X-ray fluorescence tomography of individual municipal solid waste and biomass fly ash particles

Information about Cd distribution inside single municipal solid waste and biomass fly ash particles is fundamental since it affects its leachability. The internal 2D distributions of the main and trace elements in such highly inhomogeneous matrixes were successfully determined by means of the combined synchrotron radiation induced micro X-ray fluorescence (micro-SRXRF) and tomography (micro-SRXRFT) techniques. Scanning micro-SRXRF measurements show Cd elemental distribution within single fly ash particles to be inhomogeneous, but no information can be obtained about its internal distribution. During micro-SRXRFT analysis, single fly ash particles are successively measured by a rotational-translational scan in a VH=2 x 5 microm2 microbeam. The 2D internal elemental distribution images, obtained by the modified simultaneous algebraic reconstruction technique algorithm, provide the size and the location of Cd-containing areas together with the location of other measurable elements. Results showed Cd concentration to be higher in the core of the fly ash particles analyzed rather than on the surface of the particles. Moreover, in both ashes, Ca-containing matrixes are found to be the main Cd-bearing phases. A possible mechanism for Cd adsorption on the fly ash particles is proposed based on the obtained results.     

Possible applications for municipal solid waste fly ash

The present study focuses on existing practices related to the reuse of Municipal Solid Waste (MSW) fly ash and identifies new potential uses. Nine possible applications were identified and grouped into four main categories: construction materials (cement, concrete, ceramics, glass and glass-ceramics); geotechnical applications (road pavement, embankments); "agriculture" (soil amendment); and, miscellaneous (sorbent, sludge conditioning). Each application is analysed in detail, including final-product technical characteristics, with a special emphasis on environmental impacts. A comparative analysis of the different options is performed, stressing the advantages but also the weaknesses of each option. This information is systemized in order to provide a framework for the selection of best technology and final products. The results presented here show new possibilities for this waste reuse in a short-term, in a wide range of fields, resulting in great advantages in waste minimization as well as resources conservation.     

Vitrification of fly ash from municipal solid waste incinerator

Fly ash from municipal solid wastes (MSW) incinerators in Korea contains a large amount of toxic materials and requires pertinent treatments. However, since fly ash in Korea has a high chlorine concentration, it is difficult to apply cementation and chemical treatment techniques. In this study, we report the vitrification of fly ash along with the properties of the glasses and leaching characteristics of heavy metal ions.Fly ash can be vitrified by melting at 1500 degrees C for 30 min with the addition of >5 wt.% of SiO2. Glasses showed Vickers hardness of 4000-5000 MPa, bending strength of 60-90 MPa and indentation fracture toughness of approximately 0.9 MPa m(1/2). Glasses also showed the excellent resistance against leaching of heavy metal ions with Cd2+ <0.04 ppm, Cr3+ <0.02 ppm, Cu2+ <0.04 ppm and Pb2+ <0.2 ppm. These results indicate that the vitrification technique is effective for the stabilization and recycling of toxic incinerator fly ash.     

Determination of the Cd-bearing phases in municipal solid waste and biomass single fly ash particles using SR-microXRF spectroscopy

By using an excitation energy of 27.0 keV, synchrotron radiation-induced micro-X-ray fluorescence (SR-microXRF) is employed to extract information regarding the composition and distribution of Cd-bearing phases in municipal solid waste (MSW) and biomass fly ashes. Significance of observation is based on statistics of totally more than 100 individual MSW and biomass fly ash particles from a fluidized bed combustion (FBC) plant. Cd concentrations in the parts-per-million range are determined. In general, although previous leaching studies have indicated Cd to be predominant in the smaller-size ash particles, in the present study Cd is more evenly distributed throughout all the particle sizes. For MSW fly ashes, results indicate the presence of Cd mainly as CdBr2 hot-spots, whereas for biomass fly ashes, which exhibit lower CdX2 concentration, a thin Cd layer on/in the particles is reported. For both ashes, Ca-containing matrixes are found to be the main Cd-bearing phases. Support for this observation is found from independent first-principles periodic density functional theory calculations. The observations are condensed into a schematic mechanism for Cd adsorption on the fly ash particles.     

Preparation of alinite cement from municipal solid waste incineration fly ash

The feasibility of partially substituting ordinary raw materials with municipal solid waste incineration (MSWI) fly ash in alinite cement production was investigated by X-ray diffraction (XRD), X-ray fluorescence spectrometry (XRF) and scanning electron microscopy (SEM). The physical properties and leaching behavior of the produced cement were also evaluated. Experimental results show that good quality clinkers can be obtained by firing the raw mixes, in which the replacement of MSWI fly ash reaches to 30%, at 1200 °C for 2 h. Alinite cements have higher early strengths at all gypsum additions, while the best result having acceptable early and 28-day strengths is obtained at 5% of gypsum addition. Results also show that the leaching toxicity of heavy metals is far lower than that of the regulatory limit at all testing ages. Based on this study, MSWI fly ash is viable as an effective, alternative raw material in alinite cement production.     

Biotoxicity evaluation of fly ash and bottom ash from different municipal solid waste incinerators

Different types of municipal solid waste incinerator (MSWI) fly and bottom ash were extracted by TCLP and PBET procedures. The biotoxicity of the leachate of fly ash and bottom ash was evaluated by Vibrio fischeri light inhibition test. The results indicate the following: (1) The optimal solid/liquid ratio was 1:100 for PBET extraction because it had the highest Pb and Cu extractable mass from MSWI fly ash. (2) The extractable metal mass from both fly ash and bottom ash by PBET procedure was significantly higher than that by TCLP procedure. (3) The metal concentrations of fly ash leachate from a fluidized bed incinerator was lower than that from mass-burning and mass-burning combined with rotary kiln incinerator. (4) The TCLP and PBET leachate from all MSWI fly ash samples showed biotoxicity. Even though bottom ash is regarded as a non-hazardous material, its TCLP and PBET leachate also showed biotoxicity. The pH significantly influenced the biotoxicity of leachate.     

Melting of municipal solid waste incinerator fly ash by waste-derived thermite reaction

This work describes a novel approach for melting municipal solid waste incinerator (MSWI) fly ash, based on self-propagating reactions, by using energy-efficient simulated waste-derived thermite. The self-propagating characteristics, the properties of the recycled alloy and slag and the partitioning of heavy metals during the process are also studied. Experimental results demonstrate that the mix ratio of fly ash to the starting mixture of less than 30% supports the development of the self-propagating reaction with a melting temperature of 1350-2200 degrees C. Furthermore, metallic iron (or alloy) and the slag were retrieved after activation of the thermite reactions among the starting mixtures. It was noted that more than 91wt.% of iron was retrieved as alloy and the rest of non-reductive oxides as slag. During the thermite reactions, the partition of heavy metals to the SFA and flue gas varied with the characteristics of the target metals: Cd was mainly partitioned to flue gas (75-82%), and partition slightly increased with the increasing fly ash ratio; Pb and Zn, were mainly partitioned to the SFA, and the partition increased with increasing fly ash ratio; Cu was partitioned to the SFA (18-31%) and was not found in the flue gas; and moreover stable Cr and Ni were not identified in both the SFA and flue gas. On the other hand, the determined TCLP leaching concentrations were all well within the current regulatory thresholds, despite the various FA ratios. This suggests that the vitrified fly ash samples were environmental safe in heavy metal leaching. The results of this study suggested that melting of municipal solid waste incinerator fly ash by waste-derived thermite reactions was a feasible approach not only energy-beneficial but also environmental-safe.     

Speciation of copper in the incineration fly ash of a municipal solid waste

The speciation of copper and zinc in the incineration fly ash of a municipal solid waste in Taiwan was investigated in the present work. By the least-squares fitted X-ray absorption near edge structural (XANES) spectroscopy, we found that CuCO3, CuOH2, and CuO (fractions of 0.09, 0.39 and 0.51, respectively) were the main copper species in the fly ash. Quantitative analysis of the extended X-ray absorption fine structural (EXAFS) spectra indicated that the bond distance of Cu-O in the fly ash was 1.96 A with a coordination number (CN) of 3.9 in the first shell of copper. In the second shell, the bond distance and CN of Cu-(O)-Cu were 2.91 A and 2.7, respectively. In addition, speciation of Zn was also examined in the same X-ray absorption energy (8780-9970 eV). The bond distance of Zn-O and Zn-O-Zn were 1.97 and 2.94 A, respectively. However, the Zn-O-Cu structure was not found because of the physically unreasonable sigma(2) (Debye-Waller factor) values in the EXAFS data fitting process.     

The hydration properties of pastes containing municipal solid waste incinerator fly ash slag

This study investigated the hydration properties of Type I, Type III and Type V cements, mixed with municipal solid waste incinerator fly ash, to produce slag-blended cement pastes. The setting time of slag-blended cement pastes that contained 40% slag showed significantly retardation the setting time compared to those with a 10% or even a 20% slag replacement. The compressive strength of slag-blended cement paste samples containing 10 and 20% of slag, varied from 95 to 110% that developed by the plain cement pastes at later stages. An increased blend ratio, due to the filling of pores by C-S-H formed during pozzolanic reaction tended to become more pronounced with time. This resulting densification and enhanced later strength was caused by the shifting of the gel pores. It was found that the degree of hydration was slow in early stages, but it increased with increasing curing time. The results indicated that it is feasible to use MSWI fly ash slag to replace up to 20% of the material with three types of ordinary Portland cement.     

Extraction of metals from municipal solid waste incinerator fly ash by hydrothermal process

This work examined the extraction properties of metallic elements from municipal incinerator fly ash under hydrothermal conditions. The ash was firstly pre-washed by distilled water, then subjected to hydrothermal treatments. The pre-washing process was effective for Na, K, Ca extraction with extraction percentages of 67%, 76% and 48%, respectively. The optimum contact time was 30 min for the pre-washing process. Five types of acids were tested for the extraction experiments and hydrochloric acid was found to be most effective for metal extraction from the ash. Compared to room condition, hydrothermal treatment accelerated the dissolution of the ash, thus promoted the reaction of acid with hazardous metals such as Cr, Cd, Pb, and furthermore, the consumption speed of acid was slowed down under hydrothermal condition. The acid simultaneously reacted with all the metal in the ash under hydrothermal condition but preferentially reacted with Ca at room condition. The optimum hydrothermal treatment temperature, time and liquid/solid ratio were 150 degrees C, 5h and 10:1 (ml:g), respectively.     

Thermal treatment of the fly ash from municipal solid waste incinerator with rotary kiln

Reuse of the fly ash from the municipal solid waste incinerator (MSWI) is a policy of Taiwan EPA. However, the fly ash is often classified as a hazardous waste and cannot be reused directly because the concentrations of heavy metals exceed the TCLP regulations. The main objective of this study is to investigate the continuous sintering behavior of fly ash with a rotary kiln and seek a solution to reduce the concentrations of heavy metal to an acceptable value. The partitions of the heavy metals in the process are also considered. The results of TCLP showed that among the metals of Cr, Cd, Cu and Pb, only the concentrations of Pb in raw fly ash exceeded the regulation. At sintering temperatures of 700, 800 and 900 degrees C, the concentration of Pb decreased in sintering products, however, the concentration of Pb still exceeded the limitation at 700 and 800 degrees C. Additionally, the water-washing was used to pre-treat the fly ash before sintering process. The washing treatment effectively reduced the leaching concentrations of Pb to agree the regulations. Therefore, water-washing followed by a sintering treatment is an available process for detoxifying the fly ash of MSWI.     

Feasibility study of using brick made from municipal solid waste incinerator fly ash slag

This study deals with the effect of MSWI slag on fired clay bricks. Brick samples were heated to temperatures which varied from 800 to 1,000 degrees C for 6h, with a heating rate of 10 degrees C/min. The material properties of the resultant material then determined, including speciation variation, loss on ignition, shrinkage, bulk density, 24-h absorption rate and compressive strength. Toxicity Characteristic Leaching Procedure tests were also conducted. The results indicate that the heavy metal concentrations in the leachates met the current regulatory thresholds. Increasing the amount of MSWI slag resulted in a decrease in the water absorption rate and an increase in the compressive strength of the MSWI-slag bricks. The 24-h absorption rate and compressive strength of the MSWI-slag brick made from samples containing slag sintered at 1,000 degrees C all met the Chinese National Standard (CNS) building requirements for second-class brick. The addition of MSWI slag to the mixture reduced the degree of firing shrinkage. This indicates that MSWI slag is indeed suitable for the partial replacement of clay in bricks.     

Microwave drying optimization and kinetic modeling of fly ash from municipal solid waste incineration

As a kind of hazardous waste, municipal solid waste incineration fly ash (MSWI FA) needs to be stored in a dry state in the process of landfill, transportation, and comprehensive utilization. Therefore, from the perspective of safety and sustainable development, it is necessary to dry as the pretreatment of MSWI FA. In this paper, MSWI FA drying experiments were carried out under different microwave power, different initial moisture content, and different particle size distribution conditions. The drying characteristics of MSWI FA were explored and the thin-layer drying kinetic model was used to explore the basic theory of the dynamics of MSWI FA drying process for the first time. The fitting analysis of the experimental data showed that the drying efficiency of MSWI FA increases gradually with the increase of microwave power and fly ash particle size, and the drying process of MSWI FA could be well represented by the Diffusion approach model (R² greater than 0.99). Through Fick's second law calculation, it was found that when the microwave power was increased from 400w to 800w, the surface diffusion coefficient increased from 1.11 × 10^-12 m²/s to 2.92 × 10^-12 m²/s, which further showed that the microwave power has a significant effect on the drying efficiency of MSWI FA.     

关于水热技术处理垃圾焚烧飞灰的研究探讨

生活垃圾焚烧飞灰含有重金属和有毒有机物,对环境危害十分严重。水热法被认为是一种有效的无害化处理技术,能将飞灰改性,降低飞灰毒性,还可以合成沸石类物质,提高产物的应用价值。本文基于垃圾焚烧飞灰理化特性,对现有的水热处理技术进行了较为全面的总结。根据水热法的机理,系统地介绍了传统水热法、微波水热法、熔融预处理的微波水热法和超声波水热法,并通过对比分析指出各方法在处理效率、处理效果等方面存在的问题。此外,还简要介绍了水热处理后飞灰的主要应用领域。最后结合近几年水热技术的研究现状,提出了新型水热技术在工业化应用上存在的大型化的局限性以及未来发展方向。     

Experimental study on alinite ecocement clinker preparation from municipal solid waste incineration fly ash

This paper presents the laboratory scale study on the preparation of ecocement clinkers, whose main mineral is alinite, from municipal solid waste incineration fly ash. X-ray diffraction technique was used to monitor the phase formation during the burning of raw mixes. Effects of compositions, firing time and firing temperature on the properties of clinkers have been investigated. The hydration behaviour of the ecocement obtained from the optimized clinkers was also studied. From the results it is observed that the characteristics of the clinkers are strongly dependent on the raw mix compositions and firing temperature but not so much on firing time. The desirable clinkers can be obtained by firing the raw mix at 1,200°C for 1?h and controlling the compositional parameters KH (lime saturation moduli) around 1.02, a (silica-alumina ratio) around 4.50, Cl (Chlorides content) around 7.6% and m (MgO content) around 1.40%. Results also show that the ecocement exhibit a faster hydration kinetics than Ordinary Portland Cement.     

Utilization of ceramic waste as fine aggregate within Portland cement and fly ash concretes

The aim of this research work was to investigate the feasibility of using ceramic waste and fly ash to produce mortar and concrete. Ceramic waste fragments obtained from local industry were crushed and sieved to produce fine aggregates. The measured concrete properties demonstrate that while workability was reduced with increasing ceramic waste content for Portland cement concrete and fly ash concrete, the workability of the fly ash concrete with 100% ceramic waste as fine aggregate remained sufficient, in contrast to the Portland cement control concrete with 100% ceramic waste where close to zero slump was measured. The compressive strength of ceramic waste concrete was found to increase with ceramic waste content and was optimum at 50% for the control concrete, dropping when the ceramic waste content was increased beyond 50%. This was a direct consequence of having a less workable concrete. However, the compressive strength in the fly ash concrete increased with increasing ceramic waste content up to 100%. The benefits of using ceramic waste as fine aggregate in concrete containing fly ash were therefore verified.     

Characteristics of PCDD/F content in fly ash discharged from municipal solid waste incinerators

Different from most previous studies with quantity-limited data, this paper presents PCDD/F content characterization in the fly ash discharged from sixteen large-scale commercial MSWIs. From the results with over hundreds of data using periodically sampling and analysis, it was found that the PCDD/F contents in the fly ash were from 9.07 to 46.68 ng/g, d.w., and if based on international toxicity equivalent quantity, they were from 0.78 to 2.86 ng I-TEQ/g, d.w. The higher chlorinated PCDDs likely dominated more than lower chlorinated PCDDs, but this tendency was not for PCDFs. The OCDD had the highest contribution to the total PCDD/F content, but if based on I-TEQ content, 2,3,4,7,8-PeCDF is the PCDD/F congener with the highest toxicity contribution. Moreover, the PCDD/F characteristic index (DCI) is suggested using the representative congener content of 2,3,4,7,8-PeCDF to characterize the fly ash. The DCI is 0.875 ± 7.6% for the fly ash discharged from the MSWI with the APCD assembly of SD, AC and BF. The findings obtained in this work provide overview information on the PCDD/F content characterization in fly ash. They will provide PCDD/F fingerprint information to distinguish from other PCDD/F sources, like steel refinery industry, hazardous waste incinerators, or cement kilns, and thus be applied to fly ash management in the environment.     

Polychlorinated biphenyls removal from weathered municipal solid waste incineration fly ash by collector-assisted column flotation

Polychlorinated biphenyls (PCBs), polychlorinated dibenzo-p-dioxins (PCDDs) and dibenzofurans (PCDFs) are highly toxic micropollutants emitted from municipal solid waste incineration (MSWI), in particular, concentrated in the unburned carbon (UC) of MSWI fly ash. Because of concerns over their adverse health effects, a number of countries have classified MSWI fly ash as hazardous material and required further treatment before its final disposal in landfills. The technologies for removing the toxic chlorinated micropollutants in the MSWI fly ash have been studied, however, until now no mature technique has been obtained in this purpose. In this research, we used a technique of collector-assisted column flotation to remove PCBs-enriched UC from MSWI fly ash. We found that 36.9% PCBs could be removed from fresh MSWI fly ash with 61.7% UC removal efficiency, whereas only 21.7% PCBs could be removed from weathered MSWI fly ash with a low UC removal efficiency of 33.7%. By adding a mixture of two kinds of surfactants: sorbitan mono-oleate and polyoxyethylene (20) sorbitan mono-oleate to the weathered fly ash slurry as the collector assistant, 39.3% PCBs was removed at the hydrophile–lipophile balance (HLB) value of 13.5, while the UC removal efficiency increased to 49.0%. The results showed that the collector assistant could enhance PCBs and UC removal efficiencies during the column flotation process, and the mechanism has been discussed in detail. Higher PCBs and UC removal efficiencies could be expected by further optimizing the conditions of collector-assisted column flotation.     

Pb stabilization in fresh fly ash from municipal solid waste incinerator using accelerated carbonation technology

Carbonation technology with CO(2) absorption was used to enhance the stabilization of heavy metals in fresh fly ash from a municipal solid waste incinerator (MSWI). The influence of fundamental parameters affecting the stabilization of heavy metals, especially Pb and diffusivity and reactivity of CO(2), was evaluated. The results indicated that the addition of 10% or more of water could remarkably accelerate the absorption of CO(2) and could also accelerate the stabilization of MSWI fly ash. The stabilization of MSWI fly ash is not distinct within 1d in the air atmosphere for low content of CO(2) (0.03%). The result of the XRD analysis indicated that CO(2) could combine with Ca(OH)(2) to form CaCO(3) and CO(2) could also combine with heavy metal oxide to form heavy metal carbonate in the adsorption of CO(2). The TGA analysis showed that MSWI fly ash has the sequestration capability of 3% (w/w) CO(2). The sequestration of CO(2) has a large impact on Pb, and the exchangeable Pb can be converted into carbonated form in rich CO(2) condition to be stabilized.     

Effects of water-washing pretreatment on bioleaching of heavy metals from municipal solid waste incinerator fly ash

Previous studies demonstrated that the bioleaching of municipal solid waste incinerator fly ash by Aspergillus niger was an efficient "green technology" for heavy metals removal, however, it demanded a long operational period. In this study, water-washing was used as a fly ash pretreatment before the bioleaching process (one-step and two-step). This pretreatment extracted 50.6% of K, 41.1% of Na, 5.2% of Ca and 1% of Cr from the fly ash. Due to the dissolution of alkali chlorides which hold particles together, fly ash particles were smashed into smaller granules by the hydraulic flushing action caused by vibration. After the pretreatment, the lag phase and bioleaching period were reduced by 45 and 30%, respectively, in one-step bioleaching of 1% (w/v) fly ash. Meanwhile, the metals extraction yield both in one-step and two-step bioleaching was increased markedly, e.g. in two-step bioleaching, 96% Cd, 91% Mn, 73% Pb, 68% Zn, 35% Cr and 30% Fe was extracted from 1% water-washed fly ash, respectively. The reduction of the bioleaching period and improvement of metals extraction yield will likely allow the practical application of the bioleaching technology for heavy metals removal from fly ash.