Incineration of doped sludges in fluidized bed. Fate and partitioning of six targeted heavy metals. I. Pilot plant used and results

Incineration of sewage sludge doped with several heavy metals was studied at small pilot plant scale in a bubbling fluidized bed of 15 cm i.d. and 5.2 m height. Some ceramic and metallic filters were tested at a relatively high temperature (600–700°C) to check their usefulness for partitioning of heavy metals in the flue gas. The work was focused on the fate of six selected heavy metals (Cr, Cd, Ni, Zn, Cu, Pb). In this process, there were four exit flows or discharges for these metals: bottom ash, coarse fly ash, cake filter or fine fly ash and flue exit gas. The distribution or partitioning of each heavy metal (HM) among these four exit flows was studied. Only cadmium and sometimes lead showed any difference between the different HMs considered. All other HMs seems to have the same fate, distribution or partitioning. Such distribution is governed or ruled by the fluid dynamics in the incinerator, cyclone and ceramic filter. Most of the HMs do not have enough residence time in this incinerator type to diffuse out of the ash particle and so remain in the particle. The amount of each HM in each exit flow in this process is governed by fluid dynamics and kinetics and not at all by thermodynamics.     

Effect of MSW source-classified collection on the emission of PCDDs/Fs and heavy metals from incineration in China

Municipal solid waste (MSW) source-classified collection represents a change in MSW management in China and other developing countries. Comparative experiments were performed to evaluate the effect of a newly established MSW source-classified collection system on the emission of PCDDs/Fs (polychlorinated dibenzo-p-dioxins and dibenzofurans) and heavy metals (HMs) from a full-scale incinerator in China. As a result of presorting and dewatering, the chlorine level, heavy metal and water content were lower, but heat value was higher in the source-classified MSW (classified MSW) as compared with the conventionally mixed collected MSW (mixed MSW). The generation of PCDDs/Fs in flue gas from the classified MSW incineration was 9.28 ng I-TEQ/Nm(3), only 69.4% of that from the mixed MSW incineration, and the final emission of PCDDs/Fs was only 0.12 ng I-TEQ/Nm(3), although activated carbon injection was reduced by 20%. The level of PCDDs/Fs in fly ash from the bag filter was 0.27 ng I-TEQ/g. These results indicated that the source-classified collection with pretreatment could improve the characteristics of MSW for incineration, and significantly decrease formation of PCDDs/Fs in MSW incineration. Furthermore, distributions of HMs such as Cd, Pb, Cu, Zn, Cr, As, Ni, Hg in bottom ash and fly ash were investigated to assess the need for treatment of residual ash.     

Partitioning characteristics of targeted heavy metals in IZAYDAS hazardous waste incinerator

Partitioning of eight targeted heavy metals (Cr, Mn, Cu, Pb, Sn, Co, Ni and Zn) was carried out during five trial burns in Izmit hazardous and clinical waste incinerator (IZAYDAS). Metal contents of the original wastes and their concentration in the bottom ash (BA), fly ash (FA), filter cake (FC) and flue gas were determined. Partitioning behavior of metals during the two-stage incineration was evaluated with respect to physico-chemical properties of feed waste and metals, and the operational conditions. Results suggest that combustion temperatures and retention times are the dominant parameters determining the volatility of metals in the first combustion chamber. Targeted metals were generally partitioned in the rank of bottom ash, filter cake, fly ash and flue gas. High filter cake/fly ash ratios showed that high temperatures in the second stage increase both the formation of gaseous metallic compounds and the enrichment of metals in fine particles. Since ESP could not be effective in removing fine particles and volatilized metallic compounds, the necessity of an additional system that would remove heavy metals efficiently was emphasized for the modern incinerators.     

Trace elements partitioning during co-firing biomass with lignite in a pilot-scale fluidized bed combustor

This study describes the partitioning of 18 trace elements (As, Ba, Cd, Co, Cr, Cu, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and 9 major and minor elements (Al, Ca, Fe, K, Mg, Na, S, Si, Ti) during co-firing of olive residue, hazelnut shell and cotton residue with high sulfur and ash content lignite in 0.3 MW(t) Middle East Technical University (METU) Atmospheric Bubbling Fluidized Bed Combustor (ABFBC) test rig with limestone addition. Concentrations of trace elements in coal, biomass, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission and mass spectroscopy (ICP-OES and ICP-MS). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Co, Cr, Cu, Li, Mn, Mo, Ni, Pb, Tl, V and Zn) are recovered in fly ash when firing lignite only. Co-firing lignite with biomass enhances partitioning of these elements to fly ash. Co-firing also shifts the partitioning of Cd, P, Sb and Sn from bottom to fly ash.     

The influence of heavy metals on partitioning of PAHs during incineration

The presence of heavy metals (Cr, Cd, Pb and Zn) in feedstock increases the partitioning of polycyclic aromatic hydrocarbons (PAHs) in the solid as well as in the gaseous phases, which has been reported in our previous study. However, the partitioning of PAHs in air-pollution control equipment (APCE) has not been investigated thus far. Hence, the present work was conducted to study the partitioning of PAHs in APCE and the effect of heavy metals on PAHs formation by varying the target heavy metals in the feedstock.A fluidized bed incineration system which includes a primary combustion chamber (sand bed), a secondary combustion chamber (freeboard), and an APCE (cyclone and scrubber) was utilized in this study. The feedstock that contained various heavy metals was fed into the incinerator, and then the PAHs in the cyclone and scrubber were analyzed to determine the effect of heavy metals on PAHs partitioning. The results indicate that the presence of Pb and Zn in feedstock facilitates the formation of PAHs.     

Partitioning behavior of trace elements during pilot-scale fluidized bed combustion of high ash content lignite

This study describes the partitioning of 20 trace elements (As, B, Ba, Cd, Co, Cr, Cu, Hg, Li, Mn, Mo, Ni, P, Pb, Sb, Se, Sn, Tl, V, Zn) and eight major and minor elements (Al, Ca, Fe, K, Mg, Na, Si, Ti) during the combustion of high ash content lignite. The experiments were carried out in the 0.3 MW(t) Middle East Technical University (METU) atmospheric bubbling fluidized bed combustor (ABFBC) test rig with and without limestone addition. Inert bed material utilized in the experiments was bed ash obtained previously from the combustion of the same lignite without limestone addition in the same test rig. Concentrations of trace elements in coal, limestone, bottom ash, cyclone ash and filter ash were determined by inductively coupled plasma optical emission spectroscopy (ICP-OES). Partitioning of major and minor elements are influenced by the ash split between the bottom ash and fly ash and that the major proportion of most of the trace elements (As, Ba, Cr, Hg, Li, Mo, Ni, Sn, V, Zn) are recovered in fly ash. Limestone addition shifts the partitioning of Ba, Cr, Mo, Ni, Sn, V, Zn from bottom ash to fly ash.     

Experimental and thermodynamic investigation on transfer of cadmium influenced by sulfur and chlorine during municipal solid waste (MSW) incineration

We used two approaches to investigate the impact of sulfur and chlorine compounds on transfer of a semivolatile heavy metal, cadmium, during municipal solid waste (MSW) incineration: experiments using a tubular furnace reactor and thermodynamic equilibrium calculations. Artificial wastes representative of typical MSW in China with and without the presence of sulfur and chlorine compounds were combusted at 850 degrees C, and the partitioning of Cd among bottom ash, fly ash and flue gas was quantified. The results indicate that sulfur compounds in the elemental form and reduced state could stabilize Cd in the form of CdS due to local reducing environment, while sulfur in the oxidized forms slightly increased Cd volatilization during incineration. In contrast, the presence of chlorine compounds significantly increased the partitioning of Cd on fly ash. Chemical equilibrium calculations show that sulfur binds with Cd and alters Cd speciation at low temperatures (<700 degrees C), while chlorine significantly increases the volatilization of Cd through formation of volatile CdCl(2) and thus its partitioning on the fly ash between 400 and 1000 degrees C. The equilibrium calculation results also suggest that SiO(2)- and Al(2)O(3)-containing minerals could function as sorbents stabilizing Cd as condensed phase solids (CdSiO(3) and CdAl(2)O(4)). These findings provide useful information on understanding the partitioning behavior of Cd and can help development of strategies to control volatilization of Cd during MSW incineration.     

The distribution of heavy metals during fluidized bed combustion of sludge (FBSC)

During combustion of wastewater treatment sludge, the inorganic constituents are converted into ash which contains the major fraction of the heavy metals present. The behaviour of heavy metals in combustion processes has been studied extensively for mostly coal combustion and waste incineration. For biomass and sludge, literature data are scarce and mostly limited to laboratory experiments. The present paper assesses the partitioning of eight heavy metals (Hg, As, Cd, Cu, Pb, Cr, Ni and Zn) in the different residues from a large-scale fluidized bed sludge combustor of 4.4 m i.d. The origin of the sludge is mostly from treating urban wastewaters (>90%), although some mixed sludge (urban+industrial, <10%) is also burnt. The different residues (bottom ash, fly ash, filter cake, scrubber effluent and stack emissions) were sampled and analysed during 33 weeks, spread over a period of 1 year. The mass balance of relevant heavy metals closes for 96.5%, inaccuracies being related to the unsteadiness of the process, the accuracy of the mass flow data monitored at the plant, and on collecting representative samples. It is also shown that all heavy metals under scrutiny, except Hg, are concentrated in the fly ash as collected in the electrostatic precipitator.     

Devolatilization of oil sludge in a lab-scale bubbling fluidized bed

Devolatilization of oil sludge pellets was investigated in nitrogen and air atmosphere in a lab-scale bubbling fluidized bed (BFB). Devolatilization times were measured by the degree of completion of the evolution of the volatiles for individual oil sludge pellets in the 5-15 mm diameter range. The influences of pellet size, bed temperature and superficial fluidization velocity on devolatilization time were evaluated. The variation of devolatilization time with particle diameter was expressed by the correlation, τ(d) = Ad(p)(N). The devolatilization time to pellet diameter curve shows nearly a linear increase in nitrogen, whereas an exponential increase in air. No noticeable effect of superficial fluidization velocity on devolatilization time in air atmosphere was observed. The behavior of the sludge pellets in the BFB was also focused during combustion experiments, primary fragmentation (a micro-explosive combustion phenomenon) was observed for bigger pellets (>10mm) at high bed temperatures (>700 °C), which occurred towards the end of combustion and remarkably reduce the devolatilization time of the oil sludge pellet. The size analysis of bed materials and fly ash showed that entire ash particle was entrained or elutriated out of the BFB furnace due to the fragile structure of oil sludge ash particles.     

Study on use of MSWI fly ash in ceramic tile

In this work, MSWI (municipal solid waste incineration) fly ash is used as a blending in production of ceramic tile by taking advantage of its high contents of SiO(2), Al(2)O(3) and CaO. Besides, macro-performance and microstructure of the product as well as its leaching toxicity in practical application were studied by means of XRD, IR and SEM analysis, and leaching toxicity and sequential chemical extraction analysis of the product. It is found that when 20% fly ash is added, the product registers a high compressive strength of 18.6MPa/cm(2) and a low water absorption of 7.4% after being sintered at 960 degrees C. It is found that the glazed tile shows excellent resistance against leaching, in accordance with HVEP stand, of heavy metals with Cd<0.0002ppm, Pb<0.0113ppm and Zn<0.0749ppm, and Hg below the low detection limit. These results show that heavy metals are cemented among the solid lattice in the product and can hardly be extracted. Leaching toxicity of heavy metals in the product, especially Hg, Pb, Zn and Cd, is substantially reduced to less than one-tenth of that in fly ash. In addition, specifications of Hg, Pb, Zn and Cd are largely changed and only a small portion of these heavy metals exists in soluble phases. These results as a whole suggest that the use of MSWI fly ash in ceramic tile constitutes a potential means of adding value.     

Sequential extraction for evaluating the leaching behavior of selected elements in municipal solid waste incineration fly ash

A sequential extraction method has been applied for the determination of binding forms of trace elements in the municipal solid waste incineration (MSWI) fly ash and evaluating their leaching behavior in view of their potential environmental impact. The elemental determinations in the different leachates are performed by ICP-AES and ICP-MS, respectively. The morphology and mineralogical phases after extraction step were performed by scanning electron microscopy (SEM). Total of 20 elements in the samples are investigated. A reference material of city waste incineration fly ash (BCR No. 176) is also tested to examine the applicability as well as accuracy of the proposed method. The sum of most elements present in the individual fractions shows a good agreement with the total elemental concentrations. The extraction efficiencies are generally higher than 80% except for that of Cr and V. The extractable data of most elements give information about the binding forms of various elements in both incineration fly ashes. It was found that the elements such as Ca, K, Na, Pb, Zn, Cd, Cu and Sr have exhibited a remarkable mobility in fly ash. More than half of them would be dissolved or exchanged under a mild leaching condition. The toxic elements such as Pb, Cd, Zn and Cu have a great potential to be released into the environment under normal conditions.     

Fate of heavy metals during municipal solid waste incineration in Shanghai

The transfer behavior of heavy metals during municipal solid waste (MSW) incineration was investigated based on 2-year field measurements in two large-scale incinerators in Shanghai. Great temporal and spatial diversification was observed. Most of Hg and Cd were evaporated and then removed by air pollution control (APC) system through condensation and adsorption processes, thus being enriched in the fine APC residues particles. Cr, Cu, and Ni were transferred into the APC residues mainly by entrainment, and distributed uniformly in the two residues flows, as well as in the ash particles with different sizes. Pb and Zn in the APC residues were from both entrainment and evaporation, resulting in the higher concentrations (two to four times) compared with the bottom ash. Arsenic was transported into the flue gas mainly by evaporation, however, its transfer coefficient was lower. Though the heavy metals contents in the APC residues were higher than that in bottom ash, more than 80% of As, Cr, Cu, and Ni, 74-94% of Zn, as well as 46-79% of Pb remained in the bottom ash, due to its high mass ratio (85-93%) in the residues. While 47-73% of Cd and 60-100% of Hg were transferred into the APC residues, respectively.     

Comparison of the characteristics of bottom and fly ashes generated from various incineration processes

This study analyzed and compared the characteristics of bottom and fly ashes from three municipal solid waste incinerators (MSWIs) in Taiwan. Different incineration furnaces were investigated, including: (1) fluidized bed, (2) mass-burning, and (3) mass-burning linked rotary kiln. The particle size distribution, morphology, mineralogical and chemical composition, and leaching behavior of heavy metals of ash samples were evaluated. The results revealed that three types of incineration processes have different characteristic for ashes due to transportation and mixing system inside furnace. Particle size distribution indicated that 28.5% of MSWI-B bottom ash has lower than 180 microm and 61.2% of MSWI-A fly ash has larger than the 250 microm. The leaching concentration of Pb exceeded the regulatory level set by the Taiwan EPA in fly ashes from MSWI-B and MSWI-C, and thus must be considered hazardous wastes. Specifically, the leaching concentration of heavy metals of fly ashes from MSWI-A (fluidized bed incinerator) was lower than that of the others, and was corresponded to the regulatory levels. Therefore, a fluidized bed incineration process appears a potential of handling heavy metals for ashes. The result was also provided the valuable information for incinerator design and operation.     

Disposal of MSWI fly ash through a combined washing-immobilisation process

The objective of this work was to investigate the feasibility of a combined washing-immobilisation process as a means of optimising the disposal of fly ash resulting from municipal solid waste incineration (MSWI) in cementitious matrices. Two different types of Italian MSWI fly ash and an ordinary Portland cement (ASTM Type I) were used. Washing pre-treatment of fly ash with water always produces a wastewater that can be successfully treated by reducing the pH to values of 6.5-7.5. This treatment is capable of removing the detected contaminants (Al, Cd, Pb, Zn) through two different mechanisms: precipitation of aluminium hydroxide and adsorption of cadmium, lead and zinc ions onto floc particles of Al(OH)(3). Setting and leaching tests on cementitious mixes prove that the hazardous sludge produced from wastewater treatment can be completely mixed with washed fly ash and this mixture can be incorporated into cementitious matrices to a great extent (75 wt.% of total solid) without the risks of an unacceptable delay of cement setting and an excessive heavy metals leachability from solidified products. The better performance of the combined washing-immobilisation process as compared to the immobilisation process of unwashed fly ash may be ascribed primarily to the ability of the washing step in promoting the formation of hydrate phases that incorporate and/or convert heavy metal compounds into less reactive forms and, secondarily, to its ability of removing significant amounts of alkali chlorides and sulphates from fly ash. As a result, MSWI fly ash is transformed into a material that adversely affects cement hydration to a much lower extent than unwashed fly ash.     

Determination of the Cd-bearing phases in municipal solid waste and biomass single fly ash particles using SR-microXRF spectroscopy

By using an excitation energy of 27.0 keV, synchrotron radiation-induced micro-X-ray fluorescence (SR-microXRF) is employed to extract information regarding the composition and distribution of Cd-bearing phases in municipal solid waste (MSW) and biomass fly ashes. Significance of observation is based on statistics of totally more than 100 individual MSW and biomass fly ash particles from a fluidized bed combustion (FBC) plant. Cd concentrations in the parts-per-million range are determined. In general, although previous leaching studies have indicated Cd to be predominant in the smaller-size ash particles, in the present study Cd is more evenly distributed throughout all the particle sizes. For MSW fly ashes, results indicate the presence of Cd mainly as CdBr2 hot-spots, whereas for biomass fly ashes, which exhibit lower CdX2 concentration, a thin Cd layer on/in the particles is reported. For both ashes, Ca-containing matrixes are found to be the main Cd-bearing phases. Support for this observation is found from independent first-principles periodic density functional theory calculations. The observations are condensed into a schematic mechanism for Cd adsorption on the fly ash particles.     

Influence of flue gas SO2 on the toxicity of heavy metals in municipal solid waste incinerator fly ash after accelerated carbonation stabilization

The influence of CO₂ content and SO₂ presence on the leaching toxicity of heavy metals in municipal solid waste incinerator (MSWI) fly ash was studied by examining the carbonation reaction of MSWI fly ash with different combinations of simulated incineration flue gases. Compared with raw ash, the leaching solution pH of carbonated ash decreased by almost 1 unit and the leaching concentrations of heavy metals were generally lower, with that of Pb decreasing from 19.45 mg/L (raw ash) to 4.08 mg/L (1# carbonated ash). The presence of SO₂ in the incineration flue gas increased the leaching concentrations of heavy metals from the fly ash to different extents after the carbonation stabilization reaction. The pH of the leaching solution was the main factor influencing the leaching concentrations of heavy metals. The increase in buffer capacity with the pH of carbonated ash caused an increase in heavy metal stability after the carbonation reaction. Accelerated carbonation stabilization of MSWI fly ash could reduce its long-term leaching concentrations (toxicity) of Cu, Pb, Se, and Zn. The leaching concentrations of heavy metals from carbonated ash also likely had better long-term stability than those from raw ash. The presence of SO₂ in the incineration flue gas increased the proportion of exchangeable state species of heavy metals; slightly increased the long-term leaching toxicity of Cu, Pb, Se, and Zn; and reduced the long-term stability of these metals in the fly ash after the carbonation reaction.     

Chromium behavior during thermal treatment of MSW fly ash.

Energy-from-waste incineration has been promoted as an environmentally responsible method for handling non-recyclable waste from households. Despite the benefits of energy production, elimination of organic residues and reduction of volume of waste to be landfilled, there is concern about fly ash disposal. Fly ash from an incinerator contains toxic species such as Pb, Zn, Cd and Cr which may leach into soil and ground water if landfilled.Thermal treatment of the fly ash from municipal solid waste has been tested and proposed as a treatment option for removal of metal species such as Pb, Cd and Zn, via thermal re-volatilization. However, Cr is an element that remains in the residue of the heat treated fly ash and appears to become more soluble. This Cr solubilization is of concern if it exceeds the regulatory limit for hazardous waste. Hence, this unexpected behavior of Cr was investigated. The initial work involved microscopic characterization of Cr in untreated and thermally-treated MSW fly ash. This was followed by determining leaching characteristics using standard protocol leaching tests and characterization leaching methods (sequential extraction). Finally, a mechanism explaining the increased solubilization was proposed and tested by reactions of synthetic chemicals.     

SEM/EDS and XRD characterization of raw and washed MSWI fly ash sintered at different temperatures

The disposal of fly ash generated during municipal solid waste incineration (MSWI) may pose a significant risk to the environment due to the possible leaching of hazardous pollutants, such as toxic metals. Sintering technology attracted more attention than the vitrification process because of its low energy needed. Generally, a preliminary washing treatment of raw fly ash with water was necessary for this sintering technology. This study investigated the composition and morphology of raw fly ash (RFA) and washed fly ash (WFA) at different sintering temperatures, and examined the newly formed minerals during sintering. Toxicity characteristic leaching procedure (TCLP) tests were carried out to investigate the effect of the washing treatment and sintering process on the leaching performance of heavy metals in fly ash. Results showed that, with an increase of sintering temperature more complex aluminosilicates were formed; the incorporation of Mg, Fe and Pb into the aluminosilicates occurred during the sintering process at higher temperatures (800 and 900 degrees C). The washing treatment reduced the leachable concentration of Cd, Pb and Ni, but increased that of Cr. A CaCrO(4) compound was considered as a potential soluble species.     

Evaluation of the distribution patterns of Pb, Cu and Cd from MSWI fly ash during thermal treatment by sequential extraction procedure

Municipal solid waste incinerator (MSWI) fly ash was frequently classified as hazardous materials as the metals' concentration of toxicity characteristic leaching procedure (TCLP) exceeded regulations. Many studies have focused on reducing the concentration of TCLP using thermal treatment and increasing the application of thermally treated slag. However, the metal patterns in MSWI fly ash with or without thermal treatment have seldom been addressed. The main objective of this study was evaluation of the distribution patterns of Pb, Cu and Cd from MSWI fly ash during thermal treatment by sequential extraction procedure. The experimental parameters included the form of pretreatment, the proportion of bottom ash (bottom ash/fly ash, B/F=0, 0.1 and 1) and the retention time. The results indicated that (1) In comparison to raw fly ash, the distribution patterns of Pb, Cu and Cd become stable in thermally treated slag. (2) Washing pretreatment caused the Pb pattern to become stable, while the influence on Cu and Cd were not significant. (3) The distribution patterns of Pb, Cu, and Cd became more stable as the retention time increased. (4) Adding bottom ash could make the distribution patterns of Pb and Cd more stable.     

Ash deposit characterisation in a large-scale municipal waste-to-energy incineration plant

The deposition of ash - combustion residues - on superheaters and heat exchanger surfaces reduce their efficiency; this phenomenon was investigated for a large-scale waste-to-energy incineration facility. Over a period of six months, ash samples were collected from the plant, which included the bottom ash and deposits from the superheater, as well as flyash from the convective heat exchanger, the economiser and fabric filters. These were analysed for particle size, unburned carbon, elemental composition and surface morphology. Element partitioning was evident in the different combustion residues, as volatile metals, such as cadmium, antimony and arsenic, were found to be depleted in the bottom ash by the high combustion temperatures (1000+°C) and concentrated/enriched in the fabric filter ash (transferred by evaporation). Non-volatile elements by contrast were distributed equally in all locations (transported by particle entrainment). The heat exchanger deposits and fabric filter ash had elevated levels of alkali metals. 82% of flyash particles from the fabric filter were in the submicron range.