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.     

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.     

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.     

Utilization of blended fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash in geopolymer

In this paper, synthesis of geopolymer from fluidized bed combustion (FBC) ash and pulverized coal combustion (PCC) fly ash was studied in order to effectively utilize both ashes. FBC-fly ash and bottom ash were inter-ground to three different finenesses. The ashes were mixed with as-received PCC-fly ash in various proportions and used as source material for synthesis of geopolymer. Sodium silicate (Na₂SiO₃) and 10 M sodium hydroxide (NaOH) solutions at mass ratio of Na₂SiO₃/NaOH of 1.5 and curing temperature of 65 °C for 48 h were used for making geopolymer. X-ray diffraction (XRD), scanning electron microscopy (SEM), degree of reaction, and thermal gravimetric analysis (TGA) were performed on the geopolymer pastes. Compressive strength was also tested on geopolymer mortars. The results show that high strength geopolymer mortars of 35.0–44.0 MPa can be produced using mixture of ground FBC ash and as-received PCC-fly ash. Fine FBC ash is more reactive and results in higher degree of reaction and higher strength geopolymer as compared to the use of coarser FBC ash. Grinding increases reactivity of ash by means of increasing surface area and the amount of reactive phase of the ash. In addition, the packing effect due to fine particles also contributed to increase in strength of geopolymers.     

Hydrodechlorination/detoxification of PCDDs,PCDFs, and co-PCBs in fly ash by using calcium polysulfide

Dioxins like polychlorinated dibenzo-p-dioxins (PCSDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) are mainly emitted from waste incinerators (WIs) and have become an international research focus because of its serious concerns over the adverse health effects. The detoxification of PCCDs/Fs and PCBs is very difficult because of their stable chemical structure. A significant hydrodechlorination/detoxification of polychlorinated 1-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs) and polychlorinated biphenyls (PCBs) were achieved in fly ash by using an aqueous mixture of calcium hydroxide and sulfur. Two different fly ashes were studied: originating from municipal waste incinerator (FA1) and industrial waste incinerator (FA2). They were heated with the aqueous mixture at 150 °C for 30 or 60 min with agitation. Higher decomposition (87%) and detoxification (87.7%) of PCDD/Fs and PCBs were achieved at 150 °C with two runs; every run was for 30 min, compared to one run for 60 min. FA2 gave higher decomposition and detoxification as compared to FA1, which might be due to higher metal content that played a catalytic role to decompose and detoxify the PCDDs, PCDFs and PCBs. The decomposition and detoxification of PCDFs in fly ash was higher than PCDDs and was augmented with increasing number of chlorides on aromatic compounds. As the highly significant decomposition and detoxification of higher concentration of PCDD/Fs and PCBs were achieved in 1 hour without additive catalyst and at low temperature of 150 °C, therefore, the developed method is cost effective and most suitable to apply on commercial/industrial level. The detail results of hydrodechlorination/detoxification of PCDD, PCDFs at different conditions are described and its mechanism is discussed.     

The effects of the mechanical–chemical stabilization process for municipal solid waste incinerator fly ash on the chemical reactions in cement paste

A water extraction process can remove the soluble salts present in municipal solid waste incinerator (MSWI) fly ash, which will help to increase the stability of the synthetic materials produced from the MSWI fly ash. A milling process can be used to stabilize the heavy metals found in the extracted MSWI fly ash (EA) leading to the formation of a non-hazardous material. This milled extracted MSWI fly ash (MEA) was added to an ordinary Portland cement (OPC) paste to induce pozzolanic reactions. The experimental parameters included the milling time (96 h), water to binder ratios (0.38, 0.45, and 0.55), and curing time (1, 3, 7 and 28 days). The analysis procedures included inductively coupled plasma atomic emission spectroscopy (ICP/AES), BET, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) imaging. The results of the analyses indicate that the milling process helped to stabilize the heavy metals in the MEA, with an increase in the specific surface area of about 50 times over that of OPC. The addition of the MEA to the OPC paste decreased the amount of Ca(OH)₂ and led to the generation of calcium–silicate–hydrates (C–S–H) which in turned increased the amount of gel pores and middle sized pores in the cement. Furthermore, a comparison shows an increase in the early and later strength over that of OPC paste without the addition of the milled extracted ash. In other words, the milling process could stabilize the heavy metals in the MEA and had an activating effect on the MEA, allowing it to partly substitute OPC in OPC paste.     

Prevention of lead leaching from fly ashes by mechanochemical treatment

Fly ashes from a municipal solid waste incinerator were subjected to mechanochemical (MC) treatment in a planetary ball mill, and the treated fly ashes were cemented with a binder. The leachability of lead (Pb) from the treated fly ashes and from the cement product were investigated, and the speciation of lead in the treated and untreated ashes was determined by X-ray absorption fine structure (XAFS) analysis. MC treatment of the fly ashes and subsequent cementation prevented Pb leaching by 99.9%, whereas MC treatment alone prevented Pb leaching by 92.8%. Analysis of the X-ray absorption near-edge spectrum of the untreated fly ashes revealed that the predominant Pb species in the ashes was PbCl₂. In contrast, the counterpart in the treated fly ashes was Pb₃O₄ insoluble in water. The formation of a species of Pb with a lower solubility in water than that of PbCl₂ was confirmed by MC treatment of PbCl₂-spiked fly ashes for 48 h, indicating the reduction of PbCl₂ in the spiked fly ashes to Pb via Pb₃O₄ during MC treatment. Our results indicate that such reduction to an insoluble species prevented Pb from leaching and that MC treatment followed by cementation is a feasible method for the recycling of fly ashes.     

Quick monitoring of pozzolanic reactivity of waste ashes

This article proposes a quick method of monitoring for pozzolanic reactivity of waste ashes by investigating the electrical conductivity of the suspension at an elevated temperature. This suspension is obtained by mixing tested pozzolan with an ordinary Portland cement (OPC) solution produced by mixing ordinary Portland cement with water. For comparison, silica fume, metakaolin, rice husk ash and river sand – whose pozzolanic reactivities range from reactive to inert – were used in the experimental investigation. The electrical conductivity of the suspension was continually recorded by using an electrical conductivity meter and stored by using a personal computer for a period of slightly over 1 day. The indicative parameters that can be related to pozzolanic reactivity were discussed and analyzed in detail. It was found that it is possible to determine the pozzolanic reactivity of fly ash within 28 h by using the proposed technique, as compared to 7 or 28 days for the determination of strength activity index according to ASTM. This technique would help concrete technologists to speedily investigate the quality of fly ash for use as a cement replacement in order to alleviate pollution caused by cement production and solve disposal problems of waste ashes.     

Effects of composing on sorption capacity of bagasse-based chars

A fresh bagasse sample (0-month) and two composted bagasse and pig manure mixed samples (1-month and 6-month) were used to produce carbon chars. Sample pyrolysis showed greater carbon char yields were obtained from the compost samples than from the bagasse sample. Fourier transform infrared spectra suggested that the chemical structures of the bagasse sample and the two compost samples were quite different, but that the three carbon chars obtained from those precursors were similar. Among the three pyrolyzed chars, the 0-month bagasse char displayed the largest sorption capacity of 3333 mg kg^?1 for the hydrophilic pollutant phenol, presumably resulting from its greater carbon content and O/C ratio. However, the sorption capacities for the hydrophobic pollutant naphthalene of the tow compost chars (3-month, 2001 mg kg^?1; 6-month, 1667 mg kg^?1) were greater than that of the 0-month bagasse char (1428 mg kg^?1). The results indicate that the compost chars had a greater preferential affinity for naphthalene than that in the bagasse char, suggesting that the compost chars possessed greater hydrophobicity.     

Solidification/stabilization of ash from medical waste incineration into geopolymers

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

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

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

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.     

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

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

Coal fly ash based carbons for SO2 removal from flue gases

Two different coal fly ashes coming from the burning of two coals of different rank have been used as a precursor for the preparation of steam activated carbons. The performance of these activated carbons in the SO₂ removal was evaluated at flue gas conditions (100 °C, 1000 ppmv SO₂, 5% O₂, 6% H₂O). Different techniques were used to determine the physical and chemical characteristics of the samples in order to explain the differences found in their behaviour. A superior SO₂ removal capacity was shown by the activated carbon obtained using the fly ash coming from a subbituminous–lignite blend. Experimental results indicated that the presence of higher amount of certain metallic oxides (Ca, Fe) in the carbon-rich fraction of this fly ash probably has promoted a deeper gasification in the activation with steam. A more suitable surface chemistry and textural properties have been obtained in this case which explains the higher efficiency shown by this sample in the SO₂ removal.     

Characterisation of agroindustrial solid residues as biofuels and potential application in thermochemical processes

In the present work, selected agroindustrial solid residues from Brazil – biosolids from meat processing wastewater treatment and mixture of sawdust with these biosolids; residues from apple and orange juice industries; sugarcane bagasse; açaí kernels (Euterpe oleracea) and rice husk – were characterised as solid fuels and an evaluation of their properties, including proximate and ultimate composition, energy content, thermal behaviour, composition and fusibility of the ashes was performed. The lower heating value of the biomasses ranged from 14.31 MJ kg^?1 to 29.14 MJ kg^?1, on a dry and ash free basis (daf), all presenting high volatile matter content, varying between 70.57 wt.% and 85.36 wt.% (daf) what improves the thermochemical conversion of the solids. The fouling and slagging tendency of the ashes was predicted based on the fuel ash composition and on the ash fusibility correlations proposed in the literature, which is important to the project and operation of biomass conversion systems. The potential for application of the Brazilian agroindustrial solid residues studied as alternative energy sources in thermochemical processes has been identified, especially concerning direct combustion for steam generation.     

Reuse potential of low-calcium bottom ash as aggregate through pelletization

Coal combustion residues which include fly ash, bottom ash and boiler slag is one of the major pollutants as these residues require large land area for their disposal. Among these residues, utilization of bottom ash in the construction industry is very low. This paper explains the use of bottom ash through pelletization. Raw bottom ash could not be pelletized as such due to its coarseness. Though pulverized bottom ash could be pelletized, the pelletization efficiency was low, and the aggregates were too weak to withstand the handling stresses. To improve the pelletization efficiency, different clay and cementitious binders were used with bottom ash. The influence of different factors and their interaction effects were studied on the duration of pelletization process and the pelletization efficiency through fractional factorial design. Addition of binders facilitated conversion of low-calcium bottom ash into aggregates. To achieve maximum pelletization efficiency, the binder content and moisture requirements vary with type of binder. Addition of Ca(OH)₂ improved the (i) pelletization efficiency, (ii) reduced the duration of pelletization process from an average of 14–7 min, and (iii) reduced the binder dosage for a given pelletization efficiency. For aggregate with clay binders and cementitious binder, Ca(OH)₂ and binder dosage have significant effect in reducing the duration of pelletization process.     

Flue gas desulfurization gypsum and coal fly ash as basic components of prefabricated building materials

The manufacture of prefabricated building materials containing binding products such as ettringite (6CaO·Al₂O₃·3SO₃·32H₂O) and calcium silicate hydrate (CSH) can give, in addition to other well-defined industrial activities, the opportunity of using wastes and by-products as raw materials, thus contributing to further saving of natural resources and protection of the environment.Two ternary mixtures, composed by 40% flue gas desulfurization (FGD) gypsum or natural gypsum (as a reference material), 35% calcium hydroxide and 25% coal fly ash, were submitted to laboratory hydrothermal treatments carried out within time and temperature ranges of 2 h–7 days and 55–85 °C, respectively. The formation of (i) ettringite, by hydration of calcium sulfate given by FGD or natural gypsum, alumina of fly ash and part of calcium hydroxide, and (ii) CSH, by hydration of silica contained in fly ash and residual lime, was observed within both the reacting systems. For the FGD gypsum-based mixture, the conversion toward ettringite and CSH was highest at 70 °C and increased with curing time. Some discrepancies in the hydration behavior between the mixtures were ascribed to differences in mineralogical composition between natural and FGD gypsum.     

Glass–ceramic from mixtures of bottom ash and fly ash

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

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

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

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.