Search Results (74)

A leachate from alkaline leaching of copper shaft furnace (CSF) dust as a hazardous waste was used in this study for performing a chemical precipitation experiment of lead, zinc, and copper. The precipitation processes for lead, zinc, and copper were theoretically optimized based on a thermodynamic study. To determine suitable operating conditions, metal phase stability, reaction mechanisms, and precipitation order were analyzed using the Hydra/Medusa and HSC Chemistry v.10 software packages. In the first experimental stage, treatment of the alkaline leachate resulted in the formation of insoluble lead sulfate (PbSO₄), while zinc remained dissolved for subsequent recovery. In the second stage, the zinc-bearing solution was treated with Na₂CO₃, producing a mixed zinc precipitate consisting of Zn₅(OH)₆(CO₃)_2(s). This study determined that the optimal conditions for chemically precipitating lead as PbSO₄ from alkaline leachate (pH 13.5) are the use of 1 mol/L H₂SO₄ at pH 3.09 and Eh 0.22 V at 25 °C, while optimal zinc precipitation from this solution (pH 3.02) is achieved with 2 mol/L Na₂CO₃ at pH 9.39 and Eh –0.14 V at 25 °C. A small amount of copper present in the solution co-precipitated and was identified as an impurity in the zinc product. The chemical composition of the resulting precipitates was confirmed by SEM–EDX analysis. Full article

The limited availability of high-quality ore deposits and the environmental hazards of metallurgical wastes highlight the importance of developing resource-efficient metal recovery technologies. Zinc kiln slag (ZKS), also known as Waelz slag, a by-product material enriched in non-ferrous metals, was processed through oxidative HCl leaching with H₂O₂ as an oxidant. Thermodynamic simulation and laboratory experiments were applied to determine optimal leaching conditions to dissolve copper, zinc, and iron. Optimal leaching efficiency was achieved with consumptions of 0.8 g HCl and 0.1 g H₂O₂ per gram of ZKS, a liquid-to-solid (L/S) ratio of 5 mL/g, a temperature of 70 °C, and a duration of 180 min, which resulted in recoveries of 96.3% Cu, 93.6% Fe, and 76.8% Zn. The solid residue with 43.5 wt.% C is promising for reuse as a reductant material in pyrometallurgical processes. Copper and arsenic were separated from the leachate via cementation with iron powder, achieving recovery rates of 98.9% and 91.2%, respectively. A subsequent two-step iron precipitation produced ferric hydroxide with 52.2 wt.% Fe and low levels of impurities. As a result, the developed novel hydrochloric acid oxidative leaching and metal precipitation route for ZKS recycling provides an efficient and sustainable alternative to conventional treatment methods. Full article

Although the exponential increase in photovoltaic installations does contribute to mitigating climate change, it has posed the problem of photovoltaic (PV) residue. As PV panels contain strategic metals, their recovery has become a priority. This paper therefore employs a mesoporous carbon impregnated with P507 extractant as adsorbent to selectively recover gallium and indium from solutions simulating the leachate of end-of-life CIGS (Copper Indium Gallium Selenide) cells in a fixed-bed. The previous batch results obtained in our lab show that both metals can be selectively separated by simply adjusting the initial pH, with large adsorption capacities (44.97 mg/g for gallium and 34.24 mg/g for indium). The obtained breakthrough curves were fitted to the Thomas, Yan, Yoon, and HSDM (Homogeneous Surface Diffusion Model) models using a simulation program developed in Python 3.12 obtaining good results in all cases (R² > 0.9). The estimated parameters were used to predict the experimental breakthrough curve for a different experiment that had not been used for parameter estimation, being the best predictive results the obtained with the HSDM. This is logical, given that unlike the other three models, it is mechanistic. Full article

Formo-phenolic-like resins were synthesized by replacing phenol with phloroglucinol, a biobased and biocompatible compound, and using different aldehydes, such as biomass-derived furaldehyde and glyoxal. Studies on the adsorption of rare earth elements from an aqueous organic acid solution indicate that these resins follow the Langmuir isotherm model, with maximum adsorption capacities ranging from 0.38 to 0.75 mmol/g. Adsorption was temperature-independent but strongly influenced by pH, with an up to fourfold increase between pH 2 and 5. Extraction kinetics were rapid, reaching equilibrium within two hours. Complete metal recovery was achieved within ten minutes using a 1 mol/L HCl desorption solution. Selectivity also varied with pH; glyoxal- and furfural-based resins showed superior separation performance at pH 2–3 and 3–4, respectively. The application of this method to real-world samples, including permanent magnet and red mud organic acid leachates, demonstrated effective extraction of rare earth elements and promising selectivity over iron (Fe), cobalt (Co), and nickel (Ni). Full article

The growing demand for ultra-low sulfur fuels has intensified interest in recovering strategic metals from the large volumes of hazardous hydrodesulfurization catalysts that are discarded yearly. This work evaluates a task-specific ionic liquid, tri-n-octylammonium bis(2-,4-,4-trimethylpentyl)-phosphinate [TOA][Cy272], synthesized by the acid–base neutralization of tri-n-octylamine and Cyanex 272. FT-IR spectroscopy confirmed complete proton transfer and the formation of a stable ion pair. Liquid–liquid extraction tests were conducted with synthetic Co–Ni–Mo solutions (0.1–2.5 g/L each), a varying ionic liquid concentration (10–50 vol%), pH (1.5–12.5), and organic/aqueous ratio (1:1). At 35 vol% of ionic liquid and pH 2, the extraction efficiency for Mo reached 94%, with separation factors βMo/Ni = 12 and βMo/Co = 7.5; Co and Ni uptake remained ≤15%. Selectivity decreased at higher metal loadings because of ionic liquid saturation, and an excessive ionic liquid amount (>35%) offered no benefit, owing to viscosity-limited mass transfer. Stripping studies showed that 1 M NH₄OH stripped about 95% Mo, while leaving Co and Ni in the organic phase; conversely, 2 M HCl removed 92–98% of Co and Ni, but <5% Mo. Overall Mo recovery of about 95% was obtained by a two-step extraction/stripping scheme. The results demonstrate that [TOA][Cy272] combines the cation exchange capability of quaternary ammonium ILs with the strong chelating affinity of organophosphinic acids, delivering rapid, selective, and regenerable separation of Mo from mixed-metal leachates and wastewater streams. Full article

The efficient recovery of rhenium (Re), a critical metal in high-tech industries, is essential to address its growing demand and reduce reliance on primary mining. In this study, we developed novel anion-exchange resins for the selective adsorption and recovery of Re(VII) ions from acidic solutions, simulating industrial by-products. The resins were synthesized from a vinylbenzyl chloride-co-divinylbenzene copolymer modified with aliphatic, heterocyclic, and aromatic weakly basic amines, selected from among bis(3-aminopropyl)amine (BAPA), 1-(2-pyrimidinyl)piperazine (PIP), thiosemicarbazide (TSC), 2-amino-3-hydroxypyridine (AHP), 1-(2-hydroxyethyl)piperazine (HEP), 4-amino-2,6-dihydroxypyrimidine (AHPI), and 2-thiazolamine (TA). The adsorption of Re on BAPA, PIP, and HEP resins obeyed the Langmuir model, and the resins exhibited high adsorption capacities, with maximum values reaching 435.4 mg Re g⁻¹ at pH 6. Furthermore, strong selectivity for ReO₄⁻ ions over competing species, including Mo, Cu, and V, was noted in solutions simulating the leachates of the by-products of Cu-Mo ores. Additionally, complete elution of Re was possible. The developed resins turned out to be highly suitable for the continuous-flow-mode adsorption of ReO₄⁻, revealing outstanding adsorption capacities before reaching column breakthrough. In this context, the novel anion-exchange resins developed offer a reference for further Re recovery strategies. Full article

Municipal solid waste (MSW) and refuse-derived fuel (RDF) incineration generate over 20 million tons of residues annually in the EU. These include bottom ash (IBA), fly ash (FA), and air pollution control residues (APCr), which pose significant environmental challenges due to their leaching potential and hazardous properties. While these residues contain valuable metals and reactive mineral phases suitable for carbonation or alkaline activation, chemical, techno-economic, and policy barriers have hindered the implementation of sustainable, full-scale management solutions. Accelerated carbonation technology (ACT) offers a promising approach to simultaneously sequester CO₂ and enhance residue stability. This review provides a comprehensive assessment of waste incineration residue carbonation, covering 227 documents ranging from laboratory studies to field applications. The analysis examines reactor designs and process layouts, with a detailed classification based on material characteristics, operating conditions, investigated parameters, and the resulting pollutant stabilization, CO₂ uptake, or product performance. In conclusion, carbonation-based approaches must be seamlessly integrated into broader waste management strategies, including metal recovery and material repurposing. Carbonation should be recognized not only as a CO₂ sequestration process, but also as a binding and stabilization strategy. The most critical barrier remains chemical: the persistent leaching of sulfates, chromium(VI), and antimony(V). We highlight what we refer to as the antimony problem, as this element can become mobilized by up to three orders of magnitude in leachate concentrations. The most pressing research gap hindering industrial deployment is the need to design stabilization approaches specifically tailored to critical anionic species, particularly Sb(V), Cr(VI), and SO₄²⁻. Full article

To ensure the sustainable use of limited resources, it is essential to establish selective and efficient recycling technologies for platinum group metals (PGMs). This study focused on the selective precipitation-based separation of Pt(IV) from hydrochloric acid (HCl) solutions in the presence of various metal ions, using trans-1,4-bis(aminomethyl)cyclohexane (BACT) as a precipitating agent. By using BACT, we succeeded in the selective separation of Pt(IV) by precipitation from HCl solutions containing Pd(II) and Rh(III). Notably, selective and efficient recovery of Pt(IV) was accomplished across various HCl concentrations, with a small amount of BACT and within a short shaking time. To evaluate the practical applicability of the method, Pt(IV) was recovered and purified from the HCl leachate of spent automotive exhaust gas purification catalysts using BACT. As a result, a high Pt recovery of 95.6% and a high purity of 99.3% were achieved. Although Pt(IV) was recovered as a precipitate containing BACT, it was found that Pt black could be readily obtained by dissolving the precipitate in HCl solution followed by reduction with sodium borohydride. Detailed structural analysis of the Pt(IV)-containing precipitate revealed that it is an ionic crystal composed of [PtCl₆]²⁻ and protonated BACT. The selective formation of this ionic crystal in HCl solution, along with its stability under such conditions, is the key to the selective recovery of Pt(IV) using BACT. Full article

Rare earth metals (REMs) are vital for high-tech industries, but their extraction from secondary sources is challenging due to environmental and technical constraints. This study investigates the ion-exchange extraction of light REMs (neodymium, praseodymium, and samarium) from sulfuric and phosphoric acid solutions, modeling industrial leachates from apatite concentrates and phosphogypsum. The study considers the use of anion- and cation-exchange resins with different functional groups for efficient and environmentally safe REM separation. Experimental sorption isotherms were obtained under static conditions at 298 K and analyzed using a thermodynamic model based on the linearization of the mass action equation. Equilibrium constants and Gibbs energy were calculated, which reveals the spontaneity of the processes. Cation-exchange resins demonstrated high selectivity towards individual REMs, while anion-exchange resins were suitable for group extraction. Infrared spectral analysis confirmed the presence of sulfate and phosphate complexes in the resin matrix, clarifying the ion-exchange mechanisms. Thermal effect measurements indicated exothermic sorption on anion-exchange resins with negative entropy and endothermic sorption on cation-exchange resins with positive entropy. The findings highlight the potential of ion-exchange resins for selective and sustainable REM recovery, offering a safer alternative to liquid extraction and enabling the valorization of industrial wastes like phosphogypsum for resource recovery. Full article

Next-generation recycling technologies must be urgently innovated to tackle huge volumes of spent batteries, photovoltaic panels or printed circuit boards (WPCBs). Current e-waste recycling industrial technology is dominated by traditional recycling technologies. Herein, ionic liquids (ILs), deep eutectic solvents (DESs) and promising oxidizing additives that can overcome some traditional recycling methods of metal ions from e-waste, used in our works from last year, are presented. The unique chemical environments of ILs and DESs, with the application of low-temperature extraction procedures, are important environmental aspects known as “Green Methods”. A closed-loop system for recycling zinc and manganese from the “black mass” (BM) of waste, Zn-MnO₂ batteries, is presented. The leaching process achieves a high efficiency and distribution ratio using the composition of two solvents (Cyanex 272 + diethyl phosphite (DPh)) for Zn(II) extraction. High extraction efficiency with 100% zinc and manganese recovery is also achieved using DESs (cholinum chloride/lactic acid, 1:2, DES 1, and cholinum chloride/malonic acid, 1:1, DES 2). New, greener recycling approaches to metal extraction from the BM of spent Li-ion batteries are presented with ILs ([N_8,8,8,1][Cl], (Aliquat 336), [P_6,6,6,14][Cl], [P_6,6,6,14][SCN] and [Benzet][TCM]) eight DESs, Cyanex 272 and D2EHPA. A high extraction efficiency of Li(I) (41–92 wt%) and Ni(II) (37–52 wt%) using (Cyanex 272 + DPh) is obtained. The recovery of Ni(II) and Cd(II) from the BM of spent Ni-Cd batteries is also demonstrated. The extraction efficiency of DES 1 and DES 2, contrary to ILs ([P_6,6,6,14][Cl] and [P_6,6,6,14][SCN]), is at the level of 30 wt% for Ni(II) and 100 wt% for Cd(II). In this mini-review, the option to use ILs, DESs and Cyanex 272 for the recovery of valuable metals from end-of-life WPCBs is presented. Next-generation recycling technologies, in contrast to the extraction of metals from acidic leachate preceded by thermal pre-treatment or from solid material only after thermal pre-treatment, have been developed with ILs and DESs using the ABS method, as well as Cyanex 272 (only after the thermal pre-treatment of WPCBs), with a process efficiency of 60–100 wt%. In this process, four new ILs are used: didecyldimethylammonium propionate, [N_10,10,1,1][C₂H₅COO], didecylmethylammonium hydrogen sulphate, [N_10,10,1,H][HSO₄], didecyldimethylammonium dihydrogen phosphate, [N_10,10,1,1][H₂PO₄], and tetrabutylphosphonium dihydrogen phosphate, [P_4,4,4,4][H₂PO₄]. The extraction of Cu(II), Ag(I) and other metals such as Al(III), Fe(II) and Zn(II) from solid WPCBs is demonstrated. Various additives are used during the extraction processes. The Analyst 800 atomic absorption spectrometer (FAAS) is used for the determination of metal content in the solid BM. The ICP-OES method is used for metal analysis. The obtained results describe the possible application of ILs and DESs as environmental media for upcycling spent electronic wastes. Full article

It is of strategic significance to extract germanium (Ge) in an ecological way for sustainable development. Adsorbents that already adsorb Ge have disadvantages such as poor selectivity and low adsorption capacity. In this study, a novel adsorbent material based on rice husk functionalized with tannic acid was developed for the efficient extraction of Ge from simulated coal fly ash leachate. The adsorption capacity of tannic acid-functionalized rice husk (TA-EPI-ORH) for Ge was 19.9 times higher than that of untreated rice husk, demonstrating significantly improved performance. The results showed that the adsorption process of Ge by TA-EPI-ORH is consistent with pseudo-second-order kinetic and Freundlich isotherm model. TA-EPI-ORH had excellent selective adsorption properties, with adsorption of 1.40 mg L⁻¹ Ge exceeding 95% and solid-liquid partition coefficients of 4380 mL g⁻¹, even in the presence of nine impurity metal ions (average concentration: 479.08 mg L⁻¹). When compared with the two main coexistence ions—aluminum (Al) and calcium (Ca)—both of which have the relatively highest concentrations (Al: 1594.20 mg L⁻¹, Ca: 1740.13 mg L⁻¹), the separation factors for Ge still maintain relatively high level with SF(Ge/Al) = 42.57 and SF(Ge/Ca) = 39.93. Compared to existing studies, TA-EPI-ORH exhibits superior selective adsorption performance even with the presence of more interfering ions. After elution of the adsorbed Ge from TA-EPI-ORH, the extraction rate of Ge with low initial concentration (1.40 mg L⁻¹) reached 85.17%, while the extraction rates of Al and Ca were only 1.02% and 1.18%, respectively. Further research revealed that the catechol groups on the surface of TA-EPI-ORH formed stable complexes with Ge, whereas the complexes with coexisting ions (e.g., Ca and Al) were unstable, thereby ensuring high selectivity for Ge. This green chemistry-based functionalization of rice husk not only enables high-value utilization of agricultural waste but also provides a sustainable and eco-friendly strategy for efficient Ge separation and recovery. Full article

The rapid growth of aluminum and graphite industries has generated substantial stockpiles of red mud and graphite tailings, which pose environmental risks due to their high heavy metal content and potential for soil and water contamination. This study investigated the leaching behavior of heavy metals from these materials post-stabilization using cement and a sulfonated oil-based ion curing agent, thereby evaluating their suitability for safe reuse. Semi-dynamic leaching experiments were employed to measure heavy metal release, supplemented by kinetic modeling to discern key leaching mechanisms. The findings indicated that the heavy metal concentrations in leachates were consistently below regulatory standards, with leaching dynamics influenced by dual mechanisms: the diffusion of ions and surface chemical reactions. A diffusion coefficient-based analysis further suggested low leachability indices for all metals, confirming effective immobilization. These results suggest that cement and curing agent-stabilized red mud–graphite tailing composites reduce environmental risks and possess characteristics favorable for resource recovery, thus supporting their sustainable use in industrial applications. Full article

Tin, although not considered a critical material in all world regions, is a key material for modern technologies. The projected scarcity of tin in the coming decades emphasizes the need for efficient recycling methods to maintain uninterrupted supply chains. This review article focuses on the recovery of tin from low-grade secondary sources, specifically obsolete printed circuit boards (PCBs) and liquid crystal displays (LCDs). In both types of waste, tin occurs in various concentrations and in different chemical forms—a few percent as metal or alloy in PCBs and several hundred ppm as tin(IV) oxide in LCDs. This article presents pretreatment methods to preconcentrate tin and enhance subsequent leaching. It discusses not only conventional acid and alkaline leaching techniques but also the use of complexing agents and the challenges associated with bioleaching. Due to the dilution of the resulting leachates, advanced methods for tin ion separation and preconcentration before final product recovery are shown. Solvometallurgical methods employing deep eutectic solvents or ionic liquids, are also discussed; although promising, they still remain under development. Full article

Soil metal(loid) pollution is a threat to ecological and environmental safety. The vegetation recovery in mining areas is of great significance for protecting soil resources. In this study, (1) we first gathered four types of soils to analyse their contamination degree, including tailings mud (TM), wasteland soil (TS) very near TM, as well as non-rhizosphere soils of pepper (PF) and maize (MF) in a farmland downstream from the TM (about 5 km). Geo-accumulation and potential ecological risk indices indicated that the soil samples were mainly polluted by antimony (Sb), arsenic (As), cadmium (Cd), chromium (Cr), lead (Pb), and copper (Cu) to different degrees. Leachates of TM resulted in increased Sb, As, and Cd accumulation in TS. (2) Then, we sampled six local plants growing in the TS to assess the possibilities of using these plants as recovery vegetation in TS, of which Persicaria maackiana (Regel) Nakai ex T. Mori absorbed relatively high Sb concentrations in the leaves and roots. (3) After that, we collected rhizosphere soil and tissue samples from eight crops on the above farmland to assess their capacities as recovering vegetation of contaminated farmland soil, of which the fruits of maize accumulated the lowest concentrations of most monitored metal(loid)s (except for Pb). Further, we compared the differences in the bacterial community structure of MF, PF, TM, and TS to assess capacities of cultivating pepper and maize to improve soil microbial community structure. The MF displayed the best characteristics regarding the following attributes: (1) the highest concentrations of OMs and total P; (2) the highest OTU numbers and diversity of bacteria; and (3) the lowest abundance of bacteria with potentially pathogenic and stress-tolerant phenotypes. Full article

Traditional mining activities in Zaruma-Portovelo (SE Ecuador) have led to high concentrations of pollutants in the Puyango River due to acid mine drainage (AMD) from abandoned waste. Dispersed alkaline substrate (DAS) passive treatment systems have shown efficacy in neutralizing acidity and retaining metals and sulfates in acidic waters, achieving near a 100% retention for Fe, Al, and Cu, over 70% for trace elements, and 25% for SO₄²⁻. However, significant solid residues are generated, requiring proper geochemical and mineralogical understanding for management. This study investigates the fractionation of elements in AMD precipitates. Results indicate that Fe³⁺ and Al³⁺ predominantly precipitate as low-crystallinity oxyhydroxysulfate minerals such as schwertmannite [Fe³⁺₁₆(OHSO₄)_12–13O₁₆·10–12H₂O] and jarosite [KFe³⁺₃(SO₄)₂(OH)₆], which retain elements like As, Cr, Cu, Pb, and Zn through adsorption and co-precipitation processes. Sulfate removal occurs via salts like coquimbite [AlFe₃(SO₄)₆(H₂O)₁₂·6H₂O] and gypsum [CaSO₄·2H₂O]. Divalent metals are primarily removed through carbonate and bicarbonate phases, with minerals such as azurite [Cu(OH)₂·2CuCO₃], malachite [Cu₂(CO₃)(OH)₂], rhodochrosite [MnCO₃], and calcite [CaCO₃]. Despite the effectiveness of DAS, leachates from the precipitates exceed regulatory thresholds for aquatic life protection, classifying them as hazardous and posing environmental risks. However, these residues offer opportunities for the recovery of valuable metals. Full article