Hydrometallurgy最新文献

There is a vast amount of globally underutilized low-grade mine tailings and leach residues, including those from primary processing of gold. In this research, the target is to recover the remaining gold (10.9 g/t) from weathered refractory iron-rich residue that had previously been subject to autoclave oxidation, subsequent cyanidation in a conventional carbon-in-leach (CIL) circuit as well as storage at tailings area. Chloride leaching has been considered as one of the most promising cyanide-free gold leaching methods and it has shown positive outcomes in treating primary gold ores, concentrates, and flotation tailings. Therefore, in the current study, the iron-rich residue investigated was subjected to chloride leaching combined with simultaneous carbon adsorption. The investigated parameters included leaching time (2–8 h), chloride concentration ([Cl⁻] = 0.2–5 M), type and concentration of oxidant ([Cu²⁺]/[Fe³⁺] = 0.1–1 M), as well as type and concentration of activated carbon (14–25 g/L), whereas S/L ratio (100 g/L), acidity (pH = 1), and temperature (90 °C) were kept constant. Leaching results indicate that up to 40% of the remaining gold could still be recovered from the investigated residue with optimized chloride leaching. According to the results, the most important parameter for gold recovery was the leaching time. Moreover, of the studied oxidants, cupric ions were shown to contribute more to gold recovery when compared to ferric ions (35% vs. 24% at [Cu²⁺]/[Fe³⁺] = 0.1 M). Nevertheless, an increase of cupric concentration from 0.1 M (low-concentrated) to 0.5 M, resulted in only a slight increase in gold recovery (from 36% to 40%), whereas no further improvement in gold recovery was achieved with a 1 M cupric concentration. Two studied activated carbon products showed equal effectiveness in gold adsorption. In-situ carbon adsorption was shown to occur effectively in chloride media, as all dissolved gold could be detected in the activated carbon, and the concentration of remaining gold in the pregnant leach solution was minimal (< 0.02 mg/L). These findings indicate that low-concentrated chloride leaching of leach residues from industrial gold processes can allow an enhanced recovery of gold from previously mined and treated raw materials.

Chalcopyrite dissolution in ferric sulfate media at ambient conditions is slow. The addition of iodide has been found to significantly improve chalcopyrite leaching in the potential range where triiodide (I₃⁻) or diiodine (I₂) is the predominant species. In the iodine-assisted chalcopyrite leaching process, elemental sulfur was proposed to be the form of sulfur product while iron precipitation was also observed. Given the potential impact of elemental sulfur and iron precipitates on chalcopyrite leaching, this study analyzed the solid leach residues collected from the iodine-assisted chalcopyrite leaching using different solid characterization techniques. The X-ray diffraction analysis of the bulk residues shows that elemental sulfur was the product of chalcopyrite leaching and that pyrite was unreactive. The cross-sectional analysis by a mineral liberation analyzer (MLA) shows that thick layers of jarosite and elemental sulfur coated the surfaces of the solid particles. Further analysis by X-Ray photoelectron spectroscopy (XPS) with a depth resolution of <10 nm confirmed that elemental sulfur was formed and that the formation of jarosite was favored at 40 and 45 °C. Despite the formation of elemental sulfur and iron precipitates, a near complete dissolution of chalcopyrite could be achieved. Further research is required to understand how the presence of iodine changes chalcopyrite leaching in such a way that surface passivation does not occur.

Jezechake Salt Lake brine in China is rich in lithium ions coexisting with relatively high concentrations of carbonate and borate anions. Both carbonate and borate anions have a pH-buffering ability to accept the exchanged H⁺ ions of lithium ion sieves, enhancing the adsorption process of Li⁺ ions. When Jezechake Salt Lake brine passes through a titanium-type ion-sieve-packed column, good lithium breakthrough occurs owing to the pH-buffering action in the brine, which is of great significance for effective lithium recovery from brines in industrial production. In addition, the boron content of Jezechake Salt Lake brine is high, and its recovery is valuable for industrial applications. Here, an N-methylglucamine resin-packed column was connected in series behind a titanium-type ion-sieve-packed column to obtain boron simultaneously with the aim of lowering the energy consumption and cost of lithium recovery. During the adsorption process, Jezechake Salt Lake brine was successively fed into the lithium and boron adsorption columns. The two packed columns were then desorbed independently through acidic solution washing to obtain the Li and B eluents. The breakthrough behavior and elution performance of Li and B in the packed columns were investigated experimentally, and the practicability and efficacy of the proposed process were assessed.

The changes in the micro-scale pore structure during the acid leaching of sandstone uranium ore significantly affect its reactive transport parameters, which, in turn, directly influence the leaching efficiency of uranium. Consequently, understanding and managing the dynamic evolution of the pore structure of sandstone at micro-scale during acid leaching is beneficial for enhancing the leaching efficiency of uranium. This paper employs a dynamic continuous water-rock reaction experiment on sandstone uranium ore to simulate the in-situ acid leaching process. Additionally, X-ray micro-computed tomography (μCT) scanning was utilized to produce three-dimensional (3D) images at various leaching stages. Subsequently, image processing techniques were employed to characterize and parameterize the pore structure within these images. The results revealed that, during the leaching process, mineral dissolution led to an increase in the interconnected pores, while there was a decrease in the isolated pores. Nonetheless, at the leading edge of the sandstone uranium ore, detachment of mineral grains occurred during the leaching process along the direction of fluid flow. The migration of mineral grains resulted in a reduction of interconnected pores and an increase in the isolated pores. The analysis of 3D images indicated that porosity, permeability, the percentage of connected pore area and the reactive surface area exhibited similar variation trends throughout the leaching process. Furthermore, the permeability, the percentage of connected pore area and the reactive surface area displayed a positive correlation with porosity. The study holds valuable insights to develop a deeper understanding of the evolutionary patterns regarding the pore structure during the in-situ acid leaching of sandstone uranium ore.

Owing to the characteristics of mineral paragenesis (equilibrium sequence of mineral phases), the hydrochloric acid leach liquors of Sn ores and Sn-containing waste materials typically contain large amounts of Pb. In this study, barium sulfate coprecipitation was employed to efficiently remove Pb from a tin chloride solution. The lead removal efficiency, reaction mechanism, and limitations were investigated by varying the Cl⁻ and SO₄²⁻ concentrations. The results showed that the structural formula of the precipitates was (Ba_xPb_y)(SO₄)₂ (x + y = 2), and its solubility product was in the range of 1 × 10⁻¹²–1 × 10⁻¹³, indicating that Pb²⁺ and Ba²⁺ were more easily precipitated in the form of complex salts. In addition, thermodynamic analysis revealed that when the Cl⁻ concentration was <1 mol/L in the Pb²⁺–Sn²⁺–Cl⁻–H₂O system, [Pb²⁺] and [PbCl⁺] were the primary species. These positively charged species were readily adsorbed onto the surface of BaSO₄ via electrostatic forces, resulting in a significant increase in the Pb content of (Ba_xPb_y)(SO₄)₂. Therefore, the Pb removal efficiency significantly improved as Cl⁻ concentration decreased. The lead removal mechanism involves a combination of adsorption and replacement processes. Based on the aforementioned fundamental study, a method involving dechlorination and coprecipitation was proposed to remove lead from an acid leaching solution of Kaldo slag. With the dechlorination via distillation, the Pb removal efficiency could reach 99.9% at 1 mol/L Cl⁻ and 0.5 mol/L SO₄²⁻.

This study reports the effect of sodium fluoride on the dissolution kinetics of pure metallic titanium in a citric acid solution. The effects of sodium fluoride concentration, citric acid concentration, temperature, stirring speed, and disc surface area were examined. The dissolution rate of titanium increases strongly with increasing citric acid and sodium fluoride concentrations. Fluoride ions react with hydrogen ions to form hydrofluoric acid, which removes the passive layer of titanium dioxide. An increase in the concentration of NaF and acid causes the formation of a brown layer on the surface of titanium. X-ray diffraction and SEM-EDX analyses showed that the layer composition is mostly of titanium fluoride (TiF₃) and titanium fluoride oxide (TiOF₂). A mixed kinetic model with an activation energy of 26.4 kJ/mol can be used to explain the reaction kinetics.

Sulfuric acid baking of monazite ((Ce,La,Th)PO₄) bearing ores is one of the major processes used in commercial production of rare earth elements. In hydrothermal vein type rare earth deposits, apatite is often found together with monazite. Rare earth enriched fluorapatite ores may also contain significant amounts of rare earths hosted in monazite. An understanding of the effect of apatite on the sulfuric acid baking of monazite is therefore important for the development of effective sulfuric acid based treatment methods for such ores. In this work, the addition of a natural hydroxyapatite (Ca₅(PO₄)₃(OH)) sample to a monazite acid bake followed by acid leach was investigated using a combination of chemical analyses, SEM-EDS, XRD and TG-DSC. Hydroxyapatite addition significantly decreased the dissolution of rare earth elements from monazite in the leach after baking at temperatures above 300 °C. For a bake temperature of 500 °C, the rare earth dissolution in the leach dropped from 80% for monazite alone, to 30% for a 1:1 (w/w) addition of hydroxyapatite. This decrease in rare earth leaching was attributed to the formation of an insoluble thorium and rare earth bearing polyphosphate. The rare earth elements were incorporated into this polyphosphate phase in preference to calcium. At 800 °C, monazite was re-formed, causing a further reduction in rare earth extraction, while simultaneous formation of calcium pyrophosphate (Ca₂P₂O₇) led to an increase in calcium and phosphorus dissolution. The detrimental effect of apatite could be partially overcome by the addition of goethite. Addition of goethite to the acid bake of a monazite/apatite mixture at 500 °C improved the total rare earth dissolution from 29% to 85% in the subsequent leach. Results also demonstrated that the order of reactivity, in terms of formation of polyphosphates is Fe > REE > Ca.

In this study, deep eutectic solvents (DESs) were employed as environmentally friendly alternatives of inorganic acid to selectively leach REEs from waste NdFeB magnets. Three DESs were tested, effective for light REE leaching, and preliminary experiments were conducted to study the selective leaching of REEs, using synthetic materials, Nd₂O₃, Fe, Fe₃O₄, and Fe₂O₃. The findings suggest that neodymium and iron should exist as Nd₂O₃ and Fe₂O₃, respectively, for selective leaching. To enhance the selective leaching of the NdFeB magnet, three pretreatment methods were applied: oxidative roasting, NaOH digestion, and NaOH digestion-oxidative roasting. During the oxidative roasting, NdFeO₃ was formed, and it hindered REE leaching, achieving the highest REE leaching efficiency of 22.5% in the guanidine hydrochloride (GUC)-lactic acid (LA) DES. To counteract NdFeO₃ formation, the NaOH digestion was introduced, yielding Nd(OH)₃ and Fe₃O₄. These were then converted to Nd₂O₃ and Fe₂O₃ through oxidative roasting. With the NaOH-digested product, selective REE leaching was achieved solely with the ethylene glycol (EG)-maleic acid (MA) DES, while it was feasible in all three DESs with the NaOH digestion-oxidative roasting. The EG-MA DES displayed the highest selectivity, with a leaching efficiency of 97.3% Nd and 0.8% Fe. Additionally, the solvent could be reused at least twice, and the leaching efficiencies of 97% for Nd and 0.7% for Fe were maintained. This selective leaching technique benefits from using environmentally friendly solvents compared to the traditional inorganic acid leaching and demonstrates high REE selectivity and solvent reusability, suggesting a novel method for REE recovery via DESs.

The impact of zinc (Zn) on the seed decomposition process of sodium aluminate solution at different caustic concentrations was investigated. The results showed that as the concentration of Zn(II) in sodium aluminate solution increased from 0 to 1000 mg/L, the decomposition efficiency of the solution and average grain size of the resulting aluminum tri-hydroxide (ATH) changed little at a caustic concentration of 141 g/L. At caustic concentrations of 160 g/L and 177 g/L, the decomposition efficiency increased from 35.8% and 21.6% to 40.6% and 24.9%, respectively, while average grain size of the ATH crystal seeds increased from 14.2 and 9.25 μm to 17.9 and 15.9 μm, respectively. The XRD, FT-IR, and SEM analyses showed that zinc can enter the ATH seeds and interact with the α-ATH crystal planes. It may also form interactions with the AlO octahedral growth structure, thus promoting solution decomposition and influencing crystal growth. The research results will provide valuable references for improving the quality of alumina products.