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.     

Urban Mining: Quality and quantity of recyclable and recoverable material mechanically and physically extractable from residual waste

The mechanically sorted dry fraction (MSDF) and Fines (<20 mm) arising from the mechanical biological treatment of residual municipal solid waste (RMSW) contains respectively about 11% w/w each of recyclable and recoverable materials. Processing a large sample of MSDF in an existing full-scale mechanical sorting facility equipped with near infrared and 2-3 dimensional selectors led to the extraction of about 6% w/w of recyclables with respect to the RMSW weight. Maximum selection efficiency was achieved for metals, about 98% w/w, whereas it was lower for Waste Electrical and Electronic Equipment (WEEE), about 2% w/w. After a simulated lab scale soil washing treatment it was possible to extract about 2% w/w of inert exploitable substances recoverable as construction materials, with respect to the amount of RMSW. The passing curve showed that inert materials were mainly sand with a particle size ranging from 0.063 to 2 mm. Leaching tests showed quite low heavy metal concentrations with the exception of the particles retained by the 0.5 mm sieve. A minimum pollutant concentration was in the leachate from the 10 and 20 mm particle size fractions.     

The effect of shredding and test apparatus size on compressibility and strength parameters of degraded municipal solid waste

In many situations, MSW components are processed and shredded before use in laboratory experiments using conventional soil testing apparatus. However, shredding MSW material may affect the target property to be measured. The objective of this study is to contribute to the understanding of the effect of shredding of MSW on the measured compressibility and strength properties. It is hypothesized that measured properties can be correlated to an R-value, the ratio of waste particle size to apparatus size. Results from oedometer tests, conducted on 63.5 mm, 100 mm, 200 mm diameter apparatus, indicated the dependency of the compressibility parameters on R-value. The compressibility parameters are similar for the same R-value even though the apparatus size varies. The results using same apparatus size with variable R-values indicated that shredding of MSW mainly affects initial compression. Creep and biological strain rate of the tested MSW are not significantly affected by R-value. The shear strength is affected by shredding as the light-weight reinforcing materials are shredded into smaller pieces during specimen preparation. For example, the measured friction angles are 32° and 27° for maximum particle sizes of 50 mm and 25 mm, respectively. The larger MSW components in the specimen provide better reinforcing contribution. This conclusion is however dependent on comparing specimen at the same level of degradation since shear strength is also a function of extent of degradation.     

Washing treatment of automotive shredder residue (ASR)

Worldwide, the amount of end-of-life vehicles (ELVs) reaches 50 million units per year. Once the ELV has been processed, it may then be shredded and sorted to recover valuable metals that are recycled in iron and steelmaking processes. The residual fraction, called automotive shredder residue (ASR), represents 25% of the ELV and is usually landfilled. In order to deal with the leachable fraction of ASR that poses a potential threat to the environment, a washing treatment before landfilling was applied. To assess the potential for full-scale application of washing treatment, tests were carried out in different conditions (L/S = 3 and 5 L/kg_TS; t = 3 and 6 h). Moreover, to understand whether the grain size of waste could affect the washing efficiency, the treatment was applied to ground (<4 mm) and not-ground samples. The findings obtained revealed that, on average, washing treatment achieved removal rates of more than 60% for dissolved organic carbon (DOC), chemical oxygen demand (COD) and total Kjeldahl nitrogen (TKN). With regard to metals and chlorides, sulphates and fluoride leachable fraction, a removal efficiency of approximately 60% was obtained, as confirmed also by EC values. The comparison between the results for ground and not-ground samples did not highlight significant differences.     

Chemical and process mineralogical characterizations of spent lithium-ion batteries: An approach by multi-analytical techniques

Mineral processing operation is a critical step in any recycling process to realize liberation, separation and concentration of the target parts. Developing effective recycling methods to recover all the valuable parts from spent lithium-ion batteries is in great necessity. The aim of this study is to carefully undertake chemical and process mineralogical characterizations of spent lithium-ion batteries by coupling several analytical techniques to provide basic information for the researches on effective mechanical crushing and separation methods in recycling process. The results show that the grade of Co, Cu and Al is fairly high in spent lithium ion batteries and up to 17.62 wt.%, 7.17 wt.% and 21.60 wt.%. Spent lithium-ion batteries have good selective crushing property, the crushed products could be divided into three parts, they are Al-enriched fraction (+2 mm), Cu and Al-enriched fraction (?2 + 0.25 mm) and Co and graphite-enriched fraction (?0.25 mm). The mineral phase and chemical state analysis reveal the electrode materials recovered from ?0.25 mm size fraction keep the original crystal forms and chemical states in lithium-ion batteries, but the surface of the powders has been coated by a certain kind of hydrocarbon. Based on these results a flowsheet to recycle spent LiBs is proposed.     

Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes

Pyrolysis of large printed circuit board (PCB) waste particle was conducted on a specially designed laboratory-scale thermobalance (Macro-TG) with sample loading of 30 g under dynamic nitrogen atmosphere. The effects of heating rate (10, 15, 20 and 25 °C min^?1) and particle size (1 mm × 1 mm, 5 mm × 5 mm, 10 mm × 10 mm and 10 mm × 20 mm) were examined. To compare the different decomposition behavior of fine and large one, the thermal decomposition of PCB waste powder (approximately 5 mg) was also performed on a thermogravimetric analyzer (common TG) under various heating rates (10, 15, 20 and 40 °C min^?1) and particle size ranges (0.198–0.165 mm, 0.165–0.074 mm, 0.074–0.055 mm and 0.055–0.047 mm). Experimental results show that large particle has a pyrolysis reaction retardancy compared to fine one. The distributed activation energy model was used to study the pyrolysis kinetics. It was found that during pyrolysis process, values of frequency factor (k₀) changed with different activation energy (E) values. On common TG, the E values range from 156.95 to 319.37 kJ mol^?1 and k₀ values range from 2.67 × 10¹³ to 2.24 × 10²⁷ s^?1. While, on Macro-TG, the range of E was 31.48–41.26 kJ mol^?1 and of the frequency factor was 19.80–202.67 s^?1.     

Recovery of yttrium from fluorescent powder of cathode ray tube,CRT: Zn removal by sulphide precipitation

This work is focused on the recovery of yttrium and zinc from fluorescent powder of cathode ray tube (CRT). Metals are extracted by sulphuric acid in the presence of hydrogen peroxide. Leaching tests are carried out according to a 2² full factorial plan and the highest extraction yields for yttrium and zinc equal to 100% are observed under the following conditions: 3 M of sulphuric acid, 10% v/v of H₂O₂ concentrated solution at 30% v/v, 10% w/w pulp density, 70 °C and 3 h of reaction.Two series of precipitation tests for zinc are carried out: a 2² full factorial design and a completely randomized factorial design. In these series the factors investigated are pH of solution during the precipitation and the amount of sodium sulphide added to precipitate zinc sulphide. The data of these tests are used to describe two empirical mathematical models for zinc and yttrium precipitation yields by regression analysis. The highest precipitation yields for zinc are obtained under the following conditions: pH equal to 2–2.5% and 10–12% v/v of Na₂S concentrated solution at 10% w/v. In these conditions the coprecipitation of yttrium is of 15–20%.Finally further yttrium precipitation experiments by oxalic acid on the residual solutions, after removing of zinc, show that yttrium could be recovered and calcined to obtain the final product as yttrium oxide. The achieved results allow to propose a CRT recycling process based on leaching of fluorescent powder from cathode ray tube and recovery of yttrium oxide after removing of zinc by precipitation. The final recovery of yttrium is 75–80%.     

Chemical characterisation of spent rechargeable batteries

A chemical characterisation of used batteries can give useful information to implement suitable recycling techniques and to estimate the flux of the different materials recovered. This work is aimed to provide quantitative data about the composition of mixed batteries (in particular, Ni–Cd, Ni-MH and Li-ion batteries) collected in a Northern Italian town in order to evaluate the feasibility of recovery processes applied to the selected material. The higher concentration of metals in the <3 mm fraction suggested that significant quantities of valuable elements could be recovered: in particular, for a kg of the <3 mm fraction deriving from disassembled batteries, about 390 g Ni and 330 g Cd can be recovered from Ni–Cd, 630 g Ni, 80 g Co from Ni-MH and 250 g Co, 110 g Ni, 120 g Cu from Li-ion ones. Leaching tests applied to the same fractions, to assess possible contaminant releases, resulted in low metal content in aqueous solutions (except for Al and Fe, the concentrations of all metals remained below 1 mg/kg). Even so, great care is required in all handling activities due to the high pH values of leachate solutions.     

Evaluation of a recycling process for printed circuit board by physical separation and heat treatment

Printed circuit boards (PCBs) from discarded personal computer (PC) and hard disk drive were crushed by explosion in water or mechanical comminution in order to disintegrate the attached parts. More parts were stripped from PCB of PC, composed of epoxy resin; than from PCB of household appliance, composed of phenol resin.In an attempt to raise the copper grade of PCB by removing other components, a carbonization treatment was investigated. The crushed PCB without surface-mounted parts was carbonized under a nitrogen atmosphere at 873–1073 K. After screening, the char was classified by size into oversized pieces, undersized pieces and powder. The copper foil and glass fiber pieces were liberated and collected in undersized fraction. The copper foil was liberated easily from glass fiber by stamping treatment.As one of the mounted parts, the multi-layered ceramic capacitors (MLCCs), which contain nickel, were carbonized at 873 K. The magnetic separation is carried out at a lower magnetic field strength of 0.1 T and then at 0.8 T. In the +0.5 mm size fraction the nickel grade in magnetic product was increased from 0.16% to 6.7% and the nickel recovery is 74%.The other useful mounted parts are tantalum capacitors. The tantalum capacitors were collected from mounted parts. The tantalum-sintered bodies were separated from molded resins by heat treatment at 723–773 K in air atmosphere and screening of 0.5 mm. Silica was removed and 70% of tantalum grade was obtained after more than 823 K heating and separation.Next, the evaluation of Cu recycling in PCB is estimated. Energy consumption of new process increased and the treatment cost becomes 3 times higher comparing the conventional process, while the environmental burden of new process decreased comparing conventional process.The nickel recovery process in fine ground particles increased energy and energy cost comparing those of the conventional process. However, the environmental burden decreased than the conventional one.The process for recovering tantalum used more heat for the treatment and therefore the energy consumption increased by 50%, when comparing with conventional process. However, the market price for tantalum is very large; the profit for tantalum recovery is added. Also the environmental burden decreased by the recycling of tantalum recovery. Therefore, the tantalum recovery is very important step in the PCB recycling. If there is no tantalum, the consumed energy and treatment cost increase in the new process, though the environmental burden decreases.     

Leaching behavior of copper from waste printed circuit boards with Brønsted acidic ionic liquid

In this work, a Brønsted acidic ionic liquid, 1-butyl-3-methyl-imidazolium hydrogen sulfate ([bmim]HSO₄), was used to leach copper from waste printed circuit boards (WPCBs, mounted with electronic components) for the first time, and the leaching behavior of copper was discussed in detail. The results showed that after the pre-treatment, the metal distributions were different with the particle size: Cu, Zn and Al increased with the increasing particle size; while Ni, Sn and Pb were in the contrary. And the particle size has significant influence on copper leaching rate. Copper leaching rate was higher than 99%, almost 100%, when 1 g WPCBs powder was leached under the optimum conditions: particle size of 0.1–0.25 mm, 25 mL 80% (v/v) ionic liquid, 10 mL 30% hydrogen peroxide, solid/liquid ratio of 1/25, 70 °C and 2 h. Copper leaching by [bmim]HSO₄ can be modeled with the shrinking core model, controlled by diffusion through a solid product layer, and the kinetic apparent activation energy has been calculated to be 25.36 kJ/mol.     

Influence of moisture content,particle size and forming temperature on productivity and quality of rice straw pellets

A large amount of rice straw is generated and left as much in paddy fields, which causes greenhouse gas emissions as methane. Rice straw can be used as bioenergy. Rice straw pellets are a promising technology because pelletization of rice straw is a form of mass and energy densification, which leads to a product that is easy to handle, transport, store and utilize because of the increase in the bulk density. The operational conditions required to produce high quality rice straw pellets have not been determined. This study determined the optimal moisture content range required to produce rice straw pellets with high yield ratio and high heating value, and also determined the influence of particle size and the forming temperature on the yield ratio and durability of rice straw pellets. The optimal moisture content range was between 13% and 20% under a forming temperature of 60 or 80 °C. The optimal particle size was between 10 and 20 mm, considering the time and energy required for shredding, although the particle size did not significantly affect the yield ratio and durability of the pellets. The optimized conditions provided high quality rice straw pellets with nearly 90% yield ratio, ?12 MJ/kg for the lower heating value, and >95% durability.     

Measurement of carbon storage in landfills from the biogenic carbon content of excavated waste samples

Landfills are an anaerobic ecosystem and represent the major disposal alternative for municipal solid waste (MSW) in the U.S. While some fraction of the biogenic carbon, primarily cellulose (Cel) and hemicellulose (H), is converted to carbon dioxide and methane, lignin (L) is essentially recalcitrant. The biogenic carbon that is not mineralized is stored within the landfill. This carbon storage represents a significant component of a landfill carbon balance. The fraction of biogenic carbon that is not reactive in the landfill environment and therefore stored was derived for samples of excavated waste by measurement of the total organic carbon, its biogenic fraction, and the remaining methane potential. The average biogenic carbon content of the excavated samples was 64.6 ± 18.0% (average ± standard deviation), while the average carbon storage factor was 0.09 ± 0.06 g biogenic-C stored per g dry sample or 0.66 ± 0.16 g biogenic-C stored per g biogenic C_.     

Evaluating the biochemical methane potential (BMP) of low-organic waste at Danish landfills

The biochemical methane potential (BMP) is an essential parameter when using first order decay (FOD) landfill gas (LFG) generation models to estimate methane (CH₄) generation from landfills. Different categories of waste (mixed, shredder and sludge waste) with a low-organic content and temporarily stored combustible waste were sampled from four Danish landfills. The waste was characterized in terms of physical characteristics (TS, VS, TC and TOC) and the BMP was analyzed in batch tests. The experiment was set up in triplicate, including blank and control tests. Waste samples were incubated at 55 °C for more than 60 days, with continuous monitoring of the cumulative CH₄ generation. Results showed that samples of mixed waste and shredder waste had similar BMP results, which was in the range of 5.4–9.1 kg CH₄/ton waste (wet weight) on average. As a calculated consequence, their degradable organic carbon content (DOCC) was in the range of 0.44–0.70% of total weight (wet waste). Numeric values of both parameters were much lower than values of traditional municipal solid waste (MSW), as well as default numeric values in current FOD models. The sludge waste and temporarily stored combustible waste showed BMP values of 51.8–69.6 and 106.6–117.3 kg CH₄/ton waste on average, respectively, and DOCC values of 3.84–5.12% and 7.96–8.74% of total weight. The same category of waste from different Danish landfills did not show significant variation. This research studied the BMP of Danish low-organic waste for the first time, which is important and valuable for using current FOD LFG generation models to estimate realistic CH₄ emissions from modern landfills receiving low-organic waste.     

Composition and production rate of medical waste from a small producer in Greece

The objective of this work was to determine the composition and production rate of medical waste from the health care facility of social insurance institute, a small waste producer in Xanthi, Greece. Specifically, produced medical waste from the clinical pathology (medical microbiology) laboratory, the X-ray laboratory and the surgery and injection therapy departments of the health facility was monitored for six working weeks. A total of 240 kg medical solid waste was manually separated and weighed and 330 L of liquid medical waste was measured and classified. The hazardous waste fraction (%w/w) of the medical solid waste was 91.6% for the clinical pathology laboratory, 12.9% for the X-ray laboratory, 24.2% for the surgery departments and 17.6% for the injection therapy department. The infectious waste fraction (%w/w) of the hazardous medical solid waste was 75.6% for the clinical pathology laboratory, 0% for the X-ray laboratory, 100% for the surgery departments and 75.6% for the injection therapy department. The total hazardous medical solid waste production rate was 64 ± 15 g/patient/d for the clinical pathology laboratory, 7.2 ± 1.6 g/patient/d for the X-ray laboratory, 8.3 ± 5.1 g/patient/d for the surgery departments and 24 ± 9 g/patient/d for the injection therapy department. Liquid waste was produced by the clinical pathology laboratory (infectious-and-toxic) and the X-ray laboratory (toxic). The production rate for the clinical pathology laboratory was 0.03 ± 0.003 L/patient/d and for the X-ray laboratory was 0.06 ± 0.006 L/patient/d. Due to the small amount produced, it was suggested that the most suitable management scheme would be to transport the hazardous medical waste, after source-separation, to the Prefectural Hospital of Xanthi to be treated with the hospital waste. Assuming this data is representative of other small medical facilities, medical waste production can be estimated for such facilities distributed around Greece.     

Anaerobic co-digestion of food waste and landfill leachate in single-phase batch reactors

In order to investigate the effect of raw leachate on anaerobic digestion of food waste, co-digestions of food waste with raw leachate were carried out. A series of single-phase batch mesophilic (35 ± 1 °C) anaerobic digestions were performed at a food waste concentration of 41.8 g VS/L. The results showed that inhibition of biogas production by volatile fatty acids (VFA) occurred without raw leachate addition. A certain amount of raw leachate in the reactors effectively relieved acidic inhibition caused by VFA accumulation, and the system maintained stable with methane yield of 369–466 mL/g VS. Total ammonia nitrogen introduced into the digestion systems with initial 2000–3000 mgNH₄–N/L not only replenished nitrogen for bacterial growth, but also formed a buffer system with VFA to maintain a delicate biochemical balance between the acidogenic and methanogenic microorganisms. UV spectroscopy and fluorescence excitation–emission matrix spectroscopy data showed that food waste was completely degraded.We concluded that using raw leachate for supplement water addition and pH modifier on anaerobic digestion of food waste was effective. An appropriate fraction of leachate could stimulate methanogenic activity and enhance biogas production.     

Aluminium recovery vs. hydrogen production as resource recovery options for fine MSWI bottom ash fraction

Waste incineration bottom ash fine fraction contains a significant amount of aluminium, but previous works have shown that current recovery options based on standard on-step Eddy Current Separation (ECS) have limited efficiency. In this paper, we evaluated the improvement in the efficiency of ECS by using an additional step of crushing and sieving. The efficiency of metallic Al recovery was quantified by measuring hydrogen gas production. The ash samples were also tested for total aluminium content with X-ray fluorescence spectroscopy (XRF). As an alternative to material recovery, we also investigated the possibility to convert residual metallic Al into useful energy, promoting H₂ gas production by reacting metallic Al with water at high pH. The results show that the total aluminium concentration in the <4 mm bottom ash fraction is on average 8% of the weight of the dry ash, with less than 15% of it being present in the metallic form. Of this latter, only 21% can be potentially recovered with ECS combined with crushing and sieving stages and subsequently recycled. For hydrogen production, using 10 M NaOH at 1 L/S ratio results in the release of 6–11 l of H₂ gas for each kilogram of fine dry ash, equivalent to an energy potential of 118 kJ.     

WEEE and portable batteries in residual household waste: Quantification and characterisation of misplaced waste

A total of 26.1 Mg of residual waste from 3129 households in 12 Danish municipalities was analysed and revealed that 89.6 kg of Waste Electrical and Electronic Equipment (WEEE), 11 kg of batteries, 2.2 kg of toners and 16 kg of cables had been wrongfully discarded. This corresponds to a Danish household discarding 29 g of WEEE (7 items per year), 4 g of batteries (9 batteries per year), 1 g of toners and 7 g of unidentifiable cables on average per week, constituting 0.34% (w/w), 0.04% (w/w), 0.01% (w/w) and 0.09% (w/w), respectively, of residual waste. The study also found that misplaced WEEE and batteries in the residual waste constituted 16% and 39%, respectively, of what is being collected properly through the dedicated special waste collection schemes. This shows that a large amount of batteries are being discarded with the residual waste, whereas WEEE seems to be collected relatively successfully through the dedicated special waste collection schemes. Characterisation of the misplaced batteries showed that 20% (w/w) of the discarded batteries were discarded as part of WEEE (built-in). Primarily alkaline batteries, carbon zinc batteries and alkaline button cell batteries were found to be discarded with the residual household waste. Characterisation of WEEE showed that primarily small WEEE (WEEE directive categories 2, 5a, 6, 7 and 9) and light sources (WEEE directive category 5b) were misplaced. Electric tooth brushes, watches, clocks, headphones, flashlights, bicycle lights, and cables were items most frequently found. It is recommended that these findings are taken into account when designing new or improving existing special waste collection schemes. Improving the collection of WEEE is also recommended as one way to also improve the collection of batteries due to the large fraction of batteries found as built-in. The findings in this study were comparable to other western European studies, suggesting that the recommendations made in this study could apply to other western European countries as well.     

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.     

Biogas from the organic fraction of municipal solid waste: Dealing with contaminants for a solid oxide fuel cell energy generator

The present work investigates electricity production using a high efficiency electrochemical generator that employs as fuel a biogas from the dry anaerobic digestion of the organic fraction of municipal solid waste (OFMSW).The as-produced biogas contains several contaminants (sulfur, halogen, organic silicon and aromatic compounds) that can be harmful for the fuel cell: these were monitored via an innovative mass spectrometry technique that enables for in-line and real-time quantification.A cleaning trap with activated carbons for the removal of sulfur and other VOCs contained in the biogas was also tested and monitored by observing the different breakthrough times of studied contaminants.The electrochemical generator was a commercial Ni anode-supported planar Solid Oxide Fuel Cell (SOFC), tested for more than 300 h with a simulated biogas mixture (CH₄ 60 vol.%, CO₂ 40 vol.%), directly fed to the anode electrode. Air was added to promote the direct internal conversion of CH₄ to H₂ and CO via partial oxidation (POx).The initial breakthrough of H₂S from the cleaning section was also simulated and tested by adding ～1 ppm(v) of sulfur in the anode feed; a full recovery of the fuel cell performance after 24 h of sulfur exposure (～1 ppm(v)) was observed upon its removal, indicating the reliable time of anode exposure to sulfur in case of exhausted guard bed.