Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

Strength, leachability and microstructure characterisation of Na2SiO3-activated ground granulated blast-furnace slag solidified MSWI fly ash.

The chemical composition and the leachability of heavy metals in municipal solid waste incinerator (MSWI) fly ash were measured and analysed. For the leachability of unstabilized MSWI fly ash it was found that the concentrations of Pb and Cr exceeded the leaching toxicity standard. Cementitious solidification of the MSWI fly ash by Na2SiO3-activated ground granulated blast-furnace slag (NS) was investigated. Results show that all solidified MSWI fly ash can meet the landfill standards after 28 days of curing. The heavy metals were immobilized within the hydration products such as C-S-H gel and ettringite through physical encapsulation, substitution, precipitation or adsorption mechanisms.     

Stabilization/solidification of ashes in clays used in the manufacturing of ceramic bricks.

This paper presents the results of the lixiviation of metals from different mixtures of fly and bottom ashes that have been stabilized and solidified in clays used in the manufacture of bricks. The ashes used for this study were obtained from a Hoffmann-type brick furnace adapted for the incineration of municipal solid waste during the manufacturing of ceramic bricks. The ashes were stabilized in clay in different proportions of clay:ash mix (99:1, 95:5, 90:10, 80:20 and 60:40). Such mixes were used to manufacture bricks that were calcined at a temperature ranging from 50 to 1100 degrees C. The clay, ashes and manufactured bricks were characterized using X-ray diffraction, fluorescent X-ray, thermogravimetry, differential thermal analysis, atomic absorption spectroscopy and scanning electronic microscopy. In addition, toxicity characteristic leaching procedure lixiviation tests were performed according to the EPA 1311 method for the determination of heavy metals. The results showed an affinity between clay and ash, and also that the bricks manufactured with these mixtures present low lixiviation levels. The tests also showed the highest decrease in the concentration of arsenic, nickel, chromium, zinc and silver for 99:1 mixtures. The 95:5 mixture was found to be the most favourable for the stabilization (greater concentration decrease) of lead and cadmium. Selenium was the metal with the lowest concentration change whereas arsenic, nickel, chromium, zinc and cadmium showed the greatest concentration change in all mixtures, with the exception of cadmium in the mixture 99:1.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

Water washing effects on metals emission reduction during municipal solid waste incinerator (MSWI) fly ash melting process

This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

Aggregate material formulated with MSWI bottom ash and APC fly ash for use as secondary building material

The main goal of this paper is to obtain a granular material formulated with Municipal Solid Waste Incineration (MSWI) bottom ash (BA) and air pollution control (APC) fly ash to be used as secondary building material. Previously, an optimum concrete mixture using both MSWI residues as aggregates was formulated. A compromise between the environmental behavior whilst maximizing the reuse of APC fly ash was considered and assessed. Unconfined compressive strength and abrasion resistance values were measured in order to evaluate the mechanical properties. From these results, the granular mixture was not suited for certain applications owing to the high BA/APC fly ash content and low cement percentages used to reduce the costs of the final product. Nevertheless, the leaching test performed showed that the concentrations of all heavy metals were below the limits established by the current Catalan legislation for their reutilization. Therefore, the material studied might be mainly used in embankments, where high mechanical properties are not needed and environmental safety is assured.     

Recycling municipal incinerator fly- and scrubber-ash into fused slag for the substantial replacement of cement in cement-mortars

Fly- and scrubber-ash (weight ratio of approximately 1:3) from municipal solid waste incinerators (MSWI) are a major land-fill disposal problem due to their leaching of heavy metals. We uniformly mixed both types of ash with optimal amounts of waste glass frit, which was then melted into a glassy slag. The glassy slag was then pulverized to a particle size smaller than 38 μm for use as a cement substitute (20–40% of total cement) and blended with sand and cement to produce slag-blended cement-mortar (SCM) specimens. The toxicity characteristics of the leaching procedure tests on the pulverized slag samples revealed that the amount of leached heavy metals was far below regulatory thresholds. The compressive strength of the 28-day cured SCM specimens was comparable to that of ordinary Portland cement mortars, while the compressive strength of specimens cured for 60 or 90 days were 3–11% greater. The observed enhanced strength is achieved by Pozzolanic reaction. Preliminary evaluation shows that the combination of MSWI fly- and scrubber-ash with waste glass yields a cost effective and environmentally friendly cement replacement in cement-mortars.     

Application of MSWI fly ash on acid soil and its effect on the environment

This study evaluated the feasibility of using municipal solid waste incinerator (MSWI) fly ash as acid soil amendment. In particular, changes in soil physicochemical properties and the potential environmental problems caused by the application of MSWI fly ash were investigated. The results showed that application of MSWI fly ash to the acid soil could raise the soil pH. The contents of rapidly available P and K, and slowly available K in the amended soil had a linear relationship with the addition ratio of MSWI fly ash. An addition of less than 20% of MSWI could raise the soil respiratory intensity after incubation for 3-5 days. Application of MSWI fly ash to the soil increased its content of water soluble salts and heavy metals, which could cause phytotoxicity in the plants. Therefore, the addition of MSWI fly ash to the soil should not be excessive, and less than 5-10% is an advisable addition level depending on the acidity of the soil and the plants growing on it.     

Physical-mechanical and environmental properties of sintered municipal incinerator fly ash

A step-wise treatment of Municipal Solid Waste (MSW) incinerator fly ash including washing, milling and sintering was investigated in order to manufacture ceramic materials with improved physical, mechanical and environmental properties and, possibly, to reduce the power input of the sintering process. An interpretation of the test results based on the microstructure of sintered products and sintering kinetic modeling was also attempted to identify the densification mechanisms. It was found that milling of washed fly ash represents a basic step for manufacturing high-density ceramic materials with very high compressive strengths (up to 500 N/mm2). A significant reduction in the power input of the sintering process (reduction of firing temperature from 1210 degrees C for washed fly ash to 1140 degrees C for milled-washed fly ash) is also achieved. A dense, well-sintered microstructure is formed through an intermediate-stage, liquid-phase sintering mechanism controlled by liquid-phase diffusion and grain shape accommodation. Such a microstructure is able to strongly immobilise heavy metals, thus giving good environmental properties to sintered product.     

Sintering characteristics of CaO-rich municipal solid waste incineration fly ash through the addition of Si/Al-rich ash residues

Thermal treatment is a promising technology for the fast disposal of hazardous municipal solid waste incineration (MSWI) fly ash in China. However, fly ash produced in grate incinerator (GFA) is rich in CaO and chlorides, which promote the formation of toxic hexavalent chromium [Cr(VI)] and ash agglomeration during the thermal process, inhibiting the thermal disposal of GFA. In this study, sintering characteristics of CaO-rich GFA were improved by adding Si/Al-rich MSWI ash residues. According to the results, ash agglomeration was well suppressed during thermal treatment of the mixed ash. Si/Al/Fe-compounds competed with un-oxidized Cr-compounds to react with CaO and suppressed Cr(VI) formation. Meanwhile, chlorides in GFA facilitated heavy metal volatilization from added ashes to the secondary fly ash, favoring the recovery of these metals. Ca-aluminosilicates was found as the main mineral phase in the thermally treated mixed ash, which has attractive potential for applications. The formation of the aluminosilicates made the heavy metals that remained in the treated mixed ash more stable than the thermally treated single ash.     

Utilization of municipal solid waste incineration fly ash for sulfoaluminate cement clinker production

The feasibility of partially substituting raw materials with municipal solid waste incineration (MSWI) fly ash in sulfoaluminate cement (SAC) clinker production was investigated by X-ray diffraction (XRD), compressive strength and free expansion ratio testing. Three different leaching tests were used to assess the environmental impact of the produced material. Experimental results show that the replacement of MSWI fly ash could be taken up to 30% in the raw mixes. The good quality SAC clinkers are obtained by controlling the compositional parameters at alkalinity modulus (C(m)) around 1.05, alumina-sulfur ratio (P) around 2.5, alumina-silica ratio (N) around 2.0~3.0 and firing the raw mixes at 1250 °C for 2h. The compressive strengths of SAC are high in early age while that develop slowly in later age. Results also show that the expansive properties of SAC are strongly depended on the gypsum content. Leaching studies of toxic elements in the hydrated SAC-based system reveal that all the investigated elements are well bounded in the clinker minerals or immobilized by the hydration products. Although some limited positive results indicate that the SAC prepared from MSWI fly ash would present no immediate thread to the environment, the long-term toxicity leaching behavior needs to be further studied.     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

Influence of treatment techniques on Cu leaching and different organic fractions in MSWI bottom ash leachate

The leaching of heavy metals, such as copper, from municipal solid waste incinerator (MSWI) bottom ash is of concern in many countries and may inhibit the beneficial reuse of this secondary material. Previous studies have focused on the role of dissolved organic carbon (DOC) on the leaching of copper. Recently, a study of the Energy Research Centre of The Netherlands (ECN) showed fulvic acid-type components to exist in the MSWI bottom ash leachates and to be likely responsible for the generally observed enhanced copper leaching. These findings were verified for a MSWI bottom ash (slashed circle 0.1-2 mm) fraction from an incinerator in Flanders. The filtered leachates were subjected to the IHSS fractionation procedure to identify and quantify the fractions of humic acid (HA), fulvic acid (FA) and hydrophilic organic carbon (Hi). The possible complexation of fulvic acid with other heavy metals (e.g., lead) was also investigated. The identified role of fulvic acids in the leaching of copper and other heavy metals can be used in the development of techniques to improve the environmental quality of MSWI bottom ash. Thermal treatment and extraction with a 0.2 M ammonium-citrate solution were optimized to reduce the leaching of copper and other heavy metals. The effect of these techniques on the different fractions of organic matter (HA, FA, Hi) was studied. However, due to the obvious drawbacks of the two techniques, research is focused on finding other (new) techniques to treat MSWI bottom ash. In view of this, particle size-based separation was performed to evaluate its effect on heavy metal leaching and on HA, FA and Hi in MSWI bottom ash leachates.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

Recovery of municipal waste incineration bottom ash and water treatment sludge to water permeable pavement materials

Water treatment plant sludge and municipal solid waste incinerator bottom ash are non-hazardous residues, and they can be reprocessed to produce useful materials for city public works. In this study, an effort was endeavored to investigate the properties of water permeable bricks made of water treatment sludge and bottom ash without involving an artificial aggregate step. The water treatment plant sludge was dried and ground, and the bottom ash was subjected to magnetic separation to remove ferrous metals. Both sludge and bottom ash were ground and sieved to a size of <2mm. Different contents of water treatment sludge (70-95% by weight) were mixed with bottom ash and the blocks were molded under a pressure of 110 kg/cm2. Thereafter, the molded blocks were sintered at temperatures of 900-1200 degrees C for 60-360 min. The compressive strength, permeability and water absorption rate of the sintered brick were examined and compared to relevant standards. The amount of bottom ash added in the mixture with water treatment sludge affects both the compressive strength and the permeability of the sintered bricks. The two effects are antonymous as higher bottom ash content will develop a beehive configuration and have more voids in the brick. It is concluded that a 20% weight content of bottom ash under a sintering condition of 1150 degrees C for 360 min can generate a brick with a compressive strength of 256 kg/cm2, a water absorption ratio of 2.78% and a permeability of 0.016 cm/s.     

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.     

Hydrothermal treatment of MSWI bottom ash forming acid-resistant material

To recycle municipal solid waste incinerator (MSWI) bottom ash, synthesis of hydrothermal minerals from bottom ash was performed to stabilize heavy metals. MSWI bottom ash was mixed with SiO(2), Al(OH)(3), and Mg(OH)(2) so its chemical composition was similar to that of hydrothermal clay minerals. These solid specimens were mixed with water at a liquid/solid ratio of 5. The reaction temperature was 200 degrees C, and reactions were performed for 24-240h. Generation of kaolinite/smectite mixed-layer clay mineral was found in the samples after the reaction of the mixture of bottom ash, SiO(2), and Mg(OH)(2). Calcium silicate hydrate minerals such as tobermorite and xonotlite were also generated. X-ray powder diffraction suggested the presence of amorphous materials. Leaching tests at various pHs revealed that the concentration of heavy metals in the leachates from MSWI bottom ash hydrothermally treated with SiO(2) and Mg(OH)(2) was lower than that in leachates from non-treated bottom ash, especially under acid conditions. Hydrothermal treatment with modification of chemical composition may have potential for the recycling of MSWI bottom ash.     

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.