Environmental assessment of incinerator residue utilisation

Incineration ashes may be treated either as a waste to be dumped in landfill, or as a resource that is suitable for re-use. In order to choose the best management scenario, knowledge is needed on the potential environmental impact that may be expected, including not only local, but also regional and global impact. In this study, A life cycle assessment (LCA) based approach was outlined for environmental assessment of incinerator residue utilisation, in which leaching of trace elements as well as other emissions to air and water and the use of resources were regarded as constituting the potential environmental impact from the system studied. Case studies were performed for two selected ash types, bottom ash from municipal solid waste incineration (MSWI) and wood fly ash. The MSWI bottom ash was assumed to be suitable for road construction or as drainage material in landfill, whereas the wood fly ash was assumed to be suitable for road construction or as a nutrient resource to be recycled on forest land after biofuel harvesting. Different types of potential environmental impact predominated in the activities of the system and the use of natural resources and the trace element leaching were identified as being relatively important for the scenarios compared. The scenarios differed in use of resources and energy, whereas there is a potential for trace element leaching regardless of how the material is managed. Utilising MSWI bottom ash in road construction and recycling of wood ash on forest land saved more natural resources and energy than when these materials were managed according to the other scenarios investigated, including dumping in landfill.     

Leaching of wood ash products aimed for spreading in forest floors--influence of method and L/S ratio

Use of biofuels in the form of logging residues is increasing in the European countries. This intensive forestry, where entire trees are removed from the felling sites, may contribute to a negative nutrient balance in the forest soil. Recycling of ash from the combustion of clean wood fuel, sometimes in combination with limestone or additives/binders, back into the forest soil could maintain the soil nutrient reservoir intact. Before spreading ash, it is important to determine its contents and, particularly, its decomposition pattern using reliable laboratory leaching tests. In this study, mineralogy and the leaching of Na, Ca, K, Mg, Mn, Al, Cu, Fe, P, and Zn from wood ash pellets and granules, produced both from green liquor sludge and fly ash, are examined by XRD and by subjecting these substances to three different laboratory leaching tests: upflow percolation (CEN/TS 14405), batch leaching (SS-EN12457), and a new Swedish leaching test using a magnetic stirrer. Mineral phases such as quartz, ettringite, calcite, gehlenite, and aphtitalite were identified in the ash granules and in the ash/green liquor sludge granules, by means of XRD. Six additional minerals were detected in the granules of ash only, and another six in the ash/green liquor sludge granules. At L/S 2, the batch leaching test resulted in the highest amounts of elements leached and the upflow percolation test the lowest. At L/S 10, both the batch leaching test and the upflow percolation test resulted in high amounts of elements leached. The batch leaching test at L/S 10 complies quite well with the percolation test and could be suitable for ash/green liquor sludge granule evaluation in daily practice. The magnetic stirrer test seems to underestimate the release potential of elements from granules. The batch test is simple to perform, and has the ability to dissolve 70-80% of the elements with the highest mobility from the materials under study.     

PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Quantifying the availability and the stability of trace cationic elements in fly ash

For adsorption-desorption controlled leaching processes, the total leachable mass and the adsorption constant are parameters representing the availability and the stability of trace elements in solid media. With these parameters, one can predict the leaching behavior of trace elements from solids under various pH and solid-to-liquid ratio conditions. An approach was developed in this paper to determine these parameters for model elements Cu(II), Cd(II), and Ni(II) in fly ash. This approach consists of a batch equilibrium titration, a batch equilibrium leaching with and without target element addition, and mathematical modeling. Results indicated that the adsorption constant of a trace element can be determined by modeling the adsorption ratio of the added element to the system as a function of pH. Results also indicated that the trace element originally present in fly ash had similar adsorption-desorption behavior as that added externally. By modeling the batch leaching data with and without external element addition, the total leachable mass and adsorption constant of the target element can be determined simultaneously. The total leachable mass is in agreement with experimental data from 50mM EDTA extraction.     

Color analysis of combustion ashes of seawater-soaked wood: estimation of salt concentration

The color of wood ash is normally white, but black color ash was observed when seawater-soaked wood was combusted. In order to check the conditions for generation of black ash, we examined both ashing temperatures from 500 to 800 °C and seawater salt densities for wood soaking. As seawater salt densities rose, the ash color got black at ashing temperatures of 500 and 700 °C. The colors of the ash were analyzed by a spectrophotometer, and color space L* a* b* was measured. The L* value and wood ash yield showed a negative correlation when the ashing temperature was at 600 °C. Salt concentration in wood (SC) was practicably estimated from the L* value (R ² = 0.51) by the approximation formula [SC (%) = 11.82e^?0.038L*]. By scanning electron microscope (SEM) observation, black ash of 600 °C was fully covered by translucent material. It was composed of Na, Mg and Cl by energy dispersive X-ray spectroscopy analysis, and seemed to be crystallized seawater salt. Washed black ash was also observed by SEM, translucent seawater salt was removed and the wood tissue was observed. Black ash was found to be carbonized wood tissue residue, and it was generated when seawater salt exists with a woody biomass.     

The effects of accelerated carbonation on CO2 uptake and metal release from incineration APC residues

This work presents the results of a study on accelerated carbonation of incinerator air pollution control residues, with a particular focus on the modifications in the leaching behaviour of the ash. Aqueous carbonation experiments were carried out using 100% CO₂ at different temperatures, pressures and liquid-to-solid ratios, in order to assess their influence on process kinetics, CO₂ uptake and the leaching behaviour of major and trace elements. The ash showed a particularly high reactivity towards CO₂, owing to the abundance of calcium hydroxides phases, with a maximum CO₂ uptake of ～250 g/kg. The main effects of carbonation on trace metal leaching involved a significant decrease in mobility for Pb, Zn and Cu at high pH values, a slight change or mobilization for Cr and Sb, and no major effects on the release of As and soluble salts. Geochemical modelling of leachates indicated solubility control by different minerals after carbonation. In particular, in the stability pH range of carbonates, solubility control by a number of metal carbonates was clearly suggested by modelling results. These findings indicate that accelerated carbonation of incinerator ashes has the potential to convert trace contaminants into sparingly soluble carbonate forms, with an overall positive effect on their leaching behaviour.     

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.     

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.     

Element associations in ash from waste combustion in fluidized bed

The incineration of MSW in fluidized beds is a commonly applied waste management practice. The composition of the ashes produced in a fluidized bed boiler has important environmental implications as potentially toxic trace elements may be associated with ash particles and it is therefore essential to determine the mechanisms controlling the association of trace elements to ash particles, including the role of major element composition. The research presented here uses micro-analytical techniques to study the distribution of major and trace elements and determine the importance of affinity-based binding mechanisms in separate cyclone ash particles from MSW combustion. Particle size and the occurrence of Ca and Fe were found to be important factors for the binding of trace elements to ash particles, but the binding largely depends on random associations based on the presence of a particle when trace elements condensate in the flue gas.     

High temperature air-blown woody biomass gasification model for the estimation of an entrained down-flow gasifier

A high temperature air-blown gasification model for woody biomass is developed based on an air-blown gasification experiment. A high temperature air-blown gasification experiment on woody biomass in an entrained down-flow gasifier is carried out, and then the simple gasification model is developed based on the experimental results. In the experiment, air-blown gasification is conducted to demonstrate the behavior of this process. Pulverized wood is used as the gasification fuel, which is injected directly into the entrained down-flow gasifier by the pulverized wood banner. The pulverized wood is sieved through 60 mesh and supplied at rates of 19 and 27kg/h. The oxygen-carbon molar ratio (O/C) is employed as the operational condition instead of the air ratio. The maximum temperature achievable is over 1400K when the O/C is from 1.26 to 1.84. The results show that the gas composition is followed by the CO-shift reaction equilibrium. Therefore, the air-blown gasification model is developed based on the CO-shift reaction equilibrium. The simple gasification model agrees well with the experimental results. From calculations in large-scale units, the cold gas is able to achieve 80% efficiency in the air-blown gasification, when the woody biomass feedrate is over 1000kg/h and input air temperature is 700K.     

Leaching of heavy metals from chromated copper arsenate (CCA) treated wood after disposal

Wood treated by preservatives is commonly found in solid waste. Among the different types of preserved wood, chromated copper arsenate (CCA) treated wood recently has received much attention due to the scale of usage and its significant role in soil and water contamination. As the ash of CCA treated wood would be hazardous if the wood were to be incinerated, this is not a good alternative, and the best available disposal method is thus landfilling in the US, Canada and Australia. Leaching of the metals from preserved wood that is disposed in unlined landfills for construction debris pollutes the soil and water environments. Several factors affecting leaching of the metals from wood, including pH of the leachant, temperature, the duration of leaching and the type of leachant, were investigated. These factors affect each of the metals, chromium, copper and arsenic, differently. A comparison of these effects on each metal was performed. The results of the experiments showed that the pH of the leachants has a significant effect on the leaching process, and sulfuric acid (pH 3) is the most effective leachant compared to nitric and acetic acid (pH 3-4-5). The amounts of leached chromium, copper and arsenic by sulfuric acid (pH 3) during 15 days were, respectively, 0.2, 0.14 and 0.15 mg more than leachates by nitric acid (pH 5) on the basis of 1g of wood (initial contents of 1.03 mg, 0.42 g and 0.8 mg per g of wood). Most of the leaching occurs in the first 5 days, and the rate of leaching decreases significantly after 5 days. Increasing temperature increases the amount of leached metals, and arsenic is the least resistant metal to the leaching when the temperature increases. Increasing the temperature from 15 degrees C to 35 degrees C during 15 days increases the amount of leached chromium, copper and arsenic by acetic acid at pH 5 by about 0.1, 0.4 and 1.2mg per g of wood, respectively.     

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.     

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

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

Calcium phosphate stabilization of fly ash with chloride extraction

Municipal solid waste incinerator by products include fly ash and air pollution control residues. In order to transform these incinerator wastes into reusable mineral species, soluble alkali chlorides must be separated and toxic trace elements must be stabilized in insoluble form. We show that alkali chlorides can be extracted efficiently in an aqueous extraction step combining a calcium phosphate gel precipitation. In such a process, sodium and potassium chlorides are obtained free from calcium salts, and the trace metal ions are immobilized in the calcium phosphate matrix. Moderate calcination of the chemically treated fly ash leads to the formation of cristalline hydroxylapatite. Fly ash spiked with copper ions and treated by this process shows improved stability of metal ions. Leaching tests with water or EDTA reveal a significant drop in metal ion dissolution. Hydroxylapatite may trap toxic metals and also prevent their evaporation during thermal treatments. Incinerator fly ash together with air pollution control residues, treated by the combined chloride extraction and hydroxylapatite formation process may be considered safe to use as a mineral filler in value added products such as road base or cement blocks.     

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%).     

Effect of sewage sludge content on gas quality and solid residues produced by cogasification in an updraft gasifier

In the present work, the gasification with air of dehydrated sewage sludge (SS) with 20wt.% moisture mixed with conventional woody biomass was investigated using a pilot fixed-bed updraft gasifier. Attention was focused on the effect of the SS content on the gasification performance and on the environmental impact of the process. The results showed that it is possible to co-gasify SS with wood pellets (WPs) in updraft fixed-bed gasification installations. However, at high content of sewage sludge the gasification process can become instable because of the very high ash content and low ash fusion temperatures of SS. At an equivalent ratio of 0.25, compared with wood pellets gasification, the addition of sewage sludge led to a reduction of gas yield in favor of an increase of condensate production with consequent cold gas efficiency decrease. Low concentrations of dioxins/furans and PAHs were measured in the gas produced by SS gasification, well below the limiting values for the exhaust gaseous emissions. NH(3), HCl and HF contents were very low because most of these compounds were retained in the wet scrubber systems. On the other hand, high H(2)S levels were measured due to high sulfur content of SS. Heavy metals supplied with the feedstocks were mostly retained in gasification solid residues. The leachability tests performed according to European regulations showed that metals leachability was within the limits for landfilling inert residues. On the other hand, sulfate and chloride releases were found to comply with the limits for non-hazardous residues.     

Mobility of organic carbon from incineration residues

Dissolved organic carbon (DOC) may affect the transport of pollutants from incineration residues when landfilled or used in geotechnical construction. The leaching of dissolved organic carbon (DOC) from municipal solid waste incineration (MSWI) bottom ash and air pollution control residue (APC) from the incineration of waste wood was investigated. Factors affecting the mobility of DOC were studied in a reduced 2(6-1) experimental design. Controlled factors were treatment with ultrasonic radiation, full carbonation (addition of CO2 until the pH was stable for 2.5h), liquid-to-solid (L/S) ratio, pH, leaching temperature and time. Full carbonation, pH and the L/S ratio were the main factors controlling the mobility of DOC in the bottom ash. Approximately 60 weight-% of the total organic carbon (TOC) in the bottom ash was available for leaching in aqueous solutions. The L/S ratio and pH mainly controlled the mobilization of DOC from the APC residue. About 93 weight-% of TOC in the APC residue was, however, not mobilized at all, which might be due to a high content of elemental carbon. Using the European standard EN 13 137 for determination of total organic carbon (TOC) in MSWI residues is inappropriate. The results might be biased due to elemental carbon. It is recommended to develop a TOC method distinguishing between organic and elemental carbon.     

Heavy metal speciation in various types of fly ash from municipal solid waste incinerator

Fly ash (FA) from municipal solid waste incinerators has been known as hazardous waste, which is mostly because of the high content of heavy metal and dioxins. Besides the content, the form of the heavy metals in fly ash is also very important, because it is tightly related with the leaching behavior of fly ash in diverse circumstances. To evaluate the environment potential risk of fly ash, the Tessier chemical extraction method was adopted. In this study, four kinds of fly ash were examined, one sample from China (CFA) and the other three from Japan (RFA, CaFA and NaFA). Five metal elements were detected and they were Ni, Cr, Cd, Pb, and Cu. The result of total heavy metals’ concentration showed CFA has the lowest content. As to the Tessier chemical extraction experiments, the results show that Cd, Pb, and Cu have higher leaching risk in the environment than other heavy metals. The result of leaching test experiment showed that the more exchangeable speciation of Cd, Cr and Pb in FA, the more it could leach out in natural environment.     

Leaching behavior of heavy metals and PAHs from MSWI bottom ash in a long-term static immersing experiment

Bottom ash is the main solid residue (in weight) which is produced by municipal solid waste incineration (MSWI) facilities. This material is composed of a mineral matrix and may be used as secondary raw material for construction purpose. However, for this specific application the leaching behavior of the environmentally relevant elements under field conditions is different from the predicted behavior based on results obtained from the standardized leaching test. Therefore, a 70-day simulative experiment has been carried out in this study to investigate the release of major heavy metals (Cu and Pb) and polycyclic aromatic hydrocarbons (PAHs) from several particle fractions of bottom ash under a static leaching condition, where bottom ash was immersed in water at different initial pH values. Results showed that: (1) the leaching behavior of Cu and Pb was much similar with that depicted by the standardized leaching tests, and fit well with the solubility-controlling mechanism; (2) the sorption mechanism on the neoformed phases may control the solubility of Pb, whereas the dissolved organic carbon (DOC) may play an important role in the solubility of Cu; and (3) the leached PAHs were degraded during the later period of leaching process.