Water washing effects on metals emission reduction during municipal solid waste incinerator (MSWI) fly ash melting process

This study investigated that water washing effects on the metals emission reduction in melting of municipal solid waste incinerator (MSWI) fly ash. Experimental conditions were conducted at liquid-to-solid (L/S) ratio 10, 20, and 100 for water-washing process and its subsequent melting treatment at 1450 °C for 2 h. The simple water-washing process as a pre-treatment for MSWI fly ash can remove most of the chlorides, leachable salts, and amphoteric heavy metals from the MSWI fly ash, resulting in the washed ash having lowered chlorine content. MSWI fly ashes washed by L/S ratio 10 and above that were melted at 1450 °C produced slag containing relatively high vitrificaton ratio of Cu and Pb. Besides, the vitrification ratios of Na, K, Ca, and Mg in washed MSWI fly ash were also higher than that of MSWI fly ash. The results indicated that washed MSWI fly ash can reduce the emission of metallic chlorides during its subsequent melting treatment.     

Solidification/stabilisation of arsenic bearing fly ash from the metallurgical industry. Immobilisation mechanism of arsenic

When a fly ash waste material from a copper refining process containing large amounts of As2O3 is solidified using cement and lime, the arsenic concentration in the leachate can be lowered to ca. 5 mg/l in a saturated solution of Ca(OH)2. It is shown that the decrease of the concentration in the leachate, mainly of As(III), is due to the formation of insoluble CaHAsO3 in the leachate in the presence of Ca(OH)2. This method is compared with a method whereby use is made of oxidation of the waste before solidification to oxidise As(III) to As(V) using H2O2. The arsenic concentration in the leachate of the extraction test of an oxidised S/S sample was lowered to ca. 0.5 mg/l, a factor of 10 below the one for a non-oxidised sample. It is shown that the decrease of the concentration in the leachate mainly of As(V) is due to the formation of insoluble Ca3(AsO4)2 in the presence of Ca(OH)2. Extensive use was made of the speciation program MINTEQA2, to clarify the immobilisation of arsenic.     

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.     

Distribution of remaining Cd in MSWI fly ash washed with nitric acid

Municipal solid waste incineration (MSWI) fly ash is by-product and hazardous waste produced from MSWI plant. In the MSWI fly ash there are high contents heavy metals, among which cadmium (Cd) is more active and toxic. Although inorganic acid leaching is an effective way to remove heavy metals out from the MSWI fly ash and nitric acid has great efficiency for Cd removal, little literature reported the redistribution of remaining Cd in the MSWI fly ash. This investigation focused on the change of different factions (exchangeable, bound to carbonates, bound to Fe–Mn oxides, bound to organic matter and residual) of Cd in treated (i.e. washed with nitric acid) MSWI fly ash. Sequence extraction procedures (SEP) have been used to derive different fractions of Cd, results indicated that fractions of Cd have changed significantly after nitric acid washing procedures. Due to the changes of main compounds and microstructures stable Cd (bound to organic matter and residual) had opportunity to leach out, which resulted in a higher potential risk (or higher bioavailability index) for living creatures, although the total amount of Cd decreased. X-ray diffraction (XRD) and images of scanning electron microscope (SEM) proved these changes in washed MSWI fly ash.     

Recycling MSWI bottom and fly ash as raw materials for Portland cement

Municipal solid waste incineration (MSWI) ash is rich in heavy metals and salts. The disposal of MSWI ash without proper treatment may cause serious environmental problems. Recently, the local cement industry in Taiwan has played an important role in the management of solid wastes because it can utilize various kinds of wastes as either fuels or raw materials. The objective of this study is to assess the possibility of MSWI ash reuse as a raw material for cement production. The ash was first washed with water and acid to remove the chlorides, which could cause serious corrosion in the cement kiln. Various amounts of pre-washed ash were added to replace the clay component of the raw materials for cement production. The allowable limits of chloride in the fly ash and bottom ash were found to be 1.75% and 3.50% respectively. The results indicate that cement production can be a feasible alternative for MSWI ash management. It is also evident that the addition of either fly ash or bottom ash did not have any effect on the compressive strength of the clinker. Cement products conformed to the Chinese National Standard (CNS) of Type II Portland cement with one exception, the setting time of the clinker was much longer.     

An examination of the exothermic nature of fluidized bed combustion (FBC) residues

Circulating fluidized bed combustion (CFBC) ashes from nine operational periods at the 183 MWe CFBC boiler at Point Aconi were examined for exothermic behaviour. Bed ashes and fly ashes were investigated using a Parr 1455 solution calorimeter. Limited tests were also carried out with additional samples from Point Aconi and from the 160 MWe TVA Bubbling Fluidized Bed Combustion boiler to evaluate the effects of particle size and aging on exothermic behaviour. For the Point Aconi ashes, heat release from the bed ash ranged from 11 to 52 J/g, and the maximum heat release rates ranged from 0.06 to 0.17 J/g/s. For the fly ash heat release varied from 114 to 187 J/g and the maximum heat release rates ranged from 0.8 to 1.9 J/g/s. In the fly ash samples, 50% or more of available CaO was converted to Ca(OH)₂, while for the bed ash a third or less of the CaO was converted to Ca(OH)₂. The exothermicity of the bed ash is directly proportional to the CaO content of the ash. However, this is not true for the fly ash. The exothermic behaviour of fresh FBC ash appeared to be greatly reduced by exposure in air over a 48-h period. Another conclusion of this work is that particle size effects the exothermic behaviour.     

Physical-mechanical and environmental properties of sintered municipal incinerator fly ash

A step-wise treatment of Municipal Solid Waste (MSW) incinerator fly ash including washing, milling and sintering was investigated in order to manufacture ceramic materials with improved physical, mechanical and environmental properties and, possibly, to reduce the power input of the sintering process. An interpretation of the test results based on the microstructure of sintered products and sintering kinetic modeling was also attempted to identify the densification mechanisms. It was found that milling of washed fly ash represents a basic step for manufacturing high-density ceramic materials with very high compressive strengths (up to 500 N/mm2). A significant reduction in the power input of the sintering process (reduction of firing temperature from 1210 degrees C for washed fly ash to 1140 degrees C for milled-washed fly ash) is also achieved. A dense, well-sintered microstructure is formed through an intermediate-stage, liquid-phase sintering mechanism controlled by liquid-phase diffusion and grain shape accommodation. Such a microstructure is able to strongly immobilise heavy metals, thus giving good environmental properties to sintered product.     

The effects of the mechanical–chemical stabilization process for municipal solid waste incinerator fly ash on the chemical reactions in cement paste

A water extraction process can remove the soluble salts present in municipal solid waste incinerator (MSWI) fly ash, which will help to increase the stability of the synthetic materials produced from the MSWI fly ash. A milling process can be used to stabilize the heavy metals found in the extracted MSWI fly ash (EA) leading to the formation of a non-hazardous material. This milled extracted MSWI fly ash (MEA) was added to an ordinary Portland cement (OPC) paste to induce pozzolanic reactions. The experimental parameters included the milling time (96 h), water to binder ratios (0.38, 0.45, and 0.55), and curing time (1, 3, 7 and 28 days). The analysis procedures included inductively coupled plasma atomic emission spectroscopy (ICP/AES), BET, mercury intrusion porosimetry (MIP), X-ray diffraction (XRD), and nuclear magnetic resonance (NMR) imaging. The results of the analyses indicate that the milling process helped to stabilize the heavy metals in the MEA, with an increase in the specific surface area of about 50 times over that of OPC. The addition of the MEA to the OPC paste decreased the amount of Ca(OH)₂ and led to the generation of calcium–silicate–hydrates (C–S–H) which in turned increased the amount of gel pores and middle sized pores in the cement. Furthermore, a comparison shows an increase in the early and later strength over that of OPC paste without the addition of the milled extracted ash. In other words, the milling process could stabilize the heavy metals in the MEA and had an activating effect on the MEA, allowing it to partly substitute OPC in OPC paste.     

Chloride extraction for quality improvement of municipal solid waste incinerator ash for the concrete industry.

Coal ash from power stations has long been used successfully in the cement industry as binders in several Portland formulations. This is not the case for municipal solid waste (MSW) ash as chloride concentrations, ranging from 10 to 200 g kg(-1) dry weight in the bottom and fly ash, respectively, exceed the maximum allowable concentration in most cement mixtures. To reduce chloride content in MSW bottom ash, a laboratory investigation was carried out based on the exhaustive washing in tap water. The influence of operative parameters such as temperature, granulometric properties and solid/liquid ratio of extraction was evaluated. In addition to optimization of the mentioned operative parameters for full-scale application, the paper gives preliminary indications on mechanistic aspects of the washing operation.     

Recovery of MSWI and soil washing residues as concrete aggregates

The aim of the present work was to study if municipal solid waste incinerator (MSWI) residues and aggregates derived from contaminated soil washing could be used as alternative aggregates for concrete production.Initially, chemical, physical and geometric characteristics (according to UNI EN 12620) of municipal solid waste incineration bottom ashes and some contaminated soils were evaluated; moreover, the pollutants release was evaluated by means of leaching tests. The results showed that the reuse of pre-treated MSWI bottom ash and washed soil is possible, either from technical or environmental point of view, while it is not possible for the raw wastes.Then, the natural aggregate was partially and totally replaced with these recycled aggregates for the production of concrete mixtures that were characterized by conventional mechanical and leaching tests. Good results were obtained using the same dosage of a high resistance cement (42.5R calcareous Portland cement instead of 32.5R); the concrete mixture containing 400 kg/m³ of washed bottom ash and high resistance cement was classified as structural concrete (C25/30 class). Regarding the pollutants leaching, all concrete mixtures respected the limit values according to the Italian regulation.     

Lead immobilization in mechanochemical fly ash recycling

In previous studies, we focused on a mechanochemical process for recycling fly ash for use in cement; this process was expected to immobilize heavy metals in the fly ash, a desirable outcome in light of the fact that recycled fly ash is commonly used in the synthesis of inorganic materials. Here, we investigated the leaching of lead (Pb) from fly ash treated by a mechanochemical process and from cement prepared from the treated fly ash. We used lead oxide (PbO), a typical Pb compound in fly ash, as a model substance. Mechanochemical treatment of the fly ash inhibited Pb leaching by 93%, and further inhibition (more than 99.9%) was observed in cement produced from the treated fly ash. During the mechanochemical treatment, PbO was reduced to Pb by iron from the stainless-steel mill used for processing, and the lower solubility of Pb in water resulted in immobilization of the Pb.     

脱硝催化剂的失活机理及其再生技术

采用SEM、XRD和XRF对电厂失活脱硝催化剂进行表征,探讨其失活原因和机理。结果表明:电厂脱硝催化剂失活的主要原因是活性组分V的流失及碱金属K、碱土金属Ca和As元素造成的催化剂中毒,烟气中飞灰的沉积也有一定的影响。经吹扫、水洗、酸洗和V负载再生,催化剂的各项物化性质基本恢复,NOx转化率基本达到新鲜催化剂的水平。水洗主要去除催化剂中的碱金属,酸洗主要去除As2O3,负载V补充催化剂活性组分。V再生催化剂在较高温度下的抗硫性能更好。     

A study of disposed fly ash from landfill to replace Portland cement

The landfills of fly ash are the problem of all power plants because this disposed fly ash is not used in any work. This research studies the potential of using disposed fly ashes which have disposal time of 6-24 months from the landfill of Mae Moh power plants in Thailand to replace Portland cement type I. Median particle sizes of disposed fly ashes between 55.4 and 99.3 microm were ground to reduce the sizes to about 7.1-8.4 microm. Both original and ground disposed fly ashes were investigated on physical and chemical properties. Compressive strengths of disposed fly ash mortars were determined when Portland cement type I was replaced by disposed fly ashes at the rate of 10%, 20%, and 30% by weight of cementitious material (Portland cement type I and disposed fly ash). The results presented that most particles of original disposed fly ashes were solid and sphere with some irregular shape while those of ground disposed fly ashes were solid and irregular shape. CaO and LOI contents of disposed fly ashes with different disposal times had high variation. The compressive strengths of original disposed fly ash mortars were low but those of ground disposed fly ash mortars at the age of 7 days were higher than 75% of the standard mortar and increased to be higher than 100% after 60 days. From the results, it could be concluded that ground disposed fly ashes were excellent pozzolanic materials and could be used as a partial replacement of cement in concrete, even though they were exposed to the weather for 24 months.     

The disposal of radioactive ferric floc

An iron hydroxide floc is used as treatment for adsorbing low amounts of actinides during nuclear fuel re-processing. This waste is cemented only after pre-treatment with Ca(OH)(2). Characterisation of all simulant material has been undertaken using XRD, TGA and SEM/EDS. The floc is a moderately alkaline colloidal slurry containing approximately 15wt% solids, with the main particulate being an amorphous hydrated iron oxide. The main phase formed during pre-treatment appears to be an X-ray amorphous hydrated calcium-ferrate phase. Embedded within this are small amounts of crystalline Ca(OH)(2), calcite, Fe(6)(OH)(12)(CO(3)), Ca(6)Fe(2)(SO(4))(3)(OH)(12).26H(2)O and Ca(3)B(2)O(6), and can form depending on concentrations of Ca(OH)(2) and time. Apart from Ca(OH)(2) and calcite, none of the crystalline phases detected during pre-treatment are detected when the floc is encapsulated in an OPC/PFA composite cement hydrated for 90 days. The main crystalline phase detected in the hardened wasteform is a solid solution hydrogarnet, Ca(3)AlFe(SiO(4))(OH)(8), known as C(3)(A,F)SH(4) in cement chemistry nomenclature.     

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%).     

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,并分析这几类处理技术的优缺点。同时,介绍了将飞灰用作生产水泥材料、建筑材料、烧制多孔陶粒轻骨料及制备混凝土几种资源化利用途径。对今后飞灰的处理及资源化利用提出了展望。     

Release of salts from municipal solid waste combustion residues

Residues from fluidized bed combustion of municipal solid waste were investigated with respect to their leaching behavior and possible extraction of salts. The total water extractable amounts of Na, K, Ca, Cl(-), Br(-), F(-) and SO(4)(2-) along with the total dissolved solids of bottom, hopper, cyclone and bag house filter ashes were determined. A simple multistage washing process (using water as the extraction medium) was tested in lab scale experiments. The effect of variations in parameters, such as water to ash weight ratio, contact time, temperature and number of extraction steps was investigated. The leaching behavior of untreated and washed cyclone and bag house filter ashes was evaluated by a two-step batch-leaching test, i.e. the CEN test. The ashes investigated in this study can be arranged according to their decreasing water extractable contents and total dissolved solids as follows: filter ash > cyclone ash > hopper ash > bottom ash. A triple extraction with water at liquid to solid ratio 2 and extraction time 5 min gave the best results for the extraction of Ca, Na, K, Cl(-) and SO(4)(2-) from the cyclone as well as from the filter ashes. The leached amounts of salts in the CEN test performed on the washed cyclone ash were considerably lower than the corresponding amounts released from the unwashed ash. Thus, the washed cyclone ash was made more stable with respect to salt leachability. On the other hand, large amounts of salts were leached from the washed filter ashes as well as from unwashed filter ashes. Therefore, it can be concluded that three stage water extraction is not a suitable stabilization method for this type of filter ashes.     

Utilization of municipal solid waste incineration fly ash for sulfoaluminate cement clinker production

The feasibility of partially substituting raw materials with municipal solid waste incineration (MSWI) fly ash in sulfoaluminate cement (SAC) clinker production was investigated by X-ray diffraction (XRD), compressive strength and free expansion ratio testing. Three different leaching tests were used to assess the environmental impact of the produced material. Experimental results show that the replacement of MSWI fly ash could be taken up to 30% in the raw mixes. The good quality SAC clinkers are obtained by controlling the compositional parameters at alkalinity modulus (C(m)) around 1.05, alumina-sulfur ratio (P) around 2.5, alumina-silica ratio (N) around 2.0~3.0 and firing the raw mixes at 1250 °C for 2h. The compressive strengths of SAC are high in early age while that develop slowly in later age. Results also show that the expansive properties of SAC are strongly depended on the gypsum content. Leaching studies of toxic elements in the hydrated SAC-based system reveal that all the investigated elements are well bounded in the clinker minerals or immobilized by the hydration products. Although some limited positive results indicate that the SAC prepared from MSWI fly ash would present no immediate thread to the environment, the long-term toxicity leaching behavior needs to be further studied.     

Utilization of industrial by-products for the production of controlled low strength materials (CLSM)

Industrial by-products were used for the production of controlled low-strength material (CLSM). CLSM, also known as 'flowable fill' is used as a replacement of compacted soil in cases where the application of the latter is difficult or impossible. The low mechanical requirements (compared with structural concrete) enable the use of industrial by-products for the production of CLSM. In this study cement kiln dust, asphalt dust, coal fly ash, coal bottom ash and quarry waste were tested for the possibility of producing CLSM with large proportions of those wastes. The results showed that in most cases, CLSM with good properties could be made with significant amounts of dust (25-50%w), especially when the dust has some cementing or pozzolanic potential as do fly ash and cement kiln dust.     

Aggregate material formulated with MSWI bottom ash and APC fly ash for use as secondary building material

The main goal of this paper is to obtain a granular material formulated with Municipal Solid Waste Incineration (MSWI) bottom ash (BA) and air pollution control (APC) fly ash to be used as secondary building material. Previously, an optimum concrete mixture using both MSWI residues as aggregates was formulated. A compromise between the environmental behavior whilst maximizing the reuse of APC fly ash was considered and assessed. Unconfined compressive strength and abrasion resistance values were measured in order to evaluate the mechanical properties. From these results, the granular mixture was not suited for certain applications owing to the high BA/APC fly ash content and low cement percentages used to reduce the costs of the final product. Nevertheless, the leaching test performed showed that the concentrations of all heavy metals were below the limits established by the current Catalan legislation for their reutilization. Therefore, the material studied might be mainly used in embankments, where high mechanical properties are not needed and environmental safety is assured.