Separation Of Mn Research Articles

Separation of Co(II), Mn(II), and Ni(II) by solvent extraction with Cyanex 272 and D2EHPA from the sulfuric acid leaching solution of spent lithium-ion batteries

Spent lithium-ion batteries contain valuable metals such as cobalt, lithium, manganese and nickel. Smelting reduction of spent LIBs at high temperature results in metallic alloys. Therefore, it is necessary to recover the valuable metal ions present in the sulfuric acid leaching solutions of the metallic alloys. In this work, solvent extraction experiments were performed to separate the three metal ions, Co(II), Mn(II) and Ni(II) present in the leaching solutions of the metallic alloys. Synthetic sulfate solutions were prepared and commercial organophosphorous extractants were employed. First, both Co(II) and Mn(II) were completely extracted in one stage by using 40% saponified 0.3 M Cyanex 272, leaving Ni(II) in the raffinate. The small amount of Ni(II) co-extracted into Cyanex 272 was removed by two stages of cross-current scrubbing using pure CoSO4 solution. The effect of pH and CoSO4 concentration of the scrubbing solution on the scrubbing of Ni(II) was investigated. The Co(II) and Mn(II) present in the scrubbed Cyanex 272 were completely stripped by 0.05 M H2SO4 solution. Batch simulation experiments for the three stage of counter-current extraction with 1 M D2EHPA verified that Mn(II) and Co(II) were completely separated by selective extraction of Mn(II) into D2EHPA, leaving Co(II) in the raffinate. By consecutive extraction with Cyanex 272 and D2EHPA, pure solutions of Co(II), Mn(II) and Ni(II) with purity higher than 99.9% can be recovered from the starting solutions. A process was proposed for the treatment of sulfuric acid leaching solutions of spent LIBs containing Co(II), Mn(II) and Ni(II) by solvent extraction.

Simulation of Magnetic Separation of Metal Ions in Aqueous Electrolytes

The magnetic separation of metal ions provides an alternative solution to traditional separation techniques such as pyrometallurgy, hydrometallurgy, biometallurgy or electrodialysis. Compared to traditional techniques that either use large amounts of chemicals (usually inorganic acids combined with reducing agent), produce large amounts of sludge as solid waste, consume a large amount of energy, or are difficult to separate ions of different charges [1], the magnetic separation of the metal ions can separate ions based on their magnetic susceptibility. This method is environmentally friendly [2] and consumes a small amount of energy (particularly when the system is designed using permanent magnets instead of electromagnets). The goal of this presentation is twofold. First, we derive the set of transport equations that need to be used to simulate the magnetic separation of metal ions in aqueous solutions. Then, we use these transport equations to simulate the magnetic separation process in various magnetic systems and predict the efficiency of magnetic separation of different systems.The mathematical model developed here is based on coupling the three-dimensional Navier-Stokes equations for flow transport with the drift (migration)-diffusion equations of ion transport [3] in the presence of magnetic field gradients. Both the drift-diffusion model and the Navier-Stokes equations include the magnetic force term as an additional driving force. By solving the entire system of equations self-consistently we analyze the effect of the diffusivity, concentration gradients, magnetic field gradients and fluid velocity over the capturing properties of the system. A detailed presentation of the mathematical model, underlying assumptions of the model, limiting cases, numerical implementation in three-dimensional structures, and simulations results will be presented at the meeting. In addition, we will present predictions for the magnetic separation of Li, Fe, Ni, Mn, and Co from the solution phase. Fortunately, these ions have significantly different magnetic susceptibility, which vary over more than 3 orders of magnitude, and which allows for the efficient extraction and separation of the elements from the solution and from each other.

Development of an Efficient Process for the Separation of Co(ii), Mn(ii), and Ni(ii) from Chloride Solution by Precipitation

ABSTRACT The demand for nickel, cobalt, and manganese is increasing owing to their critical role in the performance of lithium-ion batteries. Precipitation is simpler to operate than solvent extraction in the separation of metal ions. In this work, precipitation-based procedures were developed to separate Co(II), Mn(II) and Ni(II) from synthetic chloride solutions. Dimethylglyoxime (DMG) was effective in selectively precipitating Ni(II) from the chloride solutions containing Co(II) and Mn(II). Solution pH greatly affected the precipitation of Ni(II) by DMG. In the first procedure, Ni(II) was first precipitated using DMG from solution with initial pH 6 at a DMG/Ni(II) molar ratio of 3, a reaction time of 30 min and then Co(II) was separated from the filtrate by precipitation with Na2S, with optimal conditions being an initial pH of 6, a Na2S/Co(II) molar ratio of 2 and a reaction time of 15 min. In the second procedure, both Ni(II) and Co(II) was simultaneously precipitated with Na2S, leaving Mn(II) in the filtrate. Then the mixed sulfides of Co(II) and Ni(II) were dissolved by using HCl solution containing NaClO as an oxidizing agent. From the leaching solution, Ni(II) was separated by precipitation with DMG. Optimum conditions for the separation conditions were obtained. In both procedures, the separation degree among the three metal ions was higher than 99%. The developed procedures were simple and effective for the separation of the three metal ions compared to solvent extraction.

Comparison of separation of Mn(II), Co(II), and Ni(II) by oxidative precipitation between chloride and sulfate solutions

In hydrometallurgy, precipitation would be easier and simpler than solvent extraction as a separation operation. In this work, the separation performance of Co(II), Mn(II) and Ni(II) by oxidative precipitation was investigated. For this purpose, NaClO was employed as an oxidizing agent and the separation behavior of the three ions was compared between chloride and sulfate solutions by varying some factors such as the dosage of NaClO, solution pH and reaction temperature. By controlling the molar ratio of NaClO to Mn(II), manganese ions(II) were easily separated as MnO2 by oxidative precipitation from both chloride and sulfate solutions. At the same experimental conditions, precipitation percentage of Co(II) from chloride solution was higher than that from sulfate solution, which can be ascribed to the stronger tendency of Co(II) to form complexes with chloride ion than with sulfate ions. Addition of NaCl to sulfate solution and oxidative precipitation at high temperature enhanced the precipitation percentage of Co2O3 and thus separation degree between Co(II) and Ni(II) was improved. Under the optimum conditions, MnO2 and Co2O3 powders with 99.9% purity were completely recovered by oxidative precipitation from chloride solution. By contrast, the purities of the MnO2 and Co2O3 thus recovered from sulfate solution were only 76 and 91%, respectively. Our results indicated that chloride solution would be more effective than sulfate solution in separating Mn(II) and Co(II) by oxidative precipitation with NaClO. Therefore, the use of chloride-based leaching solutions such as HCl and FeCl3 might be better for the leaching medium of spent lithium-ion batteries.

Efficient separation and recovery of Co and Ni from ammonium sulfate roasting‐water leaching solutions of oceanic cobalt‐rich crusts by sulfide precipitation and P507–Cyanex 272 synergistic extraction

AbstractOceanic cobalt‐rich crusts contain many valuable metals including Co, Ni, Cu, and Mn, of which Co and Ni are scarce metal resources on terrestrial land. Co, Ni, Cu, and Mn in cobalt‐rich crusts can be efficiently extracted by the ammonium sulfate roasting‐water leaching (ARWL) process, but separating and recovering Co and Ni from the leaching solution containing high concentrations of Mn is a challenging problem. In this study, a combination of sulfide precipitation and P507–Cyanex 272 synergistic extraction is proposed for the separation and recovery of Co and Ni from the ARWL solutions of oceanic cobalt‐rich crusts. Under the optimum sulfide precipitation conditions, Co and Ni were precipitated with 99.85% and 99.63% efficiency, respectively, while Mn was coprecipitated with only .79% efficiency. The Co–Ni mixed sulfides were dissolved by dilute sulfuric acid under oxidative conditions to obtain a solution containing 12.584 g/L Co, 11.012 g/L Ni, and a small amount of Mn. Subsequently, Co and Mn were extracted from this solution using P507–Cyanex 272 synergistic extraction, the single‐stage extraction efficiencies of Co and Mn were 95.76% and 99.73%, respectively, and the coextraction efficiency of Ni was 3.02%, under the conditions of a feed solution pH of 3.0, an extractant saponification degree of 70%, a total extractant concentration of 20% (P507 to Cyanex 272 ratio of 3:7), and an O/A ratio of 1.1:1. The results of the thermodynamic study showed that the reaction of Co extraction by this mixed extraction system was exothermic. Ni in the organic phase was washed with an H2SO4 concentration of .12 mol/L, followed by stripping of Co and Mn with an H2SO4 concentration of .6 mol/L. Mn in the stripping solution was removed by oxidative precipitation with (NH4)2S2O8, after which the Co3O4 product was obtained by precipitation with (NH4)2C2O4 and calcination. Similarly, NiC2O4·2H2O can be obtained from the raffinate by (NH4)2C2O4 precipitation. Finally, a flowsheet was developed for the separation and recovery of Co, Ni, Cu, and Mn from the ARWL solutions of oceanic cobalt‐rich crusts. The study provides a promising scheme for the recovery of various valuable metals from deep‐sea cobalt‐rich crusts or manganese nodules.

Efficient adsorption and separation of Mn–Cu–Cd composite pollutants using MOF-based calcium alginate composite hydrogels

ZIF-8, a metal–organic framework that has significant benefits such as a substantial specific surface area, abundant active sites, and high porosity, has extensive application in environmental remediation.

Selective Separation of Li, Ni, Co and Mn from Model Spent Li Ion Battery Cathode by Dry Processing using Combination of Chlorination and Oxidation

Selective Separation of Li, Ni, Co and Mn from Model Spent Li Ion Battery Cathode by Dry Processing using Combination of Chlorination and Oxidation

Separation of Cr and Mn by polysulfone (PSF) based ultrafiltration (UF) membranes anchored with nanoparticles - Mathematical analysis of rejection properties

Separation of heavy metals to obtain potable water for domestic and agricultural applications is important considering health effects, bioaccumulation properties and applicability. The separation of Cr and Mn salts by Donnan exclusion are investigated using polysulfone (PSF) based membranes modified by anchoring ZnO nanoparticles. Use of Acid-treated ZnO nanoparticle enhnanced rejection properties for Cr and Mn (97.12 and 98.37%, respectively) for membranes based on 40% PSF, 8% PEG -400 and 0.8% ZnO. The use of polyethylene glycol (PEG)with molecular weight of 200 Da enhanced rejection properties to ~ 99%. This would provide excellent pathway for PSF membrane modification without affecting stability.Separation was dependent uponconcentrations of PSF, PEG, ZnO nanoparticles in dope solution, and bubble point pressure, pore size, number of pores, etc. Analysis of these properties and effect would provide pathway for design of membranes for heavy metal removal and process applications. Hence, they were analyzed using R studio multi-attribute linear regression model. Membrane performance regression analysis provided correlation with 95% fitting accuracy with 0.98 coefficient of regression, suggesting good relationship between predicted and observed data. This shows the applicability of model to save time and cost involved in designing membrane formation parameters and properties with optimized applicability.

Efficient separation of Li and Mn from spent LiMn2O4 cathode materials by NH4HSO4 reduction roasting-selective ammonia leaching

With the imminent peak in the retirement of rechargeable lithium-ion batteries worldwide, the development of efficient methods for recycling valuable elements from LIBs has attracted considerable attention. In this work, a novel method of NH4HSO4 reduction roasting-selective ammonia leaching was proposed to thoroughly separate Li and Mn from the spent LiMn2O4 cathode materials. Using the TG-DSC-FTIR, XRD, SEM-EDS and ICP methods, the detailed mechanism of reduction roasting process was revealed, showing that the Mn4+ and Mn3+ in the spinel structure of LiMn2O4 were reduced by the NH4+ from the molten ammonium salt, and transformed into water-soluble MnSO4 and Li2Mn2(SO4)3. According to the water-leaching performance of the roasting products, the sulfation conversion rate of Mn reaches 98.1 %, while Li is almost completely transformed under the optimal roasting conditions (475 ℃, 60 min). Using the NH3·H2O-air leaching-system, complete separation of Li and Mn can be achieved. It was shown that the introduction of air into the ammonia solution at a rate of 0.2 L/min under the optimal leaching condition leads to Mn precipitation in the form of nanoscale Mn3O4 particles with a precipitation rate of over 99.99 %, while Li still remains completely leached. Based on the in situ detection of the oxidation reduction potential and pH during the selective leaching, the key mechanism of efficient Mn precipitation was revealed. that is, the increasing potential accelerates the oxidation of Mn(OH)2, and the rapid consumption of Mn(OH)2 promotes the hydrolysis of Mn2+, thereby achieving a significant improvement in the separation efficiency of Li and Mn.

Extraction of valuable metals from spent cathode materials by reductive roasting in methane atmosphere

Against the backdrop of the increasing amounts of lithium-ion batteries, it is reducing environmental pollution and relieving the stress on resource requirements through the sustainable recycling of spent lithium batteries. Here we targeted the reduction of the material phase by methane roasting and then achieved a step separation of Li, Ni, Co, and Mn by differentiation in water solubility and magnetic strength. The principal reduction factors were also optimized. The results show that the spent cathode powder converts mainly to water-soluble Li2CO3, that the leaching selectivity of lithium is 100%, and that other metals can be separated by wet magnetic separation under optimal conditions. A reasonable explanation of the phase conversion during the reduction process is provided, and a preliminary process evaluation is presented at the end. Notably, this work has the strengths of step recovery of elements, rapid processing, and zero chemical use, which has great potential for the industrial recycling field and provides a new idea for the development of green and efficient valuable metal recovery technologies for spent LIBs.

Recovery of Nickel and Cobalt Metal Powders from the Leaching Solution of Spent Lithium-Ion Battery by Solvent Extraction and Chemical Reduction

ABSTRACT Spent lithium-ion batteries (LIBs) contain some valuable metals. Smelting reduction of spent LIBs produces metallic alloys containing Co, Cu, Fe, Mn, and Ni. Leaching of the metallic alloys with inorganic acid solutions and subsequent separation of Cu(II), Fe(III) and Mn(II) results in a solution containing Co(II) and Ni(II). In this work, solvent extraction and chemical reduction experiments were performed to recover pure metals from this solution. Cobalt(II) was first separated from Ni(II) by solvent extraction with saponified Cyanex 272. Batch simulation experiments based on the McCabe-Thiele diagram for the extraction of Co(II) verified the complete separation of Co(II) from Ni(II). Hydrazine was then employed as a reducing agent for Co(II) and Ni(II) from the stripping solution and the raffinate, respectively. The effect of several variables on the reduction such as the molar ratio of hydrazine to metal ion, reaction time, temperature, and solution pH was investigated. It was found that the reduced metals could be dissolved owing to the oxidizing action of hydrazonium in acidic solution. Addition of NH4Cl was effective in suppressing the dissolution of the reduced metals. Especially, there was an optimum molar ratio of NH4Cl at which maximum reduction of Co(II) was obtained. The recovery percentages of Co and Ni powder were higher than 99.1% and 99.9%, respectively, and the purity of the reduced metals was higher than 99.9%.

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.

Comparison of phosphorus-based extractants on manganese separation from citrate leach solutions for recycling of lithium-ion batteries

The performance requirements of modern lithium-ion batteries (LIBs) necessitate the use of a number of scarce and strategically sensitive metals such as lithium and cobalt. Recycling end-of-life LIBs reduces the demand on the primary sources of these metals and helps reduce the environmental impact of LIB waste. Citric acid has proven to be an effective environmentally friendly and sustainable lixiviant; however, the formation of metal citrate complexes complicates subsequent metal separation processes such as solvent extraction. This study enhances the understanding of LIB metal separation from citric acid media by comparing the metal separation performance of phosphorus-based liquid-liquid extractants from a citric acid leach. The optimum Mn(II) extraction pH decreases as the extractant’s phosphorus oxidation state increases from phosphinic to phosphonic to phosphoric, due to the oxygen atoms that surround the central phosphorus atom. The maximum Mn(II) separation with Cyanex 272, PC-88A, and D2EHPA was observed at pHs of 6, 3, and 3, respectively. D2EHPA further provided the best separation of Mn(II) over Al, Co, Li, and Ni with separation factors of 137, 191, 118, and 601, respectively. No research is currently available on the metal separation performance of phosphonic (PC-88A) or phosphinic (Cyanex 272) organic extractants from citric acid media.Significance: This study is the first to investigate the use of phosphonic and phosphinic extractants for metal separation from citric acid leach solutions, towards using citric acid as an environmentally friendly lixiviant. The phosphoric extractant, D2EHPA, enabled successful and sequential separation and extraction of aluminium, manganese and lithium, making the process technologically feasible and attractive.

Separation of base metals from reduction smelt-alloy of spent lithium-ion batteries by ferric sulfate leaching, cementation, solvent extraction and oxidative precipitation

We propose a hydrometallurgical process to recover Ni, Co, Cu, Mn, and Fe from ferric sulfate synthetic leaching solution whose composition was similar to the real leach liquor of spent lithium-ion batteries (LIBs). Copper(II) was completely separated by cementation with iron powder at room temperature for 20 min. Afterward, H2O2 was added to the raffinate to oxidize Fe(II) to Fe(III). Multi-stage cross-current extraction with 2.0 M D2EHPA and stripping with 60% aqua regia completely removed iron from the solution. The separation of Mn(II) over Co(II) and Ni(II) was carried out by oxidative precipitation, in which Mn(II) was oxidized to MnO2 at the molar ratio NaClO to Mn(II) of 4.0 at pH 3.0. Following this, most of Co(II) together with 11% of Ni(II) were coprecipitated from the Mn(II) free filtrate at the molar ratio of NaClO to Co(II) of 7.0. From the filtrate containing Ni(II) of pH 3.0, the Ni(II) ions were completely recovered using Na2C2O4 as a precipitant at the same molar ratio of oxalate to Ni(II). Continuous experiments at the optimum condition of each step verified that Cu(II), Fe(III), and Mn(II) were completely separated by cementation, solvent extraction, and oxidative precipitation. The proposed process for base metal recovery from spent LIBs offers several advantages, such as low energy requirements and products with high purity.

Direct Production of Ni–Co–Mn Mixtures for Cathode Precursors from Cobalt-Rich Lithium-Ion Battery Leachates by Solvent Extraction

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.

Magnetite@poly(p-phenylenediamine) core–shell composite modified with salicylaldehyde for adsorption and separation of Mn (VII) from polluted water

Magnetite@poly(p-phenylenediamine) core–shell composite modified with salicylaldehyde for adsorption and separation of Mn (VII) from polluted water

Separation of Co and Mn from acetic acid leaching solution of spent lithium-ion battery by Cyanex272

Spent lithium-ion batteries (LIBs) contain large amounts of scarce metals, such as Li, Co, Al, Ni, and Mn, and are precious secondary resources. The leaching of spent LIBs using organic acids is considered to be an effective and feasible method for recovering these metals. However, the separation of Li, Co, Ni, and Mn in a solution is difficult to achieve. Using an extractant consisting of 15 % Cyanex272, 10 % tributyl phosphate, and 75 % sulfonated kerosene (v/v) and an organic to aqueous phase ratio of 1:1, over 90.13 % of Al, 95.72 % of Co, and 98.93 % of Mn were extracted. Only 2.05 % of Li and 2.68 % of Ni were co-extracted. The slope method and infrared spectra analysis showed that the extraction processes of Al, Co, and Mn with Cyanex272 follow cationic exchange mechanisms; the acetate anions introduced during the leaching participated in the extraction mechanism of Co. The thermodynamic parameters of Gibb’s free energy, enthalpy change, and entropy change for the extraction reactions were all lower than zero, indicating that the extraction reactions are exothermic and spontaneous and increase the disorder. After washing with NH4HSO4 1 M, most of the Co and Mn were removed, and a negligible amount of Al was lost. By adding 2.5 times the stoichiometric amount of (NH4)2S2O8 to the washing solution and heating at 363.15 K for 40 min, 99.3 % of the Mn was precipitated as MnO2 with a purity of 96.73 %. After removing Mn, Co2+ was precipitated as CoC2O4·2 H2O using anhydrous oxalic acid; Co3O4 with a purity of 98.13 % was subsequently obtained by calcination. This study demonstrates the potential of hydrometallurgical processes for the treatment of spent LIBs and provides insights into strategies for the utilization of secondary resources.

Effective separation of Zn, Fe, and Mn from roasting-water leaching solution of blast-furnace dust using a precipitation-solvent extraction process

Effective separation of Zn, Fe, and Mn from roasting-water leaching solution of blast-furnace dust using a precipitation-solvent extraction process

Separation of Ni(II), Co(II), Mn(II), and Si(IV) from Synthetic Sulfate and Chloride Solutions by Ion Exchange

Separation of Ni(II), Co(II), Mn(II), and Si(IV) from Synthetic Sulfate and Chloride Solutions by Ion Exchange

Solvent Extraction for Separation of 99.9% Pure Cobalt and Recovery of Li, Ni, Fe, Cu, Al from Spent LIBs

In this work, hydrometallurgical recycling of metals from high-cobalt-content spent lithium-ion batteries (LIBs) from laptops was studied using precipitation and solvent extraction as alternative purification processes. Large amounts of cobalt (58% by weight), along with nickel (6.2%), manganese (3.06%) and lithium (6.09%) are present in LiCoO2 and Li2CoMn3O8 as prominent Co-rich phases of the electrode material. The pregnant leach solution (PLS) that was generated by leaching in the presence of 10% H2O2 using 50 g/L pulp density at 80 °C for 4 h contained 27.4 g/L Co, 3.21 g/L Ni, 1.59 g/L Mn and 3.60 g/L Li. The PLS was subjected to precipitation at various pH using 2 M NaOH but the purification performance was poor. To improve the separation of Mn and other impurities and in order to avoid the loss of cobalt and nickel, separation studies were carried out using a solvent extraction technique using di-(2-ethylhexyl) phosphoric acid (D2EHPA) and bis-(2,4,4-trimethylpentyl) phosphinic acid (Cyanex 272). Overall, this study examines the fundamentals of separating and synthesizing 99.9% pure Co sulfate from leach liquor of spent laptop LIBs with remarkably high cobalt content.