The environmental fate of heavy metals arising from a MSW incineration plant

Pollutant fluxes from municipal solid waste (MSW) incinerators are of a certain concern, especially gaseous emissions from the stack, which constitute the major effluent from the plant. In this work, heavy metals in soil and vegetation sampled in different sites around the plant are compared with those found in the gaseous emissions from an incinerator: the suspected source and environmental matrices are observed together, in order to detect a possible relationship of cause and effect, using statistical methods. The incinerator examined, regarding dimension and technology, can be considered a typical Italian one. Heavy metal concentrations in soil and vegetation show a clear dependence on sampling year; similar behaviour can be found in emission fluxes referring to the same years. A dependence on the distance from the incinerator is also apparent. This study supplies a methodological approach that can be easily extended and applied to other suspected contamination sources.     

Characterization of PCDD/Fs and heavy metals from MSW incineration plant in Harbin

The characterization of PCDD/Fs and heavy metals in the flue gas and fly ash of Harbin municipal solid waste (MSW) incineration plant, located in the northeast of China, was investigated in this study. The MSW was treated in a twin internal fluidized (TIF) bed incinerator. The results indicate that the emission of PCDD/Fs into the environment is 0.02 ng I-TEQ/m3 and the level of PCDD/Fs in the fabric filter fly ash is 0.7982 ng I-TEQ/g. The leachability levels of Pb, Cd and Hg in the fly ash are below the limits of environmental protection standard in China. However, the contents of Cu, Zn, and Hg are high in the fly ash. This suggests that the fly ash is a hazardous waste that requires special treatment and disposal. The practice of more than four years of operation shows that the TIF bed incinerator is very suitable and practical for China.     

Fixation and partitioning of heavy metals in slag after incineration of sewage sludge

Fixation of heavy metals in the slag produced during incineration of sewage sludge will reduce emission of the metals to the atmosphere and make the incineration process more environmentally friendly. The effects of incineration conditions (incineration temperature 500-1100°C, furnace residence time 0-60min, mass fraction of water in the sludge 0-75%) on the fixation rates and species partitioning of Cd, Pb, Cr, Cu, Zn, Mn and Ni in slag were investigated. When the incineration temperature was increased from 500 to 1100°C, the fixation rate of Cd decreased from 87% to 49%, while the fixation rates of Cu and Mn were stable. The maximum fixation rates for Pb and Zn and for Ni and Cr were reached at 900 and 1100°C, respectively. The fixation rates of Cu, Ni, Cd, Cr and Zn decreased as the residence time increased. With a 20min residence time, the fixation rates of Pb and Mn were low. The maximum fixation rates of Ni, Mn, Zn, Cu and Cr were achieved when the mass fraction of water in the sludge was 55%. The fixation rate of Cd decreased as the water mass fraction increased, while the fixation rate of Pb increased. Partitioning analysis of the metals contained in the slag showed that increasing the incineration temperature and residence time promoted complete oxidation of the metals. This reduced the non-residual fractions of the metals, which would lower the bioavailability of the metals. The mass fraction of water in the sludge had little effect on the partitioning of the metals. Correlation analysis indicated that the fixation rates of heavy metals in the sludge and the forms of heavy metals in the incinerator slag could be controlled by optimization of the incineration conditions. These results show how the bioavailability of the metals can be reduced for environmentally friendly disposal of the incinerator slag.     

The privatization effect of MSW incineration services by using data envelopment analysis

This paper attempts to compare the relative efficiency across MSW incineration facilities under the three operating modes including government-owned government-operated (GOO), government-owned private-operated (GOPO), and private-owned private-operated (POPO) by using the Data Envelopment Analysis (DEA), and to examine the factor in affecting the efficiency variation. The results show that technical efficiency scores are 0.7538, 0.9046 and 0.9917 for GOO, GOPO and POPO, respectively. An ANOVA is conducted and the analysis result confirms that the operating mode has significant impact on technical efficiencies. A further examination on the operating contracts signed between governments and operating firms of GOPO facilities finds that both the price protection and quantity protection also play vital roles in affecting efficiencies.     

Thermodynamic analysis of the role of chlorine and sulfur environments during combustion and incineration processes

 In order to control the emission of trace metals from combustion and incineration systems, sorbents and filters are sometimes used. However, the effectiveness of these methods is greatly affected by the volatility of the metals and the way in which they speciate during combustion, and afterwards during condensation, and physical or chemical sorption. Although there has been a lot of research into the mechanisms by which trace metals speciate and subsequently appear in submicron particles, the details of these mechanisms are not yet thoroughly understood. In this study, a chemical equilibrium approach was used to qualitatively determine the speciation of lead, cadmium, and chromium in Cl and S environments. The reaction conditions of sorbents were also tested numerically in order to understand the reaction behavior of metals with sorbents. This article reports the influence of different concentrations of Cl and SO₂ on Pb, Cd, and Cr speciation, as representatives of other trace elements. The partitioning behavior of metals during combustion was also examined for Cl and S. The results obtained indicate that most metals exist in the vapor phase, even at low temperatures, when chlorine is present. However, the addition of SO₂ enhances the formation of the condensed phase, except at extremely high temperatures. This observation was not significant for Cd or Cr. The higher the concentration of Cl the higher the retention of trace metals in the vapor phase, even at low temperatures. Results from comparisons of the reactivities of mixed metals with Cl indicate that the presence of Fe limits the reactivity of most trace metals with Cl except at higher concentrations. In the presence of Fe, alkali metals are the first to react with Cl. If Fe is not present, most trace metals react with Cl, and the activity increases with higher concentrations. On the other hand, the partitioning characteristics of S show that its presence generally means that metals remain in the condensed phase. Sulfur is more reactive with alkali metals than with other trace metals. Received: June 6, 2001 / Accepted: April 30, 2002     

Volatility of heavy metals during incineration of tannery sludge in the presence of chlorides and phosphoric acid.

Knowledge of the behaviour of heavy metals in the combustion process is a most important factor in selecting disposal alternatives for waste materials. Accordingly, in this work, the vaporization behaviour of highly concentrated heavy metals (Pb, Zn, Cu and Cr) in tannery sludge were investigated experimentally. The sludge was spiked with various chlorine compounds (i.e. PVC, FeCl3, CaCl2 and NaCl) and pre-treated with phosphoric acid in order to evaluate the capacity of enhancement and weakening of the volatility of the heavy metals contained in tannery sludge. The experimental results show that the vaporization percentages increased with increasing ratio of Cl/sludge and temperature, and the accelerating and increasing effect of the addition of chlorides on the vaporization percentage of heavy metals was dependent on the release capacity of chlorine radicals. The vaporization percentages of lead and zinc increased by 15-20%, whereas those of copper and chromium increased by only about 3 and 10% at 800 degrees C. However, heavy metals were not expected to be completely released in the combustion process in spite of the high ratio of Cl/sludge. Alternately, heavy metals contained in tannery sludge can be immobilized effectively by pre-treatment with phosphoric acid. When the 85% phosphoric acid accounted for 10% of dry basis of tannery sludge, the phosphate-treated sludge showed the lowest vaporization percentage of about 3-15% with formation of Ca18Cu3(PO4)14, Ca9Cr(PO4)7, Ca19Zn2(PO4)14 and PbMgP2O7 in the bottom ash.     

Mathematical modelling of MSW incineration on a travelling bed

The rising popularity of incineration of municipal solid waste (MSW) calls for detailed mathematical modelling and understanding of the incineration process. In this paper, governing equations for mass, momentum and heat transfer for both solid and gaseous phases in a moving bed in a solid-waste incineration furnace are described and relevant sub-models are presented. The burning rates of volatile hydrocarbons in the moving bed of solids are limited not only by the reaction kinetics but also the mixing of the volatile fuels with the under-fire air. The mixing rate is averaged across a computation cell and correlated to a number of parameters including local void fraction of the bed, gas velocity and a length scale comparable to the particle size in the bed. A correlation equation is also included to calculate the mixing in the freeboard area immediately next to the bed surface. A small-scale fixed bed waste incinerator was built and test runs were made in which total mass loss from the bed, temperature and gas composition at different locations along the bed height were measured. A 2-D bed-modelling program (FLIC) was developed which incorporates the various sub-process models and solves the governing equations for both gases and solids. Thermal and chemical processes are mainly confined within a layer about 5-9 times in thickness of the averaged particle size in the burning bed. For a large part of the burning process, the total mass loss rate was constant until the solid waste was totally dried out and a period of highly rising CO emission followed. The maximum bed temperature was around 1200 K. The whole burning process ended within 60 min. Big fluctuations in species concentration were observed due to channelling and subsequent 'catastrophic' changes in the local bed conditions. Reasonably good agreement between modelling and measurements has been achieved. Yet the modelling work is complicated by the channelling phenomenon in the bed. Numerical simulations without consideration of the channelling effect produced very good agreement with experiments concerning the total mass loss, but significant discrepancy exists for temperature and gas composition profiles. Transient phenomena such as the breaking of waste particles and the "catastrophic" creation of new burning channels occurring during waste incineration is a vital area requiring further investigation at the fundamental level. The underlying theory of bed behaviour must be extended to include these transient events.     

Leaching of heavy metals by citric acid from fly ash generated in municipal waste incineration plants

The leaching behavior of heavy metals from municipal waste incineration (MWI) fly ash was investigated in this study. The leaching process includes two steps, i.e., fly ash was firstly washed with water, and then subjected to citric acid leaching. The main parameters of the washing process such as liquid/solid ratio, washing time, and number of washing were tested. The optimum conditions for water washing were found as follows: washing time 5–10 min, liquid/solid ratio 10:1 (ml:g), and number of washing was twice; under these conditions, 86% Na, 70% K, 12% Ca, 1.2% Al, and 0.5% Pb were removed from the fly ash in the prewashing. From the results of screening tests of leaching lixiviants, citric acid was found to be the most effective leaching agent, taking account of its environmentally benign characteristics. Optimum metal extraction can be achieved with citric acid under the following conditions: pH 3.0, liquid/solid ratio 40 (ml:g), citric acid concentration 0.10 mol/dm³, contact time 20 min at room temperature.     

我国垃圾焚烧发电CDM项目开发难点与实践分析

基于我国目前垃圾焚烧发电CDM项目的开发现状,从不同的角度比较和分析了该类项目的特点,总结了其项目公示阶段出现的问题并对方法学修正内容进行了说明。同时,以实际项目为例,着重探讨了额外性论证中的投资比较分析、普及性分析等难点问题,最终得出结论并提出建议。     

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

On the effect of MSW moisture content on meeting target recycling rates

A mathematical model to calculate the recycle rates for packaging materials from the municipal solid wastes (MSW) built from the dry mass values that are obtained from the corresponding wet masses and their respective moisture contents is presented in this work. A possible universal methodology is also described to be used with the previous model so that reliable comparisons between indicators for different regions are feasible. Furthermore, this mathematical model demonstrates the effect of the moisture content of packaging materials on their recycling rates and constitutes a fundamental tool for operators and persons responsible for MSW management to define new policies and technical measures viewing the improvement of recycling rates. A theoretical study and the application of the model to the MEMSW of the Lisbon region shows that the moisture content of the mixed wastes plays a dominant role in the recycling rates of packaging materials such as paper, plastics and glass. Moreover, accounting for all relevant masses in the dry basis yields higher recycling rate values: increases of 32.8% for paper, 50% for plastics and 44.6% glass are observed.     

Leaching behavior of heavy metals from municipal solid waste incineration bottom ash and its geochemical modeling

With the increase in the number of municipal solid waste incineration (MSWI) plants constructed in China recently, great attention has been paid to the heavy metal leaching toxicity of MSWI residues. In this study, the effects of various parameters, including extractant, leaching time, liquid-to-solid ratio, leachate pH, and heavy metal content, on the release properties of Cd, Cr, Cu, Ni, Pb, and Zn from MSWI bottom ash were investigated. Partial least-squares analysis was employed to highlight the interrelationships between the factors and response variables. Both experimental research and geochemical modeling using Visual MINTEQ software were conducted to study the pH-dependent leaching behavior of these metals in fresh and weathered bottom ash, considering precipitation/dissolution and surface complexation reactions (adsorption by hydrous ferric oxide and amorphous aluminum oxide/hydroxide). The results showed that leachate pH was the predominant factor influencing heavy metal leachability. The leaching of Cu, Pb, and Zn was mainly controlled by precipitation/dissolution reactions, whereas surface complexation had some effect on the leaching of Cr, Cd, and Ni for certain pH ranges. The modeling results aggreed well with the experimental results. Part of this work was presented at the Fourth International Conference on Combustion, Incineration/Pyrolysis and Emission Control (i-CIPEC)     

垃圾焚烧烟气中二(噁)英零排放技术实践

介绍了绍兴新民热电有限公司用煤和垃圾混烧循环流化床技术处理城市生活垃圾，焚烧烟气经活性炭吸附、半干法和布袋除尘器净化工艺处理后，烟气中二噁英接近零排放。     

Effect of natural ageing on volume stability of MSW and wood waste incineration residues

This paper presents the results of a study on the effect of natural weathering on volume stability of bottom ash (BA) from municipal solid waste (MSW) and wood waste incineration. BA samples were taken at different steps of treatment (fresh, 4 weeks and 12 weeks aged) and then characterised for their chemical and mineralogical composition and for volume stability by means of the mineralogical test method (M HMVA-StB), which is part of the German quality control system for using aggregates in road construction (TL Gestein-StB 04). Changes of mineralogical composition with the proceeding of the weathering treatment were also monitored by leaching tests. At the end of the 12 weeks of treatment, almost all the considered samples resulted to be usable without restrictions in road construction with reference to the test parameter volume stability.     

Experimental study on flue gas purifying of MSW incineration using in-pipe jet adsorption techniques

This paper presents the experimental research process and results about flue gas purifying of municipal solid wastes (MSW) incineration using in-pipe jet adsorption techniques. MSW incineration was carried out in a fluidized bed test rig, and the flue gas purifying was carried out in an in-pipe jet adsorption test rig. The experimental results are as follows: when the feedstock of activated carbon is 1.6g/Nm(3), the desulfurization efficiency is 83%, the denitrification efficiency is 41%, and the dechlorination efficiency is 27%. The order of purifying effect of the three kinds of adsorbents on acidic gases from MSW incineration is activated carbon>activated bauxite>kaolin. Comparison of adsorption capabilities of the three kinds of adsorbents to heavy metals shows that activated carbon is the best additive to remove Cd, Pb and Cu, kaolin is inferior, and activated bauxite is the worst one. However, activated bauxite is the best additive to remove Hg, and it can remove Cd effectively. PAHs in fly ash are dominated by three-, four-, and five-ringed PAHs, and PAHs in the flue gas mainly include three- and four-ringed PAHs. When the injected quantity of additive is constant, the order of cleaning effect on PAHs is kaolin>activated carbon>activated bauxite. These three kinds of adsorbents have different purifying effects on acidic gases, heavy metals and PAHs in the flue gas from MSW incineration. In general, activated carbon has a better adsorption capability.     

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.     

Impact of moisture on volatility of heavy metals in municipal solid waste incinerated in a laboratory scale simulated incinerator

In this work, the impact of moisture on the volatility of heavy metals present in municipal solid wastes (MSW) in a laboratory scale simulated incinerator was studied, using synthetic waste consisting of 5.4 g of wood powder, 2.6 g lava, 1.9 polythene, 0.19 g polyvinyl chloride, and a given quantity of water and heavy metals represented by lead, zinc and copper in forms of metallic, chlorides and oxides. It is found that the presence of high moisture in MSW will greatly reduce the volatilization of heavy metals in MSW in the incineration process. The volatilization behavior of chlorides, oxides and the metallic species with respect to the effect of moistures is quite different. For copper, the presence of moisture in MSW depresses the volatilization of oxides, and increases that of chloride and the metallic species, while in contrast, the volatilization of both lead and zinc is always depressed by the presence of moisture in MSW, regardless of the chemical forms used. The chemical mechanisms, which govern the volatilization behaviors of different chemical forms in the incineration process, are proposed. Hydrolysis, dewatering of hydrolyzed species, sublimation, chemical transformation of less volatiles to more volatiles or reverse, may participate in and affect the volatilization of heavy metals in MSW.