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.     

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.     

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.     

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.     

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.     

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.     

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.     

Alkali activation processes for incinerator residues management

Incinerator bottom ash (BA) is produced in large amount worldwide and in Italy, where 5.1 millions tons of municipal solid residues have been incinerated in 2010, corresponding to 1.2–1.5 millions tons of produced bottom ash. This residue has been used in the present study for producing dense geopolymers containing high percentage (50–70 wt%) of ash. The amount of potentially reactive aluminosilicate fraction in the ash has been determined by means of test in NaOH. The final properties of geopolymers prepared with or without taking into account this reactive fraction have been compared. The results showed that due to the presence of both amorphous and crystalline fractions with a different degree of reactivity, the incinerator BA geopolymers exhibit significant differences in terms of Si/Al ratio and microstructure when reactive fraction is considered.     

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.     

Hydrothermal solidification behavior of municipal solid waste incineration bottom ash without any additives

Municipal solid waste incineration (MSWI) bottom ash could be solidified with and without slaked lime (calcium hydroxide) addition by a hydrothermal method under steam pressure of 1.56 MPa at 200 °C for up to 72 h. Experimental results showed that CSH gel or tobermorite exerted a main influence on strength development, and without any additives CSH gel was easy to form, while slaked lime addition favored to form tobermorite. Tobermorite seemed to exert a larger effect on the strength development than CSH gel. Leaching results showed that the concentrations of heavy metals dissolved from the solidified specimens were effectively reduced after hydrothermal processing. The immobilization was mainly due to the tobermorite or CSH gel formation, and Pb²⁺ and Zn²⁺ seemed to be fixed more readily than Cr⁶⁺, which might be the reason that the structural Ca²⁺ within tobermorite or CSH gel was exchanged by Pb²⁺ and Zn²⁺ more easily than Cr⁶⁺. In addition, there existed a close relationship between leaching concentration and strength enhancement, and a higher strength seemed to exert a larger effect on immobilization of heavy metals.     

An LCA model for waste incineration enhanced with new technologies for metal recovery and application to the case of Switzerland

A process model of municipal solid waste incinerators (MSWIs) and new technologies for metal recovery from combustion residues was developed. The environmental impact is modeled as a function of waste composition as well as waste treatment and material recovery technologies. The model includes combustion with a grate incinerator, several flue gas treatment technologies, electricity and steam production from waste heat recovery, metal recovery from slag and fly ash, and landfilling of residues and can be tailored to specific plants and sites (software tools can be downloaded free of charge). Application of the model to Switzerland shows that the treatment of one tonne of municipal solid waste results on average in 425 kg CO₂-eq. generated in the incineration process, and 54 kg CO₂-eq. accrue in upstream processes such as waste transport and the production of operating materials. Downstream processes, i.e. residue disposal, generates 5 kg CO₂-eq. Savings from energy recovery are in the range of 67 to 752 kg CO₂-eq. depending on the assumptions regarding the substituted energy production, while the recovery of metals from slag and fly ash currently results in a net saving of approximately 35 kg CO₂-eq. A similar impact pattern is observed when assessing the MSWI model for aggregated environmental impacts (ReCiPe) and for non-renewable resource consumption (cumulative exergy demand), except that direct emissions have less and no relevance, respectively, on the total score. The study illustrates that MSWI plants can be an important element of industrial ecology as they provide waste disposal services and can help to close material and energetic cycles.     

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.     

Pilot scale evaluation of the BABIU process – Upgrading of landfill gas or biogas with the use of MSWI bottom ash

Biogas or landfill gas can be converted to a high-grade gas rich in methane with the use of municipal solid waste incineration bottom ash as a reactant for fixation of CO₂ and H₂S. In order to verify results previously obtained at a laboratory scale with 65–90 kg of bottom ash (BA), several test runs were performed at a pilot scale, using 500–1000 kg of bottom ash and up to 9.2 N m³/h real landfill gas from a landfill in the Tuscany region (Italy). The input flow rate was altered. The best process performance was observed at a input flow rate of 3.7 N m³/(h t_BA). At this flow rate, the removal efficiencies for H₂S were approximately 99.5–99%.     

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.     

Phosphorus recovery from sewage sludge ash through an electrodialytic process

The electrodialytic separation process (ED) was applied to sewage sludge ash (SSA) aiming at phosphorus (P) recovery. As the SSA may have high heavy metals contents, their removal was also assessed. Two SSA were sampled, one immediately after incineration (SA) and the other from an open deposit (SB). Both samples were ED treated as stirred suspensions in sulphuric acid for 3, 7 and 14 days. After 14 days, phosphorus was mainly mobilized towards the anode end (approx. 60% in the SA and 70% in the SB), whereas heavy metals mainly electromigrated towards the cathode end. The anolyte presented a composition of 98% of P, mainly as orthophosphate, and 2% of heavy metals. The highest heavy metal removal was achieved for Cu (ca. 80%) and the lowest for Pb and Fe (between 4% and 6%). The ED showed to be a viable method for phosphorus recovery from SSA, as it promotes the separation of P from the heavy metals.     

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.     

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.     

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.     

Comparative study on the characteristics of fly ash and bottom ash geopolymers

This research was conducted to compare geopolymers made from fly ash and ground bottom ash. Sodium hydroxide (NaOH) and sodium silicate (Na(2)SiO(3)) solutions were used as activators. A mass ratio of 1.5 Na(2)SiO(3)/NaOH and three concentrations of NaOH (5, 10, and 15M) were used; the geopolymers were cured at 65 degrees C for 48 h. A Fourier transform infrared spectrometer (FT-IR), differential scanning calorimeter (DSC), and scanning electron microscope (SEM) were used on the geopolymer pastes. Geopolymer mortars were also prepared in order to investigate compressive strength. The results show that both fly ash and bottom ash can be utilized as source materials for the production of geopolymers. The properties of the geopolymers are dependent on source materials and the NaOH concentration. Fly ash is more reactive and produces a higher degree of geopolymerization in comparison with bottom ash. The moderate NaOH concentration of 10 M is found to be suitable and gives fly ash and bottom ash geopolymer mortars with compressive strengths of 35 and 18 MPa.     

Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.