Effects of the type of sintering atmosphere on the chromium leachability of thermal-treated municipal solid waste incinerator fly ash

The sintering process offers an opportunity to combine detoxification and resource recovery for the treatment of municipal solid waste (MSW) incinerator fly ash. However, the chromium (Cr) in the sintered fly ash becomes more readily leachable with increasing sintering time and temperature, thus posing severe threats to the environment and human health when the sintered ash is recycled or reused. This study investigated the enhanced leachability of fly ash containing Cr, by heating the chromium (III) oxide (Cr2O3)-spiked fly ash to 800 degrees C in atmospheres containing air, nitrogen gas (N2), and 5% H2 + 95% N2, respectively. The results indicated that trivalent chromium was converted to its soluble hexavalent form during sintering in the air atmosphere; whereas sintering in a nitrogen atmosphere significantly reduced the leachability of Cr due to lack of oxygen (O2) to oxidize. The effects of the sintering temperature on the total chromium content and the leaching concentration in the toxicity characteristic leaching procedure (TCLP) extract are also discussed.     

Combustion studies of high moisture content waste in a fluidised bed

The combustion of three high moisture content waste materials in a fluidised bed combustor has been investigated and a comparison with co-firing of these materials with coal in the same combustor has been made. Waste materials burnt were olive oil waste, municipal solid waste and potato, which is representative of vegetable waste. Mixtures of up to 20% mass concentration water in the waste were fed to the combustor. Above that value the moisture content was too high to sustain combustion without addition of coal. Measurements of CO, NOx, SO2 temperatures were made and the carbon combustion efficiency evaluated. Co-firing with coal resulted in markedly higher combustion efficiencies with an increase of approximately 10-80% when burning the simulated MSW. However, this was much lower than the value of 93% when coal was burnt on its own. It was also much lower than the value obtained, average 90%, when co-firing potato and olive oil waste with coal and there was little difference in the combustion efficiency between the two types of waste and with increasing moisture content. It was concluded that the high ash content of the simulated MSW 26%, compared with 5% in the other two waste materials resulted in slower burning and consequently the char particles were elutriated from the bed without being fully burnt. In term of gaseous emissions during co-combustion, CO emission is relatively insensitive to change in waste fraction. While emission of SO2 can be reduced as the waste fraction increases as a result of fuel-S dilution. But in terms of percent fuel-S converted, it is actually increased by increasing waste fraction. Emissions of NO and N2O increase slightly with MSW fraction.     

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.     

Trace element partitioning in ashes from boilers firing pure wood or mixtures of solid waste with respect to fuel composition,chlorine content and temperature

Trace element partitioning in solid waste (household waste, industrial waste, waste wood chips and waste mixtures) incineration residues was investigated. Samples of fly ash and bottom ash were collected from six incineration facilities across Sweden including two grate fired and four fluidized bed incinerators, to have a variation in the input fuel composition (from pure biofuel to mixture of waste) and different temperature boiler conditions. As trace element concentrations in the input waste at the same facilities have already been analyzed, the present study focuses on the concentration of trace elements in the waste fuel, their distribution in the incineration residues with respect to chlorine content of waste and combustion temperature.Results indicate that Zn, Cu and Pb are dominating trace elements in the waste fuel. Highly volatile elements mercury and cadmium are mainly found in fly ash in all cases; 2/3 of lead also end up in fly ash while Zn, As and Sb show a large variation in distribution with most of them residing in the fly ash. Lithophilic elements such as copper and chromium are mainly found in bottom ash from grate fired facilities while partition mostly into fly ash from fluidized bed incinerators, especially for plants fuelled by waste wood or ordinary wood chips. There is no specific correlation between input concentration of an element in the waste fuel and fraction partitioned to fly ash. Temperature and chlorine content have significant effects on partitioning characteristics by increasing the formation and vaporization of highly volatile metal chlorides. Zinc and cadmium concentrations in fly ash increase with the incineration temperature.     

Finished leather waste chromium acid extraction and anaerobic biodegradation of the products

Due to the amounts of chromium in the leachate resulting from leather leaching tests, chromium sulfate tanned leather wastes are very often considered hazardous wastes. To overcome this problem, one option could be recovering the chromium and, consequently, lowering its content in the leather scrap. With this objective, chromium leather scrap was leached with sulfuric acid solutions at low temperature also aiming at maximizing chromium removal with minimum attack of the leather matrix. The effects of leather scrap dimension, sulfuric acid and sodium sulfate concentration in the solutions, as well as extraction time and temperature on chromium recovery were studied, and, additionally, organic matrix degradation was evaluated. The best conditions found for chromium recovery were leather scrap conditioning using 25 mL of concentrated H₂SO₄/L solution at 293 or 313 K during 3 or 6 days. Under such conditions, 30–60 ± 5% of chromium was recovered and as low as 3–6 ± 1% of the leather total organic carbon (TOC) was dissolved. Using such treatment, the leather scrap area and volume are reduced and the residue is a more brittle material showing enhanced anaerobic biodegradability. Although good recovery results were achieved, due to the fact that the amount of chromium in eluate exceeded the threshold value this waste was still hazardous. Thus, it needs to be methodically washed in order to remove all the chromium de-linked from collagen.     

A case study of waste management at the Northern Finnish pulp and paper mill complex of Stora Enso Veitsiluoto Mills

This work presents the current waste management system at the pulp and paper mill complex of Stora Enso Oyj Veitsiluoto Mills at Kemi, Northern Finland. This paper covers examples of case studies carried out at the mill and describes how the wastes and by-products are utilized as a neutralizing agent for acidic wastewaters (i.e., green liquor dregs from the causticizing process), as a hardener in filling mine cavities (i.e., ash from the fluidized bed boiler), as a landscaping agent (i.e., ash as well as the fibre clay from chemical wastewater treatment plant), as a hydraulic barrier material for landfills (i.e., fibre clay), and as a soil enrichment agent (i.e., calcium carbonate from the precipitated calcium carbonate plant). In addition, the wood waste from the wood-handling plant, sawmill, packaging pallet plant and from the groundwood mill, as well as the biosludge from the biological wastewater treatment plant, are all incinerated in the fluidized bed boiler for energy production. Due to effective utilization of the solid wastes generated at the mills, the annual amount of waste to be disposed of in the landfill has decreased between 1994 and 2004 from 42,990 to 6083 tonn (expressed as wet weight). The paper also gives an overview of the relevant European Union legislation on the forest industry and on waste management, as well as of the pulping process and of the generation of major solid wastes in the pulp and paper mills.     

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     

Circulating fluidized bed incineration of industrial solid wastes

A pilot scale test facility of a circulating fluidized bed incinerator was established to generate design and operation data and help assess the technical feasibility for industrial applications. The use of high turbulence in the combustion zone and feeding an acid-capturer directly into the incinerator to absorb acid gases eliminates the costly afterburner and scrubber. This paper presents some systematic incineration tests of uniform industrial wastes such as paper mill sludge cake, rubber waste and petroleum coke. Sludge cakes with high moisture and low heating values can be treated to a low emission level by co-firing with coal. The high superficial gas velocity has improved combustion efficiency but increases NO_x emissions. However, sulphur content has almost no influence on sulphur retention. The problems of CO/NO_x emissions and circulation stability are also discussed.     

Metal distribution in incineration residues of municipal solid waste (MSW) in Japan

This study aimed to identify distribution of metals and the influential factors on metal concentrations in incineration residues. Bottom ash and fly ash were sampled from 19 stoker and seven fluidized bed incinerators, which were selected to have a variety of furnace capacity, furnace temperature, and input waste. In the results, shredded bulky waste in input waste increased the concentration of some metals, such as Cd and Pb, and the effect was confirmed by analysis of shredded bulky waste. During MSW incineration, lithophilic metals such as Fe, Cu, Cr, and Al remained mainly in the bottom ash while Cd volatilized from the furnace and condensed to the fly ash. About two thirds of Pb and Zn was found in the bottom ash despite their high volatility. Finally, based on the results obtained in this study, the amount of metal in incineration residues of MSW was calculated and the loss of metal was estimated in terms of mass and money. A considerable amount of metal was found to be lost as waste material by landfilling of incineration residues.     

Valorization of titanium metal wastes as tanning agent used in leather industry

The development of new tanning agents and new technologies in the leather sector is required to cope with the increasingly higher environmental pressure on the current tanning materials and processes such as tanning with chromium salts. In this paper, the use of titanium wastes (cuttings) resulting from the process of obtaining highly pure titanium (ingots), for the synthesis of new tanning agent and tanning bovine hides with new tanning agent, as alternative to tanning with chromium salts are investigated. For this purpose, Ti waste and Ti-based tanning agent were characterized for metal content by inductively coupled plasma mass spectrometry (ICP-MS) and chemical analysis; the tanned leather (wet white leather) was characterized by Scanning Electron Microscope/Energy Dispersive Using X-ray (Analysis). SEM/EDX analysis for metal content; Differential scanning calorimetric (DSC), Micro-Hot-Table and standard shrinkage temperature showing a hydrothermal stability (ranged from 75.3 to 77 °C) and chemical analysis showing the leather is tanned and can be processed through the subsequent mechanical operations (splitting, shaving). On the other hand, an analysis of major minor trace substances from Ti-end waste (especially vanadium content) in new tanning agent and wet white leather (not detected) and residue stream was performed and showed that leachability of vanadium is acceptable. The results obtained show that new tanning agent obtained from Ti end waste can be used for tanning bovine hides, as eco-friendly alternative for chrome tanning.     

Co-combustion of agricultural residues with coal in a fluidized bed combustor

Power generation from biomass is an attractive technology that utilizes agricultural residual waste. In order to explain the behavior of biomass-fired fluidized bed incinerator, biomass sources from agricultural residues (rice husk and palm kernel) were co-fired with coal in a 0.15m diameter and 2.3m high fluidized bed combustor. The combustion efficiency and carbon monoxide emissions were studied and compared with those for pure coal combustion. Co-combustion of a mixture of biomass with coal in a fluidized bed combustor designed for coal combustion increased combustion efficiency up to 20% depending upon excess air levels. Observed carbon monoxide levels fluctuated between 200 and 900 ppm with the addition of coal. It is evident from this research that efficient co-firing of biomass with coal can be achieved with minimal modifications to existing coal-fired boilers.     

稻壳混煤燃烧对NOx 排放的影响

利用循环流化床试验平台分析稻壳混煤燃烧对NOx 排放的影响。结果表明，贫煤混合稻壳后燃烧，当燃烧温度恒定时，NOx的排放量随着燃料中稻壳所占比重增加而降低；当燃料中稻壳所占比重恒定时，NOx的排放量随着燃烧温度的升高而增加。     

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.     

Combined incineration of industrial wastes with in-plant residues in fluidized-bed utility boilers--decision relevant factors.

In Austria more than 50% of the high-calorific industrial residues and wastes generated are utilized for energy recovery in industrial utility boilers. This study investigated full-scale trials of combined incineration of in-plant residues with various industrial wastes. These trials were carried out in order to learn how the alternatively used fuel influences the incineration process itself as well as the quantity and quality of the various incineration products. The currently used fuel, which consisted of in-plant residues as well as externally acquired waste wood and the refuse-derived fuel (RDF) mixtures used during the full-scale trials are characterized in terms of material composition as well as chemical and physical parameters. An input-output mass balance for the incineration plant (two fluidized bed combustion units, 20 and 30 MW, respectively) has been established, based on the data collected during the full-scale incineration trials. Furthermore, pollutant concentrations in the off-gas as well as the solid incineration residue are reported. It is not only the pollutant content but also a variety of other internal as well as external factors that have to be considered if a company is to decide whether or not to thermally utilize specific waste types. Therefore a strengths and weaknesses profile for several types of waste and the specific industrial boiler is also presented.     

Element associations in ash from waste combustion in fluidized bed

The incineration of MSW in fluidized beds is a commonly applied waste management practice. The composition of the ashes produced in a fluidized bed boiler has important environmental implications as potentially toxic trace elements may be associated with ash particles and it is therefore essential to determine the mechanisms controlling the association of trace elements to ash particles, including the role of major element composition. The research presented here uses micro-analytical techniques to study the distribution of major and trace elements and determine the importance of affinity-based binding mechanisms in separate cyclone ash particles from MSW combustion. Particle size and the occurrence of Ca and Fe were found to be important factors for the binding of trace elements to ash particles, but the binding largely depends on random associations based on the presence of a particle when trace elements condensate in the flue gas.     

Thermal behaviour of chrome shavings and of sludges recovered after digestion of tanned solid wastes with calcium hydroxide

The thermal behaviour of chrome shavings and of sludges recovered after digestion of tanned wastes with Ca(OH)2 was studied. Ashes obtained after incineration of wastes at various temperatures were analysed by X-ray diffraction and EDX method. The main crystallized phases present in the ash obtained at 600 degrees C are Cr2O3 and NaCl. The diffractograms revealed an increase in the intensities of the chromium oxide peaks and a very notable decrease of the amount of sodium chloride at 1100 degrees C. EDX analysis revealed a total disappearance of the chlorine peak at this temperature. Scanning electron micrographs show that the waste lost its fibrous aspect when the temperature increases. Formation of aggregates was noted after 550 degrees C. Combustion of organic matters and decarbonation phenomenon are the main stages observed on GTA and DTA curves of sludges. These phenomena are, respectively, exothermic and endothermic. The diffractogram of sludges recorded at 550 degrees C, in the presence of a constant oxygen surplus, revealed the presence of CaCrO4 and CaCO3.     

沸腾炉大气污染物的生成与排放特征分析

以20台沸腾炉(功率小于等于60 MW)的燃料特性分析数据和大气污染物的排放实测数据为基础,利用统计分析方法,研究了燃烧过程中排放的颗粒物(PM)、SO_2和NO_x初始排放浓度的影响因素,分析了沸腾炉PM、SO_2和NO_x排放现状,探讨了我国中小型沸腾炉PM、SO_2和NO_x排放管理控制的潜力和可行性.实验结果表明:在锅炉运行负荷大于等于80%的条件下,中小型沸腾炉PM的初始排放浓度基本上不受锅炉出力、过量空气系数和燃煤灰分含量的影响;燃煤的硫含量越高,SO_2初始排放浓度越高;过量空气系数越大,燃煤挥发分越低,NO_x初始排放浓度越高.     

Synthesis of chromium-containing pigments from chromium recovered from leather waste

Cobalt-chromite green and chrome-tin pink pigments have been prepared from chromium extracted from leather shavings produced as a waste product of the leather-tanning industry. The alkaline agent (NaOH, CaO, MgO, NH4OH) used in the extraction process influences the nature of the final product. The effect of the NH4OH:CaO ratio on the final product in the case of cobalt-chromite green was examined. The pigments obtained were characterized by FT-IR and X-ray diffraction (XRD). Colour measurements were compared with those recorded from materials prepared from pure Cr2O3. The leaching of Cr(VI) from the materials was examined by UV spectroscopy.     

Assessment of mobility and bioavailability of contaminants in MSW incineration ash with aquatic and terrestrial bioassays

Incineration of municipal solid waste (MSW) is a waste treatment method which can be sustainable in terms of waste volume reduction as well as a source of renewable energy. In the process fly and bottom ash is generated as a waste material. The ash residue may vary greatly in composition depending on the type of waste incinerated and it can contain elevated levels of harmful contaminants such as heavy metals. In this study, the ecotoxicity of a weathered, untreated incineration bottom ash was characterized as defined by the H14 criterion of the EU Waste Framework Directive by means of an elemental analysis, leaching tests followed by a chemical analysis and a combination of aquatic and solid-phase bioassays. The experiments were conducted to assess the mobility and bioavailability of ash contaminants. A combination of aquatic and terrestrial bioassays was used to determine potentially adverse acute effects of exposure to the solid ash and aqueous ash leachates. The results from the study showed that the bottom ash from a municipal waste incineration plant in mid-Sweden contained levels of metals such as Cu, Pb and Zn, which exceeded the Swedish EPA limit values for inert wastes. The chemical analysis of the ash leachates showed high concentrations of particularly Cr. The leachate concentration of Cr exceeded the limit value for L/S 10 leaching for inert wastes. Filtration of leachates prior to analysis may have underestimated the leachability of complex-forming metals such as Cu and Pb. The germination test of solid ash and ash leachates using T. repens showed a higher inhibition of seedling emergence of seeds exposed to the solid ash than the seeds exposed to ash leachates. This indicated a relatively low mobility of toxicants from the solid ash into the leachates, although some metals exceeded the L/S 10 leaching limit values for inert wastes. The Microtox® toxicity test showed only a very low toxic response to the ash leachate exposure, while the D. magna immobility test showed a moderately high toxic effect of the ash leachates. Overall, the results from this study showed an ecotoxic effect of the solid MSW bottom ash and the corresponding ash leachates. The material may therefore pose an environmental risk if used in construction applications. However, as the testing of the solid ash was rather limited and the ash leachate showed an unusually high leaching of Cr, further assessments are required in order to conclusively characterize the bottom ash studied herein as hazardous according to the H14 criterion.     

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.