Search Results (17)

Industrial effluents containing zinc, cadmium, and nickel represent both an environmental challenge and a valuable secondary resource. This study investigates the simultaneous recovery of Zn(II), Cd(II), and Ni(II) from nitric acid solutions using di-(2-ethylhexyl) phosphoric acid (D2EHPA) dissolved in commercial diesel fuel in a continuous counter-current semi-pilot mixer–settler extraction system. The effects of key operating parameters, including aqueous-phase pH, initial metal concentration, phase ratio, contact time, stirring speed, and stripping agent, were systematically evaluated. Metal concentrations were determined by atomic absorption spectrometry, while Fourier-transform infrared spectroscopy was employed to investigate the extraction mechanism. The optimum operating conditions were pH 2.45 for Zn(II) and pH 5.38 for Cd(II) and Ni(II), a phase ratio of V_A/V_O = 1.5/3.5, and a stirring speed of 700 rpm. Under these conditions, high extraction efficiencies were achieved, with Zn(II), Cd(II), and Ni(II) recoveries of 98.52%, 76.86%, and 84.04%, respectively. FTIR characterization, together with slope analysis, suggested a dimeric cation-exchange extraction mechanism involving D2EHPA species in the organic phase. Among the stripping agents evaluated under the present experimental conditions, 0.5 M H₂SO₄ produced the highest stripping efficiencies for Zn(II), Cd(II), and Ni(II). Although the stripping efficiencies remained moderate, particularly for Cd(II) and Ni(II), these results demonstrate the relative effectiveness of H₂SO₄ compared with the other stripping agents examined. Further optimization of the stripping conditions is expected to improve metal recovery. The proposed process shows significant potential for industrial wastewater treatment, metal recovery, and resource valorization. Full article

Rare earth elements (REEs) are predominantly separated by using mixer–settler solvent extraction technology. While this method has been utilized in the industry, it does have a few setbacks, such as requirement of large module footprint to compensate for inefficient separation. Likewise, researchers have turned to membrane separation technology to address these challenges faced by mixer–settler solvent extraction. Supported liquid membranes (SLMs) are a viable alternative in membrane separation technology as they exhibit similar conceptual designs to that of solvent extraction, albeit requiring smaller amounts of organic carrier and lower module footprint compared to mixer settler solvent extraction. In this research, the application of an electrospun membrane was explored using SLMs for the separation between light REEs (LREEs) and heavy REEs (HREEs). To do this, the study initially employs the usage of neodymium (Nd) and dysprosium (Dy) as the baseline for LREEs and HREEs, and later using real REE leachate for the separation between LREEs and HREEs. This study also investigates the effects of different pH of feed solution, organic carrier loading, and stripping concentrations. Overall, to achieve higher selectivity of Nd/Dy, a higher pH of feed solution of 5, a low loading of organic carrier at 10 wt%, and a low stripping concentration of 1 M H₂SO₄ was recommended. For the separation of LREEs and HREEs, a separation factor of 2.38 was achieved with a recovery of 10.43% of LREEs in under 60 min by using a small-scale membrane of 4 cm² effective area. Long term operation indicates a stable LREE/HREE separation performance using the optimized condition. Full article

Mixer-settlers are pivotal in the solvent extraction industry, yet spatial control of agitation to intensity separation remains underexplored. This study proposes a novel strategy by localizing agitation strictly within the dispersion band. Through the developed computational fluid dynamics coupled population balance model (CFD-PBM) resolving droplet breakup/coalescence dynamics and laboratory experiments, it demonstrates that the agitator position critically governs dispersion band thickness and separation efficiency. It should be emphasized there was no significant difference between the experimental and the simulated. Optimal separation is achieved only when the agitation zone overlaps the dispersion band, balancing droplet fragmentation and coalescence while minimizing turbulence in settling regions. Conventional uniform agitation designs are suboptimal due to spatial sensitivity. The CFD-PBM framework establishes a physics-based tool for scalable mixer-settler design, enabling energy-efficient separation by decoupling mixing and settling energetics. This work provides an advanced solution for using the solvent extraction via targeted agitation optimization, emphasizing both scientific rigor and industrial applicability. Full article

The increasing demand for critical metals essential for renewable energy technologies necessitates efficient and environmentally sustainable extraction methods. Ilmenite (FeTiO₃) and similar ore deposits serve as abundant sources of primary elements while also incorporating a suite of strategically significant trace elements, including REEs and Hf, among others. Mixer–settler units are extensively utilized in metal purification processes. It is important to develop approaches for tracking the metal’s extraction process online and optimizing flow dynamics. One widely adopted technique for evaluating the flow dynamics of the various components is the residence time distribution (RTD) measurement, which provides insights into the hydrodynamic behavior of process reactors. This study explored the application of radiotracer techniques for online monitoring of solvent extraction processes in hydrometallurgy, focusing on Hf recovery. A mixer–settler system was employed using di(2-ethylhexyl) phosphoric acid (D2EHPA) as the extractant and the 1M HNO₃ aqueous phase of Ti ore. The radiotracer ¹⁸¹Hf was synthesized via neutron activation and introduced into the system to track phase distribution and RTD. Real-time monitoring revealed over 95% extraction efficiency within 133 min (8000 s). The RTD studies validated system performance using perfect mixers in series and axial dispersion models. The calculated mean residence time of 100 min (6000 s) closely aligned with the theoretical 104 min (6240 s), confirming the model accuracy. The findings demonstrate the viability of radiotracers in monitoring solvent extraction, offering real-time insights into flow dynamics and extraction efficiency. Full article

Hydrophobic eutectic solvents (HES) show significant promise as extractants for metal ions. At their current stage of development, however, they have many disadvantages, such as high costs, limited data on reusability and, often, lower extraction efficiency when compared with traditional extraction systems. This study investigates the physico-chemical properties of five HES formulations based on 1-octanol in combination with camphor, 2′-hydroxypropiophenone, menthol, 1-octanoic acid, and thymol. The 1-octanol/camphor HES exhibited substantially higher extraction efficiency for Fe(III) ions than a solution of 1-octanol in toluene at the same concentration. Furthermore, it showed stability when used in a mixer-settler type extractor. The 1-octanol/camphor HES achieved a rapid extraction and re-extraction rate, with phase contact time reduced to just 2 min, without loss of extraction efficiency. Using the supported liquid membrane method, the proposed Oct/Cam HES enabled a threefold concentration of iron ions in the raffinate phase under continuous operation, confirming its potential for reusability. Full article

The recycling of lithium-ion batteries is increasingly important for both resource recovery and environmental protection. However, the complex composition of cathode and anode materials in these batteries makes the efficient separation of metal mixtures challenging. Hydrometallurgical methods, particularly liquid extraction, provide an effective means of separating metal ions, though they require periodic updates to their extraction systems. This study introduces a hydrophobic deep eutectic solvent composed of trioctylphosphine oxide, di(2-ethylhexyl)phosphoric acid, and menthol, which is effective for separating Ti(IV), Co(II), Mn(II), Ni(II), and Li⁺ ions from hydrochloric acid leachates of NMC (LiNi_xMn_yCo_1−x−yO₂) batteries with LTO (Li₄Ti₅O₁₂) anodes. By optimising the molar composition of the trioctylphosphine oxide/di(2-ethylhexyl)phosphoric acid/menthol mixture to a 4:1:5 ratio, high extraction efficiency was achieved. The solvent demonstrated stability over 10 cycles, and conditions for its regeneration were successfully established. At room temperature, the DES exhibited a density of 0.89 g/mL and a viscosity of 56 mPa·s, which are suitable for laboratory-scale extraction processes. Experimental results from a laboratory setup with mixer-settlers confirmed the efficiency of separating Ti(IV) and Co(II) ions in the context of their extraction kinetics. Full article

The separation of Rare Earth Elements (REEs) is an important step in the valorization of REE ore and aims at producing individual rare earth compounds for the market. The separation is carried out industrially by solvent extraction (SX) using interconnected circuits consisting of cascades of mixer-settlers. The design of a REE separation circuit implies the selection of the operating conditions and of the number of mixer-settlers required to achieve a target degree of purity for the separated elements. This design work is either carried out by piloting a circuit or using a mathematical simulation. Independent of the method, the world expertise in this area is limited. This paper describes a simulation method requiring a minimum of calibration effort, which can be used to design a complete REE separation plant. The simulation enables assessment of the effect of the number of mixer-settlers per extraction, the scrubbing and stripping stage, as well as the pH of the aqueous solution and organic-phase contents of free and loaded extractant on the purity of the separated REEs. The simulation tool presented here has been developed from a fundamental analysis of the chemical reactions involved in the solvent extraction process. Unlike most of the simulation methods documented in the literature, the method requires no empirical calibration. The proposed method is validated using data from laboratory batch tests and with published data from continuous pilot and industrial REE separation circuits. The application of the simulation tool is illustrated with the planning of the test conditions for a forthcoming pilot test work and with the simulation of a 9-REE product SX separation plant. Full article

Pseudo-liquid membranes are extraction devices in which a liquid membrane phase is retained in an apparatus consisting of two interconnected chambers while feed and stripping phases pass through the stationary liquid membrane phase as mobile phases. The organic phase of the liquid membrane sequentially contacts the aqueous phases of the feed and stripping solutions in the extraction and stripping chambers, recirculating between them. This extraction separation method, called multiphase pseudo-liquid membrane extraction, can be implemented using traditional extraction equipment: extraction columns and mixer-settlers. In the first case, the three-phase extraction apparatus consists of two extraction columns connected at the top and bottom by recirculation tubes. In the second case, the three-phase apparatus consists of a recycling close-loop, which includes two mixer-settler extractors. In this study, the extraction of copper from sulfuric acid solutions in two-column three-phase extractors was experimentally studied. A 20% solution of LIX-84 in dodecane was used as the membrane phase in the experiments. It was shown that the extraction of copper from sulfuric acid solutions in the apparatuses studied was controlled by the interfacial area in the extraction chamber. The possibility of the purification of sulfuric acid wastewaters from copper using three-phase extractors is shown. To increase the degree of extraction of metal ions, it is proposed to equip two-column three-phase extractors with perforated vibrating discs. To further increase the efficiency of extraction using the pseudo-liquid membrane method, it is proposed to use multistage processes. The mathematical description of multistage three-phase pseudo-liquid membrane extraction is discussed. Full article

Liquid–liquid extraction has proven to be an aid in biologics manufacturing for cell and component separation. Because distribution coefficients and separation factors can be appropriately adjusted via phase screening, especially in aqueous two-phase systems, one stage is frequently feasible. For biologics separation, aqueous two-phase systems have proven to be feasible and efficient. The simple mixer–settler equipment type is still not standard in biologics manufacturing operations. Therefore, a scalable digital twin would be of aid for operator training, process design under the regulatory demanded quality by design approach for risk analysis, design and control space definition, and predictive maintenance. Autonomous operation is achieved with the aid of process analytical technology to update the digital twin to real time events and to allow process control near any optimal operation point. Autonomous operation is first demonstrated with an experimental feasibility study based on an industrial type example of pDNA manufacturing via lysis from E. coli with and without cell separation performance. Full article

In this study the extractive capability of Mextral 5640H was investigated for extraction of copper from a heap leach liquor. In this regard, the influence of parameters such as pH (0.2–2.8), extractant concentration in kerosene diluent (2.5%–10% v/v), temperature (25–70 °C), contact time (0–300 s), stirring speed (100–1200 rpm), phase ratio (O/A) (0.6–1.8) and Cu initial concentration (0.5–2 g/L) in the leach liquor were examined and optimized. The findings demonstrated that the Mextral 5640H extractant had a very high efficiency and selectivity in copper extraction from the leachate. 98.17% Cu, with less than 0.5% of Fe and Mn, were extracted at pH 1.6, 10% (v/v) Mextral 5640H concentration, ambient temperature (25 °C), 400 rpm stirring speed, 2 min contact time and an O/A phase ratio of 1:1. Under equilibrium conditions it was found that one mol of Cu is extracted by 7 mol of Mextral 5640H. Additionally, analysis using a McCabe–Thiele diagram suggests a two-stage extraction to reach the maximum extraction of copper (99.5%) from the leachate at operational condition using industrial mixer-settlers. Furthermore, a thermodynamic study was conducted, and the measured values of ΔH = 15.13 kJ/mol, ΔG = −6.95 kJ/mol and ΔS = 74.10 J/mol/K indicate an endothermic, spontaneous nature and high affinity of copper extraction. Full article

To promote the implementation of liquid membrane separations in industry, we have previously proposed extraction methods called three- and multi-phase extraction. The three-phase multi-stage extraction is carried out in a cascade of bulk liquid membrane separation stages, each comprising two interconnected (extraction and stripping) chambers. The organic liquid membrane phase recycles between the chambers within the same stage. In multi-phase extraction, each separation stage includes a scrubbing chamber, located between the extraction and stripping chambers. The three- and multi-phase multi-stage extraction technique can be realized either in a series of mixer–settler extractors or in special two- or multi-chamber extraction apparatuses, in which the convective circulation of continuous membrane phase between the chambers takes place due to the difference in emulsion density in the chambers. The results of an experimental study of the extraction of phenol from sulfuric acid solutions in the three-phase extractors with convective circulation of continuous membrane phase are presented. Butyl acetate was used as an extractant. The stripping of phenol from the organic phase was carried out with 5–12% NaOH aqueous solutions. The prospects of using three-phase extractors for wastewater treatment from phenol are shown. An increase in the efficiency of three-phase extraction can be achieved by carrying out the process in a cascade of three-phase apparatuses. Full article

A novel solvent extraction scheme was developed for the processing of Co-rich lithium-ion battery (LIB) leachate to a Ni–Co–Mn (NCM) sulfate mixture that can be directly used in the precursor synthesis of LIB cathodes. Conventional hydrometallurgical recycling of spent LIBs usually aims at separation of Li, Ni, Co, and Mn into pure fractions, which is simplified here. Operating pH and the number of extraction stages for each separation were evaluated from batch equilibrium experiments. Two continuous countercurrent extractions with bis(2-ethylhexyl) hydrogen phosphate (D2EHPA) and one with Cyanex 272 were studied in bench-scale mixer-settler equipment, and a Ni–Co–Mn solution with n(Ni):n(Co) = 14.16 and n(Ni):n(Mn) = 8.06 was obtained. The Ni:Co:Mn molar ratio in the NCM mixture can be adjusted to, for example, 8:1:1 using a Co-rich raffinate from the same process, and no additional transition metal salts are required for tuning the composition. Stripping raffinate containing 102.7 g L⁻¹ Co at 99.8% relative purity was obtained from Cyanex 272 extraction. The main benefit of the process concept is that the solvent extraction separations can be operated with less stringent requirements than when producing pure metal salts. Full article

Solvent extraction (SX) is one of the most widely applied hydrometallurgical processes in copper production from oxide ore. As the high-grade ore deposits have been developed and depleted, now only low-grade ore deposits are being developed and are therefore facing obstacles of extreme processing conditions. This results in leaching gangue minerals and requires a more complicated solvent extraction system. Recently, synergistic solvent extraction has been introduced to separate copper from the leached solution with high impurities. However, operational obstacles arise due to the complicated solvent extraction process, including multi-stages of extraction, and using more than one extractant in a single solvent extraction system. The phase separation in solvent extraction is one of the major issues in field operation. A poor phase separation could affect the entire process and eventually cause production loss. Therefore, in this study, the phase separation behaviours were studied in consideration of the field operation. Major parameters considered in the study were the type of diluent, temperature, mixing speed, solution pH and Oxidation Reduction Potential (ORP), and addition of impurities (flocculant and colloidal silica). The phase separation behaviours in the continuous counter-current SX system using a pilot-scale mixer-settler in the above conditions was investigated. Full article

Unit operations (UO) are mostly used in non-ferrous extractive metallurgy (NFEM) and usually separated into three categories: (1) hydrometallurgy (leaching under atmospheric and high pressure conditions, mixing of solution with gas and mechanical parts, neutralization of solution, precipitation and cementation of metals from solution aiming purification, and compound productions during crystallization), (2) pyrometallurgy (roasting, smelting, refining), and (3) electrometallurgy (aqueous electrolysis and molten salt electrolysis). The high demand for critical metals, such as rare earth elements (REE), indium, scandium, and gallium raises the need for an advance in understanding of the UO in NFEM. The aimed metal is first transferred from ores and concentrates to a solution using a selective dissolution (leaching or dry digestion) under an atmospheric pressure below 1 bar at 100 °C in an agitating glass reactor and under a high pressure (40–50 bar) at high temperatures (below 270 °C) in an autoclave and tubular reactor. The purification of the obtained solution was performed using neutralization agents such as sodium hydroxide and calcium carbonate or more selective precipitation agents such as sodium carbonate and oxalic acid. The separation of metals is possible using liquid (water solution)/liquid (organic phase) extraction (solvent extraction (SX) in mixer-settler) and solid-liquid filtration in chamber filter-press under pressure until 5 bar. Crystallization is the process by which a metallic compound is converted from a liquid into a crystalline state via a supersaturated solution. The final step is metal production using different methods (aqueous electrolysis for basic metals such as copper, zinc, silver, and molten salt electrolysis for REE and aluminum). Advanced processes, such as ultrasonic spray pyrolysis, microwave assisted leaching, and can be combined with reduction processes in order to produce metallic powders. Some preparation for the leaching process is performed via a roasting process in a rotary furnace, where the sulfidic ore was first oxidized in an oxidic form which is a suitable for the metal transfer to water solution. UO in extractive metallurgy of REE can be successfully used not only for the metal wining from primary materials, but also for its recovery from secondary materials. Full article

A study has been carried out on Ta and Nb recovery by a liquid-liquid extraction process using 4-methylacetophenone (4-MAcPh) as the organic phase. The 4-MAcPh was compared to methyl isobutyl ketone (MIBK) with respect to extraction efficiencies (D values) at different concentrations of H₂SO₄ in the aqueous phase. The results showed a similar extraction of Nb for both solvents. However, for Ta, extraction efficiency is increased by a factor of 1.3 for 4-MAcPh. In addition, the MIBK solubilized completely after 6 mol∙L⁻¹ of H₂SO₄ against only a loss of 0.14–4% for 4-MAcPh between 6 and 9 mol∙L⁻¹ of H₂SO₄. The potential of 4-MAcPh has also been studied to selectively recover Ta from a model capacitor waste solution. The results showed a selectivity for Ta in the presence of impurities such as Ag, Fe, Ni and Mn. The 4-MAcPh also presents the advantage of having physicochemical properties adapted to its use in liquid-liquid extraction technologies such as mixer-settlers. Full article