Recovery Of Manganese Research Articles

Assessing the environmental footprints of the manganese recovery process from low-grade ore to synthesize manganese ferrite

Assessing the environmental footprints of the manganese recovery process from low-grade ore to synthesize manganese ferrite

Separation of Valuable Metals in The Recycling of Lithium Batteries via Solvent Extraction

With the development trend and technological progress of lithium batteries, the battery market is booming, which means that the consumption demand for lithium batteries has increased significantly, and, therefore, a large number of discarded lithium batteries will be generated accordingly. Solvent extraction is a promising approach because it is simple. Solvent extraction is low in time consumption and is easy to industrialize. This paper is focused on the selective recovery of cobalt (Co), nickel (Ni), and manganese (Mn) contained in leachate obtained by digesting a cathodic material from spent lithium batteries with hydrochloric acid. After leaching the cathodic material, Mn was selectively extracted from leachate by using solvent extraction with D2EHPA diluted in kerosene in an optimized condition. Afterward, Co was extracted from the Mn-depleted aqueous phase using Cyanex272 diluted in kerosene. Finally, the raffinate obtained via a stripping reaction with H2SO4 was used in the Ni extraction experiments. Cyanex272 extractant was employed to separate Ni and Li. The process can recover more than 93% of Mn, 90% of Co, and 90% of Ni. The crucial material recovered in the form of sulfuric acid solutions can be purified and returned to the manufacturer for use. This process proposes a complete recycling method by effectively recovering Mn, Co, and Ni with solvent extraction, to contribute to the supply of raw materials and to reduce tensions related to mineral resources for the production of lithium batteries.

Recycling of Li-Ion Batteries from Industrial Processing: Upscaled Hydrometallurgical Treatment and Recovery of High Purity Manganese by Solvent Extraction

ABSTRACT Manganese plays a central role in lithium-ion batteries (LIBs) but its recycling is rarely addressed when compared to other valuable metals present in LIBs, such as Co and Ni. Thus, the main goal of this work was to study and achieve the separation of Mn from Co and Ni by solvent extraction from a leachate obtained from LIBs using hydrochloric acid in an upscaled reactor, which is an innovative aspect of this work. The results confirmed the high selectivity of D2EHPA towards Mn, which could be completely extracted in two stages (0.5 M D2EHPA at pH 2.5). The main co-extracted metals were Al, Cu and Co, but with lower concentrations than Mn. The behavior of minor impurities such as Zn and Mg was also monitored. Scrubbing using manganese chloride was crucial to remove impurities from the loaded organic and prevent their presence in the stripping product, and high O:A ratios negatively affected the scrubbing efficiency. Keeping the concentration of HCl up to 0.5 M in the stripping stage helped to limit the stripping of impurities. Manganese oxide was precipitated as a product with 99.5% purity (with traces of Zn, Cu and Co), which could be reused in the battery value chain.

Efficient separation and recovery of lithium and manganese from spent lithium-ion batteries powder leaching solution

Spent lithium-ion batteries recycling have become the key to the sustainable development of new energy vehicle industry due to its potential environmental risks and scarcity of critical metals. In this paper, rapid separation and efficient recovery of lithium and manganese were achieved through “manganese precipitation - acid leaching of manganese - impurities removal by sulfide precipitation” for the leaching solution of spent lithium-ion batteries powder. Based on the thermodynamic simulation of element precipitation behavior in Li+-Mn2+-Ni2+-Co2+-F−-SO42−-Ca(OH)2-H2O system, Ca(OH)2 was used to adjust the system pH of Li-Mn solution to 10, the elements such as Mn, Ni, Co, Ca and F were precipitated simultaneously as Mn(OH)2(s), Ni(OH)2(s), Co(OH)2(s), CaSO4(s) and CaF2(s). Whereas the loss rate of lithium was less than 0.2 %. Battery-grade lithium carbonate (Li2CO3 99.80 %) was prepared from the lithium purification solution with the carbonation method. Using 30 % H2O2 as reductant, the leaching rate of Mn from the manganese precipitate residue was 99.77 %. In order to realize the deep purification of manganic acid leaching solution, solid manganese sulfide was selected as the precipitant, and impurities such as Co, Ni, Ca and F were selectively precipitated as CoS(s), NiS(s) and CaF2(s), respectively, at pH = 5.0. Subsequently, battery-grade manganese sulfate was successfully prepared from the pure MnSO4 solution by evaporation - crystallization. In this study, the introduction of cationic impurities such as Na+ and NH4+ was avoided during Li-Mn separation and acid-leachate purification through the selection of suitable neutralizer and sulfide precipitant. As a result, the process flow was greatly simplified, and the direct yields of lithium and manganese were effectively improved.

Selective recovery of manganese and lead from electrolytic manganese residues in a sulfuric acid solution with galena as the reductant

Electrolytic manganese residues (EMRs) were considered as typical industrial solid wastes owing to a large amount of Mn and other elements such as soluble sulphate. Here, lead-chemistry was innovatively proposed to treat EMRs based on the transformation of lead phases including PbS, PbSO4 and PbCO3. During the first stage H2SO4 leaching with galena as the reductant, Mn leaching efficiency reached 98.0% in a 1.5 mol/L H2SO4 solution with m(galena)/m(EMR) = 0.1. Meanwhile, Pb was enriched in the H2SO4 leaching residue with a content of 53.0 wt%. Subsequently, >77.2% of Pb was recovered in the form of PbCO3 product through NH4Ac leaching and (NH4)2CO3 precipitation in a 4 mol/L NH4Ac solution. Finally, the NH4Ac leaching agent was successfully regenerated after removing remaining CO32− and SO42− via PbCO3 and BaSO4 precipitation. The regenerated leaching solution indicated a higher Pb recovery to 85.4% owing to an increasing NH4Ac concentration to 5 mol/L during circulation leaching. This study provided a feasible method for the effective recovery of Mn and Pb, which was beneficial for the clean utilization of EMRs.

Rare metals recycling from spent NCM cathode materials and simultaneous dehydrofluorination of polyvinylidene fluoride (PVDF) in subcritical water

Several studies have examined the recovery of lithium (Li), nickel (Ni), cobalt (Co), and manganese (Mn) from used lithium-ion batteries (LIBs). However, the environmentally friendly and cost-effective leaching and efficient separation of rare metals from the active cathode material of LIBs remains a challenge. In this study, we present a novel route for the extraction of high-value metals from the NCM cathode material of spent LIBs using subcritical water-containing polyvinylidene fluoride (PVDF). The experimental parameters such as reaction temperature, time, liquid–solid and mass ratios, were carefully investigated. The raw cathode material and the solid residues before and after leaching were characterized using ICP-OES, XRD, FT-IR and SEM-EDS analyses. Results showed that the maximum extraction efficiencies of Li, Ni, Co, and Mn of (98.69, 98.24, 97.52, and 99.04) %, respectively, were achieved under the optimized conditions of 350 °C, 2 h, 1:3 mass ratio, and 60:1 mL/g liquid–solid ratio. Meanwhile, the experimental results of leaching kinetics revealed that the reaction in the system was controlled by the surface chemical reaction model with the linear fitting degree of (R2 = 0.97–0.99) and the calculated activation energies of 63.72 kJ/mol (for Li), 73.55 kJ/mol (for Ni), 74.99 kJ/mol (for Co), and 71.88 kJ/mol (for Mn). The overall findings of this research concluded that the PVDF-assisted subcritical water extraction process is a beneficial and a promising alternative to other existing methods.

Separation and recovery of nickel cobalt manganese lithium from waste ternary lithium-ion batteries

In this paper, a combination of precipitation and solvent extraction was used to study the separation and recovery of nickel, cobalt, manganese and lithium from the acid leach solution of wasted ternary lithium-ion battery cathode materials. The effects of sulfuric acid concentration, hydrogen peroxide addition, liquid-to-solid ratio, time and temperature on the metal leaching rate were optimized, and the leaching kinetic analysis showed that the metal leaching was controlled by both the diffusion of the solid-phase product layer and the chemical reaction, but the diffusion of the solid-phase product layer was dominant. Dimethylglyoxime (DMG) was first used to remove nickel as Ni-(C4H8N2O2)2, and P204 and C272 were used to extract manganese and cobalt ions from the post-nickel removal solution step by step. The effects of volume fraction of organic solvent, O/A, pH of the aqueous phase and extraction time on the extraction rate were optimized, and the extraction mechanism was analyzed by FT-IR and slope method as a cation exchange reaction, specifically the ionic exchange of metal ions with H+ in the POH of the organic solvent, and also the coordination of trace metal ions with the PO, Finally, the metals in loaded organic phase were stripped to the solution by dilute sulfuric acid which were recovered as MnO2, CoC2O4 and Li2CO3, respectively. The recovery rates for nickel, cobalt, manganese and lithium in the whole process were 96.84 %, 81.46 %, 92.65 % and 91.39 % respectively, a technical route to recover nickel, cobalt, manganese and lithium from ternary LIBs was optimized, and extractants and DMG in the process could be recycled and reused.

Hydrometallurgical recovery of manganese and nickel and isolation of tantalum from obsolete tantalum capacitor

Tantalum capacitor demand is rapidly growing, primarily from the electronic and superalloy industries. Indeed, the global tantalum market is anticipated to boost at a compound annual growth rate of around 6% over the next decade. With increasing technological advancements, electronics' obsolescence rate has also increased. The obsolete capacitors from these electronics are a rich secondary resource for recycling strategically and economically significant metals. In this article, we have developed an environment-friendly hydrometallurgical route for recovery of manganese and nickel from the tantalum capacitors. Firstly, silica-free tantalum capacitor procured after pre-processing was leached using hydrochloric acid (1–3 M) for preferred dissolution of manganese and nickel, to facilitate a tantalum-rich residue. Manganese was then selectively separated from leach liquor using solvent extraction with D2EHPA and CYANEX272, with the extraction efficiency of each reagent compared. Quantitative dissolution of both manganese (99.9%) and nickel (98.9%), with no tantalum dissolution, was witnessed under the optimized leaching condition of 3 M HCl, 50 g/l pulp density, 60 °C, and 120 min. Kinetic data for manganese and nickel in the temperature range of 30–60 °C demonstrated the leaching reaction at the surface to be the rate controlling step. D2EHPA and CYANEX272 each showed excellent selectivity for manganese under the optimized conditions. However, CYANEX272 proved to be a better extractant in light of higher extraction efficiency in single-stage extraction (∼75%), than D2EHPA (∼40%), with less organic consumption. Above 99% manganese was selectively extracted with predicted 2-stages extraction by McCabe-Thiele plot using CYANEX272 under the optimized condition.

Development of a chemical-free process utilizing ozone oxidative precipitation for the recovery of cobalt and manganese from acid mine drainage

Acid mine drainage (AMD) has been identified as a viable secondary resource of Co, and Mn. However, recovery of these elements while treating AMD is challenging due to the unfavorable pH and Eh conditions for Co-Mn precipitation. This study investigated the effects of various ligands (hydroxide, carbonate, ammonium, sulfate, and phosphate) and oxidizers (sodium persulfate, potassium permanganate, and ozone) on the precipitation of Co-Mn from AMD through experimental and solution chemistry studies. Ozone was found to be the most effective agent for the recovery of these elements. Based on the results, an AMD treatment process was formulated for selective recovery of multiple critical elements, including Al, REEs, Co, and Mn. More than 95 % of Co and Mn were recovered through the proposed process utilizing chemical-less ozone oxidative precipitation. A precipitate containing 0.9 % Co and 54.6 % Mn was obtained from an AMD source containing 0.9 ppm Co and 41.8 ppm Mn.

New method for selective recovery of manganese from NCM-based cathode material of spent Li-ion batteries

ABSTRACT This study provides a new leaching method for selective recovery of manganese from the spent NCM-based cathode active material of lithium-ion secondary batteries (LIBs). The recovery method involves the use of aqueous Mn(II) phase spontaneously generated in sulfate media as a reducing agent, in which Ni(III) and Co(III) are reduced to soluble species while Mn(II) precipitates as Mn(IV) oxides simultaneously. To optimize the process, the effects of time, temperature, and acid concentration on the leaching behavior were investigated. As a result, two-step successive leaching at an optimal condition was proposed, by which the dissolution efficiency of Co and Ni reached up to 99% and ~100%, respectively while Mn leaching was restricted to 15.5%. The leaching residue mainly consisted of manganese oxide (MnO2), containing Mn ~40%. The amount of Mn in the residue increased to ~70% by calcinating at 650 °C, which converted its phase into Mn2O3 and Mn3O4. Therefore, our two-step leaching technique will lead to the recovery of nearly all the contents of Li, Co, and Ni in addition to ~70% purity Mn as supplemental benefit from spent LIB materials without using any oxidants or reductants.

Studies of Selective Recovery of Zinc and Manganese from Alkaline Batteries Scrap by Leaching and Precipitation.

Recovery of zinc and manganese from scrapped alkaline batteries were carried out in the following way: leaching in H2SO4 and selective precipitation of zinc and manganese by alkalization/neutralization. As a result of non-selective leaching, 95.6–99.7% Zn was leached and 83.7–99.3% Mn was leached. A critical technological parameter is the liquid/solid treatment (l/s) ratio, which should be at least 20 mL∙g−1. Selective leaching, which allows the leaching of zinc only, takes place with a leaching yield of 84.8–98.5% Zn, with minimal manganese co-leaching, 0.7–12.3%. The optimal H2SO4 concentration is 0.25 mol∙L−1. Precipitation of zinc and manganese from the solution after non-selective leaching, with the use of NaOH at pH = 13, and then with H2SO4 to pH = 9, turned out to be ineffective: the manganese concentrate contained 19.9 wt.% Zn and zinc concentrate, and 21.46 wt.% Mn. Better selectivity results were obtained if zinc was precipitated from the solution after selective leaching: at pH = 6.5, 90% of Zn precipitated, and only 2% manganese. Moreover, the obtained concentrate contained over 90% of ZnO. The precipitation of zinc with sodium phosphate and sodium carbonate is non-selective, despite its relatively high efficiency: up to 93.70% of Zn and 4.48–93.18% of Mn and up to 95.22% of Zn and 19.55–99.71% Mn, respectively for Na3PO4 and Na2CO3. Recovered zinc and manganese compounds could have commercial values with suitable refining processes.

Effective Separation and Recovery of Manganese and Potassium from Biomass Ash by Solvent Extraction.

Manganese (Mn) is considered an important, energy-critical metal due to its leading role in the production of electrochemical energy storage devices. One valuable source of Mn is hyperaccumulator plants used for the phytoremediation of contaminated soil. In this study, stems and leaves of ginger (Zingiber officinale), which accumulate Mn at moderate levels (∼0.2 wt %) and potassium (K) at high levels (>5 wt %), were analyzed to assess the potential of recovering metals from this plant. The extraction behaviors of Mn and K were studied using raw and ash samples (100–600 °C). It was crucial to set an appropriate incineration temperature (300 °C) to selectively extract K (∼96%) and Mn (∼90%) using water and nitric acid over two consecutive steps. Additionally, citric acid, a cost-effective and environmentally friendly solvent, was just as effective (∼85%) as nitric acid in extracting Mn. X-ray absorbance near-edge spectroscopy and X-ray diffraction analysis of the ash before and after extractions were applied to elucidate the extraction mechanism. The results revealed that selective extraction of both compounds was possible due to the change in the oxidative state of Mn(II) (soluble in water) into Mn(III) and Mn(IV) (insoluble in water) during sample incineration. Simultaneously, there were complex reactions associated with the changes within potassium carbonate compounds; however, these did not affect the K extraction efficiency.

Manganese bioleaching: an emerging approach for manganese recovery from spent batteries

Manganese bioleaching: an emerging approach for manganese recovery from spent batteries

Recovery of lithium, cobalt, nickel, and manganese from spent lithium-ion batteries through a wet-thermal process

Recycling end-of-life lithium-ion batteries (LIBs) as a problematic waste stream has become an urgent area of research worldwide. This paper details an efficient, simple, and environmentally friendly technique for metal recovery from a mixture of three types of spent LIBs cathodes. By using the carbothermal process, Li is first isolated in solid lithium carbonate with minimal emission, and to optimize Li isolation the effects of temperature, holding time, and graphite dosage are investigated. Under optimal carbothermal conditions of 700°C, 60 min, and 15% graphite, phases of CoO, NiO, Li2CO3, and small amounts of Ni and Co are formed. This stage is followed by dissolution in cold water where 94.6% of Li is recovered under optimal leaching conditions. After filtration, the residual component is reduced by the second carbothermal reduction under vacuum at 900°C for 120 min, resulting in the formation of high purity metals.

Hydrometallurgical Recovery of Manganese from Ferruginous Manganese Ore by Reductive-Acid Leaching with Sodium Dithionite

Hydrometallurgical Recovery of Manganese from Ferruginous Manganese Ore by Reductive-Acid Leaching with Sodium Dithionite

Selective Recovery of Manganese from Low-Grade Ferruginous Manganese Ores Through SO2 Leaching

Selective Recovery of Manganese from Low-Grade Ferruginous Manganese Ores Through SO2 Leaching

Microwave-enhanced reduction of manganese from a low-grade pyrolusite ore using pyrite: process optimization and kinetic studies.

The inefficient leaching of manganese is the main factor hindering the commercialization of the reduction process during manganese recovery using pyrite as the reducing agent. Hence, a new method for improving recovery efficiency and reducing the cost is required. This study uses microwave heating as a strengthening method to extract Mn2+ from pyrolusite and the leaching conditions are optimized. It was found that the extraction rate of Mn2+ could reach 95.07% under microwave heating through the conditions of H2SO4 is 1.2mol/L, m(pyrolusite)/m(pyrite) equals to 10:2, leaching temperature is 90 ℃, and a liquid-solid (L/S) ratio of 10:1. The achieved extraction rate was higher than that of 75.08% under the conventional heating achieved at the same conditions. Besides, experimental studies have found that microwave heating can change the process and direction of chemical reactions, shorten the reaction time, and reduce sulfuric acid. Finally, the kinetic study indicates that the leaching process under microwave heating is controlled by surface chemical reactions. The equation of leaching kinetics is 1 - (1 - x)1/3 = 3425.32/r0·[H2SO4]1.316·[FeS2/MnO2]0.907·exp(- 45.03/(RT)·t. The activation energy is 45.03kJ/mol. Meanwhile, through a scanning electron microscope and particle size analyzer, microwave heating has a significant influence on reducing the ore diameter and increasing the specific surface area of the sample. This study aims to provide an experimental trial case for studying the mechanism of microwave-enhanced leaching process during manganese recovery using pyrite as the reducing agent. The reported kinetics research may guide the development of the industrial application for Mn recovery.

An efficient and green method to separate iron and manganese from ferromanganese ore by suspension magnetization roasting and magnetic separation

Despite the rich reserves of ferromanganese ore, it can only be discarded as waste rock due to the difficulty of its development and the unavailability of conventional methods. In this study, suspension magnetization roasting (SMR) and low-intensity magnetic separation (LIMS) were used to process ferromanganese ore. Under the optimum conditions, magnetic products with an iron grade of 69.66% at an iron recovery of 98.17% and nonmagnetic products with a manganese grade of 51.60% at a manganese recovery of 88.48% were obtained. X-ray diffraction (XRD), vibrating sample magnetometry (VSM), X-ray photoelectron spectroscopy (XPS), and scanning electron microscopy and energy-dispersive spectrometry (SEM–EDS) were used to analyze the process mechanism. The data show that the newly generated products had greatly enhanced magnetic properties and that the surface became rougher and more porous after SMR-LIMS. Finally, hematite was transformed into magnetite in the magnetic product, and other minerals were transformed into the nonmagnetic product, realizing no tailing recycling or utilization.

Tannic acid as a novel and green leaching reagent for cobalt and lithium recycling from spent lithium-ion batteries

Tannic acid–acetic acid is proposed as novel and green chemicals for cobalt and lithium recycling from spent lithium-ion batteries through a leaching process. The synergism of both acids was documented through batch and continuous studies. Tannic acid promotes cobalt dissolution by reducing insoluble Co3+ into soluble Co2+, while acetic acid is critical to improve the dissolution and stabilize the metals in the pregnant leach solution. Based on batch studies, the optimum conditions for metal recovery at room temperature are acetic acid 1 M, tannic acid 20 g/L, pulp density 20 g/L, and stirring speed 250 rpm (94% cobalt and 99% lithium recovery). The kinetic study shows that increasing temperature to 80 °C improves cobalt and lithium recovery from 65 to 90% (cobalt) and from 80 to 99% (lithium) within 4 h at sub-optimum condition (tannic acid 10 g/L). Kinetic modeling suggests the leaching process was endothermic, and high activation energy indicates a surface chemical process. For other metals, the pattern of manganese and nickel recovery trend follows the cobalt recovery trend. Copper recovery was negatively affected by tannic acid. Iron recovery was limited due to the weak acidic condition of pregnant leach solution, which is beneficial to improve leaching selectivity.

Study of Manganese Recovery in the CaO-SiO<sub>2</sub>-MgO-Al<sub>2</sub>O<sub>3</sub>-MnO-Fe<sub>2</sub>O<sub>3</sub> System by Thermodynamic Simulation

The results of thermodynamic simulation of the manganese recovery in the CaO-SiO2-MgO-Al2O3-MnO-Fe2O3 system by carbon are presented. Parameters of the initial system are temperature range 1400-at a step of , a total pressure of 0.1 MPa, and N2. The composition of the oxide system is corresponded by the manganese ore (wt %) 1.1 MnO2, 44.3 MnO, 28.4 CaO, 9.3 SiO2, 5.4 MgO, 0.3 Al2O3, 11.2 Fe2O3 and silicomanganese slag. It contains (wt %) 16.3 MnO, 18.4 CaO, 52 SiO2, 7.8 MgO, 5.26 Al2O3, and 0.24 FeO. The amount of silicomanganese slag in the system was 0, 5, 12, and 25%. Carbon is used as a reducing agent. Its consumption is increased by 5% from the stoichiometry for the recovery of Fe and Mn and by 8% of the metal mass for the formation of iron, manganese, and silicon carbides. The simulation is carried out using HSC Chemistry 6.12 () software package. The thermodynamic characteristics of the Fe3C, Fe2O3, FeO, MnO2, Mn, Mn3C, Mn5C2, Mn7C3, Mn23C6, and SiC compounds existing in the database are refined. It was determined that an increase in the melt temperature from 1400 to increases the degree of manganese recovery (ηMn) for all compositions of the systems. An increase of the silicomanganese slag content in the mixture from 0 to 25% decreases ηMn from 89.3 to 85% at and from 95.8 to 91.5% at . The chemical composition of the high-carbon ferromanganese alloy is (wt %): 71.9-72.8 Mn, 16.6-17.9 Fe, 0.015-1.64 Si, and 9-. The simulation results can be used to develop a technology for producing a high-carbon ferromanganese when silicomanganese slag is involved in metallurgical processing.