Selective leaching of lithium from spent lithium-ion batteries using sulfuric acid and oxalic acid

Traditional hydrometallurgical methods for recovering spent lithium-ion batteries(LIBs)involve acid leaching to simultaneously extract all valuable metals into the leachate.These methods usually are followed by a series of separation steps such as precipitation,extraction,and stripping to separate the individual valuable metals.In this study,we present a process for selectively leaching lithium through the synergistic effect of sulfuric and oxalic acids.Under optimal leaching conditions(leaching time of 1.5 h,leaching temperature of 70°C,liquid-solid ratio of 4 mL/g,oxalic acid ratio of 1.3,and sulfuric acid ratio of 1.3),the lithium leaching efficiency reached89.6%,and the leaching efficiencies of Ni,Co,and Mn were 12.8%,6.5%,and 21.7%.X-ray diffraction(XRD)and inductively coupled plasma optical emission spectrometer(ICP-OES)analyses showed that most of the Ni,Co,and Mn in the raw material remained as solid residue oxides and oxalates.This study offers a new approach to enriching the relevant theory for selectively recovering lithium from spent LIBs.

Recovery of Li, Ni, Co and Mn from spent lithium-ion batteries assisted by organic acids: Process optimization and leaching mechanism

The proper recycling of spent lithium-ion batteries(LIBs)can promote the recovery and utilization of valuable resources,while also negative environmental effects resulting from the presence of toxic and hazardous substances.In this study,a new environmentally friendly hydro-metallurgical process was proposed for leaching lithium(Li),nickel(Ni),cobalt(Co),and manganese(Mn)from spent LIBs using sulfuric acid with citric acid as a reductant.The effects of the concentration of sulfuric acid,the leaching temperature,the leaching time,the solid-liquid ratio,and the reducing agent dosage on the leaching behavior of the above elements were investigated.Key parameters were optimized using response surface methodology(RSM)to maximize the recovery of metals from spent LIBs.The maxim-um recovery efficiencies of Li,Ni,Co,and Mn can reach 99.08%,98.76%,98.33%,and 97.63%.under the optimized conditions(the sulfuric acid concentration was 1.16 mol/L,the citric acid dosage was 15wt%,the solid-liquid ratio was 40 g/L,and the temperature was 83℃ for 120 min),respectively.It was found that in the collaborative leaching process of sulfuric acid and citric acid,the citric acid initially provided strong reducing CO_(2)^(-),and the transition metal ions in the high state underwent a reduction reaction to produce transition metal ions in the low state.Additionally,citric acid can also act as a proton donor and chelate with lower-priced transition metal ions,thus speeding up the dissolution process.

Leaching of vanadium from stone coal with sulfuric acid

The effects of roasting, mass ratio of H2SO4 to stone coal, leaching temperature, liquid-to-solid ratio, grinding fineness of stone coal, and two-stage counter-current leaching on the vanadium leaching ratio were studied. The results show that the vanadium leaching ratio of roasted stone coal through two-stage counter-current leaching can reach 65.1% at the mass ratio of H2SO4 to stone coal of 20%, leaching temperature of 95℃, leaching time of 30 h, liquid-to-solid ratio of 1.1 mL·g^-1, and grinding fineness of 0.1 mm, which can serve as an experimental basis for the production of vanadium from stone coal.

Kinetics of nickel leaching from roasting-dissolving residue of spent catalyst with sulfuric acid

Sulfuric acid leaching process was applied to extract nickel from roasting-dissolving residue of a spent catalyst, the effect of different parameters on nickel extraction was investigated by leaching experiments, and the leaching kinetics of nickel was analyzed. The experimental results indicate that the effects of particle size and sulfuric acid concentration on the nickel extraction are remarkable; the effect of reaction temperature is mild; while the effect of stirring speed in the range of 400-1 200 r/min is negligible. Decreasing particle size or increasing sulfuric acid concentration and reaction temperature, the nickel extraction efficiency is improved. 93.5% of nickel in residue is extracted under suitable leaching conditions, including particle size （0.074-0.100） mm, sulfuric acid concentration 30% （mass fraction）, temperature 80 ~C, reaction time 180 min, mass ratio of liquid to solid 10 and stirring speed 800 r/min. The leaching kinetics analyses shows that the reaction rate of leaching process is controlled by diffusion through the product layer, and the calculated activation energy of 15.8 kJ/mol is characteristic for a diffusion controlled process.

Pressure leaching of zinc silicate ore in sulfuric acid medium

Zinc silicate ore was characterized mineralogically and the results showed that zinc exists mainly as hemimorphite and smithsonite in the sample.Sulfuric acid pressure leaching of zinc silicate ore was carried out to assess the effect of particle size,sulfuric acid concentration,pressure,reaction time and temperature on the extraction of zinc and the dissolution of silica.Under the optimum conditions employed,up to 99.25% of zinc extraction and 0.20% silica dissolution are obtained.The main minerals in leaching residue are quartz and small amounts of undissolved oxide minerals of iron,lead and aluminum are associated with quartz.

Study on mechanisms of different sulfuric acid leaching technologies of chromite

The extraction of chromate from chromite via the sulfuric acid leaching process has strong potential for practical use because it is a simple and environmentally friendly process. This paper aims to study the sulfuric acid leaching process using chromite as a raw material via either microwave irradiation or in the presence of an oxidizing agent. The results show that the main phases in Pakistan chromite are ferrichromspinel, chrompicotite, hortonolite, and silicate embedded around the spinel phases. Compared with the process with an oxidizing agent, the process involving microwaves has a higher leaching efficiency. When the mass fraction of sulfuric acid was 80% and the leaching time was 20 min, the efficiency could exceed 85%. In addition, the mechanisms of these two technologies fundamentally differ. When the leaching was processed in the presence of an oxidizing agent, the silicate was leached first and then expanded. By contrast, in the case of leaching under microwave irradiation, the chromite was dissolved layer by layer and numerous cracks appeared at the particle surface because of thermal shock. In addition, the silicate phase shrunk instead of expanding.

Sulfuric acid leaching of high iron-bearing zinc calcine

Sulfuric acid leaching of high iron-bearing zinc calcine was investigated to assess the effects of sulfuric acid concentration, liquid-to-solid ratio, leaching time, leaching temperature, and the stirring speed on the leaching rates of zinc and iron. The results showed that the sulfuric acid concentration, liquid-to-solid ratio, leaching time, and leaching temperature strongly influenced the leaching of zinc and iron, whereas stirring speed had little influence. Zinc was mainly leached and the leaching rate of iron was low when the sulfuric acid concentration was less than 100 g/L. At sulfuric acid concentrations higher than 100 g/L, the leaching rate of iron increased quickly with increasing sulfuric acid concentration. This behavior is attributed to iron-bearing minerals such as zinc ferrite in zinc calcine dissolving at high temperatures and high sulfuric acid concentrations but not at low temperatures and low sulfuric acid concentrations.

Kinetic study of high-pressure acid leaching of Mg and Ni from serpentine

Inner Mongolian serpentine ore was subjected to sulfuric acid leaching tests,and the effects of the leaching process parameters on the leaching efficiency of different metals were investigated.The leaching efficiency of Mg,Fe,Al,Ni,and Co reaches 93.98%,60.09%,82.08%,90.58%,and 94.06%,respectively,under the leaching conditions of 5 mol/L H_(2)SO_(4),liquid/solid ratio of 4 mL/g,and leaching temperature 100℃.Hence,the valuable metals in serpentine were effectively recovered by sulfuric acid leaching.The leaching behaviors of Mg,Fe,and a small amount of Al were analyzed using X-ray diffraction.The results show that the unreacted Mg and Fe remained as MgFe_(2)O_(4),and Al formed Al_(2)Si_(2)O_(5)(OH)_(4) in the leaching residue.The kinetics of Mg and Ni in the leaching process was studied respectively.The leaching kinetics of Mg conformed to the shrinking core model with an activation energy of 16.95 kJ/mol,which was controlled by the combination of the diffusion and chemical reaction.The leaching kinetics of Ni accorded with the Avrami equation with an activation energy of 11.57 kJ/mol,which was controlled by diffusion.In the study,the valuable metal elements were extracted from serpentine minerals with high efficiency and low cost,which possessed important practical values.

Mechanochemical leaching of chalcopyrite concentrate by sulfuric acid

This study aimed to introduce a new cost-effective methodology for increasing the leaching efficiency of chalcopyrite concentrates at ambient temperature and pressure. Mechanical activation was employed during the leaching（mechanochemical leaching） of chalcopyrite concentrates in a sulfuric acid medium at room temperature and atmospheric pressure. High energy ball milling process was used during the leaching to provide the mechanochemical leaching condition, and atomic absorption spectroscopy and cyclic voltammetry were used to determine the leaching behavior of chalcopyrite. Moreover, X-ray diffraction and scanning electron microscopy were used to characterize the chalcopyrite powder before and after leaching. The results demonstrated that mechanochemical leaching was effective; the extraction of copper increased significantly and continuously. Although the leaching efficiency of chalcopyrite was very low at ambient temperature, the percentages of copper dissolved in the presence of hydrogen peroxide（H2O2） and ferric sulfate（Fe2（SO4）3） after 20 h of mechanochemical leaching reached 28% and 33%, respectively. Given the efficiency of the developed method and the facts that it does not require the use of an autoclave and can be conducted at room temperature and atmospheric pressure, it represents an economical and easy-to-use method for the leaching industry.

Agglomeration and leaching behaviors of copper oxides with different chemical binders

The chemical binder is one of the critical factors affecting ore agglomeration behavior and leaching efficiency.In this study,we in-vestigated the effect of the type of binder and mass fraction of the H_(2)SO_(4)solution used on the curing,soaking,and leaching behavior of ag-glomerations.The results revealed that Portland cement(3CaO·SiO_(2),2CaO·SiO_(2),and 3CaO·Al_(2)O_(3))was the optimal binder for obtaining a well-shaped,stable agglomeration structure.A higher extraction rate was achieved when using Portland cement than that obtained using sodi-um silicate,gypsum,or acid-proof cement.An excessive geometric mean size is not conducive to obtaining well-shaped agglomerations and desirable porosity.Using computed tomography(CT)and MATLAB,the porosity of two-dimensional CT images in sample concentrations L1-L3 was observed to increase at least 4.5vol%after acid leaching.Ore agglomerations began to be heavily destroyed and even to disinteg-rate when the sulfuric acid solution concentration was higher than 30 g/L,which was caused by the excessive accumulation of reaction products and residuals.

Sulfuric acid leaching kinetics of South African chromite

The sulfuric acid leaching kinetics of South African chromite was investigated. The negative influence of a solid product layer constituted of a silicon-rich phase and chromium-rich sulfate was eliminated by crushing the chromite and by selecting proper leaching con- ditions. The dimensionless change in specific surface area and the conversion rate of the chromite were observed to exhibit a proportional re- lationship. A modified shrinking particle model was developed to account for the change in reactive surface area, and the model was fitted to experimental data. The resulting model was observed to describe experimental findings very well. Kinetics analysis revealed that the leach- ing process is controlled by a chemical reaction under the employed experimental conditions and the activation energy of the reaction is 48 kJ.mol-1.

Phase, Microstructure and Beneficiation of Manganese Ore by Acid Leaching

In this research work, sawdust was used as a reducing agent for sulphuric acid leaching of manganese ore from Prang Ghar, Lower Mohmand Agency, Pakistan. X-ray diffraction of the powdered sample indicated the presence of Hausmannite (Mn3O4), Calcium Aluminum Silicate Hydrate, Silica (SiO2) and Hematite (Fe2O3). X-ray diffraction and the energy dispersive spectroscopic analysis show that the manganese ore sample was siliceous in nature. In the present study, six process parameters were investigated i.e. the particle size of the ore, leaching temperature, time duration, Mn ore amount, sulphuric acid concentration and amount of sawdust. Manganese extraction of 88.93 (wt%) was achieved for a leaching time of 60 minutes at 120°C using 5% (v/v) H2SO4 concentration for 10 g Mn ore and 5 g sawdust. The results demonstrate that sawdust is a low cost, renewable and non-hazardous reducing agent in comparison to other available reagents.

Producing High Purity Nickel Metal Powder from Nickel Wastes through Acidic Leaching by Sulfuric Acid

Nickel has found increasing application in electronic,automobile manufacturing,plating,and metal industries and so on.Producing high quality metal powders to satisfy increasing demand for advanced materials is of very high importance.There are a few numbers of standard powder production techniques.An acidic leaching has been applied in present research.Sulfuric acid has been used to leach nickel wastes of plating industry.To produce nickel oxide powder furnaces with no protecting atmosphere and to produce pure nickel powder,tube furnace with hydrogen atmosphere has been applied.Variables performed in the research are time,density of sulfuric acid,and amount of hydrogen peroxide.To analyze powders produced,EDS element analysis and to determine size of powder particles,SEM has been applied.It was shown by the results that the highest amount of nickel dissolution in sulfuric acid(98%)has taken place during one hour and there is a direct relationship between hydrogen peroxide amount and nickel dissolution in sulfuric acid.

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vana-dium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L^-1, a leaching tem-perature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10：1 mL·g^-1, and oxygen pressure at 0.2 MPa, the leaching rate of vana-dium reaches 97.69%.

Pressure acid leaching of zinc sulfide concentrate

Effects of particle size of the zinc sulfide concentrate,leaching temperature,solid-to-liquid ratio and additive amount on pressure acid leaching process of the zinc sulfide concentrate were studied.The results indicate that the additive can improve the reaction kinetics and the conversion rate.And sulfur can be successfully separated from the zinc sulfide concentrate as elemental sulfur.The reasonable experiment parameters are obtained as follows:the leaching temperature 150℃,oxygen partial pressure 1 MPa,additive amount 1%,solid-to-liquid ratio 1:4,leaching time 2 h,initial sulfuric acid concentration 15%,and particle size less than 44μm.Under the optimum conditions,the leaching rate of the zinc can reach 95%and the reduction rate of the sulfur can reach 90%.

Decomposition mechanism of chromite in sulfuric acid–dichromic acid solution

The sulfuric acid leaching process is regarded as a promising, cleaner method to prepare trivalent chromium products from chromite; however, the decomposition mechanism of the ore is poorly understood. In this work, binary spinels of Mg–Al, Mg–Fe, and Mg–Cr in the powdered and lump states were synthesized and used as raw materials to investigate the decomposition mechanism of chromite in sulfuric acid–dichromic acid solution. The leaching yields of metallic elements and the changes in morphology of the spinel were studied. The experimental results showed that the three spinels were stable in sulfuric acid solution and that dichromic acid had little influence on the decomposition behavior of the Mg–Al spinel and Mg–Fe spinel because Mg^(2+), Al^(3+), and Fe^(3+) in spinels cannot be oxidized by Cr^(6+). However, in the case of the Mg–Cr spinel, dichromic acid substantially promoted the decomposition efficiency and functioned as a catalyst. The decomposition mechanism of chromite in sulfuric acid–dichromic acid solution was illustrated on the basis of the findings of this study.

Ultra fast microwave-assisted leaching for the recovery of copper and tellurium from copper anode slime

The decomposition of copper anode slime heated by microwave energy in a sulfuric acid medium was investigated. Leaching experiments were carried out in a multi-mode cavity with microwave assistance. The leaching process parameters were optimized using response surface methodology（RSM）. Under the optimized conditions, the leaching efficiencies of copper and tellurium were 99.56% ± 0.16% and 98.68% ± 0.12%, respectively. Meanwhile, a conventional leaching experiment was performed in order to evaluate the influence of microwave radiation. The mechanism of microwave-assisted leaching of copper anode slime was also investigated. In the results, the microwave technology is demonstrated to have a great potential to improve the leaching efficiency and reduce the leaching time. The enhanced recoveries of copper and tellurium are believed to result from the presence of a temperature gradient due to the shallow microwave penetration depth and the superheating at the solid-liquid interface.

Leaching process and kinetics of manganese in low-grade manganese ore

Manganese was extracted from leaching low-grade manganese ore in sulfuric acid medium. The effects of granule diameter, leaching time, liquid/solid ratio (V/W) and the concentration of sulfuric acid were investigated through orthogonal and single factor experiments. The experimental results showed that the optimal leaching conditions are, size of 0.054mm, 120 minutes of reaction time, 3(V/W) of liquid/solid ratio and 30% of the concentration of sulfuric acid (g/g). Under those conditions, the leaching efficiency is 96.73%. The kinetics of the leaching process is in accordance with the characteristics of fractal reaction.

Recovery of scandium from silicate minerals by high-pressure leaching in sulfuric acid

This study investigated the leaching of scandium from a Sc-bearing silicate ore.The Sc concentrate obtained by beneficiation pre-enrichment has 1.03×10^(−4) wt%Sc and 14.66 wt%Fe.The main Sc-bearing minerals are limonite,chlorite,sericite,and hornblende,in the form of isomorphism.High-pressure leaching(HPL)with sulfuric acid(98 wt%)and NaF was used to dispose this samples.The Sc leaching efficiency of 91.82%was obtained under the optimum conditions,which are pressure of 5.0×10^(5) Pa,A/O value of 1.1,L/S value of 1.8,NaF dosage of 2 wt%,at 130℃ for 6 h.The X-ray diffraction(XRD)and scanning electron microscopy(SEM)results show that the residue is mainly quartz phase in the multihole shape.Compared with ordinary leaching for silicate,high-pressure leaching has significant advantages in saving acid and energy consumption.

Acidithiobacillus ferrooxidans-硫酸酸溶联合浸出金川铜镍硫化矿尾矿砂实验研究

金川铜镍硫化矿尾矿砂富含Cu、Ni和Co等金属,为对其进行回收,对新尾矿库不同深度的尾矿砂分别进行了直接硫酸酸溶浸出与A.f.-硫酸酸溶联合浸出实验,利用ICP-AES分析了不同阶段浸出液中Cu2+、Ni2+、Co2+含量。实验结果表明,A.f.-硫酸酸溶联合浸出工艺对尾矿砂中有价金属Cu、Ni和Co的浸出效果优于单独酸溶浸出工艺。其中,A.f.-硫酸酸溶联合浸出法对1m深度的尾矿砂中Cu、Ni、Co的浸出率最高,分别达到95.78%、98.01%和75.13%,而单独硫酸酸溶作用的离子浸出率分别为75.69%、74.33%和42.33%。