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.     

Kinetic vaporization of heavy metals during fluidized bed thermal treatment of municipal solid waste

Heavy metals volatilization during thermal treatment of model solid waste was theoretically and experimentally investigated in a fluidized bed reactor. Lead, cadmium, zinc and copper, the most four conventional heavy metals were investigated. Particle temperature model and metal diffusion model were established to simulate the volatilization of CdCl₂ evaporation and investigate the possible influencing factors. The diffusion coefficient, porosity and particle size had significant effects on metal volatilization. The higher diffusion coefficient and porosity resulted in the higher metal evaporation. The influence of redox conditions, HCl, water and mineral matrice were also investigated experimentally. The metal volatilization can be promoted by the injection of HCl, while oxygen played a negative role. The diffusion process of heavy metals within particles also had a significant influence on kinetics of their vaporization. The interaction between heavy metals and mineral matter can decrease metal evaporation amount by forming stable metallic species.     

Thermodynamic analysis on heavy metals partitioning impacted by moisture during the MSW incineration

A thermodynamic calculation was carried out to predict the behavior and speciation of heavy metals (HMs), Pb, Zn, Cu, and Cd, during municipal solid waste (MSW) incineration with the different moisture levels. The calculation was based on the minimization of the total Gibbs free energy of the multi-components and multi-phases closed system reaching chemical equilibrium. The calculation also indicated the reaction directions and tendencies of HMs components. The impacts of chlorine additives (No PVC, 1%PVC, and 5%PVC) and moisture on the behavior of HMs were investigated at different temperature levels in the system (750 °C, 950 °C, and 1150 °C). Furthermore, because the incineration temperature falls down with the increase in moisture in waste, the co-influence of moisture and temperature in combusting MSW on the HMs was also studied with the given chlorine (as 1%PVC + 0.5%NaCl). The results showed that in the non-chlorine system, the impact of the moisture on Pb, Zn, and Cu was not significant, and the ratio of compound transformation was less than 10%, except the Cd compounds at 950 °C and 1150 °C. In the system with low chlorine (as 1%PVC) at constant temperature, the chlorides of HMs (Cd, Pb, Zn, and Cu) transferred to oxides, and when the content of chlorine rose up (as 5%PVC), the ratio of the chlorides of HMs (Cd, Pb, Zn, and Cu) transferring to oxides fell down noticeably. When the moisture varied together with the temperature, the Zn and Cu compounds transferred from chlorides to oxides with increase in moisture as well as decrease in temperature. At the temperature of 700–1000 °C, the impact of temperature on Pb and Cd was little and the moisture was the main factor; while at the temperature of 1000–1200 °C, the impact of increase in moisture and decrease in temperature on Pb and Cd was almost equal and reversed.     

Chemical changes and leachate mass balance of municipal solid waste bottom ash submitted to weathering

A study on the chemical stability of municipal solid waste (MSW) bottom ash submitted to weathering was carried out in order to identify and quantify the physico-chemical maturation mechanisms in a large heap (375 tonnes) over a period of about 18 months. The mineralogy and chemical composition of MSW bottom ash were analysed on fresh and maturated material. Calcite is the predominant newly formed mineral during bottom ash maturation, combined with aluminium hydroxides and various sulphates. Lead and zinc are trapped primarily by newly formed carbonates. Monitoring of the pore water and the outlet leachates revealed a marked contrast in the physico-chemical conditions within the heap and at the outlet. The salinity of the fluids peaked at around 16 g/l within the first few weeks and then progressively decreased to fluctuate between 5 and 8 g/l. Due to the high pH of the pore water, the average concentrations of heavy metals in the heap are high: 42.7, 9.6 and 0.8 mg/l for Cu, Pb and Zn. At the heap outlet, however, the leachates are buffered by carbonate precipitation due to equilibration with atmospheric CO2. Copper complexed as a chloride at the outlet remains at a relatively high concentration (10.2 mg/l), whereas Pb and Zn concentrations are below the limit of detection (<25 microg/l). A mass balance carried out over the 18 months of monitoring indicated that 86% of remobilized material within the heap is evacuated from the system. Within the heap, carbonation trapped 43 and 54% of the calcium and bicarbonate flux. The copper, lead and zinc flux at the heap outlet represent only 34, 18 and 19% of the actual remobilized mass of heavy metals.     

Laboratory study on the behaviour of spent AA household alkaline batteries in incineration

The quantitative evaluation of emissions from incineration is essential when Life Cycle Assessment (LCA) studies consider this process as an end-of-life solution for some wastes. Thus, the objective of this work is to quantify the main gaseous emissions produced when spent AA alkaline batteries are incinerated. With this aim, batteries were kept for 1h at 1273K in a refractory steel tube hold in a horizontal electric furnace with temperature control. At one end of the refractory steel tube, a constant air flow input assures the presence of oxygen in the atmosphere and guides the gaseous emissions to a filter system followed by a set of two bubbler flasks having an aqueous solution of 10% (v/v) nitric acid. After each set of experiments, sulphur, chlorides and metals (As, Cd, Co, Cr, Cu, Fe, Hg, Mn, Ni, Pb, Sb, Tl and Zn) were analyzed in both the solutions obtained from the steel tube washing and from the bubblers. Sulphur, chlorides and metals were quantified, respectively, using barium sulfate gravimetry, the Volhard method and atomic absorption spectrometry (AAS). The emissions of zinc, the most emitted metal, represent about 6.5% of the zinc content in the batteries. Emissions of manganese (whose oxide is the main component of the cathode) and iron (from the cathode collector) are negligible when compared with their amount in AA alkaline batteries. Mercury is the metal with higher volatility in the composition of the batteries and was collected even in the second bubbler flask. The amount of chlorides collected corresponds to about 36% of the chlorine in the battery sleeve that is made from PVC. A considerable part of the HCl formed in PVC plastic sleeve incineration is neutralized with KOH, zinc and manganese oxides and, thus, it is not totally released in the gas. Some of the emissions are predictable through a thermodynamic data analysis at temperatures in the range of 1200-1300K taking into account the composition of the batteries. This analysis was done for most of potential reactions between components in the batteries as well as between them and the surrounding atmosphere and it reasonably agrees the experimental results. The results obtained show the role of alkaline batteries at the acid gases cleaning process, through the neutralization reactions of some of their components. Therefore, LCA of spent AA alkaline batteries at the municipal solid waste (MSW) incineration process must consider this contribution.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

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.     

Alteration of municipal solid waste incineration bottom ash focusing on the evolution of iron-rich constituents

Municipal solid waste incineration (MSWI) bottom ash contains a considerable amount of Fe-rich constituents. The behaviors of these constituents, such as dissolution and precipitation, are quite important as they regulate the distribution of a series of ions between the liquid (percolated fluid) and solid (ash deposit) phases. This paper studied both fresh and weathered MSWI bottom ash from the mineralogical and geochemical viewpoint by utilizing optical microscopy, scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), and powder X-ray diffraction. The analysis results revealed that for the fresh bottom ash, iron preferentially existed in the chemical forms of spinel group (mainly Fe(3)O(4), and a series of Al- or Ti- substituted varieties), metallic inclusions (including Fe-P, Fe-S, Fe-Cu-Pb), hematite (Fe(2)O(3)) and unburned iron pieces. In the 1-20 years weathered bottom ash collected from a landfill site, interconversions among these Fe-rich constituents were identified. Consequently, numerous secondary products were developed, including goethite (α-FeOOH), lepidocrocite (γ-FeOOH), hematite, magnetite, wustite (FeO), Fe-Si-rich gel phase. Of all these transformation products, hydrous iron oxides were the most common secondary minerals. Quantitative chemical analysis of these secondary products by SEM/EDX disclosed a strong association between the newly formed hydrous iron oxides and heavy metals (e.g. Pb, Zn, Ni, and Cu). The results of this study suggest that the processes of natural weathering and secondary mineralization contribute to reduction of the potential risks of heavy metals to the surrounding environments.     

Experimental study on flue gas purifying of MSW incineration using in-pipe jet adsorption techniques

This paper presents the experimental research process and results about flue gas purifying of municipal solid wastes (MSW) incineration using in-pipe jet adsorption techniques. MSW incineration was carried out in a fluidized bed test rig, and the flue gas purifying was carried out in an in-pipe jet adsorption test rig. The experimental results are as follows: when the feedstock of activated carbon is 1.6g/Nm(3), the desulfurization efficiency is 83%, the denitrification efficiency is 41%, and the dechlorination efficiency is 27%. The order of purifying effect of the three kinds of adsorbents on acidic gases from MSW incineration is activated carbon>activated bauxite>kaolin. Comparison of adsorption capabilities of the three kinds of adsorbents to heavy metals shows that activated carbon is the best additive to remove Cd, Pb and Cu, kaolin is inferior, and activated bauxite is the worst one. However, activated bauxite is the best additive to remove Hg, and it can remove Cd effectively. PAHs in fly ash are dominated by three-, four-, and five-ringed PAHs, and PAHs in the flue gas mainly include three- and four-ringed PAHs. When the injected quantity of additive is constant, the order of cleaning effect on PAHs is kaolin>activated carbon>activated bauxite. These three kinds of adsorbents have different purifying effects on acidic gases, heavy metals and PAHs in the flue gas from MSW incineration. In general, activated carbon has a better adsorption capability.     

Comparison of methods for leaching heavy metals from composts

This paper presents the determination of total iron, copper, zinc, chromium, nickel, lead, cadmium and mercury contents in the compost obtained from sorted municipal organic solid waste applying the following methods of sample mineralization: 40% hydrofluoric acid with preliminary incineration of a sample, a mixture of concentrated nitric(V) and chloric(VII) acids with preliminary incineration of organic matter and a mixture of nitric(V) and chloric(VII) acids without sample incineration. The speciation analysis of Tessier was used to estimate the bioavailability of the metals. Elution degrees of the mobile forms of the metals from the compost with 10% nitric(V) acid and 1 mol/dm(3) hydrochloric acid were compared. The contents of the elements in the eluates were determined applying atomic absorption spectrometry.     

Influence of calcium chloride on the thermal behavior of heavy and alkali metals in sewage sludge incineration

In order to separate and reuse heavy and alkali metals from flue gas during sewage sludge incineration, experiments were carried out in a pilot incinerator. The experimental results show that most of the heavy and alkali metals form condensed phase at temperature above 600 degrees C. With the addition of 5% calcium chloride into sewage sludge, the gas/solid transformation temperature of part of the metals (As, Cu, Mg and Na) is evidently decreased due to the formation of chloride, while calcium chloride seems to have no significant influence on Zn and P. Moreover, the mass fractions of some heavy and alkali metals in the collected fly ash are relatively high. For example, the mass fractions for Pb and Cu in the fly ash collected by the filter are 1.19% and 19.7%, respectively, which are well above those in lead and copper ores. In the case of adding 5% calcium chloride, the heavy and alkali metals can be divided into three groups based on their conversion temperature: Group A that includes Na, Zn, K, Mg and P, which are converted into condensed phase above 600 degrees C; Group B that includes Pb and Cu which solidify when the temperature is above 400 degrees C; and Group C that includes As, whose condensation temperature is as low as 300 degrees C.     

Effect of multi-factors interaction on trace lead equilibrium during municipal solid waste incineration

The thermodynamic equilibrium of trace lead during the waste incineration was calculated on the basis of the minimization of the total Gibbs energy. The effect of incineration condition and MSW components on Pb distribution was investigated mainly in the view of the interaction of related elements. In the oxygen-rich condition, incineration temperature affects Pb distribution by the interaction of Cl, Ca and Na. In the fuel-rich condition, incineration temperature affects Pb distribution directly by the thermal transition of PbS(s) to PbCl(g) and the thermal transition of PbCl(g) to Pb(g). Air ratio has significant effect on Pb distribution by the interaction of H, O and Cl. The liberated Cl in oxidizing condition is far less than that in reducing condition. Na has the top priority to bond with Cl, than Ca only at low temperature and H only at high temperature, so the effect of Cl on Pb distribution depends on the content of Na and Ca. S promotes Pb volatilization by the interaction with Na in oxygen-rich and chlorine-poor condition and depresses Pb volatilization by the formation of PbS(s) directly without interaction with other elements in fuel-rich condition.     

Effect of unburned carbon on lead, zinc, and copper recovery from molten fly ash by chloride-induced volatilization

The present work focuses on investigation of the effective recovery of heavy metals from molten fly ash by applying chloride-induced volatilization. In particular, the effect of unburned carbon on the chloride-induced volatilization of lead, zinc, and copper from model and real molten fly ashes was investigated in the temperature range 873–1173 K under a N₂ atmosphere. As a result, almost 100% of lead and a significant proportion of zinc were volatilized from the real molten fly ash samples at 1173 K. In contrast, for the model fly ash, volatilization ratios of lead and zinc at 1173 K were only 85% and 25%, respectively. Further, the results of X-ray diffraction analysis suggested that PbO in molten fly ash was converted either to Pb₂OCl₂ or Pb by respective chlorination and reduction reactions. Meanwhile ZnO and CuO in the molten fly ash were reduced to Zn and Cu by reaction with unburned carbon. Subsequently, Pb, Zn, and Pb₂OCl₂ were volatilized, but Cu remained in the solid residue. Finally, the volatilization ratio of zinc increased with the addition of carbon, and more than 98% of zinc was volatilized at 1173 K from a fly ash with a carbon content of 20%.     

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.     

Environmental impact assessment of the incineration of municipal solid waste with auxiliary coal in China

The environmental impacts of waste incineration with auxiliary coal were investigated using the life-cycle-based software, EASEWASTE, based on the municipal solid waste (MSW) management system in Shuozhou City. In the current system, MSW is collected, transported, and incinerated with 250kg of coal per ton of waste. Based on observed environmental impacts of incineration, fossil CO(2) and heavy metals were primary contributors to global warming and ecotoxicity in soil, respectively. Compared with incinerators using excess coal, incineration with adequate coal presents significant benefits in mitigating global warming, whereas incineration with a mass of coal can avoid more impacts to acidification, photochemical ozone and nutrient enrichment because of increased electricity substitution and reduced emission from coal power plants. The "Emission standard of air pollutants for thermal power plants (GB13223-2011)" implemented in 2012 introduced stricter policies on controlling SO(2) and NO(x) emissions from coal power plants. Thus, increased use of auxiliary coal during incineration yields fewer avoided impacts on acidification and nutrient enrichment. When two-thirds of ash is source-separated and landfilled, the incineration of rest-waste presents better results on global warming, acidification, nutrient enrichment, and even ecotoxicity in soil. This process is considered a promising solution for MSW management in Shuozhou City. Weighted normalized environmental impacts were assessed based on Chinese political reduction targets. Results indicate that heavy metal and acidic gas emissions should be given more attention in waste incineration. This study provides scientific support for the management of MSW systems dominated by incineration with auxiliary coal in China.     

Effect of carbon particles on heavy metal emissions under ash-melting conditions

In Japan, incineration ash is subjected to a melting process to reduce waste volume and to stabilize hazardous heavy metals. In previous articles, we reported that large quantities of volatile metals are emitted under ash-melting conditions at temperatures higher than 1200°C and that such emissions are considerably increased under reducing conditions. However, the emission behavior in the presence of large amounts of char particles was unclear, and we suspected that emissions under these conditions might differ from emissions under the previous conditions. Therefore, we investigated heavy metal emissions and the melting characteristics of ash in the presence of carbon particles. In this experiment, a small crucible with ash and carbon was rapidly heated using a high-frequency induction-heating furnace to simulate the melting ash gasification with carbon. As a result, it was found that additive carbon can promote emissions of heavy metals such as zinc and lead and control the melt of the ash.     

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.     

Effect of chlorine on volatilization of Na, K, Pb, and Zn compounds from municipal solid waste during gasification and melting in a shaft-type furnace

In the present work, a shaft-type furnace model in which the furnace column is divided into multiple cells was proposed and equilibrium reaction calculation software was used to describe the model. The model was used to study the effects of gasification and melting conditions such as temperature, oxygen partial pressure, and chlorine content on the volatilization behaviors of the low-boiling-point metals Na, K, Pb, and Zn during the gasification and melting process of municipal solid waste in a shaft-type furnace. Consequently, the volatilization ratios of Na, K, Pb, and Zn compounds in the exhaust gas from a pilot plant shaft-type furnace were found to be in good agreement with the calculation results, and the Na, K, Pb, and Zn compounds were volatilized mainly as metal chlorides in the temperature range up to approximately 1173 K. With a further rise in temperature, these low-boiling point metals were volatilized as metallic forms. It was found that almost 100% of Pb and Zn compounds were volatilized regardless of the chlorine content in municipal solid waste; in contrast, the volatilization rates of Na and K increased when the chlorine content increased. Finally, Na, K, Pb, and Zn compounds were converted from reduced metals to metal chlorides such as NaCl, KCl, PbCl₂, and ZnCl₂ with an increase in the ratio of chlorine to each metal.     

Ammoniacal leaching and recovery of copper from alloyed low-grade e-waste

The paper concerns a hydrometallurgical method for selective recovery of copper from low-grade electric and electronic wastes. The following consecutive stages were proposed: smelting of the scraps to produce Cu–Zn–Ag alloy, leaching of the alloy in ammoniacal solution, and selective copper electrowinning. Cu–Zn–Ag alloy was a polymetallic and five-phase system. It was leached in chloride, carbonate, sulfate and thiosulfate solutions. This resulted in the separation of the metals, wherein metallic tin and silver as well as lead salts remained in the slimes, while copper and zinc were transferred to the electrolyte. Copper was selectively recovered from the ammoniacal solutions by the electrolysis, leaving zinc ions in the electrolyte. The best conditions of the alloy treatment were obtained in the ammonia–carbonate system, where the final product was copper of high purity (99.9 %) at the current efficiency of 60 %. Thiosulfate solution was not applicable for the leaching of the copper alloy due to secondary reactions of the formation of copper(I) thiosulfate complexes and precipitation of copper(I) sulfide, both inhibiting dissolution of the metallic material.     

Behavior of As,Cd, Co,Cr, Cu,Pb, Ni,and Zn at the soil/plant interface around an uncontrolled landfill (Casablanca,Morocco)

The present work undertaken in the environmental context aims to study the distribution of heavy metals in plants that grow naturally around uncontrolled landfills. The study's goal was to identify plants that can be used to remediate contaminated soils. For this purpose, 14 plants species and their rhizospheric soil samples were collected and analyzed for arsenic, cadmium, cobalt, chromium, copper, lead, nickel, and zinc by inductively coupled plasma‐atomic emission spectrometry. The results showed the presence of elevated metal concentrations in soil, many exceeding the regulatory values, and that many species exhibited an ability to accumulate multiple metals in their shoots and roots without sustaining toxicity. This was confirmed by bioconcentration and translocation factors generally higher than 1.