Characterization of alkali-activated thermally treated incinerator bottom ash

The fine fraction (<14mm) of incinerator bottom ash (IBA) obtained from a UK energy from waste plant has been milled and thermally treated at 600, 700, 800 and 880 degrees C. Treated materials have been activated with Ca(OH)(2) (10wt%) and the setting times and compressive strengths at different curing times measured. In addition to decomposition of CaCO(3) to CaO, thermal treatment increases the content of gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)). Thermally treated samples were significantly more reactive than milled IBA and heating to 700 degrees C produced a material which rapidly set. Silica, gehlenite and wollastonite were the main crystalline phases present in hydrated samples and a mixed sulphate-carbonate AFm-type phase (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33).11H(2)O) formed. Significant volumes of gas were generated during curing and this produced a macro-porous microstructure that limited strength to 2.8MPa. The new materials may have potential for use as controlled low-strength materials.     

Influences of chemical activators on incinerator bottom ash

This research has applied different chemical activators to mechanically and thermally treated fine fraction (<14 mm) of incinerator bottom ash (IBA), in order to investigate the influences of chemical activators on this new pozzolanic material. IBA has been milled and thermally treated at 800 degrees C (TIBA). The TIBA produced was blended with Ca(OH)(2) and evaluated for setting time, reactivity and compressive strength after the addition of 0.0565 mole of Na(2)SO(4), K(2)SO(4), Na(2)CO(3), K(2)CO(3), NaOH, KOH and CaCl(2) into 100g of binder (TIBA+Ca(OH)(2)). The microstructures of activated IBA and hydrated samples have been characterized by X-ray diffraction (XRD) and thermogravimetry (TG) analysis. Thermal treatment is found to produce gehlenite (Ca(2)Al(2)SiO(7)), wollastonite (CaSiO(3)) and mayenite (Ca(12)Al(14)O(33)) phases. The thermally treated IBA samples are significantly more reactive than the milled IBA. The addition of Na(2)CO(3) can increase the compressive strength and calcium hydroxide consumption at 28-day curing ages. However, the addition of Na(2)SO(4), K(2)SO(4), K(2)CO(3), NaOH and KOH reduces the strength and hydration reaction. Moreover, these chemicals produce more porous samples due to increased generation of hydrogen gas. The addition of CaCl(2) has a negative effect on the hydration of TIBA samples. Calcium aluminium oxide carbonate sulphide hydrate (Ca(4)Al(2)O(6)(CO(3))(0.67)(SO(3))(0.33)(H(2)O)(11)) is the main hydration product in the samples with activated IBA, except for the sample containing CaCl(2).     

Evolution of iron speciation during hydration of C4AF

It is now well accepted and demonstrated that calcium silicate, calcium aluminate and calcium sulfo aluminate (ettringite, AFm) phases exhibit a good capability to fix metals and metalloids. Unfortunately the role of minor phases and especially calcium-ferric aluminate phase, shorthand C4AF is not well defined. In other systems like in soils or sediments iron phases play a key role in the fixation of pollutant. In cement sorption isotherms, indicated that various metals can be retained by the C4AF hydrated products. Therefore the capabilities of those phase to retain heavy metal should not be neglected. Previous investigations have shown that the minerals formed during the hydration of C4AF are similar to those formed from C3A (pure tri-calcium aluminate) under comparable conditions. Nevertheless no investigation was conducted at the molecular level and there is still a controversy whether Fe substitutes for Al in the hydrated minerals in whole or in part, or if it forms FeOOH clusters scattered throughout the matrix. In this context we have conducted XAS experiments using synchrotron radiation. It was found that the hydration of C4AF forms C3AH6 (hydrogarnet) in which Fe randomly substitutes for Al as well as an amorphous FeOOH phase. Intermediate products like AFm (i.e., an ill organized lamellar phase) are also formed but rapidly evolve to C3AH6; iron does not seem to be incorporated in the AFm structure.     

Crystal-chemistry of alteration products of vitrified wastes: implications on the retention of polluting elements

Alteration products of vitrified wastes coming from the incineration of household refuse (MSW) are described. Two vitrified wastes containing 50% and 70% of fly ash and a synthetic stained-glass with a composition close to that of an ancient glass (medieval stained-glass) were altered under different pH conditions (1, 5.5 corresponding to demineralized water and 10) during 181 days. Under acidic condition, the alteration layer is made of an amorphous hydrated silica gel impoverished in most of the initial elements. A minor phase MPO(4)*nH(2)O, where M represents Fe, Ti, Al, Ca and K cations, also constitutes the altered layer of the synthetic stained-glass. Under neutral and basic conditions, the altered layer is made of an amorphous hydrated silica gel and a crystallized calcium phosphate phase. The silica gel is depleted in alkalis and alkali-earth elements but contains significant amounts of aluminium, magnesium and transition elements, whereas the calcium phosphate is a hydroxylapatite-like phase with P-Si substitutions and a Ca/P ratio depending on the pH of the solution. This study shows: (i) the strong influence of pH conditions on the crystal-chemistry of alteration products and thus on the mechanisms of weathering resulting in different trapping of polluting elements, and (ii) that glass alteration does not necessary produce thermodynamically stable phases which has to be taken into account for the prediction of the long-term behavior.     

Nickel immobilization in ceramic matrix admixed with waste nickel hydroxide

WAXS examinations performed with nickel hydroxide samples heated to various temperatures showed that freshly settled wet nickel hydroxide sample contains some amount of crystalline beta-Ni(OH)(2) structure and its share increased when sample was dried during 3 weeks at ambient temperature. However, the share significantly decreased when the sample was dried at 110 degrees C and more so at 250 degrees C. Crystalline phase traces of Ni(OH)(2) disappeared after sample burning at 980 degrees C and instead the distinct presence of crystalline NiO was determined. The above samples were examined for solubility in stoichiometric amount of sulphuric acid diluted with water to pH 1.9 and 2.8. Solubility was determined by measuring nickel ion concentration in leachate by the AAS method. The dissolving rate was found to decrease with the rise of temperature to which the nickel hydroxide samples were heated. The solubility of Ni(OH)(2) sample burnt at 980 degrees C was undetectable during 90 h solubility-testing time likely due to its transformation into sparingly soluble crystalline NiO. The latter is considered to be the reason for effective immobilization of waste nickel hydroxide in ceramic prepared by blending with clay and sintering at 980 degrees C.     

A thermodynamic approach to the hydration of sulphate-resisting Portland cement

A thermodynamic approach is used to model changes in the hydrate assemblage and the composition of the pore solution during the hydration of calcite-free and calcite-containing sulphate-resisting Portland cement CEM I 52.5 N HTS. Modelling is based on thermodynamic data for the hydration products and calculated hydration rates for the individual clinker phases, which are used as time-dependent input parameters. Model predictions compare well with the composition of the hydrate assemblage as observed by TGA and semi-quantitative XRD and with the experimentally determined compositions of the pore solutions. The calculations show that in the presence of small amounts of calcite typically associated with Portland cement, C-S-H, portlandite, ettringite and calcium monocarbonate are the main hydration products. In the absence of calcite in the cement, however, siliceous hydrogarnet instead of calcium monocarbonate is observed to precipitate. The use of a higher water-to-cement ratio for the preparation of a calcite-containing cement paste has a minor effect on the composition of the hydrate assemblage, while it significantly changes the composition of the pore solution. In particular, lower pH value and higher Ca concentrations appear that could potentially influence the solubility and uptake of heavy metals and anions by cementitious materials.     

Solidification/stabilisation of arsenic bearing fly ash from the metallurgical industry. Immobilisation mechanism of arsenic

When a fly ash waste material from a copper refining process containing large amounts of As2O3 is solidified using cement and lime, the arsenic concentration in the leachate can be lowered to ca. 5 mg/l in a saturated solution of Ca(OH)2. It is shown that the decrease of the concentration in the leachate, mainly of As(III), is due to the formation of insoluble CaHAsO3 in the leachate in the presence of Ca(OH)2. This method is compared with a method whereby use is made of oxidation of the waste before solidification to oxidise As(III) to As(V) using H2O2. The arsenic concentration in the leachate of the extraction test of an oxidised S/S sample was lowered to ca. 0.5 mg/l, a factor of 10 below the one for a non-oxidised sample. It is shown that the decrease of the concentration in the leachate mainly of As(V) is due to the formation of insoluble Ca3(AsO4)2 in the presence of Ca(OH)2. Extensive use was made of the speciation program MINTEQA2, to clarify the immobilisation of arsenic.     

Ceramic processing of incinerator bottom ash

The <8 mm fraction of aged incinerator bottom ash from a commercial incinerator (energy from waste) plant has been collected at regular intervals, characterised and processed to form ceramic materials. Ashes were sieved, wet ball milled, dried, compacted and sintered at temperatures between 1080 and 1115 degrees C. Variations in the chemical composition and mineralogy of the milled ash, and the mineralogy, physical properties and leaching of sintered products have been assessed. Milling produces a raw material with consistent chemical and mineralogical composition with quartz (SiO(2)), calcite (CaCO(3)), gehlenite (Ca(2)Al(AlSi)O(7)) and hematite (Fe(2)O(3)) being the major crystalline phases present. Different batches also milled to give consistent particle size distributions. Sintering milled incinerator bottom ash at 1110 degrees C produced ceramics with densities between 2.43 and 2.64 g/cm(-3) and major crystalline phases of wollastonite (CaSiO(3)) and diopside (CaMgSi(2)O(6)). The sintered ceramics had reduced acid neutralisation capacity compared to the as-received ash and exhibited reduced leaching of Ca, Mg, Na and K under all pH conditions. The leaching of heavy metals was also significantly reduced due to encapsulation and incorporation into glassy and crystalline phases, with Cu and Al showing greatly reduced leaching under alkali conditions.     

Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Removal of cadmium ion by means of synthetic hydroxyapatite

The reaction behaviour of synthetic hydroxyapatite [Ca10(PO4)6(OH)2] (HAP) toward cadmium ion was investigated for the Cd/Ca molar ratio in the range 1-0.005, by means of ions, pH measurements and XRD, SEM, IR techniques. The reaction behaviour between HAP and cadmium ion could be explained by a formation of an amorphous phase and/or a sorption mechanism.     

Comparison of two types of municipal solid waste incinerator fly ashes with different alkaline reagents in washing experiments

In this study, we propose a "washing-calcination-conversion of washed fly ash into cement material with bottom ash" (WCCB) system to reduce the amount of fly ash that must be specially treated so it can be used as raw cement material. Calcium hydroxide (Ca(OH)2) is widely used in air-pollution control devices of incinerators while sodium bicarbonate (NaHCO3) is not. We conducted single-, double-, and triple-washing experiments to compare the washing characteristics of two types of fly ash. Unlike NaHCO3 fly ash, Ca(OH)2 fly ash has almost twice as much washed residue and almost 2.5 times more chlorine after the same washing procedure. After washing once, the washing frequency is also important for NaHCO3 fly ash, while the mixing time and liquid/solid ratio are more critical for Ca(OH)2 fly ash. The use of NaHCO3 is more suitable for the WCCB system.     

Understanding the chemical and mineralogical properties of the inorganic portion of MSWI bottom ash

This paper investigates the changes of mineralogical composition of bottom ash in the environment. The chemical and mineralogical bulk composition was determined by X-ray fluorescence (XRF) and X-ray powder diffraction (XRPD) Rietveld method. Single bottom ash particles were investigated by optical microscopy, scanning electron microscopy with quantitative energy-dispersive X-ray microanalysis (SEM/EDX) and electron probe micro analysis (EPMA). SEM/EDX and EPMA are valuable complement to bulk analysis and provide means for rapid and sensitive multi-elemental analysis of ash particles. The fresh bottom ash consists of amorphous (>30 wt.%) and major crystalline phases (>1 wt.%) such as silicates, oxides and carbonates. The mineral assemblage of the fresh bottom ash is clearly unstable and an aging process occurs by reaction towards an equilibrium mineral phase composition in the environmental conditions. The significant decrease of anhydrite and amorphous contents was observed in the aged bottom ash, leading to the formation of ettringite, hydrocalumite and rosenhahnite under atmospheric conditions. In the water-treated sample, the calcite contents increased significantly, but ettringite was altered by the dissolution and precipitation processes in part, to produce gypsum, while the remaining part reacted with chloride to form hydrocalumite. Gypsum and other Ca based minerals may take up substantial amounts of heavy metals and subsequently control leaching behaviour of bottom ash.     

Petrographic and spectroscopic characterization of phosphate-stabilized mine tailings from Leadville,Colorado

The use of soluble PO4(3-) and lime as a heavy metal chemical stabilization agent was evaluated for mine tailings from Leadville, Colorado. The tailings are from piles associated with the Wolftone and Maid of Erin mines; ore material that was originally mined around 1900, reprocessed in the 1940s, and now requires stabilization. The dominant minerals in the tailings are galena (PbS), cerrusite (PbCO3), pyromorphite (Pb5(PO4)3Cl), plumbojarosite (Pb0.5Fe3(SO4)2(OH)6), and chalcophanites ((Pb,Fe,Zn,Mn)Mn2O5 x 2H2O). The tailings were treated with soluble PO4(3-) and lime to convert soluble heavy metals (principally Pb, Zn, Cu, Cd) into insoluble metal phosphate precipitates. The treatment process caused bulk mineralogical transformations as well as the formation of a reaction rind around the particles dominated by Ca and P. Within the mineral grains, Fe-Pb phosphosulfates, Fe-Pb sulfates (plumbojarosite), and galena convert to Fe-Ca-Pb hydroxides. The Mn-Pb hydroxides and Mn-(+/-Fe)-Pb hydroxides (chalcophanites) undergo chemical alteration throughout the grains during treatment. Bulk and surface spectroscopies showed that the insoluble reaction products in the rind are tertiary metal phosphate (e.g. (Cu,Ca2)(PO4)2) and apatite (e.g. Pb5(PO4)3Cl) family minerals. pH-dependent leaching (pH 4,6,8) showed that the treatment was able to reduce equilibrium concentrations by factors of 3 to 150 for many metals; particularly Pb2+, Zn2+, Cd2+, and Cu2+. Geochemical thermodynamic equilibrium modeling showed that apatite family and tertiary metal phosphate phases act as controlling solids for the equilibrium concentrations of Ca2+, PO4(3-) Pb2+, Zn2+, Cd2+, and Cu2+ in the leachates during pH-dependent leaching. Both end members and ideal solid solutions were seen to be controlling solids.     

Utilizing a database to interpret leaching characteristics of lead from bottom ashes of municipal solid waste incinerators

This study focuses on evaluation and quantification of factors affecting leachability of lead from bottom ashes of municipal solid waste incinerators (MSWI) by utilizing a database. The database, which was constructed with data collected from sources such as research papers, questionnaires and reports, consists of 1149 data sets on 508 MSWI plants. Factors chosen as affecting lead leachability included: pH in the leachate, loss on ignition of bottom ash, total content of lead, and content of main elements such as Fe, Mn, Si and Al. The lead leachability was reduced to a minimum at neutral pH, increased with increasing pH and, especially, showed an abrupt increase at pH levels above 12. The main factor controlling the pH of the leachate appeared to be leachable Ca(2+) originating from portlandite (Ca(OH)(2)). Leaching concentration increased with increasing total contents of lead, and the relationship between leaching of lead and loss on ignition showed no distinct tendencies. The lead leaching ratio increased with decreasing total contents of Si, Mn and Fe. It is evident, therefore, that these numerous factors determine the leachability of lead in a simultaneous and complex manner.     

The effect of supercritical carbon dioxide treatment on the leachability and structure of cemented radioactive waste-forms

The former process for the cementation of transuranic (TRU) low-level wastes poses several technical problems. Specifically in the US a TRU waste-form has not yet passed the Waste Isolation Pilot Plant prohibition for free liquid. For this reason, treatment of the portland cement based waste-form with supercritical carbon dioxide (SCCO₂) is shown to satisfy regulations. The effect of SCCO₂ treatment by applying different CO₂ pressure and temperature conditions (8.4 MPa<p<28 MPa, 35°C<T<62°C) on the leachability, phase constitution, and microstructure of surrogate-doped portland cement type I/II samples is presented. Leaching studies were performed using a synthetic groundwater leaching procedure. Changes in phase constitution of the major crystalline phases (Ca(OH)₂, CaCO₃) as well as the microstructure were measured by X-ray diffraction and scanning electron microscopy. SCCO₂ treatment at 8.4 MPa and 35°C can be shown as the most promising conditions to satisfy the requirements of the Department of Transportation (DOT) and to enhance the natural aging reaction of cement paste by carbonation, combined with the lowest release rates of the surrogates ²³²Th, and ^151/153Eu.     

Characterization of MSWI bottom ashes towards utilization as glass raw material

The characterization of the bottom ashes produced by two Portuguese municipal solid waste incinerators (MSWI) was performed with the aim of assessing the feasibility of using this waste as raw material in the production of glass that can be further processed as glass-ceramics for application in construction. Density and particle size distribution measurements were carried out for physical characterization. Chemical characterization revealed that SiO(2), a network glass former oxide, was present in a relatively high content (52-58wt%), indicating the suitability for this waste to be employed in the development of vitreous materials. CaO, Na(2)O and K(2)O, which act as fluxing agents, were present in various amounts (2-17wt%) together with several other oxides normally present in ceramic and glass raw materials. Mineralogical characterization revealed that the main crystalline phases were quartz (SiO(2)) and calcite (CaCO(3)) and that minor amounts of different alkaline and alkaline-earth aluminosilicate phases were also present. Thermal characterization showed that the decomposition of the different compounds occurred up to 1100 degrees C and that total weight loss was <10wt%. Heating both bottom ashes at 1400 degrees C for 2h resulted in a melt with suitable viscosity to be poured into a mould, and homogeneous black-coloured glasses with a smooth shiny surface were obtained after cooling. The vitrified bottom ashes were totally amorphous as confirmed by X-ray diffraction. The results from the present experimental work indicate that the examined bottom ashes can be a potential material to melt and to obtain a glass that can be further processed as glass-ceramics to be applied in construction.     

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.     

The effect of accelerated carbonation on the properties of cement-solidified waste forms

Ordinary Portland cement blended with blast furnace slag and pulverised fuel ash was used to solidify two industrial wastes containing large amounts of metals. The solidified mixes were carbonated using an accelerated regime previously established and compared for strength development, leaching characteristics and phase development against their non-carbonated analogues. A significant difference in the immobilisation of metals such as Zn, Ni and As was recorded for samples in which carbonation was optimised. The work has shown that by controlling mix parameters it is possible to improve the immobilisation of specific metals. Electron microanalysis showed that this is partly due to the precipitation of calcite in the solidified waste pore structure. Carbonation was also found to accelerate C₃S hydration in all carbonated samples and to modify the morphology of residual cement grains through the formation of a calcite coating over de-calcified hydration rims. Some metals appear to be incorporated in both of these zones.     

超滤膜系统污染物的形貌及组成分析

通过SEM、能谱、FTIR以及电感耦合等离子体质谱的分析方法对被污染超滤膜面的无机污染物、有机污染物和微生物进行了识别和分析。研究结果表明:超滤膜面无机污染物主要为Fe(OH)3、Cu(OH)2、Al(OH)3和Si等胶体物和少量CaSO4;有机污染物主要为多菌霉素类化合物;微生物可能富含铁类化合物。同时污染膜的清洗液分析结果说明该超滤膜污染物主要为无机胶体和有机物。     

Nitrate and nitrite injection during municipal solid waste anaerobic biodegradation

Nitrified leachate recirculation has been proposed as a promising strategy for sustainable landfill management. In four test reactors, nitrate or nitrite was added (250 mg N-NO(x)(-)L(-1)) during municipal solid waste biodegradation. Nitrogen-oxides reduction reactions were monitored. Denitrification was the main nitrogen reducing reaction observed. On one hand, during the acidogenic waste degradation phase, as high amounts of volatile fatty acids (VFA) were present, nitrogen-oxides reductions were interpreted as heterotrophic denitrifications. On the other hand, denitrification reactions occurring during the late methanogenic phase were accompanied by sulphate productions and, as VFA were not detected, it was probably an autotrophic reaction. Denitrification inhibition was observed once. Ammonium concentration increased suggesting the occurrence of a dissimilatory nitrate reduction to ammonium (DNRA). Statistical treatment of analytical data revealed that only H(2)S concentration had a significant negative effect on N(2) production in our system. NO production was observed once when nitrite was injected during the acidogenic phase resulting in a total waste degradation inhibition. These results indicate that the consequences of nitrified leachate recirculation in full-scale landfills need to be carefully examined especially during the acidogenic phase or in the presence of waste containing high quantities of sulphur.