Investigation of hydrogen generation from municipal solid waste incineration fly ash

Hydrogen generation from municipal solid waste incineration fly ash was investigated to understand the influences of contacting method, kinds of contact solution, liquid to solid ratio, and particle size distribution of materials. Redox properties of materials and hydrogen generation were also studied. The largest quantity of gas generated in contact with water was 29.1 ml/g-ash, most of which was hydrogen. Fluidized bed fly ash generated more gas than stoker fly ash. In order to calculate the hydrogen generation potential (the maximum quantity of gas generated in contact with water), a novel system using a Y-shaped test tube and NaOH was utilized. This method gives values which are related to the quantity of generated gas in contact with water. A relationship between the aluminum content and hydrogen generation potential was observed, especially for fluidized bed fly ash. The reducing potential of fluidized bed fly ash was higher than that of stoker fly ash. Only fluidized bed fly ash showed a positive correlation between aluminum content and reducing potential, and between reducing potential and hydrogen generation potential. These results suggest that fluidized bed fly ash contains more Al⁰ than stoker fly ash. Received: September 11, 1998 / Accepted: March 19, 1999     

Metallic-phase lead in slag of municipal solid waste incineration ash and leaching characteristics

Metallic phases in slags and their influence on the leaching characteristics were investigated. The proportions of metallic phase in four slags were 0.028%, 0.24%, 1.87%, and 3.05% by weight. The lead content was 10–248 mg/kg in bulk slag after metal removal, while in the metallic phase it was 579–7390 mg/kg. Lead concentrations in the metallic phase were more than ten times higher than in slags after metal removal. Lead was distributed in the metallic phase at 2.0%, 8.3%, 10.3%, and 47.4%. The concentrations of all metallic elements in metallic phases were much higher than in bulk slag. Iron, copper, and nickel had accumulated in magnetic metals, while aluminum and zinc were found in nonmagnetic metals. As regards chromium, manganese, lead, and tin, the proportion of metallic phases depended on the slag samples. By removing metallic phases, both water and pH 4 leachable lead decreased. The basic principles of melting residues containing lead are the separation of lead as a metal in reductive melting, and the containment of lead ions into uniform glassy particles in oxidization melting. Melting slag can be seen to contribute to environmental preservation by facilitating the recycling of materials through the separation of metals from melting slag. Received: February 21, 2000 / Accepted: July 27, 2000     

Chlorine promotes antimony volatilization in municipal waste incineration

Antimony volatilization in municipal waste incineration was studied. Two municipal waste samples and antimony(III) oxide (Sb₄O₆) were heated to 500°C and 700°C in an air stream in a quartz furnace. The volatilization of Sb₄O₆ occurred more at 700°C that at 500°C. Conversely, antimony volatilization form municipal waste was stronger at 500°C than at 700°C. This implies that antimony from municipal waste is volatilized as chloride instead of oxide. The chlorine sources for antimony chlorination, a gas-phase reaction involving hydrochloric acid and a solid-phase reaction of inorganic chlorine, e.g., CaCl₂, were compared. Only the solid-phase reaction could offer enough active chlorine to induce chlorination of antimony oxide. Received: July 2, 1998 / Accepted: January 28, 1999     

Metal releases from a municipal solid waste incineration air pollution control residue mixed with compost

The influence of 10 wt.% mature compost was tested on the heavy metal leachate emissions from a calcium-rich municipal solid waste incineration air pollution control residue (MSWI APC). Apart from elongated columns (500 and 1250 mm), an otherwise norm compliant European percolation test setup was used. More than 99% of the metals Al, As, Cd, Cr, Cu, Fe and Ni were left in the APC residue after leaching to a liquid-to-solid ratio (L/S) of 10. Apparent short-term effects of elevated leachate DOC concentrations on heavy metal releases were not detected. Zn and Pb leachate concentrations were one order of magnitude lower for L/S 5 and 10 from the pure APC residue column, which suggests a possible long-term effect of compost on the release of these elements. Prolonging the contact time between the pore water and the material resulted in elevated leachate concentrations at L/S 0.1 to L/S 1 by a factor of 2. Only Cr and Pb concentrations were at their maxima in the first leachates at L/S 0.1. Equilibrium speciation modelling with the PHREEQC code suggested portlandite (Ca(OH)2) to control Ca solubility and pH.     

Thiourea leaching of gold from processed municipal solid waste incineration residues

Incineration is one of the key technologies in disposal of municipal waste, which produces municipal solid waste incineration (MSWI) residues with high valuable metal contents. The recycling strategy for the MSWI residues is typically focused on the recovery of scrap metals yielding processed municipal solid waste incineration residues (PIR) as the main byproduct. However, the PIR still contains valuable metals, particularly gold, which cannot be extracted by conventional methods. Here, we evaluated the feasibility of using the 0.5–2.0 mm grain size fraction of PIR containing 28.82 ± 1.62 mg/kg of gold as raw material for a two-stage extraction process. In the first stage the alkalic fine-grained PIR was acidified with a solution of 20% (v/v) of HCl-containing flue gas cleaning liquid that is obtained by the municipal waste incineration plant itself as a waste product. In the second stage we leached the acidified fine-grained PIR by thiourea with Fe³⁺ as an oxidant. Application of the thiourea-Fe³⁺ leaching system resulted in recovery of 16.4 ± 1.56 mg/kg of gold from the fine-grained PIR within 6 h of incubation. Due to high gold market prices, upscaling of the suggested technology can represent a suitable strategy for gold recovery from PIR and other MSWI residues.

     

Improved quartz furnace method for chlorine and sulfur determination in municipal solid waste

 A method of determining the chlorine (Cl) and sulfur (S) in municipal solid waste (MSW) was studied. The quartz furnace method was improved in two ways: recovery from ash by hot extraction with dilute nitric acid, and avoidance of the volatilization of alkali (earth) metal chlorides by setting the sample combustion temperature at 600°C. In a comparison with the bomb method, using nine sets of kitchen garbage and waste plastics, the bomb method yielded a 15%–25% lower value than the improved quartz furnace method. Combustion in the bomb was frequently incomplete, resulting in recovery losses of Cl and S. The average kitchen garbage involved 5.2 mg Cl/g, of which at least 24.1% would be converted to HCl. Plastics contained 23 mg Cl/g generating 88.1% HCl on average. In the same way, kitchen garbage contained 3.0 mg S/g, generating 52.3% SO _x , whereas plastics contained 1.1 mg S/g with 55.1% SO _x formation. Received: March 20, 2002 / Accepted: October 13, 2002     

Substance flow analysis of coplanar PCBs released from waste incineration processes

Previous reports have focused on the emission of coplanar polychlorinated biphenyls (Co-PCBs) which have a toxic mechanism similar to that of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/DFs) released from municipal solid waste (MSW) incineration. Such emissions accounted for a small percentage of all the dioxins (PCDDs/DFs and Co-PCBs) recorded at the toxicity equivalent (TEQ) level. There is, however, very little information about Co-PCBs, such as the quantities being released and their effect on overall environmental pollution. The aim of this research has been to clarify the substance flow of Co-PCBs from MSW incineration processes. The results reveal that whereas the input of Co-PCBs into the MSW incineration facilities in Kyoto City was 0.13–0.29 μg-TEQ per ton waste, the total output of Co-PCBs (the sum of Co-PCBs released from emission gas, fly ash, and bottom ash) was 4.9 μg-TEQ per ton waste. The total output was therefore found to be higher than the total input. Over 90% of the total PCBs were decomposed in the incineration process. In comparing the profiles of congeners and homologues, those in the MSW were found to be similar to those detected in the atmosphere and products containing PCBs, but different from those in the MSW incineration gas. Received: August 26, 1998 / Accepted: March 2, 1999     

生活垃圾焚烧发电厂二恶英对人体健康的风险评价

介绍了生活垃圾焚烧过程中二恶英的产生机理、对人体的危害及控制措施,以某生活垃圾焚烧发电厂环境影响评价为例,提出了二恶英对人体健康风险评价方法,同类项目环境影响评价提供借鉴。     

Recycling of air pollution control residues from municipal solid waste incineration into lightweight aggregates

This work focuses on the assessment of technological properties and on the leaching behavior of lightweight aggregates (LWA) produced by incorporating different quantities of air pollution control (APC) residues from municipal solid waste (MSW) incineration. Currently this hazardous waste has been mostly landfilled after stabilization/solidification. The LWA were produced by pelletizing natural clay, APC residues as-received from incineration plant, or after a washing treatment, a small amount of oil and water. The pellets were fired in a laboratory chamber furnace over calcium carbonate. The main technological properties of the LWA were evaluated, mainly concerning morphology, bulk and particle densities, compressive strength, bloating index, water adsorption and porosity. Given that APC residues do not own expansive (bloating) properties, the incorporation into LWA is only possible in moderate quantities, such as 3% as received or 5% after pre-washing treatment.The leaching behavior of heavy metals from sintered LWA using water or acid solutions was investigated, and despite the low acid neutralization capacity of the synthetic aggregates, the released quantities were low over a wide pH range.In conclusion, after a washing pre-treatment and if the percentage of incorporation is low, these residues may be incorporated into LWA. However, the recycling of APC residues from MSW incineration into LWA does not revealed any technical advantage.     

国内城市生活垃圾焚烧飞灰研究现状及进展

随着我国经济快速发展及城市化水平提升,城市生活垃圾产量越来越大,焚烧逐渐成为城市生活垃圾处理的主要方式.但焚烧会产生大量的垃圾焚烧飞灰(以下简称飞灰),飞灰属于危险废物.论述了飞灰的来源、成分、特性及危害,介绍了飞灰的处理处置技术:水泥固化技术、化学药剂稳定化技术、熔融固化技术、水热稳定化技术和水泥窑协同处理技术,并分...     

Production of cement clinkers from municipal solid waste incineration (MSWI) fly ash

This communication reports the laboratory scale study on the production of cement clinkers from two types of municipal solid waste incineration fly ash (MSW ash) samples. XRD technique was used to monitor the phase formation during the burning of the raw mixes. The amount of trace elements volatilized during clinkerization and hydration, as well as leaching behaviours of the clinkers obtained from optimum compositions, were also evaluated. From the results it is observed that all of the major components of ordinary Portland cement (OPC) clinkers are present in the produced clinkers. Results also show the volatilization of considerable amounts of Na, K, Pb, Zn and Cd during the production of clinkers. However, major parts of the toxic elements remaining in the clinkers appear to be immobilized in the clinkers phases. Hydration studies of the clinkers obtained from optimum compositions show that the clinkers prepared from raw MSW ash are more reactive than the washed MSW ash based clinkers. TG/DTA analyses of the hydrated pastes show the formation of hydration products, which are generally found in OPC and OPC derived cements. The initial study, therefore, shows that more than 44% of MSW ash with the addition of very small amounts of silica and iron oxide can be used to produce cement clinkers. The amount of CaCO3 necessary to produce clinkers (approximately 50%) is also smaller than the same required for the conventional process (more than 70%).     

Studies on the pyrolysis behavior of gasification and melting systems for municipal solid waste

 It is important to investigate the pyrolysis processes of municipal solid waste (MSW) in the same way as for any mixture comprised of multiple substances. In this article, a two-reaction model for a variety of MSW mixtures is proposed to predict mass changes due to pyrolysis. In order to formulate the model based on pyrolysis kinetics, we conducted experiments to determine the kinetic model parameters. By thermal analysis of the typical components of MSW, mass changes attributable to the pyrolysis reaction were found at about 350°C for paper, 400°–500°C for plastics, and 200°–400°C for garbage (dry condition). Activation energies were obtained by the Ozawa method based on the mass changes in pyrolysis. Thus, the pyrolysis behavior is formulated as a function of temperature. Then the pyrolysis mass change of the mixture can be predicted by using a weighted sum of the individual components. The model proved useful in experiments with real waste (refuse-derived fuels). Furthermore, the weight yields (pyrolysis gas, tars, solid residues) of the mixture can be calculated by their additive property after measuring the mass balance of each component. Received: May 11, 2001 / Accepted: November 16, 2001     

Mass balance of arsenic and antimony in municipal waste incinerators

The arsenic and antimony balance in two municipal waste incinerators was investigated. Initially, the production rates of ash and wet scrubber effluent were estimated. Then the arsenic and antimony in the ash and wet scrubber effluent were determined, which gave an estimate of the elemental balance. The total amounts of arsenic and antimony in the municipal waste were 0.9 g/t and 30–44 g/t, respectively. The distributions to fly ash were 45–47% and 33–74% for arsenic and antimony, respectively. The distribution mechanisms of arsenic and antimony are discussed from the viewpoints of their thermodynamics as well as their initial valencies, which greatly affect their behaviour. Received: July 2, 1998 / Accepted: February 27, 1999     

Investigation on the humification of municipal solid waste incineration residue and its effect on the leaching behavior of dioxins

In this study, we investigated the humification of municipal solid waste incineration residue through identification of extracted humic substances, and examined the leachability of dioxins by batch leaching test. The samples were incineration residues excavated from lysimeters 6-8 years after being filled. The results of investigation of humic substances showed that the top layers from the surface to a depth of 30-70 cm contained more humic substances than the other layers judging from the color of the samples and optical characteristics of the extracts. In particular, humification in the lysimeter filled with a small amount of compost had progressed through all the layers, not only the top one. The tests revealed that the leaching concentrations of dioxins increased with advanced humification and showed relatively good correlation to dissolved organic carbon (DOC) of leachate at each lysimeter. Humification advances from the surface first, and DOC generated from the humification may preferentially carry down the highly chlorinated dioxin compounds such as O8CDD as DOC-dioxin complexes. Comparing the content and leaching concentration according to depth, we observed not only a decrease in dioxin content but also an increase in leaching of the highly chlorinated dioxins at deeper layers in the lysimeters with the compost. This tendency seemed to result from biological activities.     

Health risk assessment of air emissions from a municipal solid waste incineration plant--a case study

A health risk assessment of long-term emissions of carcinogenic and non-carcinogenic air pollutants has been carried out for the municipal solid waste incinerator (MSWI) of the city of Taranto, Italy. Ground level air concentrations and soil deposition of carcinogenic (Polychlorinated Dibenzo-p-Dioxins/Furans and Cd) and non-carcinogenic (Pb and Hg) pollutants have been estimated using a well documented atmospheric dispersion model. Health risk values for air inhalation, dermal contact, soil and food ingestion have been calculated based on a combination of these concentrations and a matrix of environmental exposure factors. Exposure of the surrounding population has been addressed for different release scenarios based on four pollutants, four exposure pathways and two receptor groups (children and adults). Spatial risk distribution and cancer excess cases projected from plant emissions have been compared with background mortality records. Estimated results based on the MSWI emissions show: (1) individual risks well below maximum acceptable levels, (2) very small incremental cancer risk compared with background level.     

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H₂S; the average concentration of H₂S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H₂S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H₂S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H₂S (in order of ppbv). Regarding NH₃, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv).Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv.H₂S/NH₃, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.     

Fabric-filter-supported catalyst for removal of harmful solid and gaseous compounds in municipal waste incinerator exhaust gas: characteristics of NO x reduction

We have investigated a fabric-filter-supported catalyst for removing harmful solid and gaseous compounds simultaneously from municipal incinerator exhaust gas. We studied the ways in which the efficiency of NO _x removal is influenced by filter temperature, gas flow rate, and catalyst content. The reduction of the catalyst content by mechanical reverse washing was investigated, and the state of the catalyst supported in the fabric filter was also observed using a scanning electron microscope. The catalyst supported by the fabric filter showed a removal efficiency above 75% when the filter temperature was 200°C, the gas flow rate was 1 m/min, and the catalyst content of the fabric filter was above 300 g/m². The catalyst was supported uniformly on the fibers of the fabric filter, and fine catalyst particles remained on the fibers after mechanical reverse washing. Received: October 15, 1997 / Accepted: March 19, 1999     

Quantification of the resource recovery potential of municipal solid waste incineration bottom ashes

Municipal solid waste incineration (MSWI) plays an important role in many European waste management systems. However, increasing focus on resource criticality has raised concern regarding the possible loss of critical resources through MSWI. The primary form of solid output from waste incinerators is bottom ashes (BAs), which also have important resource potential. Based on a full-scale Danish recovery facility, detailed material and substance flow analyses (MFA and SFA) were carried out, in order to characterise the resource recovery potential of Danish BA: (i) based on historical and experimental data, all individual flows (representing different grain size fractions) within the recovery facility were quantified, (ii) the resource potential of ferrous (Fe) and non-ferrous (NFe) metals as well as rare earth elements (REE) was determined, (iii) recovery efficiencies were quantified for scrap metal and (iv) resource potential variability and recovery efficiencies were quantified based on a range of ashes from different incinerators. Recovery efficiencies for Fe and NFe reached 85% and 61%, respectively, with the resource potential of metals in BA before recovery being 7.2%ww for Fe and 2.2%ww for NFe. Considerable non-recovered resource potential was found in fine fraction (below 2 mm), where approximately 12% of the total NFe potential in the BA were left. REEs were detected in the ashes, but the levels were two or three orders of magnitude lower than typical ore concentrations. The lack of REE enrichment in BAs indicated that the post-incineration recovery of these resources may not be a likely option with current technology. Based on these results, it is recommended to focus on limiting REE-containing products in waste for incineration and improving pre-incineration sorting initiatives for these elements.     

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)     

The estimation of N2O emissions from municipal solid waste incineration facilities: The Korea case

The greenhouse gases (GHGs) generated in municipal solid waste (MSW) incineration are carbon dioxide (CO₂), methane (CH₄), and nitrous oxide (N₂O). In South Korea case, the total of GHGs from the waste incineration facilities has been increasing at an annual rate 10%. In these view, waste incineration facilities should consider to reduce GHG emissions.This study is designed to estimate the N₂O emission factors from MSW incineration plants, and calculate the N₂O emissions based on these factors. The three MSW incinerators examined in this study were either stoker or both stoker and rotary kiln facilities. The N₂O concentrations from the MSW incinerators were measured using gas chromatography-electron capture detection (GC-ECD) equipment.The average of the N₂O emission factors for the M01 plant, M02 plant, and M03 plant are 71, 75, and 153 g-N₂O/ton-waste, respectively. These results showed a significant difference from the default values of the intergovernmental panel on climate change (IPCC), while approaching those values derived in Japan and Germany. Furthermore, comparing the results of this study to the Korea Energy Economics Institute (KEEI) (2007) data on waste incineration, N₂O emissions from MSW incineration comprised 19% of the total N₂O emissions.