Hydrometallurgy最新文献

With a decline in high-grade molybdenum reserves, the development of other types of molybdenum resources have received increasing attention. Vanadium shale is a multi-metal shale and fine-grained sedimentary rock comprising small grains and various minerals. After leaching and extracting vanadium, the solution often contains a low concentration of molybdenum. However, because of the low molybdenum concentration, many processing plants treat it as an acidic wastewater, which wastes molybdenum resources and carries the risk of environmental pollution. The leaching process of vanadium shale mostly involves high-temperature and high-pressure operations, which greatly increase the content of impurity ions such as aluminium and phosphorus in the pregnant leach solution. These impurity ions increase the difficulty in separating and recovering molybdenum. In this study, the adsorption and separation of molybdenum at leach liquor of low molybdenum concentration were investigated. The effects of different factors such as: (i) pH of feed solution, (ii) adsorption time, and (iii) presence of impurity ions, aluminium and phosphorus, on the adsorption and separation of molybdenum using five different anion-exchange resins, D201, D296, D301, D314, and D301R, were investigated. The static adsorption and desorption test results showed a molybdenum adsorption capacity of 222 mg/g at pH = 1.5 by the D301 resin. The desorption efficiency using 20% NH₄OH was 96.1%. The adsorption efficiencies of aluminium and phosphorus were 1.31% and 3.10%, respectively. This is a better choice for separating molybdenum from complex solutions. The experimental results from spectra and theoretical calculations showed that the -NH group of D301 resin was combined with the O atoms of MoO₃·3H₂O, Al(SO₄)₂⁻, and H₂PO₄⁻ by electrostatic attraction. The binding energies of these three species were − 311 kJ/mol, −231 kJ/mol, and − 62.0 kJ/mol respectively, indicating that D301 resin preferentially adsorbed MoO₃·3H₂O. Based on the above results, the D301 resin can adsorb molybdenum(VI) in complex solutions under low pH conditions, and this study is expected to promote the comprehensive recovery of valuable metals from vanadium shale.

Hydrometallurgical processes for managing industrial waste have attracted significant attention due to tightening global standards on toxic emissions. Among these processes, the use of non-volatile hydrophobic deep eutectic solvents (HDESs) has emerged as a promising approach to optimising extraction processes. In this study, HDESs incorporating tributyl phosphate (TBP) and di(2-ethylhexyl)phosphoric acid (D2EHPA) were investigated in the context of the extraction and separation of elements found in lithium‑iron phosphate batteries, including lithium, aluminium, iron and copper. The physical properties of the HDESs, such as density, viscosity and refractive index, were characterized and the interactions between their components were analysed using infrared spectroscopy. Considering the different classes of extractants represented by D2EHPA and TBP, extraction efficiency for target metals was evaluated across a range of hydrochloric acid concentrations (1–10 mol/L). Optimal conditions for re-extraction (stripping) were identified for extractant regeneration and the production of individual metal ion solutions. Results demonstrated that Fe³⁺ ions could be extracted with an efficiency exceeding 99% across the majority of acidity levels, while Al³⁺ ions exhibited similar efficiency from a pH of 1.4. In contrast, Cu²⁺ ions showed limited extraction (<5%) at lower pH values but the level of extraction increased to 50% at pH 1.9 and above. Leveraging these findings, a sequential extraction scheme is proposed for Al³⁺, Cu²⁺, Fe³⁺ and Li⁺ from their mixture, based on a gradual reduction in solution acidity.

Glycine has been intensively investigated as a “green” lixiviant for precious and base metals. Alkaline glycine solutions to extract Ni from sulfide resources has shown promising results. However, a considerable amount of Ni will be lost in the wash solutions when leaching residues are washed during solid-liquid separation of the leachates from their respective leach residues. In this context, this study explored Ni recovery from alkaline glycine-based wash solutions using a polyamide nanofiltration membrane. In the tests using synthetic single and multi-metal solutions, the membrane achieved >95% rejection of Ni in the selected ranges of glycine/Ni molar ratio (up to 5), pressure (15–30 bar), initial nickel concentration (0.5–1.5 g/L), sodium sulfate background concentration (∼30 g/L) and under the use of different pH modifiers (aqueous ammonia and caustic soda). When using a real solution, the concentrations of Ni and other major elements (Cu, S, Co, Mg, Zn) in the final retentate increased by about 5 times at 80 wt% permeate recovery, leaving <3 mg/L major elements in permeate. The permeate stream could be recycled in the washing stage, and the retentate stream could be combined with the pregnant leach solution (PLS) for metals recovery. The investigation demonstrates some of the technical optionality for nickel recovery from filter wash solutions utilising nanofiltration within the context of alkaline glycine-based leach technology and preliminarily demonstrates where it can be used in the structure of flowsheets to recover valuable base metals and reagents for recycle. However, the increased membrane resistance causing a low permeate flux should be concerned due to the considerable dissolved salts, precipitation of gypsum and the increasing feed concentration over time.

In heap leach operations, metal recovery is fundamentally controlled by the ore's particle size distribution (PSD), which determines mineral exposure characteristics, the rate of leaching reactions, and fluid flow phenomena. A fluent circulation of solution through the heap is important for successful leach plant operation. The pore networks inside 6-in. diameter leach columns from the Rochester mine were scanned by X-ray Computed Tomography (XCT) at a voxel size of 100 μm, to estimate the permeability by Lattice Boltzmann Method (LBM). The bottom sections of 6-in. columns had much less porosity and corresponding permeability than the top sections. PSD of the bottom and top sections showed no migration of fines, and gravity compression reduced the bottom sections' permeability. The pore networks inside 4-in. diameter leach columns with controlled PSD were scanned by XCT at a higher resolution with a voxel size of 68 μm. In addition to the large particles (rocks) and pore network, another phase of agglomerated fines from local fluid movement was identified. This phase of agglomerated fines can overwhelm the volume of the pore network inside leach columns and thus reduce the permeability, leading to possible ponding issues in the heap.

The harmful effects of sulfur and organic substances pose constraints on the green and sustainable development of the Bayer process for alumina production. This research aims to develop a method that utilizes H₂O₂ to remove sulfur and organic substances during the digestion stage of bauxite, based on the mineralogical investigation of sulfur and organic substance. The extent of removal of S²⁻ and total organic carbon reached 95.6% and 68.0%, respectively, under most suitable conditions of 12% H₂O₂ dosage, temperature of 533 K, and duration of 80 min. Based on thermodynamic calculations, it is suggested that S²⁻ is oxidized to SO₄²⁻. Additionally, the free radical reaction mechanism of organic substances in H₂O₂ wet oxidation of Bayer liquor is proposed. The results confirm that this method does not introduce any impurities and does not have any impact on the digestion efficiency of alumina and the Bayer process.

A green chemistry process has been developed to recycle cathode material from end-of-life lithium ion batteries. NCM111 (LiNi_1/3Co_1/3Mn_1/3O₂) was completely leached with 13 M formic acid to produce two groups of salts with different solubilities: sparingly soluble cobalt, manganese, and nickel (CMN) formates and highly soluble lithium formate. During leaching, CMN formate salts exceeded their solubility limit in the pregnant leach solution (PLS) and crystallized. Mixed CMN formate salts were recovered by filtering the PLS. Lithium was completely recovered by evaporating the filtered PLS then thermally decomposing the lithium formate obtained in air to lithium carbonate. The purity of the lithium carbonate was 98.1 wt%.

The leaching process was optimized through response surface methodology experiments. The minimum time required to completely leach NCM111 with 13 M formic acid was 30.8 h. Optimum leaching conditions were L/S = 2.81 mL/g (equivalent to S/L = 356 g/L) and T = 95 °C. During leaching, 98% of CMN formate salts exceeded their solubility limit and crystallized from the PLS.

The recycling process is simple and generates no liquid or solid waste products. The only reagent is 13 M formic acid. The only by-products are water vapour, which can be condensed and reused, and carbon dioxide gas.

In the intensive cyanidation of gravity gold concentrates, sodium m-nitrobenzene sulfonate (NBS) is often used to supplement dissolved oxygen as the oxidant in the process. A previous paper presented the results of a largely electrochemical study of the behaviour of NBS during cyanidation of gold. The results confirmed that NBS acts as an oxidant in the cyanidation of gold and that the mixed potential model can be applied to describe the mechanism of its action. This paper explores the corresponding oxidation of sulfide minerals, that inevitably are contained in gold concentrates, by either dissolved oxygen or NBS. Using electrochemical techniques it was found that dissolved oxygen is effective in the oxidation of several sulfide minerals at pH values between 9 and 11. The effect of cyanide on both the anodic and cathodic processes has been studied. NBS has been found to be ineffective as an oxidant for all minerals tested except galena, even in the presence of cyanide.

In the intensive cyanidation of gravity gold concentrates, sodium m-nitrobenzene sulfonate (NBS) is often used to supplement dissolved oxygen as the oxidant in the process. This paper presents the results of a largely electrochemical study of the behaviour of NBS during cyanidation. The results have confirmed that NBS acts as an oxidant in the cyanidation of gold and that the mixed potential model can be applied to describe the mechanism of its action.

The mixed potential is a good initial indicator of the rate of gold dissolution and, as expected, the anodic dissolution of pure gold in cyanide solutions is characterized by passivation at potentials above about −0.35 V.

The reduction of oxygen under the conditions of the present study occurs in two 2-electron steps with peroxide as an intermediate. Dissolution of gold occurs at potentials in the diffusion-controlled region for the first step. The cathodic reduction of NBS occurs in the same potential region as the reduction of oxygen. The reaction is first order in the concentration of NBS and is largely independent of the pH. The stoichiometry of the reaction involves six moles of gold per mole of NBS confirming that the amine is the final product of reduction of NBS.

Rates of gold dissolution in various solutions have been measured using a calibrated linear polarisation method. The rate increases approximately linearly with increasing NBS concentration and is independent of pH. The rate in 0.5 g/L NBS is approximately the same as in oxygenated solutions.

A relatively simple titration has been adapted for use in determining NBS concentrations.

Three platinum group metals (PGMs), platinum (Pt), palladium (Pd), and rhodium (Rh), are key components in automotive catalytic convertors, playing a pivotal role in controlling harmful emissions. The recycling and recovery of Pt, Pd, and Rh from spent automotive catalysts (SACs) have gained increasing attention as essential measures to mitigate resource depletion, supply risks, and environmental impacts. Due to the growing demand for automobiles and increasingly stricter environmental regulations, a substantial amount of spent automotive catalysts is generated annually, leading to increased interest in their efficient recycling and recovery of the PGMs they contain. Hydrometallurgical processes, particularly chloride leaching and ion exchange, have emerged as promising methods for efficient PGM extraction and separation from these discarded catalysts.

This review includes a critical examination of recent advances and innovations in both chloride leaching and ion exchange methods, highlighting their effectiveness in terms of Pt, Pd, and Rh recyclability and recovery efficiency from spent catalysts. The study offers valuable insights into the efficacy of their recycling from SACs through various processes. The importance of investigating the solution chemistry of PGMs in chloride media is highlighted and the leaching of SACs has been explored using various chloride media, including AlCl₃, NaCl, CaCl₂, MgCl, and NH₄Cl, alongside a range of inorganic and organic leaching agents such as HCl, H₂SO₄, HNO₃, acetic acid, citric acid, and oxidizing agents like H₂O₂, NaClO, NaClO₃, Fe³⁺, Cl₂, and Cu²⁺. This work is critically reviewed, examining the influence of key parameters investigated on the leaching efficiency of PGMs, such as HCl, Cl⁻, and oxidizing concentrations, temperature, solid-to-liquid ratio (S/L), particle size, and leaching time. Furthermore, it evaluates the effectiveness of pretreatment techniques such as calcination, salt roasting, and pre-reduction methods involving high temperatures, hydrogen gas flow, formic acid, hydrazine hydrate, and Zn-vapor treatments. The review then turns to the efficacy of the ion exchange method, utilizing a diverse range of anion exchange resins for the selective adsorption of PGMs as well as various elution reagents for the selective desorption of PGMs from loaded resins, aiming to recover them selectively from chloride leach solutions. Therefore, this study seeks to contribute to the development of strategies for recycling and reusing PGMs from SACs, with a view to reducing the industry's dependence on primary raw materials and promoting principles of the circular economy.

In hydrometallurgical recovery of LIB metals, ion exchange (IX) has hitherto played only a minor role. Separation experiments were conducted in single laboratory-scale IX columns with the aim of laying the foundation for a continuously operated multicolumn IX process similar to a simulated moving bed (SMB) configuration. In this study, the initial process developed earlier was improved by reducing the number of process steps and external streams. The desorption step with oxalate solution was examined in single-column batch experiments to ensure complete desorption of iron in the proposed continuous multicolumn IX process. Additionally, the volume flowrates were adjusted to achieve acceptable switch times of 25 min in an SMB configuration. It was found that the bead size of the resin is a critical factor in IX recovery of battery metals. The raffinate purity for the case of processing 2.5 BV lithium-ion battery waste leachate (LIBWL) improved from 97.2 % to 99.8 % when the resin bead size was reduced from 0.55 ± 0.05 mm to 0.4 ± 0.04 mm and a narrower bead size distribution. The LIBWL feed concentration was varied to mimic the dilution of fresh feed in an SMB set-up. The percentage recovery of Co and Ni decreased from 93.7 % and 96.6 % to 80.8 % and 89.4 %, respectively, when the LIBWL was diluted. This was a result of the decrease in concentration of impurity metals in the feed. Less impurity metals were sorbed and consequently, more ion exchange sites were available for the sorption of the target metals, which enhanced the retention of Co and Ni. The results were used to develop an IX column operation strategy and to suggest an initial SMB design. The multicolumn configuration presented in this work offers great potential for continuous production of high-purity Li, Ni and Co-containing raffinate (> 99.5 %).