Accelerated carbonation of different size fractions of bottom ash from RDF incineration

This paper investigates the effects of accelerated carbonation on the characteristics of bottom ash from refuse derived fuel (RDF) incineration, in terms of CO₂ uptake, heavy metal leaching and mineralogy of different particle size fractions. Accelerated aqueous carbonation batch experiments were performed to assess the influence of operating parameters (temperature, CO₂ pressure and L/S ratio) on reaction kinetics. Pressure was found to be the most relevant parameter affecting the carbonation yield. This was also found to be largely dependent on the specific BA fraction treated, with CO₂ uptakes ranging from ～4% for the coarse fractions to ～14% for the finest one. Carbonation affected both the mineralogical characteristics of bottom ash, with the appearance of neo-formation minerals, and the leaching behaviour of the material, which was found to be mainly related to the change upon carbonation in the natural pH of the ash.     

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.     

Changes in mineralogical and leaching properties of converter steel slag resulting from accelerated carbonation at low CO2 pressure

Steel slag can be applied as substitute for natural aggregates in construction applications. The material imposes a high pH (typically 12.5) and low redox potential (Eh), which may lead to environmental problems in specific application scenarios. The aim of this study is to investigate the potential of accelerated steel slag carbonation, at relatively low pCO₂ pressure (0.2 bar), to improve the environmental pH and the leaching properties of steel slag, with specific focus on the leaching of vanadium. Carbonation experiments are performed in laboratory columns with steel slag under water-saturated and -unsaturated conditions and temperatures between 5 and 90 °C. Two types of steel slag are tested; free lime containing (K3) slag and K1 slag with a very low free lime content. The fresh and carbonated slag samples are investigated using a combination of leaching experiments, geochemical modelling of leaching mechanisms and microscopic/mineralogical analysis, in order to identify the major processes that control the slag pH and resulting V leaching. The major changes in the amount of sequestered CO₂ and the resulting pH reduction occurred within 24 h, the free lime containing slag (K3-slag) being more prone to carbonation than the slag with lower free lime content (K1-slag). While carbonation at these conditions was found to occur predominantly at the surface of the slag grains, the formation of cracks was observed in carbonated K3 slag, suggesting that free lime in the interior of slag grains had also reacted. The pH of the K3 slag (originally pH ± 12.5) was reduced by about 1.5 units, while the K1 slag showed a smaller decrease in pH from about 11.7 to 11.1. However, the pH reduction after carbonation of the K3 slag was observed to lead to an increased V-leaching. Vanadium leaching from the K1 slag resulted in levels above the limit values of the Dutch Soil Quality Decree, for both the untreated and carbonated slag. V-leaching from the carbonated K3 slag remained below these limit values at the relatively high pH that remained after carbonation. The V-bearing di-Ca silicate (C2S) phase has been identified as the major source of the V-leaching. It is shown that the dissolution of this mineral is limited in fresh steel slag, but strongly enhanced by carbonation, which causes the observed enhanced release of V from the K3 slag. The obtained insights in the mineral transformation reactions and their effect on pH and V-leaching provide guidance for further improvement of an accelerated carbonation technology.     

Leaching behaviour of elements and evaluation of pre-treatment methods for municipal solid waste incinerator residues in column leaching tests.

Two new pre-treatment methods (water-washing/carbonation and carbonation/phosphate stabilization) of municipal solid waste (MSW) incinerator residues were evaluated by column leaching tests under aerobic conditions and anaerobic conditions (which were changed to aerobic conditions after 10 months). A mixture of bottom ash and fly ash (5:1 ratio) was pre-treated using each method. Shredded incombustible residues (SIR) were added to each ash preparation in proportions similar to the ratios present in landfills. For comparison, landfill wastes typical of Japan, namely, a mixture of bottom ash, chelating-pre-treated fly ash, and SIR, were also examined. Leachate samples were collected periodically and analysed over a 15-month period. When compared with chelating pretreatment, both water-washing/carbonation and carbonation/ phosphate stabilization reduced the leaching of Pb, Al, and Cu by about one to two orders of magnitude. Moreover, the initial concentrations of Ca and Pb in leachates from column of water-washing/carbonation were 56-57% and 84-96% less than those from the column of carbonation/phosphate stabilization. Therefore, water-washing/carbonation was considered to be a promising approach to obtain early waste stabilization and to reduce the release of heavy metals to near-negligible levels. The leaching behaviour of elements was also discussed.     

Mechanical properties and leaching modeling of activated incinerator bottom ash in Portland cement blends

In the present study the evolution of mechanical strength and the leaching behavior of major and trace elements from activated incinerator bottom ash/Portland cement mixtures were investigated. Chemical and mechanical activation were applied with the purpose of improving the reactivity of bottom ash in cement blends. Chemical activation made use of NaOH, KOH, CaCl₂ or CaSO₄, which were selected for the experimental campaign on the basis of the results from previous studies. The results indicated that CaCl₂ exhibited by far the best effects on the evolution of the hydration process in the mixtures; a positive effect on mechanical strength was also observed when CaSO₄ was used as the activator, while the gain in strength produced by KOH and NaOH was irrelevant. Geochemical modeling of the leaching solutions provided information on the mineral phases responsible for the release of major elements from the hardened materials and also indicated the important role played by surface sorption onto amorphous Fe and Al minerals in dictating the leaching of Pb. The leaching of the other trace metal cations investigated (Cu, Ni and Zn) could not be explained by any pure mineral included in the thermodynamic database used, suggesting they were present in the materials in the form of complex minerals or phase assemblages for which no consistent thermodynamic data are presently available in the literature.     

Environmental behaviour of a construction made of a mixture of hydraulic binders and air pollution control residues from municipal solid waste incineration Part 2. Simulation tests and validation of the source term modelling

The reuse of waste materials requires the development of assessment methods for the long-term release of pollutants (source term) from wastes (or materials containing wastes) in contact with water. These methods depend on the scenario conditions: characteristics of the materials (especially physical structure and composition), contact with water… The scenario studied here is a water storage reservoir for fire extinguishing. The reservoir construction is made of a mixture of hydraulic binders and air pollution control (APC) residues from municipal solid waste incinerator (MSWI). The modelling of the source term is performed in five steps ranging from the physico-chemical characterisation of the material to the validation of the proposed model by means of field simulation devices. This paper follows a first publication on source term modelling using laboratory tests which therefore concerns the comparison of the results obtained with the previously established model. The first laboratory scale simulation test aims at taking into account the role of the leachate carbonation in the leaching behaviour of the studied material. The results obtained show that air carbonation of the leachate does not fundamentally change mass transfer mechanisms of easily soluble species (especially for alkaline metals). For these species, the use of the apparent diffusional model (model proposed in the previous paper) is, therefore, at first, a satisfactory solution for the prediction of long term leaching behaviour. The field scale test enables us to validate and calibrate the release model determined on a laboratory scale basis.     

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.     

Effect of carbonation on the leaching of organic carbon and of copper from MSWI bottom ash

In Flanders, the northern part of Belgium, about 31% of the produced amount of MSWI bottom ash is recycled as secondary raw material. In view of recycling a higher percentage of bottom ash, a particular bottom ash fraction (Ø 0.1–2 mm) was studied. As the leaching of this bottom ash fraction exceeds some of the Flemish limit values for heavy metals (with Cu being the most critical), treatment is required.Natural weathering and accelerated carbonation resulted in a significant decrease of the Cu leaching. Natural weathering during 3 months caused a decrease of Cu leaching to <50% of its original value, whereas accelerated carbonation resulted in an even larger decrease (to ca. 13% of its initial value) after 2 weeks, with the main decrease taking place within the first 48 h.Total organic carbon decreased to ca. 70% and 55% of the initial concentration in the solid phase, and to 40% and 25% in the leachate after natural weathering and after accelerated carbonation, respectively. In the solid material the decrease of the Hy fraction was the largest, the FA concentration remained essentially constant. The decrease of FA in the leachate can be attributed partly to an enhanced adsorption of FA to Fe/Al (hydr)oxides, due to the combined effect of a pH decrease and the neoformation of Al (hydr)oxides (both due to carbonation). A detailed study of adsorption of FA to Fe/Al (hydr)oxides showed that significant adsorption of FA occurs, that it increases with decreasing pH and started above pH 12 for Fe (hydr)oxides and around 10 for Al (hydr)oxides. Depending whether FA or Hy are considered the controlling factor in enhanced Cu leaching, the decreasing FA or Hy in the leachate explains the decrease in the Cu leaching during carbonation.     

Accelerated carbonation of municipal solid waste incineration fly ashes

As a result of the EU Landfill Directive, the disposal of municipal solid waste incineration (MSWI) fly ash is restricted to only a few landfill sites in the UK. Alternative options for the management of fly ash, such as sintering, vitrification or stabilization/solidification, are either costly or not fully developed. In this paper an accelerated carbonation step is investigated for use with fly ash. The carbonation reaction involving fly ash was found to be optimum at a water/solid ratio of 0.3 under ambient temperature conditions. The study of ash mineralogy showed the disappearance of lime/portlandite/calcium chloride hydroxide and the formation of calcite as carbonation proceeded. The leaching properties of carbonated ash were examined. Release of soluble salts, such as SO4, Cl, was reduced after carbonation, but is still higher than the landfill acceptance limits for hazardous waste. It was also found that carbonation had a significant influence on lead leachability. The lead release from carbonated ash, with the exception of one of the fly ashes studied, was reduced by 2-3 orders of magnitude.     

Technical and environmental long-term properties of industrial residues--summary of field and laboratory investigations

In Sweden, use of industrial residues is still hindered by concern for their long-term properties. A three-year research project was therefore initiated aiming to (1) identify the crucial processes of ageing related to the usefulness of residues in roads; (2) investigate the consequences of these processes for technical and environmental properties of the residues, and (3) propose a method for accelerated ageing to predict the long-term properties. This paper gives an overview of the project methodology, a summary of the test results and references to papers where further details are given.The project, running through 2006-2008, compared naturally aged samples of two residues used as sub-bases in existing asphalt paved roads with samples of fresh residues from producers’ piles. Steel slag of electric arc furnace (EAF) type and municipal solid waste incinerator (MSWI) bottom ash were chosen. The samples were thoroughly characterised in order to identify which ageing processes had been crucial.The results showed that:

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Bottom ash from the pavement edge was more aged than bottom ash from the road centre. However, no difference in pH was found, instead the differences were caused by differences in water exposure.

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Steel slag from the pavement edge showed traces of carbonation and leaching processes, whereas slag from the road centre was identical to fresh slag.

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Water exposure to the subbase materials after ten years in an asphalt paved road was calculated to less than 0.1-0.5 litres per kg.

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Ageing reactions in steel slag and MSWI bottom ash, ready for use, were too small to be verified by laboratory measurement of deformation properties under loaded conditions.

An accelerated ageing test for steel slag was set up to achieve the carbonation (decrease in pH) and leaching that was observed in the pavement edge material.An accelerated ageing test for bottom ash was set up to achieve the pozzolan reactions that were observed in SEM analyses of in situ specimens.It is recommended to use uncrushed particles when properties of aged material are studied, in order to preserve the original particle surfaces.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Effects of carbonation and leaching on porosity in cement-bound waste

Porosity is possibly an important parameter with respect to leaching of constituents from cement monoliths. During its lifetime, the pore structure of cementitious matrices changes due to carbonation and leaching. This paper discusses the effects of both accelerated carbonation and continuous leaching on the porosity, and, conversely, how porosity affects leaching properties. Two sample types are investigated: a mortar with MSWI-bottom ash substituting the sand fraction and a cement paste with 30 wt% of the cement substituted by a flue gas cleaning residue. The samples have been intensively carbonated in a 20% CO(2) atmosphere for up to 60 days and were subsequently leached. The porosity was investigated by mercury intrusion porosimetry. Accelerated carbonation decreases total porosity by 12% in the case of 60 days of treatment of bottom ash mortars, whereas continuous leaching during 225 days increases it by 16%. Both carbonation and leaching decrease the amount of smaller capillary pores. Carbonation decreases both porosity and pH. Decreasing porosity diminishes leaching of sodium and potassium, while the decrease in pH increases leaching. However, the former process dominates the latter, resulting in a net decreasing effect of carbonation on the release of sodium and potassium from these cement matrices.     

Temporary stabilization of air pollution control residues using carbonation

Carbonation presents a good prospect for stabilizing alkaline waste materials. The risk of metal leaching from carbonated waste was investigated in the present study; in particular, the effect of the carbonation process and leachate pH on the leaching toxicity of the alkaline air pollution control (APC) residues from municipal solid waste incinerator was evaluated. The pH varying test was conducted to characterize the leaching characteristics of the raw and carbonated residue over a broad range of pH. Partial least square modeling and thermodynamic modeling using Visual MINTEQ were applied to highlight the significant process parameters that controlled metal leaching from the carbonated residue. By lowering the pH to 8-11, the carbonation process reduced markedly the leaching toxicity of the alkaline APC residue; however, the treated APC residue showed similar potential risk of heavy metal release as the raw ash when subjected to an acid shock. The carbonated waste could, thereby, not be disposed of safely. Nonetheless, carbonation could be applied as a temporary stabilization process for heavy metals in APC residues in order to reduce the leaching risk during its transportation and storage before final disposal.     

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.     

Characterization and Leaching of Coal Fly Ash

Physical characteristics, chemical composition and leaching behaviour of a waste fly ash from a coal-fired power station are reported. Particle size distribution was studied by the following techniques: sedimentation in a liquid medium; sedimentation in an air flow; and Fraunhofer diffraction of a laser beam. Results obtained by the different methods are in good agreement. Mineralogical content and chemical composition were determined by X-ray diffraction, electronic microprobe and X-ray fluorescence. Acid leaching of the samples was investigated, using the following strong acids in sequence: HCl+ HNO₃, H₂F₂, HClO₄. Analysis of leachates by atomic absorption shows trace metals In, Tl, Ge, Cu, Ga, Pb, Ni, Co, Mn, Cd, Zn, Cr.In this work fly ashes from a Spanish power plant are characterized according to the type of particles, size distribution and chemical composition by means of physical methods. Three particle size fractions are leached by acids and analysis of trace elements in the leaching liquor is carried out. The concentration of trace metals is somewhat higher in the particles of smallest size.     

Physical containment of municipal solid waste incineration bottom ash by accelerated carbonation

Accelerated carbonation of municipal solid waste incineration residues is effective for immobilizing heavy metals. In this study, the contribution of the physical containment by carbonation to immobilization of some heavy metals was examined by some leaching tests and SEM–EDS analysis of untreated, carbonated, and milled bottom ash after carbonation that was crushed with a mortar to a mean particle size of approximately 1 μm. The surface of carbonated bottom ash particles on SEM images seemed mostly coated, while there were uneven micro-spaces on the surface of the untreated bottom ash. Results of Japan Leaching Test No. 18 (JLT18) for soil pollution showed that milling carbonated bottom ash increased the pH and EC. The leaching concentration of each element tended to be high for untreated samples, and was decreased by carbonation. However, after the milling of carbonated samples, the leaching concentration became high again. The immobilization effect of each element was weakened by milling. The ratio of physical containment effect to immobilization effects by accelerated carbonation was calculated using the results of JLT18. The ratio for each element was as follows: Pb: 13.9–69.0 %, Cu: 12.0–49.1 %, Cr: 24.1–99.7 %, Zn: 20.0–33.3 %, and Ca: 28.9–63.4 %.     

Mineralogy and pore water chemistry of a boiler ash from a MSW fluidized-bed incinerator

This paper presents an investigation of the mineralogy and pore water chemistry of a boiler ash sampled from a municipal solid waste fluidized-bed incinerator, subject to 18 months of dynamic leaching in a large percolation column experiment. A particular focus is on the redox behaviour of Cr(VI) in relation to metal aluminium Al⁰, as chromium may represent an environmental or health hazard. The leaching behaviour and interaction between Cr(VI) and Al⁰ are interpreted on the basis of mineralogical evolutions observed over the 18-month period and of saturation indices calculated with the geochemical code PhreeqC and reviewed thermodynamic data. Results of mineralogical analyses show in particular the alteration of mineral phases during leaching (e.g. quartz and metal aluminium grains), while geochemical calculations suggest equilibria of percolating fluids with respect to specific mineral phases (e.g. monohydrocalcite and aluminium hydroxide). The combination of leaching data on a large scale and mineralogical analyses document the coupled leaching behaviour of aluminium and chromium, with chromium appearing in the pore fluids in its hexavalent and mobile state once metal aluminium is no longer available for chromium reduction.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.