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.     

Reducing volatilization of heavy metals in phosphate-pretreated municipal solid waste incineration fly ash by forming pyromorphite-like minerals

This research investigated the feasibility of reducing volatilization of heavy metals (lead, zinc and cadmium) in municipal solid waste incineration (MSWI) fly ash by forming pyromorphite-like minerals via phosphate pre-treatment. To evaluate the evaporation characteristics of three heavy metals from phosphate-pretreated MSWI fly ash, volatilization tests have been performed by means of a dedicated apparatus in the 100-1000 °C range. The toxicity characteristic leaching procedure (TCLP) test and BCR sequential extraction procedure were applied to assess phosphate stabilization process. The results showed that the volatilization behavior in phosphate-pretreated MSWI fly ash could be reduced effectively. Pyromorphite-like minerals formed in phosphate-pretreated MSWI fly ash were mainly responsible for the volatilization reduction of heavy metals in MSWI fly ash at higher temperature, due to their chemical fixation and thermal stabilization for heavy metals. The stabilization effects were encouraging for the potential reuse of MSWI fly ash.     

Application of MSWI fly ash on acid soil and its effect on the environment

This study evaluated the feasibility of using municipal solid waste incinerator (MSWI) fly ash as acid soil amendment. In particular, changes in soil physicochemical properties and the potential environmental problems caused by the application of MSWI fly ash were investigated. The results showed that application of MSWI fly ash to the acid soil could raise the soil pH. The contents of rapidly available P and K, and slowly available K in the amended soil had a linear relationship with the addition ratio of MSWI fly ash. An addition of less than 20% of MSWI could raise the soil respiratory intensity after incubation for 3-5 days. Application of MSWI fly ash to the soil increased its content of water soluble salts and heavy metals, which could cause phytotoxicity in the plants. Therefore, the addition of MSWI fly ash to the soil should not be excessive, and less than 5-10% is an advisable addition level depending on the acidity of the soil and the plants growing on it.     

Utilization of municipal solid waste incineration (MSWI) fly ash in ceramic brick: product characterization and environmental toxicity

In this study, municipal solid waste incineration (MSWI) fly ash was used as a blending in making ceramic brick based on its characterization and an orthogonal test was performed to determine the optimal mixture ratio of the materials. Besides, the fired bricks made in accordance with the optimal mixture ratio were characterized for performance, phase transformation, microstructure, leaching toxicity of the heavy metals in accordance with GB/T 2542-92 (Detection methods for bricks analysis, China) and by means of XRD, SEM and leaching toxicity analysis. It was found that the optimal mixture ratio of materials (MSWI fly ash:red ceramic clay:feldspar:gang sand) was 20:60:10:10 by mass, and the optimal sintering temperature was 950 °C. Leaching results of heavy metals from sintered bricks were reduced considerably in comparison with those from green bricks prior to sintering process. The results as a whole suggested that utilization of MSWI fly ash in ceramic brick constituted a potential means of adding value.     

The adsorption characteristics of heavy metals by various particle sizes of MSWI bottom ash

The incineration rate of municipal solid waste (MSW) has been increased because of difficulty in securing a proper disposal site for MSW in Korea. The advantage of incineration is reduction of the volume of waste; however, significant amounts of bottom ash and fly ash were generated in the incineration process. Their treatment has attracted growing interest because of the potential toxicity of hazardous heavy metals. Generally, heavy metals are less released from bottom ash than from fly ash. In this study the adsorption characteristics of heavy metals were investigated using various particle sizes of MSWI bottom ash. Since bottom ash has a broad particle size distribution, it was sieved to size classes of +20, -20, -48, -80, -100 mesh. Cation exchange capacity (CEC) was analyzed by the ammonium acetate method to evaluate the potential as an adsorbent. The CEC values and surface areas increase as the range of particle size becomes finer. The adsorption experiment was conducted using synthetic (Cu and Ni) and plating rinse water as a function of reaction time (10-180 min), liquid/solid ratio (2-100) and particle size (+20 to -100 mesh), respectively. The adsorption rate increased with decreasing particle size and with increasing liquid/solid ratio; however, the removal efficiency of Cu was higher than that of Ni. In the case of plating rinse water, the adsorption rate decreased sharply at high liquid/solid ratio, and it showed over 80% of adsorption rates for Cu and Ni at an initial pH of 3.     

The hydration characteristics and utilization of slag obtained by the vitrification of MSWI fly ash

This study investigated the effects of slag composition on the hydration characteristics of slag blended cement (SBC) pastes. Synthetic slag samples were prepared by melting CaO-modified and Al(2)O(3)-modified municipal solid waste incinerator (MSWI) fly ash. MSWI fly ash was mixed with 5% CaO and 5% Al(2)O(3) (by weight), respectively, resulting in two fly ash mixtures. These mixtures were then melted at 1400 degrees C for 30 min to produce two types of slag with different contents, designated at C-slag and A-slag. Both the C-slag and A-slag samples exhibited a pozzolanic activity index higher than the unmodified slag sample. The results show that the synthetic slags all met the Taiwan EPA's current regulatory thresholds. These synthetic slags were then blended with ordinary Portland cement (OPC) at various weight ratios ranging from 10 to 40%. The 28-day strength of the C1 paste was higher than that developed by the OPC paste, suggesting that the C-slag contributed to the earlier strength of the SBC pastes. At curing times beyond 28 days, the strength of the A1 paste samples approached that of the OPC paste samples. It can be seen from this that increasing the amount of calcium and aluminum oxide increases the early strength of SBC. The C-slag blended cement paste samples showed an increase in the number of fine pores with the curing time, showing that the C-slag enhanced the pozzolanic reactions, filling the pores. Also, the incorporation of a 10% addition of C-slag also tended to enhance the degree of hydration of the SBC pastes during the early ages (3-28 days). However, at later ages, no significant difference in degree of hydration between the OPC pastes and the SBC pastes was observed with the 10% C-slag addition. However, the incorporation of A-slag did decreased the degree of hydration. A slag blend ratio of 40% significantly decreased the hydration degree.     

Preparation of activated carbons from heavy-oil fly ashes

The use of heavy oil fly ash with high ash content (45 wt.%) as a precursor for the preparation of activated carbons has been investigated. The raw fly ash and the fly ash with lower ash content, obtained by a HCl/HF washing treatment, have been pyrolyzed at 900 degrees C and then activated with CO(2) in the temperature range of 800-900 degrees C for different times. The activated carbons have been characterised as regards the surface area and the pore volume. The evolution of the porosity has been related to the burn-off degree.     

Diopside-based glass-ceramics from MSW fly ash and bottom ash

By utilising MSW fly ash from the Shanghai Yuqiao municipal solid waste (MSW) incineration plant as the main raw material, diopside-based glass-ceramics were successfully synthesized in the laboratory by combining SiO(2), MgO and Al(2)O(3) or bottom ash as conditioner of the chemical compositions and TiO(2) as the nucleation agent. The optimum procedure for the glass-ceramics is as follows: melting at 1500 degrees C for 30 min, nucleating at 730 degrees C for 90 min, and crystallization at 880 degrees C for 10h. It has been shown that the diopside-based glass-ceramics made from MSW fly ash have a strong fixing capacity for heavy metals such as lead (Pb), chromium (Cr), cadmium (Cd) etc.     

Hydrothermal treatment of MSWI bottom ash forming acid-resistant material

To recycle municipal solid waste incinerator (MSWI) bottom ash, synthesis of hydrothermal minerals from bottom ash was performed to stabilize heavy metals. MSWI bottom ash was mixed with SiO(2), Al(OH)(3), and Mg(OH)(2) so its chemical composition was similar to that of hydrothermal clay minerals. These solid specimens were mixed with water at a liquid/solid ratio of 5. The reaction temperature was 200 degrees C, and reactions were performed for 24-240h. Generation of kaolinite/smectite mixed-layer clay mineral was found in the samples after the reaction of the mixture of bottom ash, SiO(2), and Mg(OH)(2). Calcium silicate hydrate minerals such as tobermorite and xonotlite were also generated. X-ray powder diffraction suggested the presence of amorphous materials. Leaching tests at various pHs revealed that the concentration of heavy metals in the leachates from MSWI bottom ash hydrothermally treated with SiO(2) and Mg(OH)(2) was lower than that in leachates from non-treated bottom ash, especially under acid conditions. Hydrothermal treatment with modification of chemical composition may have potential for the recycling of MSWI bottom ash.     

Strength, leachability and microstructure characterisation of Na2SiO3-activated ground granulated blast-furnace slag solidified MSWI fly ash.

The chemical composition and the leachability of heavy metals in municipal solid waste incinerator (MSWI) fly ash were measured and analysed. For the leachability of unstabilized MSWI fly ash it was found that the concentrations of Pb and Cr exceeded the leaching toxicity standard. Cementitious solidification of the MSWI fly ash by Na2SiO3-activated ground granulated blast-furnace slag (NS) was investigated. Results show that all solidified MSWI fly ash can meet the landfill standards after 28 days of curing. The heavy metals were immobilized within the hydration products such as C-S-H gel and ettringite through physical encapsulation, substitution, precipitation or adsorption mechanisms.     

Application of large volume injection GC-MS to analysis of organic compounds in the extracts and leachates of municipal solid waste incineration fly ash

Organic solvent and water extracts of fly ash from a Milan (Italy) municipal solid waste incinerator (MSWI) were analyzed by large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS) with programmable temperature vaporizer (PTV). Using injection volumes of 10-100 microl, typically over a hundred compounds were detected in organic solvent extracts and ca. 35% of them could be tentatively identified from their electron impact ionization mass spectra. A protocol for the determination of the maximum amount of a potential environmental pollutant available for leaching (availability test) was developed for four selected target compounds: pentachlorobenzene (PeCB), hexachlorobenzene (HxCB), o-terphenyl (o-TPH) and m-terphenyl (m-TPH). Key parameters, extraction time and liquid-to-solid ratio (L/S), were studied in more detail. Recoveries of PeCB, HxCB and o-TPH spiked into the fly ash samples at two concentration levels ranged from 38% to 53% for freshly spiked and from 14% to 40% for 40-day aged fly ash. Recoveries of m-TPH were 8% to 11% from freshly spiked and less than 3% from aged spiked fly ash. The native amounts in Milan MSWI fly ash, determined in an interlaboratory exercise using the developed protocol, were 31 ng/g PeCB, 34 ng/g HxCB, 72 ng/g o-TPH and 4.4 ng/g m-TPH. A separate methodology was developed for the determination of compounds extracted from fly ash by water (leaching test). Following 8-h sonication at L/S 20, the leached amounts of PeCB, HxCB and o-TPH were 1.1, 3.1 and 6.0 ng/g fly ash, respectively.     

Recycling of municipal solid waste incinerator fly ash by using hydrocyclone separation

The municipal solid waste incinerators (MSWIs) in Taiwan generate about 300,000 tons of fly ash annually, which is mainly composed of calcium and silicon compounds, and has the potential for recycling. However, some heavy metals are present in the MSWI fly ash, and before recycling, they need to be removed or reduced to make the fly ash non-hazardous. Accordingly, the purpose of this study was to use a hydrocyclone for the separation of the components of the MSWI fly ash in order to obtain the recyclable portion. The results show that chloride salts can be removed from the fly ash during the hydrocyclone separation process. The presence of a dense medium (quartz sand in this study) is not only helpful for the removal of the salts, but also for the separation of the fly ash particles. After the dense-medium hydrocyclone separation process, heavy metals including Pb and Zn were concentrated in the fine particles so that the rest of the fly ash contained less heavy metal and became both non-hazardous and recyclable.     

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.     

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.     

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.     

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.     

钛硅分子筛催化双氧水氧化水中间甲酚

探索催化双氧水氧化去除间甲酚对开发炼油厂碱渣废水处理新技术意义重大。采用钛硅分子筛催化双氧水氧化水中间甲酚,考察了反应时间、反应温度、双氧水加入量、催化剂加入量和初始溶液pH对间甲酚去除率的影响。实验结果表明：钛硅分子筛对双氧水氧化间甲酚具有显著的催化作用;在反应时间为90 min、反应温度为80 ℃、n（H₂O₂）∶n（间甲酚）为4、催化剂加入量为1.5 g/L、初始溶液pH为1.0~11.0的条件下,间甲酚去除率约为94%,间甲酚溶液的BOD₅/COD从氧化前的0.26提高到氧化后的0.38,可生化性显著提高。     

Formation characteristics of polychlorinated dibenzo-p-dioxins, polychlorinated dibenzofurans, and coplanar PCBs in fly ash from a gasification–melting process of municipal solid waste

PCDDs/DF and Co-PCB (dioxin) formations were studied with ash from a newly developed gasification and melting process for municipal solid waste. Ash samples were heated in a laboratory-scale fixed-bed reactor. Emphasis was placed on the effects of the type and composition of ash, temperatures, gas residence time, and gaseous organic precursors. Investigations using macroscopic and homologue distribution analyses led to the following conclusion. The ash from the gasification–melting process had the ability to generate dioxins in flue gas. A possible carbon source is unburned carbon in the ash samples, although this was very low (less than 0.01%). An experimental result that the level of dioxins generated from preheated fly ash obtained from a conventional incinerator was much lower than that from nonheated fly ash supported this conclusion. Dioxin concentrations obviously showed temperature dependence and peaked at 350°C. Dioxins formed in a gasification–melting process ash were readily desorbed from the surface, probably because of the low carbon content of the ash. There was no experimental evidence that gaseous organic precursors fed to the reactor generated dioxins. Therefore, an organic precursor was not essential for the formation of dioxins. A good linear relationship obtained between PCDDs/DFs and gas residence time also supported the assumption. Received: February 14, 2000 / Accepted: June 30, 2000     

Coal fly ash utilization: low temperature sintering of wall tiles

We present here a study of the sintering of fly ash and its mixture with low alkali pyrophyllite in the presence of sodium hexa meta phosphate (SHMP), a complex activator of sintering, for the purpose of wall tile manufacturing. The sintering of fly ash with SHMP in the temperature range 925-1050 degrees C produces tiles with low impact strength; however, the incremental addition of low alkali pyrophyllite improves impact strength. The impact strength of composites with 40% (w/w) pyrophyllite in the fly ash-pyrophyllite mix satisfies the acceptable limit (19.6J/m) set by the Indian Standards Institute for wall tiles. Increasing the pyrophyllite content results in an increase in the apparent density of tiles, while shrinkage and water absorption decrease. The strength of fly ash tiles is attributed to the formation of a silicophosphate phase; in pyrophyllite rich tiles, it is attributed to the formation of a tridymite-structured T-AlPO(4) phase. Scanning electron micrographs show that the reinforcing rod shaped T-AlPO(4) crystals become more prominent as the pyrophyllite content increases in the sintered tiles.     

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.