PHYSICO-CHEMICAL CHARACTERIZATION AND LEACHING OF DESULPHURIZATION COAL FLY ASH

Fly ash produced by coal combustion using two types of desulphurization process were studied: a conventional pulverized coal boiler equipped with lime injection (PCL ash), and a circulating fluidized bed combustion boiler with limestone injection (CFBC ash). The ashes were characterized completely: granulometry, morphology, mineralogy, chemical composition and behaviour to water contact. Both PCL ash and CFBC ash present similar features: fine granulometry, presence of anhydrite phase and sulphate content. However, PCL ash also shows lots of spherical particles, unlike CFBC ash, and a much higher lime content, due to the lower desulphurization rate in PC boilers. Unlike CFBC ash, most of the trace elements in PCL ash show an inverse concentration–particle size dependence. Leachates obtained from both samples are rich in soluble salts [CaSO₄and Ca(OH)₂] and arsenic and selenium are prevented from solubilizing by high lime content. In wetted PCL ash, the formation of ettringite crystals stabilizes calcium and sulphate ions. Simultaneously, arsenate, selenate and chromate anions are trapped in the crystal. CFBC ash does not really harden because the lime content is too low. However, the leached selenium concentration is cut down in wetted CFBC ash samples.     

固硫灰固化焦化废水处理外排污泥

采用机械力化学法活化循环流化床燃煤固硫灰,用于固化焦化废水处理外排污泥(CWT污泥)。探讨了固硫灰活化条件,并通过XRD和FTIR分析了固硫灰固化CWT污泥中重金属的机理。实验结果表明:当m(Ca O)∶m(Ca O+固硫灰)为20%、球磨频率为40 Hz、球磨时间为2 h时,养护28 d固硫灰固化体的平均抗压强度达到72.2 MPa;当污泥掺加量为50%(w)时,养护28 d含污泥固化体的抗压强度达到8.5 MPa,固化体浸出液中Pb2+和As5+的质量浓度分别为0.177 mg/L和0.013 mg/L,均远低于GB 5085.3—2007《危险废物鉴别标准浸出毒性鉴别》的规定限值。XRD和FTIR表征结果表明,在固硫灰活化过程中,混合体系水化生成了C—S—H凝胶、斜方钙沸石和钙矾石,可通过物理包裹、吸附及离子交换的形式实现CWT污泥中Pb2+和As5+的固化/稳定化。     

Advanced ash management technologies for CFBC ash

The combustion of high-sulphur coal demands the reduction of sulphur emissions. The sorbent most often used in sulphur capture technology is calcium-based. Ashes from technologies such as circulating fluidized bed combustion (CFBC), therefore, contain high calcium levels. The use and disposal of these ashes poses challenges, because of highly exothermic reactions with water, high-pH leachates, and excessive expansion of solidified materials. This paper looks at the potential of two post-combustion ash treatment processes, CERCHAR hydration and AWDS disposal, in solving these challenges. A high-sulphur coal-derived CFBC ash is examined, after CERCHAR hydration treatment, in conjunction with a conventionally hydrated ash, in a range of chemical, geotechnical and utilization scenarios. The ashes are used to make no-cement and roller-compacted concrete as well as Ash Water Dense Suspensions (AWDS). The solidified mortar paste from no-cement concrete is subjected to an extensive geochemical examination to determine how solidification progresses and strength develops, from a chemical point of view.     

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.     

MSWI boiler fly ashes: magnetic separation for material recovery

Nowadays, ferrous materials are usually recovered from Municipal Solid Waste Incineration (MSWI) bottom ash by magnetic separation. To our knowledge, such a physical technique has not been applied so far to other MSWI residues. This study focuses thus on the applicability of magnetic separation on boiler fly ashes (BFA). Different types of magnet are used to extract the magnetic particles. We investigate the magnetic particle composition, as well as their leaching behaviour (EN 12457-1 leaching test). The magnetic particles present higher Cr, Fe, Mn and Ni concentration than the non-magnetic (NM) fraction. Magnetic separation does not improve the leachability of the NM fraction. To approximate industrial conditions, magnetic separation is also applied to BFA mixed with water by using a pilot. BFA magnetic separation is economically evaluated. This study globally shows that it is possible to extract some magnetic particles from MSWI boiler fly ashes. However, the magnetic particles only represent from 23 to 120 g/kg of the BFA and, though they are enriched in Fe, are composed of similar elements to the raw ashes. The industrial application of magnetic separation would only be profitable if large amounts of ashes were treated (more than 15 kt/y), and the process should be ideally completed by other recovery methods or advanced treatments.     

Chemical sequential extraction of heavy metals and sulphur in bottom ash and in fly ash from a pulp and paper mill complex

A five-stage sequential extraction procedure was used to determine the distribution of 11 metals (Cd, Cr, Cu, Mo, Pb, Zn, As, Co, V, Ni, Ba), and sulphur (S) in bottom ash and in fly ash from a fluidized bed co-combustion (i.e. wood and peat) boiler of Stora Enso Oyj Oulu Mill at Oulu, Northern Finland, into the following fractions: (1) water-soluble fraction (H2O); (2) exchangeable fraction (CH3COOH); (3) easily reduced fraction (NH2OH-HCl); (4) oxidizable fraction (H2O2 + CH3COONH4); and (5) residual fraction (HF + HNO3 + HCl). Although metals were extractable in all fractions, the highest concentrations of most of the metals occurred in the residual fraction. From the environmental point of view, this fraction is the non-mobile fraction and is potentially the least harmful. The Ca concentrations of 29.3 g kg(-1) (dry weight) in bottom ash and of 68.5 g kg(-1) (dry weight) in fly ash were correspondingly approximately 18 and 43 times higher than the average value of 1.6 g kg(-1) (dry weight) in arable land in Central Finland. The ashes were strongly alkaline pH (approximately 12) and had a liming effects of 9.3% (bottom ash) and 13% (fly ash) expressed as Ca equivalents (dry weight). The elevated Ca concentrations indicate that the ashes are potential agents for soil remediation and for improving soil fertility. The pH and liming effect values indicate that the ashes also have a pH buffering capacity. From the environmental point of view, it is notable that the heavy metal concentrations in both types of ash were lower than the Finnish criteria for ash utilization.     

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.     

The long term behaviour of CFBC ash-water systems

Circulating fluidized bed combustion (CFBC) ashes in contact with water, whether in liquid or vapour form, exhibit considerable chemical activity, which can continue for more than a year. From the point of view of the setting of CFBC ash-water mixtures and their behaviour, the formation of gypsum and of ettringite are important. The crystallisation of ettringite is associated with expansion of the set mass and absorption of water into the solids, but the ash-water system as a whole shrinks. The extent of ettringite formation is reduced if carbonation of free lime can take place. There is little carbonation if the set solids are covered by water but if contact with air is not restricted, the ettringite formed earlier slowly decomposes, its place being taken by calcite and gypsum. The fate of the aluminium from decomposed ettringite is uncertain; no new crystalline Al compounds are found. It appears that ultimately most analytical lime present can become carbonated. This is environmentally beneficial since it reduces chemical activity in the landfill, and reduces the amount of CO2 released due to limestone use. The main features of the behaviour of CFBC ash-water mixtures can be reproduced in model systems (CaO-Al2O3-CaSO4-H2O) but that of real ashes is complicated by the presence of silicates and possible interactions between silica and the strongly alkaline aqueous medium. Also, aluminates present in the ash are probably more active with respect to ettringite formation than pure aluminum hydroxide.     

Sintering characteristics of CaO-rich municipal solid waste incineration fly ash through the addition of Si/Al-rich ash residues

Thermal treatment is a promising technology for the fast disposal of hazardous municipal solid waste incineration (MSWI) fly ash in China. However, fly ash produced in grate incinerator (GFA) is rich in CaO and chlorides, which promote the formation of toxic hexavalent chromium [Cr(VI)] and ash agglomeration during the thermal process, inhibiting the thermal disposal of GFA. In this study, sintering characteristics of CaO-rich GFA were improved by adding Si/Al-rich MSWI ash residues. According to the results, ash agglomeration was well suppressed during thermal treatment of the mixed ash. Si/Al/Fe-compounds competed with un-oxidized Cr-compounds to react with CaO and suppressed Cr(VI) formation. Meanwhile, chlorides in GFA facilitated heavy metal volatilization from added ashes to the secondary fly ash, favoring the recovery of these metals. Ca-aluminosilicates was found as the main mineral phase in the thermally treated mixed ash, which has attractive potential for applications. The formation of the aluminosilicates made the heavy metals that remained in the treated mixed ash more stable than the thermally treated single ash.     

Belgian MSWI fly ashes and APC residues: a characterisation study

Municipal Solid Waste Incineration (MSWI) produces different sorts of residues, bottom ash, fly ashes and Air Pollution Control (APC) residues. Generally, fly ashes and APC residues are mixed at the MSWI plant and manage as a sole residue. In this study, fly ashes and APC residues have been sampled separately at different Belgian MSWI plant and analysed by X-ray fluorescence in order to highlight the composition differences that may appear between the solids. Ca and Cl are found to be the major elements in most of the samples. Lithophilic elements, such as Al and Si, are richer in furnace and boiler ashes, as can be expected. Leaching tests also show differences between the residues; leachates from furnace and boiler ashes are alkaline while those from bag filter residues present a pH value of 6, which impacts the leaching of heavy metals (Pb and Zn). The results suggest that it could be advantageous to manage fly ashes and APC residues separately by adjusting the treatment to their specificities.     

Gypsum treated fly ash as a liner for waste disposal facilities

Fly ash has potential application in the construction of base liners for waste containment facilities. While most of the fly ashes improve in the strength with curing, the ranges of permeabilities they attain may often not meet the basic requirement of a liner material. An attempt has been made in the present context to reduce the hydraulic conductivity by adding lime content up to 10% to two selected samples of class F fly ashes. The use of gypsum, which is known to accelerate the unconfined compressive strength by increasing the lime reactivity, has been investigated in further improving the hydraulic conductivity. Hydraulic conductivities of the compacted specimens have been determined in the laboratory using the falling head method. It has been observed that the addition of gypsum reduces the hydraulic conductivity of the lime treated fly ashes. The reduction in the hydraulic conductivity of the samples containing gypsum is significantly more for samples with high amounts of lime contents (as high as 1000 times) than those fly ashes with lower amounts of lime. However there is a relatively more increase in the strengths of the samples with the inclusion of gypsum to the fly ashes at lower lime contents. This is due to the fact that excess lime added to fly ash is not effectively converted into pozzolanic compounds. Even the presence of gypsum is observed not to activate these reactions with excess lime. On the other hand the higher amount of lime in the presence of sulphate is observed to produce more cementitious compounds which block the pores in the fly ash. The consequent reduction in the hydraulic conductivity of fly ash would be beneficial in reducing the leachability of trace elements present in the fly ash when used as a base liner.     

Mercury leaching characteristics of waste treatment residues generated from various sources in Korea

In this study, mercury (Hg) leaching characteristics of the waste treatment residues (fly ash, bottom ash, sludge, and phosphor powder) generated from various sources (municipal, industrial, medical waste incinerators, sewage sludge incinerator, oil refinery, coal-fired power plant, steel manufacturing plant, fluorescent lamp recycler, and cement kiln) in Korea were investigated. First, both Hg content analysis and toxicity characteristic leaching procedure (TCLP) testing was conducted for 31 collected residue samples. The Hg content analysis showed that fly ash from waste incinerators contained more Hg than the other residue samples. However, the TCLP values of fly ash samples with similar Hg content varied widely based on the residue type. Fly ash samples with low and high Hg leaching ratios (R_L) were further analyzed to identify the major factors that influence the Hg leaching potential. Buffering capacity of the low-R_L fly ash was higher than that of the high-R_L fly ash. The Hg speciation results suggest that the low-R_L fly ashes consisted primarily of low-solubility Hg compounds (Hg₂Cl₂, Hg⁰ or HgS), whereas the high-R_L fly ashes contain more than 20% high-solubility Hg compounds (HgCl₂ or HgSO₄).     

Accelerated carbonation of municipal solid waste incineration fly ashes

As a result of the EU Landfill Directive, the disposal of municipal solid waste incineration (MSWI) fly ash is restricted to only a few landfill sites in the UK. Alternative options for the management of fly ash, such as sintering, vitrification or stabilization/solidification, are either costly or not fully developed. In this paper an accelerated carbonation step is investigated for use with fly ash. The carbonation reaction involving fly ash was found to be optimum at a water/solid ratio of 0.3 under ambient temperature conditions. The study of ash mineralogy showed the disappearance of lime/portlandite/calcium chloride hydroxide and the formation of calcite as carbonation proceeded. The leaching properties of carbonated ash were examined. Release of soluble salts, such as SO4, Cl, was reduced after carbonation, but is still higher than the landfill acceptance limits for hazardous waste. It was also found that carbonation had a significant influence on lead leachability. The lead release from carbonated ash, with the exception of one of the fly ashes studied, was reduced by 2-3 orders of magnitude.     

Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

Investigation of MSWI fly ash melting characteristic by DSC-DTA

The melting process of MSWI (Municipal Solid Waste Incineration) fly ash has been studied by high-temperature DSC-DTA experiments. The experiments were performed at a temperature range of 20-1450 degrees C, and the considerable variables included atmosphere (O(2) and N(2)), heating rates (5 degrees C/min, 10 degrees C/min, 20 degrees C/min) and CaO addition. Three main transitions were observed during the melting process of fly ash: dehydration, polymorphic transition and fusion, occurring in the temperature range of 100-200 degrees C, 480-670 degrees C and 1101-1244 degrees C, respectively. The apparent heat capacity and heat requirement for melting of MSWI fly ash were obtained by DSC (Differential Scanning Calorimeter). A thermodynamic modeling to predict the heat requirements for melting process has been presented, and it agrees well with the experimental data. Finally, a zero-order kinetic model of fly ash melting transition was established. The apparent activation energy of MSWI fly ash melting transition was obtained.     

CuCl2改性飞灰吸附气相零价汞

采用CuCl₂对循环流化床锅炉飞灰进行改性,在固定床反应器上对CuCl₂改性飞灰进行了气相零价汞（Hg⁰）吸附实验。考察了CuCl₂负载量和吸附温度对改性飞灰Hg⁰吸附能力的影响,并结合颗粒内扩散模型、准一阶动力学模型、准二阶动力学模型和耶洛维奇模型拟合结果分析该过程的控制步骤。结果表明： CuCl₂改性飞灰的Hg⁰穿透时间远大于未改性飞灰,对Hg⁰的吸附量随CuCl₂负载量的增加而增加;CuCl₂改性飞灰的Hg⁰吸附能力随吸附温度的升高先增大后减小,150 ℃为最佳吸附温度;准二阶动力学模型的拟合值与实验值相关系数最高,且该模型初始吸附速率与实验值最为接近,即准二阶动力学模型更适合于描述CuCl₂改性飞灰的Hg⁰吸附过程。     

Stabilization/solidification of fly ashes and concrete production from bottom and circulating ashes produced in a power plant working under mono and co-combustion conditions

Two combustion tests were performed in a fluidized bed combustor of a thermo-electric power plant: (1) combustion of coal; (2) co-combustion of coal (68.7% w/w), sewage sludge (9.2% w/w) and meat and bone meal (MBM) (22.1% w/w). Three samples of ashes (bottom, circulating and fly ashes) were collected in each combustion test. The ashes were submitted to the following assays: (a) evaluation of the leaching behaviour; (b) stabilization/solidification of fly ashes and evaluation of the leaching behaviour of the stabilized/solidified (s/s) materials; (c) production of concrete from bottom and circulating ashes. The eluates of all materials were submitted to chemical and ecotoxicological characterizations. The crude ashes have shown similar chemical and ecotoxicological properties. The s/s materials have presented compressive strengths between 25 and 40 MPa, low emission levels of metals through leaching and were classified as non-hazardous materials. The formulations of concrete have presented compressive strengths between 12 and 24 MPa. According to the Dutch Building Materials Decree, some concrete formulations can be used in both scenarios of limited moistening and without insulation, and with permanent moistening and with insulation.     

Sustainable alkali-activated binders with municipal solid waste incineration ashes as sand or fly ash replacement

The present study investigates the feasibility of using two types of municipality solid wastes incineration ashes, namely, fly ash and bottom ash in the production of sustainable alkali-activated binder. The ashes are collected from the incineration plant and characterized to determine their particle size distribution, specific gravity, chemical composition, and heavy metals content. The ashes are then used as either fly ash or sand replacement with five replacement ratios 0%, 5%, 10%, 15%, and 20% to produce the binder. The produced binder are characterized in terms of strength, workability, density, water absorption, thermal conductivity and stability, chemical composition, and heavy metals content. The results reflect the ability of producing sustainable alkali-activated binder with small dosage of MSWI ashes as either fly ash or sand replacement without negatively affecting its strength, workability, density, and water absorption. The ashes enhance the thermal insulation capability of the binder.

     

Low-reactive circulating fluidized bed combustion (CFBC) fly ashes as source material for geopolymer synthesis

In this contribution, low-reactive circulating fluidized bed combustion (CFBC) fly ashes (CFAs) have firstly been utilized as a source material for geopolymer synthesis. An alkali fusion process was employed to promote the dissolution of Si and Al species from the CFAs, and thus to enhance the reactivity of the ashes. A high-reactive metakaolin (MK) was also used to consume the excess alkali needed for the fusion. Reactivities of the CFAs and MK were examined by a series of dissolution tests in sodium hydroxide solutions. Geopolymer samples were prepared by alkali activation of the source materials using a sodium silicate solution as the activator. The synthesized products were characterized by mechanical testing, scanning electron microscopy (SEM), X-ray diffractography (XRD), as well as Fourier transform infrared spectroscopy (FTIR). The results of this study indicate that, via enhancing the reactivity by alkali fusion and balancing the Na/Al ratio by additional aluminosilicate source, low-reactive CFAs could also be recycled as an alternative source material for geopolymer production.     

Comparison of leaching characteristics of heavy metals from bottom and fly ashes in Korea and Japan

The objective of this research was to compare the leaching characteristics of heavy metals such as cadmium, chromium, copper, nickel, lead, etc., in Korean and Japanese municipal solid waste incineration (MSWI) ash. The rate of leaching of heavy metal was measured by KSLT and JTL-13, and the amount of heavy metals leached was compared with the metal content in each waste component. Finally, bio-availability testing was performed to assess the risks associated with heavy metals leached from bottom ash and fly ash. From the results, the value of neutralization ability in Japanese fly ash was four times higher than that in Korean fly ash. The reason was the difference in the content of Ca(OH)(2) in fly ash. The amount of lead leached exceeded the regulatory level in both Japanese and Korean fly ash. The rate of leaching was relatively low in ash with a pH in the range of 6-10. The bio-availability test in fly ash demonstrated that the amount of heavy metals leached was Pb>Cd>Cr, but the order was changed to Pb>Cr>Cd in the bottom ash. The leaching concentration of lead exceeded the Japanese risk level in all fly ashes from the two countries, but the leaching concentration of cadmium exceeded the regulatory level in Korean fly ash only.