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.

The impacts of ambiguity in preparation of 80% sulfuric acid solution and shaking time control of calibration solution on the determination of transparent exopolymer particles

The quantification of transparent exopolymer particles(TEP) by colorimetric method is of large error and low repeatability,one major reason of which is related to the absence of clear definition and evaluation for part steps of the original method.It is obscure that the 80% sulfuric acid solution,acted as the extraction solution in the determination of TEP,is prepared based on a volume ratio or mass ratio.Furthermore,the change of solubility of recently available Gum Xanthan(GX) from the market means that the original protocol is no longer applicable,and the grinding of GX stock solution with a tissue grinder is replaced by shaking with a rotating shaker in the study to prevent the excessive dissolution of GX.We found that different preparation techniques could result in the varied concentrations of 80% H_(2)SO_(4).The duration of shaking during the preparation of standard solution significantly affected the slope of the calibration curve,which caused different correction results of TEP.The impacts of different extraction solution concentrations and shaking time of GX solution on the quantification of TEP were investigated based on the field sampling and laboratory analysis.The extraction capacities of H_(2)SO_(4) with different concentrations for Alcian Blue were distinct,but had limited effect on the final measuring result of TEP.The change of the standard curve slope came along with the variation of shaking time,which markedly altered the detection limit and calibration result,and the extended shaking time was in favor of the determination of low-concentration TEP.It was suggested that the extraction solution concentration,shaking time and filtration volume of standard solution are required to be well controlled and selected to obtain more accurate results for TEP with different concentrations.

Reaction kinetics of roasting high-titanium slag with concentrated sulfuric acid

A novel method of roasting high-titanium slag with concentrated sulfuric acid was proposed to prepare titanium dioxide, and the roasting kinetics of titania was studied On the basis of roasting process. The effects of roasting temperature, particle size, and acid-to-ore mass ratio on the rate of roasting reaction were investigated. The results showed that the roasting reaction is fitted to a shrinking core model. The results of the kinetic experiment and SEM and EDAX analyses proved that the reaction rate of roasting high-titanium slag with concentrated sulfuric acid is controlled by the internal diffusion on the solid product layer. According to the Arrhenius expression, the apparent activation energy of the roasting reaction is 18.94 kJ/mol.

Theoretical Studies on Mechanism and Rate Constant of Gas Phase Hydrolysis of Glyoxal Catalyzed by Sulfuric Acid

The gas phase hydration of glyoxal （HCOCHO） in the presence of sulfuric acid （H2SO4） were studied by the high-level quantum chemical calculations with M06-2X and CCSD（T） theoretical methods and the conventional transition state theory （CTST）. The mechanism and rate constant of the five different reaction paths are consid- ered corresponding to HCOCHO＋H2O, HCOCHO＋H2O… H2O, HCOCHO… H2O＋H2O, HCOCHO＋H2O… H2SO4 and HCOCHO… H2O＋H2SOa. Results show that H2SO4 has a strong catalytic ability, which can significantly reduce the energy barrier for the hydration reaction of glyoxal. The energy barrier of hydrolysis of glyoxal in gas phase is lowered to 7.08 kcal/mol from 37.15 kcal/mol relative to pre-reactive complexes at the CCSD（T）/6- 311＋＋G（3df, 3pd）//M06-2X/6-311＋＋G（3df, 3pd） level of theory. The rate constant of the H2SO4 catalyzed hydrolysis of glyoxal is 1.34×10-11 cm3/（molecule.s）, about 1013 higher than that involving catalysis by an equal number of water molecules, and is greater than the reaction rate of glyoxal reaction with OH radicals of 1.10×10-11 cm3/（molecule·s） at the room temperature, indicating that the gas phase hydrolysis of glyoxal of H2SO4 catalyst is feasible and could compete with the reaction glyoxal＋OH under certain atmospheric condi- tions. This study may provide useful information on understanding the mechanistic features of inorganic acid-catalyzed hydration of glyoxal for the formation of oligomer.

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.

STUDY ON CONCENTRATING SULFURIC ACID SOLUTION BY VACUUM MEMBRANE DISTILLATION

Concentrating sulfuric acid solution by vacuum membrane distillation with flat PEFE membrane is explored. The effects of sulfuric acid concentration, temperature of the feed, the vacuum degree of the vacuum side on the flux of membrane distillation and the separation efficiency of acid are investigated. The results illustrate that the flux of the membrane distillation increases with the rise of feed temperature and the vacuum degree of the vacuum side, but it decreases with the rise of the sulfuric acid concentration of the feed. The separation efficiency of acid is correlated with the flux of membrane distillation; the separation efficiency of the acid can amount to 100% in the process, when operative conditions are properly controlled. It can also been obtained from the experiment that, compared with other methods of membrane distillation, the vacuum membrane distillation can obtain greater distillation flux.

Solvent extraction of vanadium from sulfuric acid solution

The behaviour of vanadium（V） extracted from sulfuric acid solution was investigated using Cyanex 923 as an extractant. The effects of the concentration of Cyanex 923 and the pH of the solution were studied. The extraction of vanadium（V） increases with the increase of Cyanex 923 concentration and shaking time. Cyanex 923 can extract vanadium（V） from sulfuric acid solution at low pH conditions, and the best pH conditions for extraction of vanadium（V） are at pH 1.0-2.0. The species extracted into the organic phase is VO2HSO4 with one molecule of Cyanex 923. Equilibrium studies were used to assess the extraction efficiency of vanadium（V） recovery from the sulfuric acid solution.

ACID RECOVERY FROM WASTE SULFURIC ACID BY DIFFUSION DIALYSIS

In the process of sulfuric acid production from pyrite, there is a lot of waste acid produced in fume washing with dilute acid. Acid recovery from this sort of waste sulfuric acid by diffusion dialysis is studied in the paper. The mass transfer dialysis coefficient of sulfuric acid of the membrane AFX is measured, the effect of the flowrate of the feed and ratio of feed to water is investigated, and the two kinds of membrane (AFX and S203) are compared. The results show that diffusion dialysis process can separate the metal cation from sulfuric acid effectively, but it is difficult to separate non cation impurities as As - and F -. The contrast tests of the two membranes show that the dialysis mass transfer coefficient of the membrane AFX is larger, while capacity of the removing impurities of membrane S203 is somewhat better.

Amelioration of Saline-Sodic Soils with Tillage Implements and Sulfuric Acid Application

Amelioration of saline-sodic soils through land preparation with three tillage implements （disc plow, rotavator and cultivator） each followed by application of sulfuric acid at 20% of gypsum （CaSO4-2H2O） requirement or no sulfuric acid application during crop growth period was evaluated in a field study for 2.5 years at three sites, i.e., Jhottianwala, Gabrika （Thabal）, and Thatta Langar, in Tehsil Pindi Bhattian, Hafizahad District, Pakistan. Within 2.5 years, there was a decrease in the salinity parameters measured （electrical conductivity, pH, and sodium adsorption ratio）, with a gradual increase in rice and wheat grain yields. It was observed that the disc plow, which not only ensured favorable yields but also helped improve soil health at all the three sites, was the most effective tillage implement. Also, application of sulfuric acid resulted in higher yields and promoted rapid amelioration of the saline-sodic soils.

Synergistic extraction of cerium from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester and Di-(2-ethyl hexyl) phosphoric acid as extractant

Synergistic extraction of cerium（IV） from sulfuric acid medium using mixture of 2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester（HEH/EHP, HL） and Di-（2-ethyl hexyl） phosphoric acid（HDEHP, HA） as extractant was investigated.The results indicated that the maximum synergistic enhancement coefficients were obtained at the mole fraction of HEH/EHP=0.6, and cerium（IV） was extracted into organic phase in the form of Ce（SO4）0.5HL2A2.A cation exchange mechanism was proposed for the synergistic extraction of Ce（IV）.The equilibrium constants and thermodynamic functions such as △G, △H, and △S were determined in the extraction of Ce（IV） from sulfuric medium using mixture of HEH/EHP and HDEHP.

Formation and Oxidation of Hydrogen Molybdenum Bronze on Platinum Electrode in Sulfuric Acid Solution

Hydrogen molybdenum bronze (HxMoO3) can be electrodeposited on platinum and oxidized in two steps to the hydrogen molybdenum bronze with less amount of hydrogen HyMoO3 (y<x) and MoO3 when platinum electrode is cycled from -0.2 to 1.3V (vs. SCE) in 0.05 mol/L Na2MoO4 + 0.5 mol/L H2SO4 solution. During the formation of HxMoO3, the electrochemical reduction of molybdate existing in the form of polymolydate is reversible and is about a five-electron transfer reaction.

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.

Chemical dehydration coupling multi-effect evaporation to treat waste sulfuric acid in titanium dioxide production process

In order to concentrate the diluted sulfuric acid from the titanium dioxide(TiO2)production of sulphate process,a new concentration process was proposed by coupling chemical dehydration and multi-effect evaporation.The ferrous sulfate monohydrate(FeSO4·H2O),as the dehydrant,was added to the diluted sulfuric acid to form ferrous sulfate heptahydrate(FeSO4·7H2O)according to the H2SO4-FeSO4-H2O phase diagrams,which partially removes the water.This process was named as Chemical Dehydration Process.The residual water was further removed by two-effect evaporation and finally 70 wt%sulfuric acid was obtained.The FeSO4·H2O can be regenerated through drying and dehydration of FeSO4·7H2O.The results show that FeSO4·H2O is the most suitable dehydrant,the optimal reaction time of chemical dehydration process is 30 min,and low temperature is favorable for the dehydration reaction.45.17%of the entire removed water can be removed by chemical dehydration from the diluted sulfuric acid.This chemical dehydration process is also energy efficient with 24.76%saving compared with the direct evaporation process.Furthermore,51.21%of the FeSO4 dissolved originally in the diluted sulfuric acid are precipitated out during the chemical dehydration,which greatly reduces the solid precipitation and effectively alleviates the scaling in the subsequent multi-effect evaporation process.

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.

Mechanism explanation for SO_2 oxidation rate of Cs-Rb-V series sulfuric acid catalyst at low temperature

The reaction kinetics of SO 2 oxidation on Cs Rb V series sulfuric acid catalyst promoted by alkali salts such as cesium and rubidium was studied. A three step reaction mechanism of SO 2 oxidation was proposed, in which it was assumed that oxidation of quadrivalent vanadium complex was a controlling step. Then, a mechanism model equation was concluded according to the three step reaction mechanism. The SO 2 oxidation rate was measured with a non gradient reactor under the conditions of temperature of 380～520?℃ and space velocity of 3?600～7?200?h -1 . Through calculating with Powell nonlinear regression method, the parameters of model equation were obtained: K 1=0.152?exp(-62?073/ (RT) ), K 2=8.18?exp(-2?384/ (RT) ), K 3=0.221?exp(-18?949/ (RT) ). It was found that the model equation could fit with all the experimental reaction rate data very well. [

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.

Hydraulic and carbonizing actions of sulfuric acid to straw pulp and paper black liquor

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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.

Effect of hydrolysis conditions on hydrous TiO_2 polymorphs precipitated from a titanyl sulfate and sulfuric acid solution

The relationship between hydrolysis conditions and hydrous titania polymorphs obtained in a titanyl sulfate and sulfmic acid solu- tion was investigated by X-ray diffraction （XRD）, scanning electron microscopy （SEM）, and high-resolution transmission electron micros- copy （HRTEM）. The results revealed that the feeding rate of the titanyl sulfate stock solution, the concentration of sulfi.Lric acid, and the seed dosage of mtile crystal could significantly affect the hydrolysis rate, thus influencing the titania crystal phase. Hydrous TiO2 in the form of rutile, anatase, or the mixture of both could be obtained in solutions of low titanium concentrations and 2.5wt% to 15wt% sulfuric acid at 100℃. When the hydrolysis rate of titanitma expressed by TiOa was more than or equal to 0.04 g/（L.min）, the hydrolysate was almost phase-pure anatase, while the main phase state was rutile when the hydrolysis rate was less than or equal to 0.01 g/（L.min）. With the hy- drolysis rate between 0.02 and 0.03 g/（L.min）, the hydrolysate contained almost equal magnitude ofrutile and anatase. It seems that although rutile phase is thermodynamically stable in very acidic solutions, anatase is a kinetically stable phase.

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.