A study of Cr(VI) in ashes from fluidized bed combustion of municipal solid waste: leaching, secondary reactions and the applicability of some speciation methods

The use of the fluidized bed technique for the combustion of municipal solid waste is a rather new concept. This type of combustor produces ash residues with somewhat different properties than the residues generated from the traditional mass burn techniques. Therefore, chemical characterization and the investigation of toxic metals behavior during ash water reactions are necessary for the safe disposal of these residues. In the present work, the total elemental composition, mineralogy and leaching behavior of ashes from the combustion of municipal solid waste in a fluidized bed combustion boiler have been investigated. The cyclone ash and, in particular, the filter ash contained considerable amounts of soluble substances, thus giving leachates with high levels of Cl-, Na+, K+, Ca2 + and Al(IIl). On the other hand, the two ash fractions taken in the boiler, the bottom and hopper ashes, were much more stable with respect to the release of salts and heavy metals. Since Cr(VI) is mobile and toxic its release from combustion residues can pose environmental problem. Even though the total Cr contents were similar in all ashes studied, the bottom ash gave about a thousand times higher levels of Cr(VI) in test leachates than the hopper, cyclone and filter ashes. However, it was found that the leached amount of Cr(VI) from the bottom ash decreased significantly when bottom ash was mixed with the hopper ash. The most probable cause for this decrease is the coupled oxidation of Al(0) to Al(III) and reduction of dissolved Cr(VI) to Cr(III). This finding that the mixing of two ash streams from the same boiler could result in the immobilization of Cr may point at a simple stabilization method. Selective extraction of water soluble, exchangeable and sparingly soluble forms of Cr(VI) was also investigated. Extraction methods were evaluated for their suitability for ash matrixes. It was found that interferences due to the presence of reducing substances in some ash materials may occur.     

Stabilization/solidification of fly ashes and concrete production from bottom and circulating ashes produced in a power plant working under mono and co-combustion conditions

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w). Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.     

Controlled combustion tests and bottom ash analysis using household waste with varying composition

The influence of the co-combustion of household waste with either sewage sludge, shredder fluff, electronic and electrical waste (WEEE) or PVC on the bottom ash quality and content was investigated under controlled laboratory conditions using a pot furnace. This laboratory approach avoids the interpretation problems related to large variations in input waste composition and combustion conditions that are observed in large scale MSW incinerators. The data for metals content, transfer coefficients and leaching values are presented relative to data for a base household waste composition that did not contain any of the added special wastes. The small WEEE invited direct measurement of precious metals content in the ashes, where measurement accuracy is facilitated by using only mobile phone scrap for small WEEE. The analyses were carried out for different particle size ranges that are of relevance to the recyclability of metals and minerals in the ashes. Positive correlations were found between elements content of the input waste and the bottom ashes, and also between increased levels of Cl, Mo and Cu in the input waste and their leaching in the bottom ashes. These correlations indicate that addition of PVC, small WEEE and shredder fluff in input waste can have a negative influence on the quality of the bottom ashes. Enrichment of Au and Ag occurred in the fractions between 0.15 and 6 mm. The precious metals content represents an economically interesting intrinsic value, even when the observed peak values are properly averaged over a larger volume of ashes. Overall, it has been shown that changes in quality and content of bottom ashes may be traced back to the varied input waste composition.     

Thermochemical treatment of sewage sludge ashes for phosphorus recovery

Phosphorus (P) is an essential element for all living organisms and cannot be replaced. Municipal sewage sludge is a carrier of phosphorus, but also contains organic pollutants and heavy metals. A two-step thermal treatment is suggested, including mono-incineration of sewage sludge and subsequent thermochemical treatment of the ashes. Organic pollutants are completely destroyed by mono-incineration. The resulting sewage sludge ashes contain P, but also heavy metals. P in the ashes exhibits low bioavailability, a disadvantage in farming. Therefore, in a second thermochemical step, P is transferred into mineral phases available for plants, and heavy metals are removed as well. The thermochemical treatment was investigated in a laboratory-scale rotary furnace by treating seven different sewage sludge ashes under systematic variation of operational parameters. Heavy metal removal and the increase of the P-bioavailability were the focus of the investigation. The present experimental study shows that these objectives have been achieved with the proposed process. The P-bioavailability was significantly increased due to the formation of new mineral phases such as chlorapatite, farringtonite and stanfieldite during thermochemical treatment.     

Reduction of hazardous elements contained in sewage sludge incineration ash

Research and experimental studies were carried out in relation to reduction of hazardous elements contained in sewage sludge incineration ash. A questionnaire survey was conducted in 69 Japanese municipalities with sewage sludge incineration facilities. Selenium content in bag filter ash and ceramic filter ash was relatively higher than that in ash of cyclone and electrostatic precipitators. It was assumed that selenium vaporized in the furnace was due to adsorb in the fly ash on filter when passing through the low-temperature filter. To reduce high boiling point heavy metals in the ash, sewage sludge and incineration ash were heated up using a small muffle furnace. As the result, the chrome and nickel contents were reduced. A decrease in the surface area of ash and the reduction of elements occurred at the same time in sewage sludge and incineration ashes tested in this study.     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Belgian MSWI fly ashes and APC residues: a characterisation study

Municipal Solid Waste Incineration (MSWI) produces different sorts of residues, bottom ash, fly ashes and Air Pollution Control (APC) residues. Generally, fly ashes and APC residues are mixed at the MSWI plant and manage as a sole residue. In this study, fly ashes and APC residues have been sampled separately at different Belgian MSWI plant and analysed by X-ray fluorescence in order to highlight the composition differences that may appear between the solids. Ca and Cl are found to be the major elements in most of the samples. Lithophilic elements, such as Al and Si, are richer in furnace and boiler ashes, as can be expected. Leaching tests also show differences between the residues; leachates from furnace and boiler ashes are alkaline while those from bag filter residues present a pH value of 6, which impacts the leaching of heavy metals (Pb and Zn). The results suggest that it could be advantageous to manage fly ashes and APC residues separately by adjusting the treatment to their specificities.     

Leachability of automotive shredder residues burned in a fluidized bed system

This paper presents the results of the study of a combustible fraction of automotive shredder residues (CASRs) and the corresponding ashes generated by combustion on a fluidized bed pilot with the aim to understand the influence of thermal treatment regarding properties for final disposal, such as landfilling. The chemical composition was evaluated and the leachability behaviour of ashes and CASR was investigated using the three more commonly used tests: the European Standard EN 12457, the US TCLP-EPA 1311 and the Dutch availability test EA NEN 7371. Different results were obtained depending on the specific conditions of the methods employed. It was found that both the CASR and the ashes contained large amounts of toxic metals and other undesirable elements, such as Cl and S. For the CASR, in addition to the leachability of organic matter above the limit set for hazardous materials, the release of heavy metals, either under alkaline and acidic conditions was significant, revealing the serious risks associated to the landfilling practices still being undertaken worldwide. Release of organic matter from ashes was insignificant, but solubility of sulphates increased and chlorides exceed the hazardous limits in the case of fly ashes. Toxic metals were found to leach from the ashes only under acidic conditions, except Pb and Cu which also leached from finer ashes at alkaline pH. Cr also leached from ashes at alkaline pH values. Both the Dutch availability and TCLP revealed much higher leaching intensities than the European Standard due to the acidity of leachants. However, it was found that ashes may be more resistant to acidification because they exhibit much higher acid neutralization capacity (ANC) than the untreated CASR. The study undertaken shows that thermal valorisation of the combustible fraction of ASR may avoid the risks associated with their landfilling; however, care has to be taken with the ashes because they also behave as hazardous residues. Although, the mass reduction provided by thermal treatment may make landfilling less expensive, a more profitable reutilization of the ashes should be developed.     

Influence of bromine on metal volatilization in waste combustion

Co-combustion tests of municipal solid waste and bromine-containing waste plastics have been performed in the TAMARA test incinerator in order to investigate the fate of bromine in waste combustion. HBr is the main bromine combustion product. Approximately 50% of the bromine inventory stays in the grate ashes, which is much more than is found for chlorine. The percentage of bromine transferred into the fly ash also exceeds that of chlorine. There is a strong indication that bromine has a promoting effect upon the volatility of most of the heavy metals that are typically mobilized by chlorine. Received: February 2, 2000 / Accepted: March 3, 2000     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Stabilization/solidification of ashes in clays used in the manufacturing of ceramic bricks.

This paper presents the results of the lixiviation of metals from different mixtures of fly and bottom ashes that have been stabilized and solidified in clays used in the manufacture of bricks. The ashes used for this study were obtained from a Hoffmann-type brick furnace adapted for the incineration of municipal solid waste during the manufacturing of ceramic bricks. The ashes were stabilized in clay in different proportions of clay:ash mix (99:1, 95:5, 90:10, 80:20 and 60:40). Such mixes were used to manufacture bricks that were calcined at a temperature ranging from 50 to 1100 degrees C. The clay, ashes and manufactured bricks were characterized using X-ray diffraction, fluorescent X-ray, thermogravimetry, differential thermal analysis, atomic absorption spectroscopy and scanning electronic microscopy. In addition, toxicity characteristic leaching procedure lixiviation tests were performed according to the EPA 1311 method for the determination of heavy metals. The results showed an affinity between clay and ash, and also that the bricks manufactured with these mixtures present low lixiviation levels. The tests also showed the highest decrease in the concentration of arsenic, nickel, chromium, zinc and silver for 99:1 mixtures. The 95:5 mixture was found to be the most favourable for the stabilization (greater concentration decrease) of lead and cadmium. Selenium was the metal with the lowest concentration change whereas arsenic, nickel, chromium, zinc and cadmium showed the greatest concentration change in all mixtures, with the exception of cadmium in the mixture 99:1.     

Fate of heavy metals and radioactive metals in gasification of sewage sludge

The fates of radioactive cadmium, strontium, cesium, cobalt, arsenic, mercury, zinc, and copper spiked into sewage sludge were determined when the sludge was gasified by a process that maximizes production of char from the sludge (ChemChar process). For the most part the metals were retained in the char product in the gasifier. Small, but measurable quantities of arsenic were mobilized by gasification and slightly more than 1% of the arsenic was detected in the effluent gas. Mercury was largely mobilized from the solids in the gasifier, but most of the mercury was retained in a filter composed of char prepared from the sludge. The small amounts of mercury leaving the gasification system were found to be associated with an aerosol product generated during gasification. The metals retained in the char product of gasification were only partially leachable with 50% concentrated nitric acid.     

Legislative and environmental issues on the use of ash from coal and municipal sewage sludge co-firing as construction material

For the economy of any co-firing process, it is important that the common waste management options of ash remain practical. Ash from bituminous coal combustion is typically handed to the construction industry. This paper describes the current European legislation on use of ash for construction purposes. Also, it presents an experimental study on the suitability of fly ash from combustion of mixtures of bituminous coal and municipal sewage sludge as additive to cement and concrete, and for use in open-air construction works, based on the ash chemical composition and the characteristics of the extract of the ash. Presently, two European standards forbid the use of ash from co-firing as additive to cement or concrete. This study shows that ash derived from coal and sewage sludge co-firing contains generally less unburned carbon, alkali, magnesium oxide, chlorine, and sulfate than coal ash. Only the concentration of free lime in mixed ash is higher than in coal, even though, at least up to 25% of the thermal input, still below the requirements of the standards. This ash also meets the requirements for the use of fly ash in open-air construction works--concentration and mobility of few elements--although this management option is forbidden to ash from co-firing. The leaching of Cd, Cr, Cu, Ni, Pb and Zn was investigated with three leaching tests. The concentration of these metals in the extracts was below the detection limit in most cases. The concentration of Cu and Zn in the extract from fly ash was found to increase with increasing share of sewage sludge in the fuel mixture. However, the concentration of these two metals in the extract is not regulated. This study indicates that excluding a priori the use of ash from co-firing as a suitable additive for construction material could cause an unnecessary burden on the environment, since probably ash would have to be disposed of in landfill. However, allowing this requires the modification of current European standards to include limitations on all elements and compounds, absent in coal but which might be present in other fuels, that are deleterious for the quality of construction materials.     

Agronomic characterisation of different types of sewage sludge: Policy implications

Spain is one of the main municipal sewage sludge producers of Europe. This paper aims to agronomically characterise different types of sewage sludge stabilised by different methods (anaerobically digested, composted, and pelletised) and deliver policy recommendations from the results of this characterisation. Anaerobic sewage sludge quality is found to be better in plants with a lower volume of water processing. Composted sludge shows the best quality from a heavy metal point of view, but its low available nitrogen content increases the input of heavy metals when spread, as compared to digested or pelletised sludge. Pelletised sludge has higher heavy metal content than anaerobically digested sludge. Despite the good quality of the sludges, future regulations, especially with regard to Cd levels, will limit the use of this waste in agriculture.     

Heavy metal release from different ashes during serial batch tests using water and acid

Most ashes contain a significant amount of heavy metals and when released from disposed or used ash materials, they can form a major environmental concern for underground waters. The use of water extracts to assess the easily mobilisable content of heavy metals may not provide an appropriate measure. This study describes the patterns of heavy metal release from ash materials in context with results from the German standard extraction method DIN-S4 (DIN 38 414 S4). Samples of four different ashes (municipal solid waste incineration ash, wood ash, brown coal ash and hard coal ash) were subjected to a number of serial batch tests with liquid renewal, some of which involved the addition of acid to neutralize carbonates and oxides. Release of heavy metals showed different patterns depending on the element, the type of material, the method of extraction and the type of the extractant used. Only a small fraction of the total heavy metal contents occurred as water soluble salts; of special significance was the amount of Cr released from the wood ash. The reaction time (1, 24 or 72 h between each extraction step with water) had only a small effect on the release of heavy metals. However, the release of most of the heavy metals was governed by the dissolution processes following proton inputs, indicating that pH-dependent tests such as CEN TC 292 or others are required to estimate long-term effects of heavy metal releases from ashes. Based on the chemical characteristics of ash materials in terms of their form and solubility of heavy metals, recommendations were made on the disposal or use of the four ash materials.     

Synthetic aggregates from combustion ashes using an innovative rotary kiln

This paper describes the use of a number of different combustion ashes to manufacture synthetic aggregates using an innovative rotary 'Trefoil' kiln. Three types of combustion ash were used, namely: incinerated sewage sludge ash (ISSA); municipal solid waste incinerator bottom ash (MSWIBA-- referred to here as BA); and pulverised fuel ash (Pfa). The fine waste ash fractions listed above were combined with a binder to create a plastic mix that was capable of being formed into 'green pellets'. These pellets were then fired in a Trefoil kiln to sinter the ashes into hard fused aggregates that were then tested for use as a replacement for the natural coarse aggregate in concrete. Results up to 28 days showed that these synthetic aggregates were capable of producing concretes with compressive strengths ranging from 33 to 51 MPa, equivalent to between 73 and 112% of that of the control concrete made with natural aggregates.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

Characterization, leachability and valorization through combustion of residual chars from gasification of coals with pine

This paper presents the study of the combustion of char residues produced during co-gasification of coal with pine with the aim of characterizing them for their potential use for energy. These residues are generally rich in carbon with the presence of other elements, with particular concern for heavy metals and pollutant precursors, depending on the original fuel used.The evaluation of environmental toxicity of the char residues was performed through application of different leaching tests (EN12457-2, US EPA-1311 TCLP and EA NEN 7371:2004). The results showed that the residues present quite low toxicity for some of pollutants. However, depending on the fuel used, possible presence of other pollutants may bring environmental risks.The utilization of these char residues for energy was in this study evaluated, by burning them as a first step pre-treatment prior to landfilling. The thermo-gravimetric analysis and ash fusibility studies revealed an adequate thermochemical behavior, without presenting any major operational risks.Fluidized bed combustion was applied to char residues. Above 700 °C, very high carbon conversion ratios were obtained and it seemed that the thermal oxidation of char residues was easier than that of the coals. It was found that the char tendency for releasing SO₂ during its oxidation was lower than for the parent coal, while for NO_X emissions, the trend was observed to increase NO_X formation. However, for both pollutants the same control techniques might be applied during char combustion, as for coal. Furthermore, the leachability of ashes resulting from the combustion of char residues appeared to be lower than those produced from direct coal combustion.     

Determination of Cu and Ni incorporation ratios in Portland cement clinker

Cu and Ni are metals found in galvanic sludges; these sludges are considered hazardous due to their heavy metal content. The main objective of this work is to determine the incorporation amount of Cu and Ni in Portland clinker when a galvanic sludge containing these metals is added to the clinker raw-material. The influence of this addition on the clinkering reactions is evaluated as well as the possibility of co-incinerating galvanic sludges containing Cu and Ni in rotary cement kilns. This study also characterizes the galvanic sludge. Samples were prepared by additions from 0.25 to 5 wt.% of a galvanic sludge to an industrial clinker raw-material. The clinkering process was simulated in a laboratory device. The following techniques were applied to characterize the raw materials and the products of the tests: chemical analysis, differential thermal analysis (DTA) and thermogravimetric analysis (TG). Leaching tests were performed in the produced clinker samples in order to verify the incorporation of the studied metals in the clinker structure. The results led to the conclusion that additions of up to 2 wt.% of a galvanic sludge containing 2.4 wt.%Cu and 1.2 wt.% Ni to clinker raw-material do not affect the clinkering reactions and that these metals are totally incorporated into the clinker.     

Sewage sludge ash to phosphorus fertiliser (II): Influences of ash and granulate type on heavy metal removal

Ashes from monoincineration of sewage sludge suggest themselves as an ideal base for inorganic fertiliser production due to their relatively high phosphorus (P)-content. However, previously they need to be detoxified by reducing their heavy metal content. The core process considered in this paper consists of three steps: mixing of the ashes with suitable chlorine-containing additives, granulation of the mixture and thermochemical treatment in a rotary kiln. Here relevant heavy metal compounds are first transformed into volatile species with the help of the additives and then evaporated from the granules.In this study two chemically different ashes and their mixture were agglomerated to two different granulate types, briquettes and rolled pellets. The resulting six different materials were subjected to thermal treatment at different temperatures. The heavy metals examined were Cu and Zn due to their strong dependence on treatment conditions and their relevance concerning thermal treatment of sewage sludge ashes. Besides, the behaviour of Cl and K was monitored and evaluated.The experiments showed that ash type and temperature are more influential on Cl and heavy metal chemistry than granulate type. Temperature is a primary variable for controlling removal in both cases. Cu removal was less dependent on both ash and granulate type than Zn. The Cl utilization was more effective for Cu than for Zn. Depending on the treatment conditions some K could be retained, whereas always all P remained in the treated material. This satisfies the requirement for complete P recycling.