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.     

Artificial carbonation for controlling the mobility of critical elements in bottom ash

In municipal solid waste incineration (MSWI), bottom ash, generated at a stoker grate type incinerator, the critical elements were identified in terms of EU regulation. The stabilizing effect of moderate carbonation (pH 8.28 ± 0.03) on critical contaminants was studied through availability and diffusion leaching protocols. Data from the performed tests were evaluated with the goal of reusing MSWI bottom ash as secondary construction material. To investigate the mobilizing effect of CO₂, suspended MSWI bottom ash was severely carbonated (pH 6.40 ± 0.07). The effect of CO₂ and its interaction with other leaching factors, such as liquid/solid (L/S) ratio, leaching time, pH, ultrasound treatment, and leaching temperature, were examined using a reduced 2^6-1 experimental design. Contaminants identified as critical were Cr, Cu, Mo, Sb, Cl⁻, and SO₄ ²⁻. Although moderate carbonation decreased the release of Cr, Cu, Mo, and Sb from compacted bottom ash, the main disadvantage remains its inability to demobilize Cl⁻ and SO₄ ²⁻. The hypothesized mobilizing effect of severe carbonation was proven. The treatment enhanced the separation of critical components (α = 0.05) (except for Cl⁻), i.e., about fivefold for Sb and about twofold for Cr, Cu, and S. Nevertheless, the prospect is good that severe carbonation could constitute the deciding key parameter to facilitate the technical feasibility of a future washing process for MSWI bottom ash.     

The weathering of municipal solid waste incineration bottom ash evaluated by some weathering indices for natural rock

The weathering of municipal solid waste incineration (MSWI) residues consists of complicated phenomena. This makes it difficult to describe leaching behaviors of major and trace elements in fresh/weathered MSWI bottom ash, which was relevant interactively to pH neutralization and formation of secondary minerals. In this study, mineralogical weathering indices for natural rock profiles were applied to fresh/landfilled MSWI bottom ash to investigate the relation of these weathering indices to landfill time and leaching concentrations of component elements. Tested mineralogical weathering indices were Weathering Potential Index (WPI), Ruxton ratio (R), Weathering Index of Parker (WIP), Vogt’s Residual Index (V), Chemical Index of Alternation (CIA), Chemical Index of Weathering (CIW), Plagioclase Index of Alternation (PIA), Silica–Titania Index (STI), Weathering Index of Miura (Wm), and Weatherability index of Hodder (Ks). Welch’s t-test accepted at 0.2% of significance level that all weathering indices could distinguish fresh and landfilled MSWI bottom ash. However, R and STI showed contrasted results for landfilled bottom ash to theoretical expectation. WPI, WIP, Wm, and Ks had good linearity with reclamation time of landfilled MSWI bottom ash. Therefore, these four indices might be applicable as an indicator to indentify fresh/weathered MSWI bottom ash and to estimate weathering time. Although WPI had weak correlation with leachate pH, other weathering indices had no significant correlation. In addition, all weathering indices could not explain leaching concentration of Al, Ca, Cu, and Zn quantitatively. Large difficulty to modify weathering indices correctly suggests that geochemical simulation including surface sorption, complexation with DOM, and other mechanisms seems to be the only way to describe leaching behaviors of major and trace elements in fresh/weathered MSWI bottom ash.     

Hydrothermal solidification of municipal solid waste incineration bottom ash with slag addition

Hydrothermal solidification of municipal solid waste incineration (MSWI) bottom ash has been carried out under saturated steam pressure (1.56 MPa) at 200 °C for up to 24 h by mixing quartz, slaked lime and water-cooled blast furnace slag (WBFS). The strength enhancement for the WBFS addition was best. The strength development was shown to be due mainly to tobermorite formation, and the tobermorite formation densified matrix, thus promoting the strength development. WBFS seemed to have a higher reactivity than the quartz during the initial hydrothermal process, which provided more silica available to harden the solidified specimens. However, a longer curing time (24 h) was favorable to the quartz dissolution for tobermorite formation, which in turn, enhanced the strength for quartz addition. Curing time affected the crystal morphology evolution, and the stubby plate of tobermorite seemed to result in a high strength enhancement in this study. Laboratory leaching tests were conducted to determine the amount of heavy metals dissolved from the final solidified specimens, and the leaching results showed that after hydrothermal processing the heavy metals dissolved from the solidified specimens were reduced effectively. As such, the hydrothermal processing may have a high potential for recycling/reusing MSWI ash on a large scale.     

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.     

Immobilization of MSWI fly ash through geopolymerization: Effects of water-wash

The present research explored the role played by water-wash on geopolymerization for the immobilization and solidification of municipal solid waste incineration (MSWI) fly ash. The water-wash pretreatment substantially promoted the early strength of geopolymer and resulted in a higher ultimate strength compared to the counterpart without water-wash.XRD pattern of water-washed fly ash (WFA) revealed that NaCl and KCl were nearly eliminated in the WFA. Aside from geopolymer, ettringite (Ca₆Al₂(SO₄)₃(OH)₁₂·26H₂O) was formed in MSWI fly ash-based geopolymer (Geo-FA). Meanwhile, calcium aluminate hydrate (Ca₂Al(OH)₇·3H₂O), not ettringite, appeared in geopolymer that was synthesized with water-washed fly ash (Geo-WFA). Leached Geo-WFA (Geo-WFA-L) did not exhibit any signs of deterioration, while there was visual cracking on the surface of leached Geo-FA (Geo-FA-L). The crack may be caused by the migration of K⁺, Na⁺, and Cl⁻ ions outside Geo-FA and the negative effect from crystallization of expansive compounds can not be excluded. Furthermore, transformation of calcium aluminate hydrate in Geo-WFA to ettringite in Geo-WFA-L allowed the reduction of the pore size of the specimen. IR spectrums suggested that Geo-WFA can supply more stable chemical encapsulation for heavy metals.Static monolithic leaching tests were conducted for geopolymers to estimate the immobilization efficiency. Heavy metal leaching was elucidated using the first-order reaction/diffusion model. Combined with the results from compressive strength and microstructure of samples, the effects of water-wash on immobilization were inferred in this study.     

Production of gaseous fuel from refuse plastic fuel via co-pyrolysis using low-quality coal and catalytic steam gasification

In this study, refuse plastic fuel (RPF) was copyrolyzed with low-quality coal and was gasified in the presence of a metal catalyst and steam. Some metal catalysts, such as Ni, NiO, and Mg, and mixtures of these with base promoters such as Al₂O₃ and Fe₂O₃ were employed in the pyrolysis and gasification processes to convert the synthesis gas into more valuable fuel gas. The operating temperatures for the pyrolysis and gasification were between 700° and 1000°C. The experimental parameters were the operating temperature, catalyst type, basic promoter type, and steam injection amount. Solid fuel samples (5 g) were fed into a semibatch-type quartz tube reactor when the reactor reached the designated temperature. The synthesis gas was analyzed by gas chromatography. The use of low-quality coal as fuel in co-pyrolysis with RPF was explored. For the co-pyrolysis of RPF and low-quality coal, the effectiveness of the catalysts for fuel gas production followed the order Mg > NiO > Ni. In catalytic gasification of RPF, the addition of Al₂O₃ seemed to reduce the activity of the corresponding catalysts Ni and Mg. The maximum fuel gas yield (92.6%) was attained when Mg/Fe₂O₃ was used in steam gasification at 1000°C.     

The neutralization behavior of MSWI bottom ash on different time scales and in different reaction systems

The neutralization behavior of municipal solid waste incineration (MSWI) bottom ash is characterized according to reaction time and reaction system. Batch and flow-through pH titrations are used to determine the acid neutralizing capacity of the MSWI bottom ash in different reaction systems. A reaction path model and a reactive transport model evaluate the detailed mechanisms and titration kinetics of the experiments. The results indicate that both the neutralization kinetics and titration kinetics of the test methods are important. They determine the relation between the time scale of the experiments and that of an actual leaching environment. Current pH titration experiments account mainly for the relatively fast neutralization reactions, so that they cannot assess the long-term neutralization processes of MSWI bottom ash. It is also found that the neutralization characteristics of MSWI bottom ash in a flow-through system are very different from those in a batch system. The movement of a pH front and the washing-out of soluble buffering components have large influences on the neutralization ability of MSWI bottom ash in a reaction system with flow-through of leachant.     

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.     

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.     

Effect of leachate recirculation on the migration of copper and zinc in municipal solid waste and municipal solid waste incineration bottom ash co-disposed landfill

Municipal solid waste incinerator (MSWI) bottom ash was allowed to be disposed of with municipal solid waste (MSW) in landfill sites in the recently enacted standard of China. In this study, three sets of simulated landfill reactors, namely, conventional MSW landfill (CL), conventional MSWI bottom ash and MSW co-disposed landfill (CCL), and leachate recirculated MSWI bottom ash and MSW co-disposed landfill (RCL), were operated to investigate the environmental impact of the co-disposal. The effect of leachate recirculation on the migration of Cu and Zn in the co-disposed landfill was also presented. The results showed that the co-disposal of MSWI bottom ash with MSW would not enhance the leaching of Cu and Zn from landfill. However, the co-disposal increased the Cu and Zn contents of the refuse in the bottom layer of the landfill from 56.7 to 65.3 mg/kg and from 210 to 236 mg/kg, respectively. The recirculation of the leachate could further increase the Cu and Zn contents of the refuse in the bottom layer of the landfill to 72.9 and 441 mg/kg, respectively. Besides these observations, the results also showed that the co-disposed landfill with leachate recirculation could facilitate the stabilization of the landfill.     

Effect of crystal size on zinc stabilization in aluminum-rich ceramic matrix

With aluminum as the predominant element, incineration residues from municipal solid waste and sewage sludge may be reused as precursors for zinc stabilization. As solid-state reactions are influenced by the crystal sizes of the reactants, the aluminum-containing components with different crystal sizes in the incineration residues may affect zinc transformation and immobilization. In this study, Al₂O₃ was prepared with a variety of crystal sizes to simulate the aluminum-rich incineration residue matrix, and ZnO was mixed with Al₂O₃ to study the zinc incorporation mechanisms. The crystal sizes of Al₂O₃ were determined using Rietveld refinement. Quantification results showed that ~?30% of zinc was incorporated into the ZnAl₂O₄ spinel when Al₂O₃ with the largest crystal size was used. However, the zinc transformation was enhanced twofold when the Al₂O₃ precursor had the smallest crystal size. This study confirmed the potential enhancement of zinc immobilization by nanoscale crystals in simulated aluminum-rich incineration residues. By improving zinc stabilization efficiencies using poorly crystallized aluminum-containing compounds instead of increasing the energy consumption by increasing the sintering temperatures, we can achieve an economic and environmental win–win scenario for the beneficial utilization of incineration residues of municipal solid waste and sewage sludge.     

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.     

Recovery of MSWI and soil washing residues as concrete aggregates

The aim of the present work was to study if municipal solid waste incinerator (MSWI) residues and aggregates derived from contaminated soil washing could be used as alternative aggregates for concrete production.Initially, chemical, physical and geometric characteristics (according to UNI EN 12620) of municipal solid waste incineration bottom ashes and some contaminated soils were evaluated; moreover, the pollutants release was evaluated by means of leaching tests. The results showed that the reuse of pre-treated MSWI bottom ash and washed soil is possible, either from technical or environmental point of view, while it is not possible for the raw wastes.Then, the natural aggregate was partially and totally replaced with these recycled aggregates for the production of concrete mixtures that were characterized by conventional mechanical and leaching tests. Good results were obtained using the same dosage of a high resistance cement (42.5R calcareous Portland cement instead of 32.5R); the concrete mixture containing 400 kg/m³ of washed bottom ash and high resistance cement was classified as structural concrete (C25/30 class). Regarding the pollutants leaching, all concrete mixtures respected the limit values according to the Italian regulation.     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

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.     

Numerical model for a watering plan to wash out organic matter from the municipal solid waste incinerator bottom ash layer in closed system disposal facilities

Bottom ash from municipal solid waste incineration (MSWI) is a main type of waste that is landfilled in Japan. The long-term elution of organic matter from the MSWI bottom ash layers is a concern because maintenance and operational costs of leachate treatment facilities are high. In closed system disposal facilities (CSDFs), which have a roof to prevent rainfall from infiltrating into the waste layers, water must be supplied artificially and its quantity can be controlled. However, the quantity of water needed and how to apply it (the intensity, period and frequency) have not been clearly defined. In order to discuss an effective watering plan, this study proposes a new washout model to clarify a fundamental mechanism of total organic carbon (TOC) elution behavior from MSWI bottom ash layers. The washout model considers three phases: solid, immobile water and mobile water. The parameters, including two mass transfer coefficients of the solid-immobile water phases and immobile-mobile water phases, were determined by one-dimensional column experiments for about 2 years. The intensity, period and frequency of watering and other factors were discussed based on a numerical analysis using the above parameters. As a result, our washout model explained adequately the elution behavior of TOC from the MSWI bottom ash layer before carbonation occurred (pH approximately 8.3). The determined parameters and numerical analysis suggested that there is a possibility that the minimum amount of water needed for washing out TOC per unit weight of MSWI bottom ash layer could be determined, which depends on the two mass transfer coefficients and the depth of the MSWI bottom ash layer. Knowledge about the fundamental mechanism of the elution behavior of TOC from the MSWI bottom ash layer before carbonation occurs, clarified by this study, will help an effective watering plan in CSDFs.     

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.     

Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation

Two bottom ashes, one air pollution control (APC) residue and one fly ash from three different Swedish municipal solid waste incineration (MSWI) plants were characterised regarding the leaching of environmentally relevant components. Characterisation was performed using a diffusion tank leaching test. The impact of carbonation on the release of eight critical components, i.e., Cl(-), Cr, Cu, Mo, Pb, Sb, Se, SO(4)(2-) and Zn, was assessed at a lab-scale and showed carbonation to have a more pronounced demobilising effect on critical components in bottom ashes than in APC residue and fly ash. From grate type incinerator bottom ash, the release of Cr decreased by 97%, by 63% for Cu and by 45% for Sb. In the investigated APC residue, the releases of Cr, Se and Pb were defined as critical, although they either remained unaffected or increased after carbonation. Cl(-) and SO(4)(2-) remained mobile after carbonation in all investigated residues.