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Selective and highly efficient extraction technologies for the recovery of critical metals including lithium, nickel, cobalt, and manganese from spent lithium-ion battery (LIB) cathode materials are essential in driving circularity. The tailored deep eutectic solvent (DES) choline chloride-formic acid (ChCl-FA) demonstrated a high selectivity and efficiency in extracting critical metals from mixed cathode materials (LiFePO4:Li(NiCoMn)1/3O2 mass ratio of 1:1) under mild conditions (80 °C, 120 min) with a solid-liquid mass ratio of 1:200. The leaching performance of critical metals could be further enhanced by mechanochemical processing because of particle size reduction, grain refinement, and internal energy storage. Furthermore, mechanochemical reactions effectively inhibited undesirable leaching of nontarget elements (iron and phosphorus), thus promoting the selectivity and leaching efficiency of critical metals. This was achieved through the preoxidation of Fe and the enhanced stability of iron phosphate framework, which significantly increased the separation factor of critical metals to nontarget elements from 56.9 to 1475. The proposed combination of ChCl-FA extraction and the mechanochemical reaction can achieve a highly selective extraction of critical metals from multisource spent LIBs under mild conditions.
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Lítio , Reciclagem , Metais , Cobalto , Fontes de Energia Elétrica , FerroRESUMO
Copper plays a crucial role in the low-carbon transformation of global communities with prevalent use of electric vehicles. This study proposed an environmentally friendly approach that utilizes a deep eutectic solvent (DES), choline chloride-ethylene glycol (ChCl-EG), as green solvent for the selective extraction of copper from scrap materials. With hydrogen peroxide as an oxidizing agent, the copper species from the printed circuit boards (PCBs) scraps were efficiently leached by the DES through oxidation-complexation reactions (conditions: 25 min, 20 °C, and 5 wt% H2O2). Molecular dynamics and density functional theory were performed to simulate the intricate cascade of interactions between copper species and hydrogen bond donors/acceptors of DES, providing insights into the mechanistic processes involved. Copper was selectively recovered from the DES leachate containing impurities (e.g., Pb2+, Sn2+, and Al3+) through electrodeposition via a diffusion-controlled reaction under a constant potential mode. A comprehensive life cycle assessment of the process demonstrated that the utilisation of DES in the extraction of copper from waste PCBs could result in significant reduction in carbon dioxide emissions (-93.6 kg CO2 eq of 1000 kg waste PCBs), thus mitigating the carbon footprint of global copper use through the proposed solvometallurgical recycling process of secondary resources.
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In the recycling of retired lithium-ion batteries (LIBs), the cathode materials containing valuable metals should be first separated from the current collector aluminum foil to decrease the difficulty and complexity in the subsequent metal extraction. However, strong the binding force of organic binder polyvinylidene fluoride (PVDF) prevents effective separation of cathode materials and Al foil, thus affecting metal recycling. This paper reviews the composition, property, function, and binding mechanism of PVDF, and elaborates on the separation technologies of cathode material and Al foil (e.g., physical separation, solid-phase thermochemistry, solution chemistry, and solvent chemistry) as well as the corresponding reaction behavior and transformation mechanisms of PVDF. Due to the characteristic variation of the reaction systems, the dissolution, swelling, melting, and degradation processes and mechanisms of PVDF exhibit considerable differences, posing new challenges to efficient recycling of spent LIBs worldwide. It is critical to separate cathode materials and Al foil and recycle PVDF to reduce environmental risks from the recovery of retired LIBs resources. Developing fluorine-free alternative materials and solid-state electrolytes is a potential way to mitigate PVDF pollution in the recycling of spent LIBs in the EV era.
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Chelant-enhanced soil washing, such as EDTA (ethylenediaminetetraacetic acid) and biodegradable EDDS ([S,S]-ethylene-diamine-disuccinic acid), has been widely studied, however, EDTA is persistent under natural conditions while EDDS has a low efficiency for Pb extraction. Therefore, we investigated the efficacy of mixed chelants (EDDS and EDTA mixture at 1:1â¯M ratio) for the removal of Cu, Zn, and Pb from a field-contaminated soil using various washing schemes (multi-pulse, step-gradient chelant, and continuous washing schemes). Speciation modelling of the target metals, mineral elements, and EDDS/EDTA was performed, while the leachability and bioaccessibility of residual metals in the treated soils were also assessed. Our results suggested that the combined use of EDDS and EDTA reached equivalent extraction efficiency of the target metals as EDTA, i.e., 50% reduction in the dosage of EDTA was made possible. This was accomplished by selective extraction of Cu by EDDS and Pb by EDTA, which was supported by the results of speciation calculation. Multi-pulse washing scheme with intermittent water rinsing steps removed entrapped metal-chelant complexes and free chelants, therefore reducing the leachability and bioaccessibility of residual metals in the treated soils. Step-gradient chelant washing with the maximum dosage of chelants in the first washing step only achieved marginal improvement but undesirably promoted Pb bioaccessibility. Continuous washing for 24â¯h enhanced metal extraction but promoted mineral dissolution, together with a large amount of uncomplexed chelants and increase in Cu leachability. Thus the combined use of EDDS and EDTA in multi-pulse washing is recommended for further studies.
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Quelantes/química , Ácido Edético/química , Recuperação e Remediação Ambiental , Etilenodiaminas/química , Metais Pesados/isolamento & purificação , Poluentes do Solo/isolamento & purificação , Solo/química , Metais Pesados/toxicidade , Poluentes do Solo/toxicidadeRESUMO
To enhance extraction of strongly bound metals from oxide minerals and organic matter, this study examined the sequential use of reductants, oxidants, alkaline solvents and organic acids followed by a biodegradable chelating agent (EDDS, [S,S]-ethylene-diamine-disuccinic-acid) in a two-stage soil washing. The soil was contaminated by Cu, Zn, and Pb at an e-waste recycling site in Qingyuan city, China. In addition to extraction efficiency, this study also examined the fate of residual metals (e.g., leachability, bioaccessibility, and distribution) and the soil quality parameters (i.e., cytotoxicity, enzyme activities, and available nutrients). The reductants (dithionite-citrate-bicarbonate and hydroxylamine hydrochloride) effectively extracted metals by mineral dissolution, but elevated the leachability and bioaccessibility of metals due to the transformation from Fe/Mn oxides to labile fractions. Subsequent EDDS washing was found necessary to mitigate the residual risks. In comparison, prior washing by oxidants (persulphate, hypochlorite, and hydrogen peroxide) was marginally useful because of limited amount of soil organic matter. Prior washing by alkaline solvents (sodium hydroxide and sodium bicarbonate) was also ineffective due to metal precipitation. In contrast, prior washing by low-molecular-weight organic acids (citrate and oxalate) improved the extraction efficiency. Compared to hydroxylamine hydrochloride, citrate and oxalate induced lower cytotoxicity (Microtox) and allowed higher enzyme activities (dehydrogenase, acid phosphatase, and urease) and soil nutrients (available nitrogen and phosphorus), which would facilitate reuse of the treated soil. Therefore, while sequential washing proved to enhance extraction efficacy, the selection of chemical agents besides EDDS should also include the consideration of effects on metal leachability/bioaccessibility and soil quality.
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Resíduo Eletrônico/análise , Recuperação e Remediação Ambiental , Metais Pesados/química , Poluentes do Solo/química , Solo/química , Quelantes/metabolismo , China , Poluição Ambiental , Reciclagem , SolubilidadeRESUMO
Experiments have been carried out to prepare char from waste bamboo scaffolding for wastewater treatment. Carbonisation parameters such as temperature, holding time, heating rate and particle size were investigated. When the material was heated to 1173 K for 2h, surface area S(BET-N(2)) and total pore volume (V(total)) were 327 m(2)/g and 0.185 cm(3)/g, respectively. Particle size and heating rate appear less influential to the yield and textural characteristics of the resultant chars. Bamboo char obtained in this study did not show very high adsorption capacities for two acid dyes (Acid Blue 25 and Acid Yellow 117) but exhibited significant uptake of Methylene Blue. The equilibrium data were modelled by three different isotherms, namely, Langmuir, Freundlich and Redlich-Peterson model. Comparing the predicted data using optimised parameters from each model based on the SSE error function, the Redlich-Peterson isotherm appears the 'best' model to correlate experimental data.
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Bambusa/química , Carvão Vegetal/química , Corantes/isolamento & purificação , Resíduos Industriais/prevenção & controle , Purificação da Água/métodos , Adsorção , Antraquinonas , Temperatura Alta , Porosidade , Poluentes Químicos da Água/isolamento & purificaçãoRESUMO
Two types of activated carbons from tyre char (with or without sulphuric acid treatment) were produced via carbon dioxide activation with BET surface areas in the range 59-1118 m(2)/g. Other characterisation tests include micropore and mesopore surface areas and volumes, pH, and elemental compositions, particularly heteroatoms such as nitrogen and sulphur. They were correlated to the adsorption capacity which were in the range of 0.45-0.71 mmol/g (untreated) and 0.62-0.84 mmol/g (acid-treated) for Acid Blue 25. In the case of larger-sized molecules like Acid Yellow 117, capacities were in the range of 0.23-0.42 mmol/g (untreated) and 0.29-0.40 mmol/g (acid-treated). Some tyre carbons exhibit a more superior performance than a microporous, commercial activated carbon (Calgon F400). By modelling the dye adsorption equilibrium data, the Redlich-Peterson isotherm is adopted as it has the lowest SSE. Based on the surface coverage analysis, a novel molecular orientation modelling of adsorbed dyes has been proposed and correlated with surface area and surface charge. For the acid dyes used in this study, molecules were likely to be adsorbed by the mesopore areas.