinerator ash, including bottom ash and stabilized fly ash in 2003, and the average ash yield is 18.67%. The total number of incinerators is expected to increase to 27, serving almost all cities in Taiwan by 2007. The authors have suggested a set of criteria based on the yield of incinerator ash (Phi) to study the ash recycle and reuse potential. The Taiwan Environmental Protection Administration has studied the treatment and reuse of MSWI ashes for many years and collected references on international experience accumulated by developed nations for establishing policies on treatment and reuse of MSWI ashes. These citations were analyzed as the basis for current governmental decision making on policies and factors to be considered for establishing policies on recycle and reuse of MSWI ashes. Feasible applications include utilization of ashes, which after sieving and separation of metal particles, produce granular materials. When granular materials comply with TCLP limitations, they can be utilized as cement additives or road base. The procedures of evaluation have been proposed in the performance criteria to be included in the proposed decision-making process of ash utilization.     

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.     

Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.