The behaviour of ashes and heavy metals during the co-combustion of sewage sludges in a fluidised bed

Co-combustion tests of dry sewage sludges with coal were performed in a pilot bubbling FBC aiming at the characterization of ashes and determining the behaviour of heavy metals in the process. The tests showed compliance with the regulatory levels as far as heavy metal emissions were concerned. The bottom ashes, which accounted for about 70% of the total ash production, were obtained in a granular form, with diameters ranging from 0.5 to 4 mm. The heavy metals were distributed in ashes obtained from different locations of the installation and their concentrations were found to vary depending on the location of capture. The increase in heavy metals content in bottom ashes was not found to lead to higher leachability and ecotoxicity compared to sewage sludges, suggesting that there could be opportunities for their further use. Mercury suffered vaporisation inside the reactor, thus leaving bottom ashes free of contamination by it. However, there was observed a strong retention of mercury in cyclone ashes due to the presence of unburned carbon which probably acted as an adsorbent. The effluent mercury was also found to be mostly associated with the particulate fraction, being less than 20% emitted in gaseous forms. The results suggested that the combustion of the sewage sludge could successfully be carried out and the amount of unburned carbon leaving the combustor but captured in cyclone was large enough to ensure substantial retention of mercury at low temperatures, hence could contribute to an improvement of the mercury release which still remains an issue of great concern to resolve during combustion of waste materials.     

Comparison of leaching characteristics of heavy metals in APC residue from an MSW incinerator using various extraction methods

This study investigates four extraction methods (water extraction, toxicity characteristics leaching procedure (TCLP), modified TCLP with pH control, and sequential chemical extraction (SCE)), each representing different liquid-to-solid (L/S) ratios, pH controls, and types of leachant, and their effects on the leaching concentration of heavy metals in municipal solid waste (MSW) incinerator air pollution control (APC) residue. The results indicated that for extraction with distilled water, the heavy metal leaching concentration (mg/l) decreased with L/S ratio, but the amount of heavy metal released (AHMR), defined as the leached amount of heavy metals to the weight of the tested sample (mg/kg), increased with an increase in L/S ratio, in the range of 2-100. The results also showed that both the leaching concentration and the amount of released metals were strongly pH-dependent in the TCLP and modified TCLP tests. In the case of pHs lower than 6.5, the leaching concentrations of Cd, Pb, Cu, Zn, and Cr decreased with an increase in pH. As pH increased higher than 6.5, Cr and Zn were almost insoluble. Meanwhile, Cd and Cu also showed a similar trend but at pHs of 8.5 and 7.5, respectively. Due to the nature of amphoteric elements, in the case of pHs higher than 7, the Pb leaching concentration increased with increasing pH. In modified TCLP tests with the pH value controlled at the same level as in the SCE test, the heavy metal speciation approached the extractable carbonate bound fraction by the SCE. Both amounts of targeted metals leached from the SCE and modified TCLP tests were much higher than those for the regular TCLP and water extraction tests.     

Experimental and numerical analysis of metal leaching from fly ash-amended highway bases

A study was conducted to evaluate the leaching potential of unpaved road materials (URM) mixed with lime activated high carbon fly ashes and to evaluate groundwater impacts of barium, boron, copper, and zinc leaching. This objective was met by a combination of batch water leach tests, column leach tests, and computer modeling. The laboratory tests were conducted on soil alone, fly ash alone, and URM-fly ash-lime kiln dust mixtures. The results indicated that an increase in fly ash and lime content has significant effects on leaching behavior of heavy metals from URM-fly ash mixture. An increase in fly ash content and a decrease in lime content promoted leaching of Ba, B and Cu whereas Zn leaching was primarily affected by the fly ash content. Numerically predicted field metal concentrations were significantly lower than the peak metal concentrations obtained in laboratory column leach tests, and field concentrations decreased with time and distance due to dispersion in soil vadose zone.     

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.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.     

Characteristics of ashes from different locations at the MSW incinerator equipped with various air pollution control devices

The characteristics of ashes from different locations at a municipal solid waste incinerator (MSWI) equipped with a water spray tower (WST) as a cooling system, and a spray dryer adsorber (SDA), a bag filter (BF) and a selective catalytic reactor (SCR) as air pollution control devices (APCD) was investigated to provide the basic data for further treatment of ashes. A commercial MSWI with a capacity of 100 tons per day was selected. Ash was sampled from different locations during the normal operation of the MSWI and was analyzed to obtain chemical composition, basicity, metal contents and leaching behavior of heavy metals. Basicity and pH of ash showed a broad range between 0.08-9.07 and 3.5-12.3, respectively. Some major inorganics in ash were identified and could affect the basicity. This could be one of the factors to determine further treatment means. Partitioning of hazardous heavy metals such as Pb, Cu, Cr, Hg and Cd was investigated. Large portions of Hg and Cd were emitted from the furnace while over 90% of Pb, Cu and Cr remained in bottom ash. However 54% of Hg was captured by WST and 41% by SDA/BF and 3.6% was emitted through the stack, while 81.5% of Cd was captured by SDA/BF. From the analysis data of various metal contents in ash and leach analysis, such capturing of metal was confirmed and some heavy metals found to be easily released from ash. Based on the overall characteristics of ash in different locations at the MSWI during the investigation, some considerations and suggestions for determining the appropriate treatment methods of ash were made as conclusions.     

Treatment and recycling of incinerated ash using thermal plasma technology

To treat incinerated ash is an important issue in Taiwan. Incinerated ashes contain a considerable amount of hazardous materials such as dioxins and heavy metals. If these hazardous materials are improperly treated or disposed of, they shall cause detrimental secondary contamination. Thermal plasma vitrification is a robust technology to treat and recycle the ash residues. Under the high temperature plasma environment, incinerated ashes are vitrified into benign slag with large volume reduction and extreme detoxification. Several one-step heat treatment processes are carried out at four temperatures (i.e. 850, 950, 1,050 and 1,150 degrees C) to obtain various "microstructure materials". The major phase to form these materials is a solid solution of gehlenite (Ca2Al2SiO7) and ?kermanite (Ca2MgSi2O7) belonging to the melilite group. The physical and mechanical properties of the microstructure materials are improved by using one-step post-heat treatment process after plasma vitrification. These microstructure materials with good quality have great potential to serve as a viable alternative for construction applications.     

Evaluation of the use of a sequential extraction procedure for the characterization and treatment of metal containing solid waste

Metal containing wastes like MSWI fly ashes and blast furnace sludge form a major environmental problem as they are polluted with heavy metals. The ash has to be landfilled or can be used as a construction material, but a pretreatment is in general necessary. Washing of the ashes with water in order to dissolve soluble salts or extracting the heavy metals with chemicals are possibilities. Blast furnace sludge contains large quantities of iron and carbon and could be recycled in the blast furnace, if the zinc content were not that high. Using a hydrometallurgical process the zinc can be removed from the sludge particles. In order to evaluate such treatment methods knowledge of the leaching behaviour of the studied material is very important. One of the factors influencing the leaching behaviour is the composition and mineralogy of the solids. A sequential extraction procedure, whereby the material is sequentially leached with different leaching solutions, can be used as an aid to characterize the material and to determine which chemical conditions are needed to obtain a sufficient extraction efficiency. To verify the accuracy of the sequential extraction procedure, a method is tested on MSWI fly ash and evaluated by comparing the results with those of leaching experiments whereby the final pH of the leaching solutions is varied over a wide range. Based upon this evaluation some suggestions for the use of the sequential extraction procedure are made and an adapted procedure is suggested, and applied to a blast furnace sludge.     

Sustainable alkali-activated binders with municipal solid waste incineration ashes as sand or fly ash replacement

The present study investigates the feasibility of using two types of municipality solid wastes incineration ashes, namely, fly ash and bottom ash in the production of sustainable alkali-activated binder. The ashes are collected from the incineration plant and characterized to determine their particle size distribution, specific gravity, chemical composition, and heavy metals content. The ashes are then used as either fly ash or sand replacement with five replacement ratios 0%, 5%, 10%, 15%, and 20% to produce the binder. The produced binder are characterized in terms of strength, workability, density, water absorption, thermal conductivity and stability, chemical composition, and heavy metals content. The results reflect the ability of producing sustainable alkali-activated binder with small dosage of MSWI ashes as either fly ash or sand replacement without negatively affecting its strength, workability, density, and water absorption. The ashes enhance the thermal insulation capability of the binder.

     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

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.     

A new way to stabilize fly ash from municipal incinerators

Heavy metals and toxic chlorinated organics, added to very low grain-size distributions, make fly ashes from municipal incinerators a very hazardous waste. For their disposal, the present general trend is, not only to stabilize chemically the ashes, i.e. to reduce the leachability of the toxic substances, but also to stabilize them mechanically, i.e. to convert them into massive, resistant, and unleachable solids. This paper describes various stabilization methods used on representative European fly ash samples, which led to the development of a new stabilization technique taking place in four stages: elimination of the alkali chlorides by dissolution; addition of a moderate quantity of phosphoric acid; calcination; and solidification with Portland clinker or cement. The principal advantages of the process are as follows: the polychlorodibenzodioxins-polychlorodibenzofurans are destroyed, the reactivity of the heavy metals is reduced drastically, the final solids have satisfactory mechanical properties, and the increase in weight of the waste to be disposed of does not exceed one fourth. Comparative results of TCLP extraction tests are presented.     

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.     

Evaluation of leaching and extraction procedures for soil and waste

Laboratory leaching tests may be used for source term determination as a basis for risk assessment for soil-groundwater pathways on contaminated sites. In order to evaluate different leaching procedures, batch extraction tests and percolation tests were performed using three reference materials produced from contaminated soil, demolition waste and municipal solid waste incinerator bottom ash. Emphasis was placed on the investigation of the leachability of the heavy metals copper and chromium, polycyclic aromatic hydrocarbons (PAHs) and the anions chloride and sulfate. Significant discrepancies between column experiments and batch/extraction tests were found for the release of PAHs and to a lesser extent for the heavy metals Cu and Cr. Additionally interlaboratory comparisons were conducted based on different leaching tests with the reference materials and evaluated using the criteria of comparability and reproducibility. The best reproducibility was achieved for all investigated substances in column tests. The reproducibility of batch tests was acceptable except for PAHs. The results from the experimental work will help establish standardized and feasible laboratory procedures as fundamental for substance specific risk assessment of contaminated sites.     

Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

Chemical properties of heavy metals in typical hospital waste incinerator ashes in China

Incineration has become the main mechanism for hospital waste (HW) disposal in China after the outbreak of Severe Acute Respiratory Syndrome (SARS) in 2003. However, little information is available on the chemical properties of the resulting ashes. In the present study, 22HW ash samples, including 14 samples of bottom ash and eight samples of fly ash, were collected from four typical HW incineration plants located across China. Chemical analysis indicated that the HW ashes contained large amounts of metal salts of Al, Ca, Fe, K, Mg, Na with a concentration range of 1.8-315gkg(-1). Furthermore, the ashes contained high concentrations of heavy metals such as Ag, As, Ba, Bi, Cd, Cr, Cu, Mn, Ni, Pb, Ti, Sb, Sn, Sr, Zn with a vast range of 1.1-121,411mgkg(-1), with higher concentrations found in the fly ash samples. Sequential extraction results showed that Ba, Cr, Ni and Sn are present in the residual fraction, while Cd existed in the exchangeable and carbonate fractions. As, Mn, Zn existed in the Fe-Mn oxide fraction, Pb was present in the Fe-Mn oxide and residual fractions, and Cu was present in the organic matter fraction. Furthermore, toxicity characteristic leaching procedure (TCLP) results indicated that leached amounts of Cd, Cu and Pb from almost all fly ash samples exceeded the USEPA regulated levels. A comparison between the HW ashes and municipal solid waste (MSW) ash showed that both HW bottom ash and fly ash contained higher concentrations of Ag, As, Bi, Cd, Cr, Cu, Pb, Ti, and Zn. This research provides critical information for appropriate HW incineration ash management plans.     

Heavy metals removal/stabilization from municipal solid waste incineration fly ash: a review and recent trends

Waste treatment using thermal technologies, such as incineration, leads to the production of pollutants and wastes, including fly ash (FA). Fly ash contains heavy metals (HMs) and other contaminants and can potentially pose high risks to the environment and negatively impact health and safety. Consequently, stabilizing fly ash prior to either use or landfilling is crucial. The toxicity of fly ash through heavy metal leaching can be assessed using leaching tests. The leaching rates of heavy metals primarily depend on the surrounding conditions as well as fly ash properties and metal speciation. Physical separation, leaching or extraction, thermal treatment and solidification/chemical stabilization are proposed as suitable approaches for fly ash treatment. Economic considerations, environmental concerns, energy consumption and processing times can define the efficiency and selection of the treatment approach. This review considers the latest findings and compares the advantages and shortcomings of different fly ash treatment methods with the aim of highlighting the recent advances in the field. The review concludes that the simultaneous implementation of various methods can lead to highly efficient heavy metals removal/stabilization while simultaneously taking economic and environmental considerations into account.

     

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.     

Vitrification of bottom ash from a municipal solid waste incinerator

During incineration of municipal solid waste (MSW), various environmentally harmful elements and heavy metals are liberated either into bottom ash, or carried away with the off-gases and subsequently trapped in fly-ash. If these minor but harmful elements are not properly isolated and immobilized, it can lead to secondary environmental pollution to the air, soil and water. The stricter environmental regulations to be implemented in the near future in The Netherlands require a higher immobilization efficiency of the bottom ash treatment. In the present study, MSW incinerator bottom ash was vitrified at higher temperatures and the slag formed and metal recovered were examined. The behaviour of soluble elements that remain in the slag is evaluated by standard leaching test. The results obtained can provide a valuable route to treat the ashes from incinerators, and to make recycling and more efficient utilization of the bottom ash possible.     

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.