Removal of carbon constituents from hospital solid waste incinerator fly ash by column flotation

Hospital solid waste incinerator (HSWI) fly ash contains a large number of carbon constituents including powder activated carbon and unburned carbon, which are the major source of polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) in fly ash. Therefore, the removal of carbon constituents could reduce PCDD/Fs in fly ash greatly. In this study, the effects of the main flotation parameters on the removal of carbon constituents were investigated, and the characteristics of the final product were evaluated. The results showed that loss on ignition (LOI) of fly ash increased from 11.1% to 31.6% during conditioning process. By optimizing the flotation parameters at slurry concentration 0.05 kg/l, kerosene dosage 12 kg/t, frother dosage 3 kg/t and air flow rate 0.06 m³/h, 92.7% of the carbon constituents were removed from the raw fly ash. Under these conditions, the froth product has LOI of 56.35% and calorific values of 12.5 MJ/kg, LOI in the tailings was below 5%, and the total toxic equivalent (TEQ) of PCDD/Fs decreased from 5.61 ng-TEQ/g in the raw fly ash to 1.47 ng-TEQ/g in the tailings. The results show that column flotation is a potential technology for simultaneous separation of carbon constituents and PCDD/Fs from HSWI fly ash.     

Precious Metals in Municipal Solid Waste Incineration Bottom Ash

Municipal solid waste incineration (MSWI) bottom ash contains economically significant levels of silver and gold. Bottom ashes from incinerators at Amsterdam and Ludwigshafen were sampled, processed, and analyzed to determine the composition, size, and mass distribution of the precious metals. In order to establish accurate statistics of the gold particles, a sample of heavy non-ferrous metals produced from 15 tons of wet processed Amsterdam ash was analyzed by a new technology called magnetic density separation (MDS). Amsterdam’s bottom ash contains approximately 10 ppm of silver and 0.4 ppm of gold, which was found in particulate form in all size fractions below 20 mm. The sample from Ludwigshafen was too small to give accurate values on the gold content, but the silver content was found to be identical to the value measured for the Amsterdam ash. Precious metal value in particles smaller than 2 mm seems to derive mainly from waste of electrical and electronic equipment (WEEE), whereas larger precious metal particles are from jewelry and constitute the major part of the economic value. Economical analysis shows that separation of precious metals from the ash may be viable with the presently high prices of non-ferrous metals. In order to recover the precious metals, bottom ash must first be classified into different size fractions. Then, the heavy non-ferrous (HNF) metals should be concentrated by physical separation (eddy current separation, density separation, etc.). Finally, MDS can separate gold from the other HNF metals (copper, zinc). Gold-enriched concentrates can be sold to the precious metal smelter and the copper-zinc fraction to a brass or copper smelter.     

Preparation and performance of arsenate (V) adsorbents derived from concrete wastes

Solid adsorbent materials, prepared from waste cement powder and concrete sludge were assessed for removal of arsenic in the form of arsenic (As(V)) from water. All the materials exhibited arsenic removal capacity when added to distilled water containing 10–700 mg/L arsenic. The arsenic removal isotherms were expressed by the Langmuir type equations, and the highest removal capacity was observed for the adsorbent prepared from concrete sludge with heat treatment at 105 °C, the maximum removal capacity being 175 mg-As(V)/g. Based on changes in arsenic and calcium ion concentrations, and solution pH, the removal mechanism for arsenic was considered to involve the precipitation of calcium arsenate, Ca₃(AsO₄)₂. The enhanced removal of arsenic for the adsorbent prepared from concrete sludge with heat treatment was thought to reflect ion exchange by ettringite. The prepared adsorbents, derived from waste cement and concrete using simple procedures, may offer a cost effective approach for arsenic removal and clean-up of contaminated waters, especially in developing countries.     

Feasibility study of the separation of chlorinated films from plastic packaging wastes

This study describes the possible separation of chlorinated plastic films (PVC and PVDC) from other heavy plastic packaging waste (PPW) by selective twist formation and gravity separation. Twists formation was mechanically induced in chlorinated plastic films, whereas twist formation did not occur in PS and PET films. After twist formation, all the films had the apparent density of less than 1.0 g/cm³ and floated in water even though the true density was more than 1.0 g/cm³. However, the apparent density of the PS and the PET films increased with agitation to more than 1.0 g/cm³, whereas that of chlorinated plastic films was kept less than 1.0 g/cm³. The main reason would be the air being held inside the chlorinated plastic films which was difficult to be removed by agitation. Simple gravity separation after twist formation was applied for artificial film with 10 wt.% of the chlorinated films and real PPW films with 9 wt.% of the chlorinated films. About 76 wt.% of the artificial PPW films and 75 wt.% of real PPW films after the removal of PP and PE were recovered as settling fraction with 4.7 wt.% and 3.0 wt.% of chlorinated plastic films, respectively. These results indicate that simple gravity separation process after twist formation can be used to reduce the chlorinated plastic concentration from mixed heavy PPW films.     

Reduction–melting combined with a Na2CO3 flux recycling process for lead recovery from cathode ray tube funnel glass

With large quantity of flux (Na₂CO₃), lead can be recovered from the funnel glass of waste cathode-ray tubes via reduction–melting at 1000 °C. To reduce flux cost, a technique to recover added flux from the generated oxide phase is also important in order to recycle the flux recovered from the reduction–melting process. In this study, the phase separation of sodium and the crystallization of water-soluble sodium silicates were induced after the reduction–melting process to enhance the leachability of sodium in the oxide phase and to extract the sodium from the phase for the recovery of Na₂CO₃ as flux. A reductive atmosphere promoted the phase separation and crystallization, and the leachability of sodium from the oxide phase was enhanced. The optimum temperature and treatment time for increasing the leachability were 700 °C and 2 h, respectively. After treatment, more than 90% of the sodium in the oxide phase was extracted in water. NaHCO₃ can be recovered by carbonization of the solution containing sodium ions using carbon dioxide gas, decomposed to Na₂CO₃ at 50 °C and recycled for use in the reduction–melting process.     

Metallic-phase lead in slag of municipal solid waste incineration ash and leaching characteristics

Metallic phases in slags and their influence on the leaching characteristics were investigated. The proportions of metallic phase in four slags were 0.028%, 0.24%, 1.87%, and 3.05% by weight. The lead content was 10–248 mg/kg in bulk slag after metal removal, while in the metallic phase it was 579–7390 mg/kg. Lead concentrations in the metallic phase were more than ten times higher than in slags after metal removal. Lead was distributed in the metallic phase at 2.0%, 8.3%, 10.3%, and 47.4%. The concentrations of all metallic elements in metallic phases were much higher than in bulk slag. Iron, copper, and nickel had accumulated in magnetic metals, while aluminum and zinc were found in nonmagnetic metals. As regards chromium, manganese, lead, and tin, the proportion of metallic phases depended on the slag samples. By removing metallic phases, both water and pH 4 leachable lead decreased. The basic principles of melting residues containing lead are the separation of lead as a metal in reductive melting, and the containment of lead ions into uniform glassy particles in oxidization melting. Melting slag can be seen to contribute to environmental preservation by facilitating the recycling of materials through the separation of metals from melting slag. Received: February 21, 2000 / Accepted: July 27, 2000     

Bio-drying and size sorting of municipal solid waste with high water content for improving energy recovery

Bio-drying can enhance the sortability and heating value of municipal solid waste (MSW), consequently improving energy recovery. Bio-drying followed by size sorting was adopted for MSW with high water content to improve its combustibility and reduce potential environmental pollution during the follow-up incineration. The effects of bio-drying and waste particle size on heating values, acid gas and heavy metal emission potential were investigated. The results show that, the water content of MSW decreased from 73.0% to 48.3% after bio-drying, whereas its lower heating value (LHV) increased by 157%. The heavy metal concentrations increased by around 60% due to the loss of dry materials mainly resulting from biodegradation of food residues. The bio-dried waste fractions with particle size higher than 45 mm were mainly composed of plastics and papers, and were preferable for the production of refuse derived fuel (RDF) in view of higher LHV as well as lower heavy metal concentration and emission. However, due to the higher chlorine content and HCl emission potential, attention should be paid to acid gas and dioxin pollution control. Although LHVs of the waste fractions with size <45 mm increased by around 2× after bio-drying, they were still below the quality standards for RDF and much higher heavy metal pollution potential was observed. Different incineration strategies could be adopted for different particle size fractions of MSW, regarding to their combustibility and pollution property.     

Cylinder cyclone (LARCODEMS) density media separation of plastic wastes

Cylindrical cyclone media separators using a suspended calcite separation media simulating industrial scale operations are demonstrated to effectively separate a wide variety of forms and a greater range of particle sizes of plastics by density than presently recycled. Purities of plastic products and recoveries obtained from mixed plastic wastes are comparable to those reported for established separations. Products of ≈100% purity with recoveries of >99% were obtained for high density fractions and >98% purities and recoveries for the low density fractions. Cyclonic centrifugal forces and/or the fine particle size of the separation media appear to minimize hydroscopic and particle shape effects.A mathematical model is proposed for defining plastic waste feed rates and treatable particle size ranges for the LARCODEMS media separator.Waste plastic separations yielded Ecart probable (Ep) values ?0.024 for a water only separation media. The Ep for 1.1 g cm^?3 separation medias was <0.032 with minimal to no variation in values for 1–8 mm particle sizes. Variation in the quality of separations is shown to be minimal with <72 μm, <45 μm and <2 μm media particle sizes. Media density offset created varied according to particle size.     

Chemical composition of material fractions in Danish household waste

The chemical composition of Danish household waste was determined by two approaches: a direct method where the chemical composition (61 substances) of 48 material fractions was determined after hand sorting of about 20 tonnes of waste collected from 2200 households; and an indirect method where batches of 80–1200 tonnes of unsorted household waste was incinerated and the content of the waste determined from the content of the outputs from the incinerator. The indirect method is believed to better represent the small but highly contaminated material fractions (e.g., batteries) than the direct method, because of the larger quantities included and the more homogenous material to sample from. Differences between the direct and the direct methods led to corrections in the of heavy metal concentration of a few fractions.The majority of the energy content of the waste originates from organic waste like paper, cardboard and organic fractions. The single fraction contributing most to the total energy content is the non-recyclable plastic fraction, contributing 21% of the energy content and 60% of the chlorine content, although this fraction comprises less than 7% by weight. Heavy metals originate mainly from inert fractions, primarily batteries.     

Treating landfill gas hydrogen sulphide with mineral wool waste (MWW) and rod mill waste (RMW)

Hydrogen sulphide (H₂S) gas is a major odorant at municipal landfills. The gas can be generated from different waste fractions, for example demolition waste containing gypsum based plaster board. The removal of H₂S from landfill gas was investigated by filtering it through mineral wool waste products. The flow of gas varied from 0.3 l/min to 3.0 l/min. The gas was typical for landfill gas with a mean H₂S concentration of ca. 4500 ppm. The results show that the sulphide gas can effectively be removed by mineral wool waste products. The ratios of the estimated potential for sulphide precipitation were 19:1 for rod mill waste (RMW) and mineral wool waste (MWW). A filter consisting of a mixture of MWW and RMW, with a vertical perforated gas tube through the center of filter material and with a downward gas flow, removed 98% of the sulfide gas over a period of 80 days. A downward gas flow was more efficient in contacting the filter materials. Mineral wool waste products are effective in removing hydrogen sulphide from landfill gas given an adequate contact time and water content in the filter material. Based on the estimated sulphide removal potential of mineral wool and rod mill waste of 14 g/kg and 261 g/kg, and assuming an average sulphide gas concentration of 4500 ppm, the removal capacity in the filter materials has been estimated to last between 11 and 308 days. At the studied location the experimental gas flow was 100 times less than the actual gas flow. We believe that the system described here can be upscaled in order to treat this gas flow.     

Development of Mn recovery process from waste dry cell batteries

High-purity Mn is necessary for high strength steel production. However, the availability of metal Mn is limited to a few countries. Therefore, as an alternative to direct purchasing of metal Mn, a process for Mn recovery was investigated. Waste dry cell batteries are considered to be one of the most feasible Mn sources. We have developed a high efficiency chemical separation system. This system consists of a three-phase chemical treatment. In the first phase, the metal components of the waste dry cell batteries were dissolved by acid, along with a reducing agent. Afterward, the undissolved carbon particles were separated by filtration. In the second phase, the dissolved Mn was selectively precipitated as manganese oxide by O₃ oxidation. Then, the precipitated manganese oxide was separated from the other metal components by filtration. Finally, in the third phase, the manganese oxide was reduced to high-purity Mn using an electric furnace.     

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.     

Strategies for the enhancement of automobile shredder residues (ASRs) recycling: Results and cost assessment

With reference to the European regulation about the management of End-of-Life Vehicles (ELVs), Directive 2000/53/EC imposes the achievement of a recycling target of 85%, and 95% of total recovery by 2015. Over the last few years many efforts have been made to find solutions to properly manage the waste coming from ELVs with the aim of complying with the targets fixed by the Directive.This paper focuses on the economical evaluation of a treatment process, that includes physical (size and density), magnetic and electrical separations, performed on the light fraction of the automobile shredder residue (ASR) with the aim of reducing the amount of waste to dispose of in a landfill and enhancing the recovery of valuable fractions as stated by the EU Directive. The afore mentioned process is able to enhance the recovery of ferrous and non-ferrous metals of an amount equal to about 1% b.w. (by weight) of the ELV weight, and to separate a high energetic-content product suitable for thermal valorization for an amount close to (but not higher than) 10% b.w. of the ELV weight.The results of the economical assessment led to annual operating costs of the treatment ranging from 300,000 €/y to 350,000 €/y. Since the considered plant treats about 13,500 metric tons of ASR per year, this would correspond to an operating cost of approximately 20–25 €/t. Taking into account the amount and the selling price of the scrap iron and of the non magnetic metal recovered by the process, thus leading to a gain of about 30 €/t per ton of light ASR treated, the cost of the recovery process is balanced by the profit from the selling of the recovered metals. On the other hand, the proposed treatment is able to achieve the fulfillment of the targets stated by Directive 2000/53/EC concerning thermal valorization and reduce the amount of waste generated from ELV shredding to landfill.     

Characterization and recycling of cadmium from waste nickel–cadmium batteries

A severe threat was posed due to improper and inefficient recycling of waste batteries in China. The present work considered the fundamental aspects of the recycling of cadmium from waste nickel–cadmium batteries by means of vacuum metallurgy separation in scale-up. In the first stage of this work, the characterization of waste nickel–cadmium batteries was carried out. Five types of batteries from different brands and models were selected and their components were characterized in relation to their elemental chemical composition and main phase. In the second stage of this work, the parameters affecting the recycling of cadmium by means of vacuum metallurgy separation were investigated and a L₁₆ (4⁴) orthogonal design was applied to optimize the parameters. With the thermodynamics theory and numerical analysis, it can be seen that the orthogonal design is an effective tool for investigating the parameters affecting the recycling of cadmium. The optimum operating parameters for the recycling of cadmium obtained by orthogonal design and verification test were 1073 K (temperature), 2.5 h (heating time), 2 wt.% (the addition of carbon powder), and 30 mm (the loaded height), respectively, with recycling efficiency approaching 99.98%. The XRD and ICP-AES analyzed results show that the condensed product was characterized as metallic cadmium, and cadmium purity was 99.99% under the optimum condition.     

Absorption behavior of chlorine and sulfur by Ca(OH)<Subscript>2</Subscript> under simulated conditions with a fluidized bed combustor

This study was carried out to investigate the absorption reaction of chlorine and sulfur with Ca(OH)₂ under simulated conditions related to the co-combustion of refuse-derived fuel and sewage sludge in the fluidized bed combustor, such as high temperature, moisture and a mixing of samples. The combustion experiments were carried out in an electrical furnace with PVC and sulfur powders as the waste samples. High-purity slaked lime powder was used to capture the chlorine and sulfur. The experimental results showed that the removal efficiencies of both chlorine and sulfur were over 90% when the mole ratios of Ca on Cl and S were over 2.5. Furthermore, simultaneous absorption was helpful in improving the removal efficiency of chlorine and sulfur. The presence of chlorine markedly increased the removal efficiency of sulfur. The removal efficiency of chlorine was the highest at 700°C in both independent and simultaneous absorption. The removal efficiency of sulfur increased as the temperature increased, but the removal efficiency of chlorine sharply decreased from 95 to 83% when the moisture content in gases increased from 0 to 20 vol%. These results were confirmed by the combustion test of granular CaCl₂.     

Recovery of valuable materials from waste liquid crystal display panel

Associated with the rapid development of the information and electronic industry, liquid crystal displays (LCDs) have been increasingly sold as displays. However, during the discarding at their end-of-life stage, significant environmental hazards, impacts on health and a loss of resources may occur, if the scraps are not managed in an appropriate way. In order to improve the efficiency of the recovery of valuable materials from waste LCDs panel in an environmentally sound manner, this study presents a combined recycling technology process on the basis of manual dismantling and chemical treatment of LCDs. Three key processes of this technology have been studied, including the separation of LCD polarizing film by thermal shock method the removal of liquid crystals between the glass substrates by the ultrasonic cleaning, and the recovery of indium metal from glass by dissolution. The results show that valuable materials (e.g. indium) and harmful substances (e.g. liquid crystals) could be efficiently recovered or separated through above-mentioned combined technology. The optimal conditions are: (1) the peak temperature of thermal shock to separate polarizing film, ranges from 230 to 240 °C, where pyrolysis could be avoided; (2) the ultrasonic-assisted cleaning was most efficient at a frequency of 40 KHz (P = 40 W) and the exposure of the substrate to industrial detergents for 10 min; and (3) indium separation from glass in a mix of concentrated hydrochloric acid at 38% and nitric acid at 69% (HCl:HNO₃:H₂O = 45:5:50, volume ratio). The indium separation process was conducted with an exposure time of 30 min at a constant temperature of 60 °C.     

Qualitative and quantitative determination of heavy metals in waste cellular phones

Twenty four waste cellular phones, manufactured between 2002 and 2011, were selected in order to determine the total heavy metal content in each of their parts (printed circuit boards (PCBs), plastic housing (PH) and liquid crystal display monitors (LCDs)) and compare the results with the permissible limits set by the 2003 Directive on Restriction of Hazardous Substances (RoHS). All the selected samples were pulverized and digested with strong acids. Inductively coupled plasma-mass spectrometry was used to measure the heavy metal content in each sample. The results revealed that concentration levels of the examined heavy metals were higher in PCBs, followed by PH and LCD in that particular order (PCB > PH > LCD). With the exception of Pb and Cr present in PCBs of mobile phones released before the year 2006, all the other metal concentrations were according to the Directive. Concentration levels of Cd, Hg were lower than the permissible limits set by the EU, either before or after the validity of the 2003 RoHS Directive. Considering their significant heavy metal content, coupled with their large quantities produced worldwide in an annual rate, waste cellular phones need to be treated under an environmentally sound management scheme, prioritizing recycling and at the same time eliminating the possibility of any harm.     

An analysis of the composition and metal contamination of plastics from waste electrical and electronic equipment (WEEE)

The compositions of three WEEE plastic batches of different origin were investigated using infrared spectroscopy, and the metal content was determined with inductively coupled plasma. The composition analysis of the plastics was based mainly on 14 samples collected from a real waste stream, and showed that the major constituents were high impact polystyrene (42 wt%), acrylonitrile–butadiene–styrene copolymer (38 wt%) and polypropylene (10 wt%). Their respective standard deviations were 21.4%, 16.5% and 60.7%, indicating a considerable variation even within a single batch. The level of metal particle contamination was found to be low in all samples, whereas wood contamination and rubber contamination were found to be about 1 wt% each in most samples. In the metal content analysis, iron was detected at levels up to 700 ppm in the recyclable waste plastics fraction, which is of concern due to its potential to catalyse redox reactions during melt processing and thus accelerate the degradation of plastics during recycling. Toxic metals were found only at very low concentrations, with the exception of lead and cadmium which could be detected at 200 ppm and 70 ppm levels, respectively, but these values are below the current threshold limits of 1000 ppm and 100 ppm set by the Restriction of Hazardous Substances directive.     

Recovery of volatile fatty acids via membrane contactor using flat membranes: Experimental and theoretical analysis

Volatile fatty acid (VFA) separation from synthetic VFA solutions and leachate was investigated via the use of a membrane contactor. NaOH was used as a stripping solution to provide constant concentration gradient of VFAs in both sides of a membrane. Mass flux (12.23 g/m² h) and selectivity (1.599) observed for acetic acid were significantly higher than those reported in the literature and were observed at feed pH of 3.0, flow rate of 31.5 ± 0.9 mL/min, and stripping solution concentration of 1.0 N. This study revealed that the flow rate, stripping solution strength, and feed pH affect the mass transfer of VFAs through the PTFE membrane. Acetic and propionic acid separation performances observed in the present study provided a cost effective and environmental alternative due to elimination of the use of extractants.     

Precious metals and rare earth elements in municipal solid waste – Sources and fate in a Swiss incineration plant

In Switzerland many kinds of waste, e.g. paper, metals, electrical and electronic equipment are separately collected and recycled to a large extent. The residual amount of municipal solid waste (MSW) has to be thermally treated before final disposal. Efforts to recover valuable metals from incineration residues have recently increased. However, the resource potential of critical elements in the waste input (sources) and their partitioning into recyclable fractions and residues (fate) is unknown. Therefore, a substance flow analysis (SFA) for 31 elements including precious metals (Au, Ag), platinum metal group elements (Pt, Rh) and rare earth elements (La, Ce, etc.) has been conducted in a solid waste incinerator (SWI) with a state-of-the-art bottom ash treatment according to the Thermo-Re® concept. The SFA allowed the determination of the element partitioning in the SWI, as well as the elemental composition of the MSW by indirect analysis. The results show that the waste-input contains substantial quantities of precious metals, such as 0.4 ± 0.2 mg/kg Au and 5.3 ± 0.7 mg/kg Ag. Many of the valuable substances, such as Au and Ag are enriched in specific outputs (e.g. non-ferrous metal fractions) and are therefore recoverable. As the precious metal content in MSW is expected to rise due to its increasing application in complex consumer products, the results of this study are essential for the improvement of resource recovery in the Thermo-Re® process.