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.     

Metal toxicity assessment of mobile phone parts using Milli Q water

Environmentally safe disposal of end-of-life (EoL) or discarded mobile phone is a serious problem on account of their ever increasing number and toxic metals contents. In the present work, metal toxicity of mobile phone plastics, printed wire boards (PWBs) and batteries were assessed through dynamic batch leaching using Milli Q (MQ) water. Phone plastics failed Toxicity Characterization Leaching Procedure (TCLP) and Waste Extraction Test (WET) for Pb as the cumulative amount of Pb leached from plastics (5.33 mg/l) exceeded the regulatory limits (5.0 mg/l) used in characterizing a waste as hazardous. Similarly, the average cumulative amount (21.83 mg/l) of Ni leached from PWBs exceeded the regulatory limit of 20 mg/l and thus PWBs failed WET. Metals leached from batteries in small amounts (Cr: 0.40 mg/l and Ni: 0.15 mg/l). The presence of Fe in the batteries and its precipitation as oxides/hydroxides in the leaching solution hindered the leaching of other metals in MQ water. Both plastics and PWBs should be treated as hazardous waste and should not be disposed in open landfills. Further, MQ water leaching could provide good simulation of metals leaching from the mobile phones disposed at landfill sites.     

Effect of nine years of animal waste deposition on profile distribution of heavy metals in Abeokuta,south-western Nigeria and its implication for environmental quality

Uncontrolled deposition of waste from animal farms is a common practice in south-western Nigeria, and the presence of heavy metals in soil constitutes environmental and health hazards by polluting the soil, ground water, adjoining streams and rivers. The study investigated the profile distribution of Mn, Pb, Cd, Zn, Fe, Cu, Ni and Cr in some tropical Alfisols in south-western Nigeria after nine years disposal of animal wastes. The amount of these metals in the soil horizons was high enough to cause health and phytotoxic risks. All the metals except Zn and Cr increased down the profile, while Mn, Pb, Cd, Fe, Cu and Ni accumulated at 80–120 cm depth. The increment of these metals at this depth over the top soil were 26%, 143%, 72%, 47%, 328% for Mn, Pb, Cd, Cu and Ni, respectively. It thus, shows their mobility and the possibility of polluting ground water. The Mn content at the poultry and cattle waste sites increased by 127% and 25%, respectively over the control, while that of cattle and swine dump site for Cd content were 9.82 and 15.63 mg kg^?1, respectively. Lead content also increased by 8.52 and 5.25 mg kg^?1, respectively.There was the accumulation of Zn and Cu at the swine dump site while the cattle dump site had the highest amounts of nickel and chromium. The least amount of Fe was recorded at the swine waste dump site. The reduction in organic matter with depths together with the reduced pH might have favored the mobility of the metals. The ranking of pollution among the sites was poultry > swine > cattle > sheep and could be due to the type of ration fed, the vaccination programmes, sanitation programmes and other management practices.     

Heavy metals in source-separated compost and digestates

The production of compost and digestate from source-separated organic residues is well established in Europe. However, these products may be a source of pollutants when applied to soils. In order to assess this issue, composts, solid and liquid digestates from Switzerland were analyzed for heavy metals (Cd, Co, Cr, Cu, Ni, Pb and Zn) addressing factors which may influence the concentration levels: the treatment process, the composition, origin, particle size and impurity content of input materials, the season of input materials collection or the degree of organic matter degradation.Composts (n = 81) showed mean contents being at 60% or less of the legal threshold values. Solid digestates (n = 20) had 20–50% lower values for Cd, Co, Pb and Zn but similar values for Cr, Cu and Ni. Liquid digestates (n = 5) exhibited mean concentrations which were approximately twice the values measured in compost for most elements. Statistical analyses did not reveal clear relationships between influencing factors and heavy metal contents. This suggests that the contamination was rather driven by factors not addressed in the present study.According to mass balance calculations related to Switzerland, the annual loads to agricultural soils resulting from the application of compost and digestates ranged between 2% (Cd) and 22% (Pb) of total heavy metal loads. At regional scale, composts and digestates are therefore minor sources of pollution compared to manure (Co, Cu, Ni, Zn), mineral fertilizer (Cd, Cr) and aerial deposition (Pb). However, for individual fields, fertilization with compost or digestates results in higher heavy metal loads than application of equivalent nutrient inputs through manure or mineral fertilizer.     

Field investigation of the quality of fresh and aged leachates from selected landfills receiving e-waste in an arid climate

The management of electronic waste (e-waste) is a serious problem worldwide and much of it is landfilled. A survey of four selected landfills in an arid region of South Australia was conducted to determine the proportion of e-waste in municipal waste and the properties of each landfill site. Leachate and groundwater samples were collected upgradient and downgradient of the landfills for analysis of polybrominated diphenyl ethers (PBDEs) and 14 metals and metalloids, including Al, As, Ba, Be, Cd, Co, Cr, Cu, Fe, Ni, Pb, Sb, V and Zn. Our data demonstrate that the selected landfills in South Australia continue to receive municipal waste containing in excess of 6%, or 25,000 tonnes per year, of e-waste. The leachates and groundwater collected from the landfills contained significantly elevated concentrations of Pb with the highest concentration in groundwater of 38 μg/l, almost four times higher than the Australian drinking water guideline of 10 μg/l. The presence of PBDEs was detected in both leachate and groundwater samples. Total PBDEs values of 2.13–59.75 ng/l in leachate samples were 10 times higher than in groundwater samples, which recorded a range of 0.41–6.53 ng/l at all sites. Moreover, the concentrations of metals and metalloids in sampled groundwater contained elevated levels of Al, As, Fe, Ni and Pb that exceeded Australian drinking water guideline values. For these reasons potential leaching of these contaminants is of concern and while difficult to attribute elevated contaminant levels to e-waste, we do not recommend continued disposal of e-waste in old landfills that were not originally designed to contain leachates. The survey also revealed temporal variation in the electrical conductivity and concentrations of As, Cd and Pb present in leachates of landfills in arid Mediterranean climates. These results are consistent with the marked variations in rainfall patterns observed for such climates. The solute concentration (EC and other ions including As, Cd and Pb) declines in the leachates during wet winter months (June to September), in contrast to tropical countries where such changes are observed during wet summer months.     

Characterization of Shredder Residues generated and deposited in Denmark

This study presents a detailed characterization of Shredder residues (SR) generated and deposited in Denmark from 1990 to 2010. It represents approximately 85% of total Danish SR. A comprehensive sampling, size fractionation and chemical analysis was carried out on entire samples as well as on each individual size fraction. All significant elemental contents except oxygen were analyzed. The unexplained “balance” was subsequently explained by oxygen content in metal oxides, carbonates, sulphates and in organics, mainly cellulose. Using mass and calorific balance approaches, it was possible to balance the composition and, thereby, estimate the degree of oxidation of elements including metals. This revealed that larger fractions (>10 mm, 10–4 mm, 4–1 mm) contain significant amount of valuable free metals for recovery. The fractionation revealed that the >10 mm coarse fraction was the largest amount of SR being 35–40% (w/w) with a metal content constituting about 4–9% of the total SR by weight and the <1 mm fine fraction constituted 27–37% (w/w) of the total weight. The lower heat value (LHV) of SR samples over different time periods (1990–2010) was between 7 and 17 MJ/kg, declining with decreasing particle size. The SR composition is greatly dependent on the applied shredding and post shredding processes at the shredding plants causing some variations. There are uncertainties related to sampling and preparation of samples for analyses due to its heterogeneous nature and uncertainties in the chemical analyses results (≈15–25%). This exhaustive characterization is believed to constitute hitherto the best data platform for assessing potential value and feasibility of further resource recovery from SR.     

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.     

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 usability of the IR,RAC and MRI indices of heavy metal distribution to assess the environmental quality of sewage sludge composts

To assess the environmental quality of compost, it is insufficient to use only total metal concentration. Therefore in this study, the stability of metals in compost and the environmental risk they pose were assessed by three indices that have been proposed for soils or sediments: the I_R, the RAC and the MRI. In mature composts, the highest bonding intensity was for Ni (0.79 < I_R < 0.93), then for Cu (0.56 < I_R < 0.65) and Pb (0.55 < I_R < 0.73), and the lowest for Zn (0.19 < I_R < 0.25). Although, both the I_R and the RAC are useful indices for evaluating the mobility of metals, they do not take into account their toxicity. Therefore, the overall classification of compost should also include the MRI, at which metal toxicity from the most available fractions is considered. Based on the MRI ranged between 10.0 and 11.6, all composts evaluated posed a low risk.     

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.     

Influence of leaching conditions for ecotoxicological classification of ash

The Waste Framework Directive (WFD; 2008/98/EC) states that classification of hazardous ecotoxicological properties of wastes (i.e. criteria H-14), should be based on the Community legislation on chemicals (i.e. CLP Regulation 1272/2008). However, harmonizing the waste and chemical classification may involve drastic changes related to choice of leaching tests as compared to e.g. the current European standard for ecotoxic characterization of waste (CEN 14735). The primary aim of the present study was therefore to evaluate the influence of leaching conditions, i.e. pH (inherent pH (～10), and 7), liquid to solid (L/S) ratio (10 and 1000 L/kg) and particle size (<4 mm, <1 mm, and <0.125 mm), for subsequent chemical analysis and ecotoxicity testing in relation to classification of municipal waste incineration bottom ash. The hazard potential, based on either comparisons between element levels in leachate and literature toxicity data or ecotoxicity testing of the leachates, was overall significantly higher at low particle size (<0.125 mm) as compared to particle fractions <1 mm and <4 mm, at pH 10 as compared to pH 7, and at L/S 10 as compared to L/S 1000. These results show that the choice of leaching conditions is crucial for H-14 classification of ash and must be carefully considered in deciding on future guidance procedures in Europe.     

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.     

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.     

Stabilization of heavy metals in MSWI fly ash using silica fume

The objective of this work was to investigate the feasibility and effectiveness of silica fume on stabilizing heavy metals in municipal solid waste incineration (MSWI) fly ash. In addition to compressive strength measurements, hydrated pastes were characterized by X-ray diffraction (XRD), thermal-analyses (DTA/TG), and MAS NMR (²⁷Al and ²⁹Si) techniques. It was found that silica fume additions could effectively reduce the leaching of toxic heavy metals. At the addition of 20% silica fume, leaching concentrations for Cu, Pb and Zn of the hydrated paste cured for 7 days decreased from 0.32 mg/L to 0.05 mg/L, 40.99 mg/L to 4.40 mg/L, and 6.96 mg/L to 0.21 mg/L compared with the MSWI fly ash. After curing for 135 days, Cd and Pb in the leachates were not detected, while Cu and Zn concentrations decreased to 0.02 mg/L and 0.03 mg/L. The speciation of Pb and Cd by the modified version of the European Community Bureau of Reference (BCR) extractions showed that these metals converted into more stable state in hydrated pastes of MSWI fly ash in the presence of silica fume. Although exchangeable and weak-acid soluble fractions of Cu and Zn increased with hydration time, silica fume addition of 10% can satisfy the requirement of detoxification for heavy metals investigated in terms of the identification standard of hazardous waste of China.     

Environmental friendly leaching reagent for cobalt and lithium recovery from spent lithium-ion batteries

We investigated an environmentally friendly leaching process for the recovery of cobalt and lithium from the cathode active materials of spent lithium-ion batteries. The easily degradable organic acid DL-malic acid (C₄H₅O₆) was used as a leaching reagent. The structural, morphology of the cathode materials before and after leaching were characterized by X-ray diffraction (XRD) and scanning electronic microscopy (SEM). The amount of Co and Li present in the leachate was determined by atomic absorption spectrophotometry (AAS). Conditions for achieving a recovery of more than 90 wt.% Co and nearly 100 wt.% Li were determined experimentally by varying the concentrations of leachant, time and temperature of the reaction as well as the initial solid-to-liquid ratio. We found that hydrogen peroxide in a DL-malic acid solution is an effective reducing agent because it enhances the leaching efficiency. Leaching with 1.5 M DL-malic acid, 2.0 vol.% hydrogen peroxide and a S:L of 20 g L^?1 in a batch extractor results in a highly efficient recovery of the metals within 40 min at 90 °C.     

Simultaneous recovery of vanadium and nickel from power plant fly-ash: Optimization of parameters using response surface methodology

Simultaneous recovery of vanadium (V) and nickel (Ni), which are classified as two of the most hazardous metal species from power plant heavy fuel fly-ash, was studied using a hydrometallurgical process consisting of acid leaching using sulfuric acid. Leaching parameters were investigated and optimized in order to maximize the recovery of both vanadium and nickel. The independent leaching parameters investigated were liquid to solid ratio (S/L) (5–12.5 wt.%), temperature (45–80 °C), sulfuric acid concentration (5–25 v/v%) and leaching time (1–5 h). Response surface methodology (RSM) was used to optimize the process parameters. The most effective parameter on the recovery of both elements was found to be temperature and the least effective was time for V and acid concentration for Ni. Based on the results, optimum condition for metals recovery (actual recovery of ca.94% for V and 81% for Ni) was determined to be solid to liquid ratio of 9.15 wt.%, temperature of 80 °C, sulfuric acid concentration of 19.47 v/v% and leaching time of 2 h. The maximum V and Ni predicted recovery of 91.34% and 80.26% was achieved.     

Study concerning the recovery of zinc and manganese from spent batteries by hydrometallurgical processes

Used batteries contain numerous metals in high concentrations and if not disposed of with proper care, they can negatively affect our environment. These metals represent 83% of all spent batteries and therefore it is important to recover metals such as Zn and Mn, and reuse them for the production of new batteries. The recovery of Zn and Mn from used batteries, in particular from Zn–C and alkaline ones has been researched using hydrometallurgical methods. After comminution and classification of elemental components, the electrode paste resulting from these processes was treated by chemical leaching. Prior to the leaching process the electrode paste has been subjected to two washing steps, in order to remove the potassium, which is an inconvenient element in this type of processes. To simultaneously extract Zn and Mn from this paste, the leaching method in alkaline medium (NaOH solution) and acid medium (sulphuric acid solution) was used. Also, to determine the efficiency of extraction of Zn and Mn from used batteries, the following variables were studied: reagents concentration, S/L ratio, temperature, time. The best results for extraction yield of Zn and Mn were obtained under acid leaching conditions (2 M H₂SO₄, 1 h, 80 °C).     

Changes in cadmium mobility during composting and after soil application

The effect of twelve weeks of composting on the mobility and bioavailability of cadmium in six composts containing sewage sludge, wood chips and grass was studied, along with the cadmium immobilization capacity of compost. Two different soils were used and Cd accumulation measured in above-ground oat biomass (Avena sativa L.). Increasing pH appears to be an important cause of the observed decreases in available cadmium through the composting process. A pot experiment was performed with two different amounts of compost (9.6 and 28.8 g per kg of soil) added into Fluvisol with total Cd 0.255 mg kg^?1, and contaminated Cambisol with total Cd 6.16 mg kg^?1. Decrease of extractable Cd (0.01 mol l^?1 CaCl₂) was found in both soils after compost application. The higher amount of compost immobilized an exchangeable portion of Cd (0.11 mol l^?1 CH₃COOH extractable) in contaminated Cambisol unlike in light Fluvisol. The addition of a low amount of compost decreased the content of Cd in associated above-ground oat biomass grown in both soils, while a high amount of compost decreased the Cd content in oats only in the Cambisol.     

Recovery of metals from waste printed circuit boards by supercritical water pre-treatment combined with acid leaching process

Waste printed circuit boards (PCBs) contain a large number of metals such as Cu, Sn, Pb, Cd, Cr, Zn, and Mn. In this work, an efficient and environmentally friendly process for metals recovery from waste PCBs by supercritical water (SCW) pre-treatment combined with acid leaching was developed. In the proposed process, waste PCBs were pre-treated by SCW, then the separated solid phase product with concentrated metals was subjected to an acid leaching process for metals recovery. The effect of SCW pre-treatment on the recovery of different metals from waste PCBs was investigated. Two methods of SCW pre-treatment were studied: supercritical water oxidation (SCWO) and supercritical water depolymerization (SCWD). Experimental results indicated that SCWO and SCWD pre-treatment had significant effect on the recovery of different metals. SCWO pre-treatment was highly efficient for enhancing the recovery of Cu and Pb, and the recovery efficiency increased significantly with increasing pre-treatment temperature. The recovery efficiency of Cu and Pb for SCWO pre-treatment at 420 °C was 99.8% and 80%, respectively, whereas most of the Sn and Cr were immobilized in the residue. The recovery of all studied metals was enhanced by SCWD pre-treatment and increased along with pre-treatment temperature. Up to 90% of Sn, Zn, Cr, Cd, and Mn could be recovered for SCWD pre-treatment at 440 °C.