Optimum Dose Of Lime And Fly Ash For Treatment Of Hexavalent Chromium–Contaminated Soil

The presence of hexavalent chromium, Cr(VI), in soil is an environmental concern due to its effect on human health. The concern arises from the leaching and the seepage of Cr(VI) from soil to groundwater. In this paper, a stabilization technology to prevent this problem was simulated on an artificial soil contaminated with hexavalent chromium. The process is a physico-chemical treatment in which the toxic pollutant is physically entrapped within a solid matrix formed by the pozzolanic reactions of lime and fly ash to reduce its leachability and, therefore, its toxicity. This paper presents the optimum ratio of fly ash and lime in order to stabilize artificial soils contaminated with 0.4 wt.% of Cr (VI) in a brief term process. The degree of chromium released from the soil was evaluated using a modified Toxicity Characteristic Leaching Procedure (TCLP) by US Environmental Protection Agency (EPA). Overall, experimental results showed reduced leachability of total and hexavalent chromium from soils treated with both fly ash and quicklime, and that leachability reduction was more effective with increasing amount of fly ash and quicklime. Stabilization percentages between 97.3% and 99.7% of the initial chromium content were achieved, with Cr(VI) concentration in the TCLP leachates below the US EPA limit for chromium of 5 mg/l. Adequate treatment was obtained after 1 day of curing with just 25% fly ash and 10% quicklime.     

Effect of sintering temperature on the properties and leaching of incinerator bottom ash.

The fine particle size fraction of municipal solid waste incinerator bottom ash is often problematic because reuse applications for this material are limited. In these experiments incinerator bottom ash with a particle size of less than 8 mm was processed using conventional ceramic production techniques involving wet milling, drying, compacting and sintering. The effect of sintering temperature on the sintered density, microstructure, acid neutralization capacity (ANC) and the release of metal ions as a function of leachate pH are reported. Sintering at 1080 degrees C produced samples with maximum density. This material contained diopside (CaMgSi2O6), clinoenstatite (Mg2Si2O6) and wollastonite (CaSiO3) as the major crystalline phases. The acid neutralization capacity of sintered samples is significantly lower than milled bottom ash, and further reduces as the sintering temperature increases. This is associated with reduced leaching of Ca from sintered ash samples under all leachate pH conditions. Heavy metals present in the incinerator bottom ash included Cr, Cu, Ni, Zn, Cd and Pb. Sintering under optimum conditions reduced the leachable fraction of these metals under aggressive acid conditions (leachate pH 3) by factors ranging from 90% for Ni to greater than 99% for Cr, Cd, Zn and Pb.     

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.     

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.     

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.     

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.     

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.     

Stabilization/solidification of MSW incineration residues from facilities with different air pollution control systems. Durability of matrices versus carbonation

This paper discusses the stabilisation/solidification process with Portland cement applied to municipal solid waste incineration residues. Two types of residues were considered: fly ash (FA) produced in an electrostatic precipitator, and air pollution control (APC) residues from a semi-dry scrubber process. Cement pastes with different percentages of FA and APC residues were characterised according to their physical properties, the effect of the hydration products and their leaching behaviour. Portland pastes prepared with APC residues showed a rapid setting velocity in comparison with setting time for those pastes substituted with FA residues. Portland cement hydration was retarded in FA pastes. Leaching test results showed that heavy metals (such as Zn, Pb and Cd) and sulphates are immobilised within the paste, whereas chlorides are only partially retained. The carbonation process increases the leachability of S04(2-) and heavy metals such as Zn and Cr.     

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.     

Demobilisation of critical contaminants in four typical waste-to-energy ashes by carbonation

Two bottom ashes, one air pollution control (APC) residue and one fly ash from three different Swedish municipal solid waste incineration (MSWI) plants were characterised regarding the leaching of environmentally relevant components. Characterisation was performed using a diffusion tank leaching test. The impact of carbonation on the release of eight critical components, i.e., Cl(-), Cr, Cu, Mo, Pb, Sb, Se, SO(4)(2-) and Zn, was assessed at a lab-scale and showed carbonation to have a more pronounced demobilising effect on critical components in bottom ashes than in APC residue and fly ash. From grate type incinerator bottom ash, the release of Cr decreased by 97%, by 63% for Cu and by 45% for Sb. In the investigated APC residue, the releases of Cr, Se and Pb were defined as critical, although they either remained unaffected or increased after carbonation. Cl(-) and SO(4)(2-) remained mobile after carbonation in all investigated residues.     

Leachability of municipal solid waste ashes in simulated landfill conditions

In Japan the volume of municipal solid waste is reduced by incineration, with fly ash and bottom ash disposed in controlled landfills. The leachability of anions and heavy metal cations, Zn, Cu and Pb, from MSW fly ash and bottom ash at different pHs was examined using batch- and column-leaching tests. The MSW ashes had a high capacity for neutralizing acids. Behaviour during leaching depended on the pH of the solution. For the volumes applied, the leachabilities of MSW fly ash were very similar at pHs from 3 to 6. Due to its amphoteric nature, Pb is leachable at pHs of approximately 10 or more, with leachate concentrations of about 3 and 3-10mg/L for the fly ash and bottom ash, respectively, much higher than for Zn and Cu. Pb concentrations for most leaching solutions were 1 and 3mg/L for the fly ash and bottom ash, respectively. Zn, and Cu leached at low concentrations for solutions of pH 3-6. Na and K ions leached at high concentrations of approximately 5000 mg/L in the first batch leaching test, decreasing to 10mg/L by the fourth leach. Ca and Mg ions leached more gradually than Na and K. Cl(-) and SO(4)(2+) ions were the major anions in the MSW ash. The high pH and cation leaching are expected to have negative impacts on the performance of clay liners.     

Thermal valorization of footwear leather wastes in bubbling fluidized bed combustion

Transformation of hide (animal skins) into leather is a complicated process during which significant amounts of wastes are generated. Footwear is the sector that consumes the major part of leather (60%). Logically, this industry is producing the largest quantity of leather wastes. The objective of this work was to demonstrate the technical feasibility of fluidized bed technology to recover the energy from burning footwear leather wastes. Considering the characteristics of leather waste, especially the heating value (12.5-21 MJ/kg), it can be considered a fairly good fuel. Moreover, leather waste has suitable characteristics for combustion, e.g., high volatile matter (76.5%) and low ash content (5.2%). Two factors deserve special attention: N3O and NOx emissions as a consequence of its unusual high nitrogen content (14.1%) and the chromium speciation because chromium is the main element of ash (3.2%) due to its use in leather tanning. A series of experiments has been carried out in a 0.1 MWt bubbling fluidized bed pilot plant. The combustion efficiency, flue gas composition and chromium speciation were investigated. Despite having high nitrogen content, a low conversion rate of fuel-N to NOx and N2O was attained. Chromium was concentrated in the solid streams and it was consistently found as Cr(III+); no presence of Cr(VI+) was detected.     

Thermal and hydrometallurgical recovery methods of heavy metals from municipal solid waste fly ash

Heavy metals in fly ash from municipal solid waste incinerators are present in high concentrations. Therefore fly ash must be treated as a hazardous material. On the other hand, it may be a potential source of heavy metals. Zinc, lead, cadmium, and copper can be relatively easily removed during the thermal treatment of fly ash, e.g. in the form of chlorides. In return, wet extraction methods could provide promising results for these elements including chromium and nickel. The aim of this study was to investigate and compare thermal and hydrometallurgical treatment of municipal solid waste fly ash. Thermal treatment of fly ash was performed in a rotary reactor at temperatures between 950 and 1050 °C and in a muffle oven at temperatures from 500 to 1200 °C. The removal more than 90% was reached by easy volatile heavy metals such as cadmium and lead and also by copper, however at higher temperature in the muffle oven. The alkaline (sodium hydroxide) and acid (sulphuric acid) leaching of the fly ash was carried out while the influence of temperature, time, concentration, and liquid/solid ratio were investigated. The combination of alkaline-acidic leaching enhanced the removal of, namely, zinc, chromium and nickel.     

Metal leachability, heavy metals, polycyclic aromatic hydrocarbons and polychlorinated biphenyls in fly and bottom ashes of a medical waste incineration facility

Medical waste from hospitals and other healthcare institutions has become an imperative environmental and public safety problem. Medical waste in Greece has become one of the most urgent environmental problems, because there are 14,000 tons produced annually, of which only a small proportion is incinerated. In the prefecture of Attica there is only one modern municipal medical waste incinerator (started 2004) burning selected infectious hospital waste (5-6 tons day(-1)). Fly and bottom residues (ashes) are collected and stored temporarily in barrels. High values of metal leachability prohibit the landfilling of these ashes, as imposed by EU directives. In the present study we determined quantitatively the heavy metals and other elements in the fly and bottom ashes of the medical waste incinerator, by inductively coupled plasma emission spectrometry (ICP) and by energy dispersive X-ray analysis (EDAX). Heavy metals, which are very toxic, such as Pb, Cd, Ni, Cr, Cu and Zn were found in high concentrations in both fly and bottom ashes. Metal leachability of fly and bottom ashes by water and kerosene was measured by ICP and the results showed that toxic metals in both ashes, such as Pb, Cr, Cd, Cu and Zn, have high leaching values. These values indicate that metals can become soluble and mobile if ash is deposited in landfills, thus restricting their burial according to EU regulations. Analysis of polychlorinated biphenyls and polycyclic aromatic hydrocarbons in fly and bottom ashes showed that their concentrations were very low. This is the first known study in Greece and the results showed that incineration of medical waste can be very effective in minimizing the most hazardous and infectious health-care waste. The presence of toxic metals with high leachability values remains an important draw back of incineration of medical waste and various methods of treating these residues to diminish leaching are been considered at present to overcome this serious technical problem.     

Environmental impact of fly ash utilization in roadway embankments

The leaching potential of heavy metals from a roadway embankment constructed of fly ash and soil mixture was studied. Leaching of eight environmentally concerned metals Ag, As, Ba, Cd, Cr, Hg, Pb, and Se from the fly ash–soil mixtures was examined through batch leaching test and column leaching test. The batch leaching test results showed that the fly ash meets the local regulatory standards for beneficial use of nonhazardous wastes. The column leach test revealed that only Ba, Cr, and Se were detectable in the effluents. The peak concentration of Ba in the effluents was much lower than the US EPA Primary Drinking Water Regulations’ maximum contaminant level (MCL). The peak concentrations of Cr and Se exceeded the MCLs only in the initial flush stage and quickly decreased to below the MCLs. Results of this study suggest a great potential for fly ash to be used in roadway embankments to enhance their mechanical properties, reduce the use of soil, and avoid the disposal of fly ash as waste.     

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.     

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.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

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.     

Development of lightweight aggregate from dry sewage sludge and coal ash

In this study, dry sewage sludge (DSS) as the principal material was blended with coal ash (CA) to produce lightweight aggregate. The effects of different raw material compositions and sintering temperatures on the aggregate properties were then evaluated. In addition, an environmental assessment of the lightweight aggregate generated was conducted by analyzing the fixed rate of heavy metals in the aggregate, as well as their leaching behavior. The results indicated that using DSS enhanced the pyrolysis–volatilization reaction due to its high organic matter content, and decreased the bulk density and sintering temperature. However, the sintered products of un-amended DSS were porous and loose due to the formation of large pores during sintering. Adding CA improved the sintering temperature while effectively decreasing the pore size and increasing the compressive strength of the product. Furthermore, the sintering temperature and the proportion of CA were found to be the primary factors affecting the properties of the sintered products, and the addition of 18–25% of CA coupled with sintering at 1100 °C for 30 min produced the highest quality lightweight aggregates. In addition, heavy metals were fixed inside products generated under these conditions and the As, Pb, Cd, Cr, Ni, Cu, and Zn concentrations of the leachate were found to be within the limits of China’s regulatory requirements.