Extraction of heavy metals from MSW incinerator fly ashes by chelating agents

An extraction process has been studied on a laboratory scale for the pretreatment of municipal solid waste (MSW) incinerator fly ash to remobilize Cr, Cu, Pb, and Zn. Five different types of fly ashes were treated with HCl, nitrilotriacetic acid (NTA), ethylendiaminetetraacetate (EDTA), or diethylenetriaminepentaacetate (DTPA) in a batch process in the pH range 2.5-10. The extraction of heavy metals by HCl was dependent on pH, increasing with increasing acid concentration. The efficiency of the chelating agents was independent of pH. By the treatment with 3.0% EDTA or DTPA, 20-50% of Cr, 60-95% of Cu, 60-100% of Pb, and 50-100% of Zn were extracted in the pH range 3-9. NTA was also effective in extracting Cr, Cu, and Zn. The maximum extraction of Cr, Cu, Pb, and Zn was obtained at 0.3-1.0% concentration of the chelating agents. NTA was effective in extracting Pb at a concentration as low as 0.1%. Extraction behavior of other elements during the treatment was also studied. The leaching test on the residues after the treatment with chelating agents showed that the fly ashes were successfully detoxified to meet the guideline for landfilling.     

The behaviour of Al in MSW incinerator fly ash during thermal treatment

Fly ash from municipal solid waste (MSW) incinerators contains leachable metals, including potentially hazardous heavy metals. The metal content of the fly ash can be reduced by thermal treatment, which vaporizes the volatile metal compounds. After heat treatment of fly ash at 1000 degrees C for 3 h, less metal was able to be leached from the thermally treated ash than from the ash without thermal treatment. Al and Cr were the exceptions. These metals were more soluble in the ash that had been thermally treated. This paper focuses on the leaching behaviour of Al only. Both simple and sequential extraction leaching tests showed that the leachable Al for the heat-treated fly ash is about twice that of the untreated fly ash. The sequential test further revealed that (i) the majority of the leachable Al is associated with Fe-Mn oxides in the fly ash, and (ii) most of the unleachable Al resides in the silicate matrices of the heat-treated and untreated fly ash. Pure chemicals, Al(2)O(3), CaO and CaCl(2), simulating the relevant ingredients in the fly ash, were used for studying their reactions at 1000 degrees C. The aluminum compounds were identified by X-ray Diffraction (XRD). Two new chemical phases produced by the thermal treatment were identified; Ca(AlO(2))(2) and 12CaO.7Al(2)O(3). Their formation suggests a mechanism whereby thermal treatment of fly ash would produce more soluble Al.     

Chemical stabilization of MSW incinerator fly ashes

In this work, the relationship between heavy metal content of fly ash and that of the solid wastes incinerated was correlated and compared. It is found that the former is a function of the latter. Hence, it is important to prevent heavy metal-rich wastes from being incinerated in order to reduce the content of toxic metals in the fly ash. The leachability of fly ash from incineration was usually beyond the scope of toxicity standard and must be properly treated before discharge. Secondly, chemical stabilization for the heavy metals in fly ash was explored. Among the chemicals used, it was found that sodium hydroxide was not suitable for the adequate extraction of the heavy metals from the fly ash. Ethylenediaminetetraacetic acid disodium salt (EDTA) was also tested and seems to be effective for the leaching of toxic metals from the fly ash. On the other hand, sodium sulfide and thiourea are one of excellent chemicals for the effective treatment of fly ashes, since they convert soluble and leachable toxic metals into non-leachable and insoluble forms such as lead and zinc sulfide or their similar forms of thiourea. These chemical species are supposed to be stable in nature. A comparison between chemical stabilization noted above and cement or asphalt solidification methods is made. Chemical stabilization processes, especially using sodium sulfide as the chemical agent, are strongly recommended for the practical uses, in terms of the volume expansion and environmental safety of the stabilized products and cost balances, in comparison with the traditional cement or asphalt solidification methods.     

Removal of hazardous metals from MSW fly ash—An evaluation of ash leaching methods

Incineration is a commonly applied management method for municipal solid waste (MSW). However, significant amounts of potentially hazardous metal species are present in the resulting ash, and these may be leached into the environment. A common idea for cleaning the ash is to use enhanced leaching with strong mineral acids. However, due to the alkalinity of the ash, large amounts of acid are needed and this is a drawback. Therefore, this work was undertaken in order to investigate some alternative leaching media (EDTA, ammonium nitrate, ammonium chloride and a number of organic acids) and to compare them with the usual mineral acids and water.All leaching methods gave a significant increase in ash specific surface area due to removal of soluble bulk (matrix) compounds, such as CaCO₃ and alkali metal chlorides. The use of mineral acids and EDTA mobilised many elements, especially Cu, Zn and Pb, whereas the organic acids generally were not very effective as leaching agents for metals. Leaching using NH₄NO₃ was especially effective for the release of Cu. The results show that washing of MSW filter ash with alternative leaching agents is a possible way to remove hazardous metals from MSW fly ash.     

MSW fly ash stabilized with coal ash for geotechnical application

The solidification and stabilization of municipal solid waste (MSW) fly ash for the purpose of minimizing the geo-environmental impact caused by toxic heavy metals as well as ensuring engineering safety (strength and soaking durability) are experimentally evaluated. The mixtures of MSW fly ash stabilized with cement and fluidized bed combustion coal fly ash (FCA) were used for unconfined compressive strength tests, leachate tests, and soaking tests. The behavior of soluble salts contained in the MSW fly ash significantly affects strength development, soaking durability, and the hardening reaction of the stabilized MSW fly ash mixtures. The cement stabilization of the MSW fly ash does not have enough effect on strength development and soaking durability. The addition of cement only contributes to the containment of heavy metals due to the high level of alkalinity. When using FCA as a stabilizing agent for MSW fly ash, the mixture exhibits high strength and durability. However, the Cd leachate cannot be prevented in the early stages of curing. Using a combination of cement and FCA as a MSW fly ash stabilizer can attain high strength, high soaking durability, and the containment of heavy metals. The stabilized MSW fly ash with cement and FCA can be practically applied to embankments.     

Extraction of metals from municipal solid waste incinerator fly ash by hydrothermal process

This work examined the extraction properties of metallic elements from municipal incinerator fly ash under hydrothermal conditions. The ash was firstly pre-washed by distilled water, then subjected to hydrothermal treatments. The pre-washing process was effective for Na, K, Ca extraction with extraction percentages of 67%, 76% and 48%, respectively. The optimum contact time was 30 min for the pre-washing process. Five types of acids were tested for the extraction experiments and hydrochloric acid was found to be most effective for metal extraction from the ash. Compared to room condition, hydrothermal treatment accelerated the dissolution of the ash, thus promoted the reaction of acid with hazardous metals such as Cr, Cd, Pb, and furthermore, the consumption speed of acid was slowed down under hydrothermal condition. The acid simultaneously reacted with all the metal in the ash under hydrothermal condition but preferentially reacted with Ca at room condition. The optimum hydrothermal treatment temperature, time and liquid/solid ratio were 150 degrees C, 5h and 10:1 (ml:g), respectively.     

The metal-leaching and acid-neutralizing capacity of MSW incinerator ash co-disposed with MSW in landfill sites

Municipal solid waste (MSW) incinerator (MSWI) bottom ash and fly ash were used as landfill cover or were co-disposed with MSW to measure their potential metal-releasing and acid-neutralizing capacity (ANC) in landfill sites. Five lysimeters (height 1.2m, diameter 0.2m), simulating landfill conditions, were used in the experiment. Four contained either bottom ash (BA) or fly ash (FA) with BA:MSW ratios of 100 and 200 g L(-1) and FA:MSW ratios of 10 and 20 g L(-1), and the fifth was the control, which contained no ash. The lysimeters were arranged so as to contain four layers, with BA or FA placed on top of MSW within each layer. Each lysimeter was recirculated with 100mL leachate using peristaltic pumps, and 100mL of the leachate was collected weekly to measure the soluble metal concentrations. The results showed that the concentrations of soluble alkali metals measured in the leachate were in the order Ca>K>Na>Mg. In addition, the concentrations of soluble alkali metals of Ca and K collected from the lysimeters containing FA were found to be higher than the concentrations from the lysimeters containing BA. The concentrations of heavy metals (Cd, Cr, Cu, Ni, and Zn) were found to be <1 mg L(-1) except for Pb, which reached 2 mg L(-1). These results suggest that for alkali metals there might be an ANC consistent with the results of an acid titration curve, which would provide suitable conditions for anaerobic digestion of the MSW in the landfill. Furthermore, heavy metals and trace metals were found in concentrations, which were too low to exert inhibitory effects on anaerobic digestion, and thus they could serve as micronutrients to exert beneficial rather than detrimental effects on landfill biostabilization.     

Influence of supercritical water treatment on heavy metals in medical waste incinerator fly ash

In this work, medical waste (MW) incinerator fly ashes from different types of incinerators were subjected to supercritical water (SCW) and SCW + H₂O₂ (SCWH) treatments. Sequential extraction experiments showed that, after SCW treatment, heavy metals in exchangeable and carbonate forms in the ashes could be transferred into other relatively stable forms, e.g., Ba and Cr into residual fraction, Cu and Pb into organic matter fraction. SCWH treatment could stabilize heavy metals in Fe–Mn oxides and residual fractions. However, the behavior of As was quite different from heavy metals, which could be leached out from residue fraction after SCW and SWCH treatments. The leached As tended to absorb onto Fe–Mn oxides and organic matters under near neutral environment, but it could react with Ca²⁺ at lower pH, increasing the mobility of this element. Therefore, it is necessary to neutralize acidic ash to near neutral condition before subjecting it to SCW and SCWH treatments so as to effectively stabilize hazardous elements in the ash. Consequently, it is believed that SCWH treatment is an effective alternative for hazardous elements detoxification in MW fly ash.     

Chromium behavior during thermal treatment of MSW fly ash.

Energy-from-waste incineration has been promoted as an environmentally responsible method for handling non-recyclable waste from households. Despite the benefits of energy production, elimination of organic residues and reduction of volume of waste to be landfilled, there is concern about fly ash disposal. Fly ash from an incinerator contains toxic species such as Pb, Zn, Cd and Cr which may leach into soil and ground water if landfilled.Thermal treatment of the fly ash from municipal solid waste has been tested and proposed as a treatment option for removal of metal species such as Pb, Cd and Zn, via thermal re-volatilization. However, Cr is an element that remains in the residue of the heat treated fly ash and appears to become more soluble. This Cr solubilization is of concern if it exceeds the regulatory limit for hazardous waste. Hence, this unexpected behavior of Cr was investigated. The initial work involved microscopic characterization of Cr in untreated and thermally-treated MSW fly ash. This was followed by determining leaching characteristics using standard protocol leaching tests and characterization leaching methods (sequential extraction). Finally, a mechanism explaining the increased solubilization was proposed and tested by reactions of synthetic chemicals.     

Effects of water-washing pretreatment on bioleaching of heavy metals from municipal solid waste incinerator fly ash

Previous studies demonstrated that the bioleaching of municipal solid waste incinerator fly ash by Aspergillus niger was an efficient "green technology" for heavy metals removal, however, it demanded a long operational period. In this study, water-washing was used as a fly ash pretreatment before the bioleaching process (one-step and two-step). This pretreatment extracted 50.6% of K, 41.1% of Na, 5.2% of Ca and 1% of Cr from the fly ash. Due to the dissolution of alkali chlorides which hold particles together, fly ash particles were smashed into smaller granules by the hydraulic flushing action caused by vibration. After the pretreatment, the lag phase and bioleaching period were reduced by 45 and 30%, respectively, in one-step bioleaching of 1% (w/v) fly ash. Meanwhile, the metals extraction yield both in one-step and two-step bioleaching was increased markedly, e.g. in two-step bioleaching, 96% Cd, 91% Mn, 73% Pb, 68% Zn, 35% Cr and 30% Fe was extracted from 1% water-washed fly ash, respectively. The reduction of the bioleaching period and improvement of metals extraction yield will likely allow the practical application of the bioleaching technology for heavy metals removal from fly ash.     

Vitrification of fly ash from municipal solid waste incinerator

Fly ash from municipal solid wastes (MSW) incinerators in Korea contains a large amount of toxic materials and requires pertinent treatments. However, since fly ash in Korea has a high chlorine concentration, it is difficult to apply cementation and chemical treatment techniques. In this study, we report the vitrification of fly ash along with the properties of the glasses and leaching characteristics of heavy metal ions.Fly ash can be vitrified by melting at 1500 degrees C for 30 min with the addition of >5 wt.% of SiO2. Glasses showed Vickers hardness of 4000-5000 MPa, bending strength of 60-90 MPa and indentation fracture toughness of approximately 0.9 MPa m(1/2). Glasses also showed the excellent resistance against leaching of heavy metal ions with Cd2+ <0.04 ppm, Cr3+ <0.02 ppm, Cu2+ <0.04 ppm and Pb2+ <0.2 ppm. These results indicate that the vitrification technique is effective for the stabilization and recycling of toxic incinerator fly ash.     

Modification of MSW fly ash by anionic chelating surfactant

This paper elucidates a study on the re-utilization and stabilization of municipal solid waste (MSW) fly ash in producing a high value-added product by the surface modification of anionic chelating surfactant on the particles. After modification, MSW fly ash can be expected using as a filler of ultra-high molecular weight polymers. The effects of anionic chelating surfactants (ACS) on surface modification of MSW fly ash and fixing capacity for heavy metals were explored. Meanwhile, the interaction mechanism between surfactants and MSW fly ash was suggested. The results showed that anionic chelating surfactants can be used to effectively modify MSW fly ash particles and achieve a high active ratio. At the same time, they also exhibited a strong fixing capacity for heavy metals. Of the two modified MSW fly ash, ED3A-modified MSW fly ash has a much higher active ratio than MAP-modified MSW fly ash at over 95%, although its fixing capacity for heavy metals was a shade lower than MAP-modified MSW fly ash.     

Biostabilization assessment of MSW co-disposed with MSWI fly ash in anaerobic bioreactors

Municipal solid waste incinerator (MSWI) fly ash has been examined for possible use as landfill interim cover. For this aim, three anaerobic bioreactors, 1.2m high and 0.2m in diameter, were used to assess the co-digestion or co-disposal performance of MSW and MSWI fly ash. Two bioreactors contained ratios of 10 and 20 g fly ash per liter of MSW (or 0.2 and 0.4 g g(-1) VS, that is, 0.2 and 0.4 g fly ash per gram volatile solids (VS) of MSW). The remaining bioreactor was used as control, without fly ash addition. The results showed that gas production rate was enhanced by the appropriate addition of MSWI fly ash, with a rate of approximately 6.5l day(-1)kg(-1)VS at peak production in the ash-added bioreactors, compared to approximately 4l day(-1)kg(-1)VS in control. Conductivity, alkali metals and VS in leachate were higher in the fly ash-added bioreactors compared to control. The results show that MSW decomposition was maintained throughout at near-neutral pH and might be improved by release of alkali and trace metals from fly ash. Heavy metals exerted no inhibitory effect on MSW digestion in all three bioreactors. These phenomena indicate that proper amounts of MSWI fly ash, co-disposed or co-digested with MSW, could facilitate bacterial activity, digestion efficiency and gas production rates.     

Thermal treatment of the fly ash from municipal solid waste incinerator with rotary kiln

Reuse of the fly ash from the municipal solid waste incinerator (MSWI) is a policy of Taiwan EPA. However, the fly ash is often classified as a hazardous waste and cannot be reused directly because the concentrations of heavy metals exceed the TCLP regulations. The main objective of this study is to investigate the continuous sintering behavior of fly ash with a rotary kiln and seek a solution to reduce the concentrations of heavy metal to an acceptable value. The partitions of the heavy metals in the process are also considered. The results of TCLP showed that among the metals of Cr, Cd, Cu and Pb, only the concentrations of Pb in raw fly ash exceeded the regulation. At sintering temperatures of 700, 800 and 900 degrees C, the concentration of Pb decreased in sintering products, however, the concentration of Pb still exceeded the limitation at 700 and 800 degrees C. Additionally, the water-washing was used to pre-treat the fly ash before sintering process. The washing treatment effectively reduced the leaching concentrations of Pb to agree the regulations. Therefore, water-washing followed by a sintering treatment is an available process for detoxifying the fly ash of MSWI.     

Behavior of high strength fly ash concrete columns under fire conditions

Fly ash concrete is finding increasing applications in construction; however there is lack of data on fire performance of fly ash concrete structural members. This paper presents results from fire resistance tests on fly ash concrete columns. Data generated from tests on high strength fly ash concrete columns is compared with those of conventional high strength concrete (HSC) columns. The effect of concrete type, fire exposure scenario, fly ash, and fibers in concrete mix on fire performance of fly ash concrete columns is discussed. Results from fire resistance tests show that fly ash concrete columns exhibit almost similar fire resistance to that of conventional HSC columns. Further, the addition of polypropylene fibers mitigates fire induced spalling in high strength fly ash concrete columns.     

Sintering of MSW fly ash for reuse as a concrete aggregate

The sintering process of municipal solid waste (MSW) fly ash was investigated in order to manufacture sintered products for reuse as concrete aggregates.Four types of fly ash resulting from different Italian MSW incineration plants were tested in this study. A modification of the chemical composition of MSW fly ash--through a preliminary four-stage washing treatment of this material with water--was attempted to improve the chemical and mechanical characteristics of sintered products.The sintering treatment of untreated or washed fly ash was performed on cylindrical compact specimens (15 mm in diameter and 20mm in height) at different compact pressures, sintering temperatures and times.The sintering process of untreated MSW fly ashes proved to be ineffective for manufacturing sintered products for reuse as a construction material, because of the adverse chemical characteristics of these fly ashes in terms of sulfate, chloride, and vitrifying oxide contents.A preliminary washing treatment of MSW fly ash with water greatly improved the chemical and mechanical characteristics of sintered products and, for all the types of fly ash tested, the sintered products satisfied the Italian requirements for normal weight aggregates for use in concretes having a specified strength not greater than 12 and 15N/mm(2), when measured on cylindrical and cubic specimens, respectively.A compact pressure of 28 N/mm(2), a sintering temperature of 1140 degrees C, and a sintering time of 60 min were the best operating conditions for manufacturing sintered products of washed MSW fly ash.     

Behaviour of concrete-filled steel tubular columns incorporating fly ash

The subject of this work is to investigate the effect of fly ash on the strength of concrete filled steel tubular columns from 28 to 365 days. A contrast study was carried out on concrete filled steel tubular columns incorporating 10–40 wt% fly ash, and for control Portland cement concrete filled steel tubular columns. The effect of pre-coating the inner surface of steel tubes with a thin layer of fly ash was also studied. Assessments of the concrete mixes were based on the compressive strength and the bond strength. The results show that a lower replacement with fly ash can improve both bond strength and compressive strength, while a higher replacement with fly ash requires a relatively longer time to achieve similar beneficial effects. Pre-coating the inner surface of steel tubes with a thin layer of fly ash can notably improve the bond strength. The microstructure of the interface between concrete and steel tube was also studied by using scanning electron microscopy analyzer.     

Melting of municipal solid waste incinerator fly ash by waste-derived thermite reaction

This work describes a novel approach for melting municipal solid waste incinerator (MSWI) fly ash, based on self-propagating reactions, by using energy-efficient simulated waste-derived thermite. The self-propagating characteristics, the properties of the recycled alloy and slag and the partitioning of heavy metals during the process are also studied. Experimental results demonstrate that the mix ratio of fly ash to the starting mixture of less than 30% supports the development of the self-propagating reaction with a melting temperature of 1350-2200 degrees C. Furthermore, metallic iron (or alloy) and the slag were retrieved after activation of the thermite reactions among the starting mixtures. It was noted that more than 91wt.% of iron was retrieved as alloy and the rest of non-reductive oxides as slag. During the thermite reactions, the partition of heavy metals to the SFA and flue gas varied with the characteristics of the target metals: Cd was mainly partitioned to flue gas (75-82%), and partition slightly increased with the increasing fly ash ratio; Pb and Zn, were mainly partitioned to the SFA, and the partition increased with increasing fly ash ratio; Cu was partitioned to the SFA (18-31%) and was not found in the flue gas; and moreover stable Cr and Ni were not identified in both the SFA and flue gas. On the other hand, the determined TCLP leaching concentrations were all well within the current regulatory thresholds, despite the various FA ratios. This suggests that the vitrified fly ash samples were environmental safe in heavy metal leaching. The results of this study suggested that melting of municipal solid waste incinerator fly ash by waste-derived thermite reactions was a feasible approach not only energy-beneficial but also environmental-safe.     

Size characterization of incinerator fly ash using sedimentation/steric field-flow fractionation

Fly ash particles emitted from municipal solid waste-incinerators are of environmental concern. This study aims to investigate the applicability of sedimentation/steric field-flow fractionation (Sd/StFFF) and to develop a Sd/StFFF method for the separation and size characterization of incinerator fly ash. This study focuses on the fly ash particles larger than approxiamtely 1 microm, which comprise more than 90% (w/w) of the fly ash. Fly ash is a complex mixture of particles having various chemical compositions, sizes, shapes, and densities. Prior to Sd/StFFF analysis, fly ash particles are prefractionated into six density classes using a modified centrifugal procedure. It was found that fly ash particles are most abundant in the density range between 2.4 and 2.8 g/cm3. Different density fractions seem to contain particles of different chemical compositions. The Sd/StFFF conditions for the size-characterization of fly ash are sample concentration, approximately 0.3% (w/v); dispersing medium, 50% ethanol in water; and carrier liquid, water with 1.0% FL-70 (ionic strength approximately 0.012 M). Sd/StFFF data show no significant differences in size distribution among different density fractions. Generally, the sizes obtained from Sd/StFFF are larger than those obtained from a Coulter Multisizer and microscopy, probably because of the irregular shapes of the fly ash particles.     

Optimization of the solidification/stabilization process of MSW fly ash in cementitious matrices

The solidification/stabilization (S/S) process of municipal solid waste (MSW) fly ash in cementitious matrices was investigated in order to ascertain the feasibility of a washing pretreatment of fly ash with water as a means of maximizing the ash content of cementitious mixtures. Four types of fly ash resulting from different Italian MSW incineration plants and ASTM Type III Portland cement were used in this study. Ash-cement mixtures with different fly ash/cement (FA/C) ratios were made using untreated and washed fly ash. Washing of fly ash with water was realized by a two-stage treatment (liquid/solid=25; mixing time=15 min for each stage). The cementitious mixtures were characterized for water demand, setting time, mechanical strength, and heavy metals leachability. Comparison between the above properties of mixtures incorporating untreated and washed fly ash (particularly, setting characteristics), coupled with economical evaluation of the S/S process when applied to untreated and washed fly ash, proved the feasibility of washing pretreatment as a means of maximizing the incorporation of MSW fly ash in cementitious matrices (ash content up to 75%-90% by weight of total solid).