A novel recovery process of metal values from the cathode active materials of the lithium-ion secondary batteries

A novel process was conducted with experiments which separated and recovered metal values such as Co, Mn, Ni and Li from the cathode active materials of the lithium-ion secondary batteries. A leaching efficiency of more than 99% of Co, Mn, Ni and Li could be achieved with a 4 M hydrochloric acid solution, 80 °C leaching temperature, 1 hour leaching time and 0.02 gml^− 1 solid-to-liquid ratio. For the recovery process of the mixture, firstly the Mn in the leaching liquor was selectively reacted and nearly completed with a KMnO₄ reagent, the Mn was recovered as MnO₂ and manganese hydroxide. Secondly, the Ni in the leaching liquor was selectively extracted and nearly completed with dimethylglyoxime. Thirdly, the aqueous solution in addition to the 1 M sodium hydroxide solution to reach pH = 11 allowed the selective precipitation of the cobalt hydroxide. The remaining Li in the aqueous solution was readily recovered as Li₂CO₃ precipitated by the addition of a saturated Na₂CO₃ solution. The purity of the recovery powder of lithium, manganese, cobalt and nickel was 96.97, 98.23, 96.94 and 97.43 wt.%, respectively.     

Leaching of vanadium from carbonaceous shale

The leaching of vanadium from carbonaceous shale using dilute H₂SO₄ was investigated, and the mechanism of leaching determined. The results showed that higher leaching efficiency of vanadium was obtained by increasing initial concentration of H₂SO₄, raising leaching temperature and prolonging leaching time. Addition of ammonium fluoride also enhanced recovery. A recovery of 92% was obtained using a liquid to solid ratio 4:1, initial H₂SO₄ concentration 18%, NH₄F addition 4.8 wt.% of carbonaceous shale, leaching temperature 95 °C and contact time 8 h; the recovery was only 56% without NH₄F. The presence of NH₄F enhanced the leaching of vanadiferous mica.     

Arsenic removal from copper ores and concentrates through alkaline leaching in NaHS media

Removal of arsenic impurity in ores and concentrates containing copper (Cu) through alkaline leaching in NaHS media was investigated in this work. Samples containing Cu from 10 to 40 wt.% and arsenic from 0.8 to 14 wt.% with enargite (Cu₃AsS₄) as main arsenic bearing mineral were used as starting materials and all leaching tests were conducted at 80 °C under normal atmospheric pressure. Solution and/or slurry potential and pH were maintained consistently below − 500 mV (SHE) and above 12.5 respectively with the addition of NaHS and NaOH, creating a reducing environment for arsenic dissolution and conversion of Cu₃AsS₄ to Cu₂S. Pulp density ranged from 100 to 1000 g/L, NaHS and NaOH reagents were added at 50–200 g/L each and leaching time varied from 10 min to 10 h.Characterization of solid samples (original and leach residue) by XRD and XRF analyses and chemical analysis of both solid and solution samples by ICP analysis showed that Cu₃AsS₄ in the starting material was completely decomposed or transformed to Cu₂S and arsenic released into solution as As (III)/As³⁺ ions (Na₃AsS₃). Over 90% of arsenic in the starting materials was removed within 1–3 h for materials with arsenic content from 1 to 4 wt.% and within 3–6 h for materials with arsenic content over 4–10 wt.%. Dissolution and analysis of leach residues obtained after leaching by ICP indicated that arsenic in the starting materials has been reduced in all cases to below 0.5 wt.%. In all test conditions dissolution of Cu and Fe into solution was not detected, indicating selective leaching of arsenic. NaHS application for removal of arsenic in Cu-ores and/or concentrates was demonstrated in this work and further research is in progress to develop a process to include treatment of arsenic leached into solution.     

La2O2CO3 supported Ni-Fe catalysts for hydrogen production from steam reforming of ethanol

La2O2CO3 was prepared by calcination of La2 (CO3)3 in the air. Catalysts Ni-Fe/La2O2CO3 with different mole ratios of Ni to Fe, Ni/La2O2CO3 and Fe/La2O2CO3 were prepared by impregnation method. The catalytic properties were evaluated on steam reforming of ethanol (SRE) from 300 to 700 ℃ under atmospheric pressure and the samples were characterized by Brunauer-Emmett-Teller method (BET), X-ray diffraction (XRD) and temperature programmed reduction (TPR). The results showed that Ni-Fe bimetallic catalysts exh...     

Reductive leaching of manganese from low-grade manganese ore in H2SO4 using cane molasses as reductant

Manganese extraction from a low-grade ore was investigated using cane molasses as a reducing agent in dilute sulfuric acid medium. The effects of concentrations of cane molasses and sulfuric acid, leaching temperature as well as reaction time were discussed. The results showed that high manganese recovery with low Fe and Al extraction yield could be obtained by analyzing the leaching efficiencies of Mn, Fe and Al during the leaching process. The optimal leaching condition was determined as 1.9 mol/L H₂SO₄ and 60.0 g/L cane molasses for 120 min at 90 °C while using particles smaller than 0.147 mm. The leaching efficiencies were 97.0% for Mn, whereas 21.5% for Al and 32.4% for Fe, respectively.     

Soda ash roasting of titania slag product from Rosetta ilmenite

A soda ash roasting process for upgrading titania slag product of Rosetta ilmenite to a high grade titanium dioxide (TiO₂) is presented. The roasting process was carried out at moderate to high temperatures to yield a reaction product that would be easily decomposed by subsequent leaching procedures. Factors affecting the roasting process; namely the soda ash ratio to the slag material, the roasting time and temperature were studied. The optimised conditions used a Na₂CO₃ to slag ratio of 0.55:1 at a roasting temperature of 850 °C for 0.5 h duration period. The impurities associated with the roasted slag were subjected to leaching with water and dilute hydrochloric acid solution leaving synthetic rutile (TiO₂) as insoluble residue. To improve the quality of the synthetic rutile, an alkaline leaching step was added to remove the excess silica present in the treated titania slag. This method is capable of producing high purity synthetic rutile assaying about 97% TiO₂.     

Effect of metal doping into Ce0.5Zr0.5O2 on catalytic activity of MnOx/Ce0.5–xZr0.5–xM0.2xOy/Al2O3 for benzene combustion

The research investigated the effect of doping two metals separately or together into Ce0.5Zr0.5O2 on the catalytic activity of MnOx/Ce0.5-xZr0.5-xM0.2xOy/Al2O3 （M=Y, Mn, Y and Mn） for catalytic combustion of benzene. The prepared catalysts were characterized by X-ray diffraction （XRD）, surface area analysis, oxygen storage capacity （OSC）, and H2-temperature programmed reduction （H2-TPR）. Catalytic test was performed on a conventional fixed bed flow reactor. The characterization results revealed that Y and Mn ions entered into the ceria-zirconia mixed oxides framework, which improved the textural properties and greatly promoted the MnOx dispersion on the support surface. The complete conversion temperature of benzene on MnOx/Ce0.4Zr0.4Y0.1Mn0.1Oy/Al2O3 was 563 K, and the selectivity of carbon dioxides was 99%. This catalyst could be applied in a wide range of GHSV and wide concentration condition, showing great potential for application.     

Autoclave processing of the products of catalytic synthesis of industrial diamonds

A process is developed for the autoclave leaching of nickel and manganese with sulfuric acid from the products of catalytic synthesis of industrial diamonds containing 20% Ni and 30% Mn. The optimum conditions for the autoclave processes are determined to be as follows: the temperature range is 150–160°C, the solution acidity is 5 N H₂SO₄ (230–240 g/l), the leaching duration is 2 h, and the number of processing steps is two. The extraction of the metals into a solution under these conditions is >99% for a total Ni + Co content of <0.4–0.5% in the autoclave leaching cake. The studies performed are related to the search for alternative ways of the catalytic preparation of industrial diamonds that can replace the nonferrous metal leaching technology using aqua regia solutions, which is mainly applied for these purposes under industrial conditions.     

Dissolution kinetics of spent petroleum catalyst using two different acidophiles

Leaching studies using spent petroleum catalyst containing Ni, V and Mo were carried out using two different acidophiles, iron oxidizing (IOB) and sulfur oxidizing (SOB) bacteria. XRD analysis proved the existence of V in oxide form, Ni in sulfide form, Mo both in oxide and sulfide forms, and sulfur in elemental state. Both bacteria showed similar leaching kinetics at the same leaching parameters, such as pH, nutrient concentration, pulp density, particle size and temperature. The dissolution kinetics for Ni and V was much higher than Mo. Bioleaching kinetics was observed to follow dual rates, initially faster followed by a slower rate. So, dissolution mechanism was based on surface- and pore-diffusion rate. The dissolution process was found to follow 1st order kinetics. Unified dissolution rate kinetics equations were developed using 1st order rate kinetics. Various thermodynamic parameters were also calculated. Rate determining step for both the bacteria were evaluated and the average D₁ (surface) and D₂ (pore) values were found to be around 7 × 10^− 9 and 1 × 10^− 10 cm² respectively. The lower value of D₂ suggested that the pore diffusion is the rate determining step during bioleaching process.     

Effect of alloying by transitional refractory metals on the microstructure and thermal stability of Al–5Zn–3Mg alloys

Abstract

The effect of additions of transitional refractory metals on the structure and properties of Al–Zn–Mg alloys, made by ingot and PM routes, was investigated. The strength of the ingot alloys especially is increased by scandium and zirconium. The modifying action of scandium inhibits recrystallisation and precipitation of the fine-grained coherent Al₃(Sc_1–xZr_x) phase. The effect is weaker in PM alloys where the ultra-high cooling rate during high pressure water atomisation produces the fine-grained structure. PM semi-products of the base composition Al–5Zn–3Mg and alloys without scandium are not recrystallised during heating to 500°C, whereas cast alloys of similar composition recrystallised on the hot extrusion stage at 400–450°C. Of the Sc alloys, Al–5Zn–3Mg–0·5Mn–0·7Zr–0·3Sc showed the highest strength (UTS?=?651 MPa, YS?=?596 MPa), whereas of the PM alloys without scandium Al–5Zn–3Mg–0·85Zr–0·22Cr–0·17Ni–0·15Ti alloy showed UTS?=?618 MPa and YS?=?553 MPa. At melt cooling rates of 10⁵–10⁶ K s^–1 the total content of transitional refractory metals must not exceed 1·5–1·7 wt-% and total content (Zn+Mg) should be <8 wt-% at a Zn/Mg ratio of 5:3.     

Comparative study of inorganic arsenic resistance of several strains of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans

The growth characteristics of several strains of Acidithiobacillus thiooxidans and Acidithiobacillus ferrooxidans were studied in the presence of soluble inorganic arsenic(III) and (V) with regard to media pH changes, total bacterial populations and sulfur oxidation rates. Most of these bacteria could reach large populations and have strong sulfur oxidation activity in the absence of arsenic. However, in the presence of up to 120 mM arsenite or arsenate, different strains showed different inorganic arsenic resistance. A. thiooxidans LYS and A. ferrooxidans BY-3 were two of the best performers which showed high arsenite resistance: up to 80 mM and 60 mM, respectively. On the other hand, A. thiooxidans JY and A. ferrooxidans TKY-2 could adapt up to 120 mM and 100 mM arsenate, respectively. These bacteria strains may play key roles in the bioleaching of arsenopyrite or in the bio-oxidation pretreatment of arsenic-bearing refractory gold sulfide ores and concentrates.     

Stability of 3CaO · Al2O3 · 6H2O in KOH + K2CO3 + H2O system for chromate production

In the novel clean chromate production process, the alkali liquor recycled to decompose the chromite ore mainly consists of KOH and K₂CO₃ which accumulates aluminium impurity and affects the quality of the product greatly. Aluminium impurity can be removed by adding CaO to precipitate as 3CaO · Al₂O₃ · 6H₂O (C₃AH₆). A study of the effects of various parameters, such as KOH concentration, K₂CO₃ concentration and temperature on the behaviour of C₃AH₆ show that C₃AH₆ is decomposed to 3CaO · Al₂O₃ · CaCO₃ · 11H₂O and CaCO₃ below 150 g L^− 1 KOH, and decomposed to Ca(OH)₂ above 150 g L^− 1 KOH. With K₂CO₃ concentration increasing, C₃AH₆ decomposes significantly, which results in more CaCO₃ or 3CaO · Al₂O₃ · CaCO₃ · 11H₂O produced. Temperature has a large positive effect on the decomposition of C₃AH₆ at 45 g L^− 1 KOH but has no significant effect at 150 g L^− 1 KOH. The optimal condition for removing aluminium impurity in the KOH + K₂CO₃ + H₂O system is 150 g L^− 1 KOH, 50 g L^− 1 K₂CO₃ and 80 °C.     

Leaching of a sphalerite concentrate with H2SO4–HNO3 solutions in the presence of C2Cl4

The enhanced leaching of sphalerite concentrates in H₂SO₄–HNO₃ solutions and the extraction of sulfur with tetrachloroethylene were studied. Variables of the process were investigated including leaching temperature, reaction time, liquid / solid ratio, and tetrachloroethylene concentration. The number of cycles that tetrachloroethylene could be recycled did not have a significant effect on zinc extraction. The results indicated that 99.6% zinc extraction was obtained after three hours of leaching at 85 °C and 0.1 MPa O₂, when 20 g of sphalerite concentrate were leached in a 200 ml solution containing 2.0 mol/L H₂SO₄ and 0.2 mol/L HNO₃, in the presence of 10 ml C₂Cl₄. Leaching rates were significantly improved under these conditions.     

Ionic conduction in BaxCe0.8Pr0.2O3-

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Preparation and thermoelectric properties of ternary rare earth sulfide γ-Ce3–xEuxS4

The effect of Eu-substitution on the density and thermoelectric properties of ternary sulfide Ce_3–xEu_xS₄ (0≤x≤0.8) compacts was investigated. Ce_3–xEu_xS₄ powders were prepared via the sulfurization of the oxide using CS₂ gas at 1473 K. The pressureless sintered Ce_3–xEu_xS₄ compacts in the atmosphere were crystallized in the γ-phase. The density of the Ce_3–xEu_xS₄ compacts increased with the increasing of Eu-substitution. Eu-substitution yielded a higher Seebeck coefficient and lower electrical resistivity. The highest value of the thermoelectric power factor of 1.41×10⁻⁴ W/K²m was obtained for the Ce_2.2Eu_0.8S₄ compact at 673 K. It indicated that Eu-substitution was effective for improving thermoelectric properties of Ce_3–xEu_xS₄.     

Sulphuric acid leaching of polymetallic nodules using paper as a reductant

Sulphuric acid leaching of manganese nodule for extraction of Cu, Ni, Co and Mn in presence of a novel cellulosic reductant, waste newspaper, has been reported. The various parameters chosen for the study were: time, temperature, H₂SO₄ concentration and amount of paper. To quantify the linear and interaction coefficients a 2³ full factorial design of experiments was followed. The regression equations were determined and the adequacy of these equations was tested by Fischer’s test. The linear coefficients for time, acid concentration and amount of paper were found to be significant for extraction of Cu, Ni, Co and Mn. While acid concentration and amount of paper showed positive interactions for Cu, Ni and Co extractions it had negative significance for Mn dissolution. Under the conditions for >97% extraction of metal values iron extraction was ∼40%. In order to reduce the iron contamination by discarding iron as jarosite effect of addition of ammonium sulphate during leaching was also studied. Iron extraction could be brought down to 14% from ∼40% with the addition of 30g/L (NH₄)₂SO₄ without affecting the recoveries of other metals.     

Kinetics of sphalerite bioleaching by Acidithiobacillus ferrooxidans

In the present study, the effect of some important parameters including particle size, pulp density and temperature on the rate of Zn dissolution from sphalerite concentrate by Acidithiobacillus ferrooxidans was investigated. The highest rate of sphalerite bioleaching was obtained at particle size, pulp density and temperature of 38–150 μm, 4% wt/vol and 33 °C respectively. The formation of a product layer over sphalerite concentrate particles was confirmed by SEM images whereas XRD, EDS and BET analysis showed that this layer is composed of elemental sulfur and is non-porous. Based on these results, it was decided that a kinetic model in which the rate of Zn dissolution is limited by diffusion of ions through a non-porous product layer is appropriate to describe the sphalerite bioleaching process. Determinations of ferrous iron ion concentration during bioleaching showed that the concentration of this ion varies significantly during bioleaching and hence the kinetic model was revised to take account of this fact. The predictions of this model had a good compatibility with the experimental data and the value of activation energy was determined as 39 kJ/mol.     

Leaching of silica from vanadium-bearing steel slag in sodium hydroxide solution

The work aims to selectively extract silica from vanadium-bearing steel slag by a leaching process. The effects of the particle size, the ratio of solid to liquid, the concentration of sodium hydroxide solution and the leaching temperature on the leaching behavior of silica from vanadium-bearing steel slag were investigated. The leaching kinetics of silica from vanadium-bearing steel slag in 30-50% w/w NaOH solutions was studied at 240 °C and the shrinking-core model was established to express the leaching kinetics of silica. The data showed that the leaching rate was controlled by the chemical reaction on the system interface and the activation energy for the process was found to be 36.4 kJ mol^− 1. By the leaching process, the majority of silica could be removed effectively from the vanadium-bearing steel slag and a residue with a low SiO₂ content of 4.28% and a high V₂O₅ content of 11.15% was obtained. Under these conditions there was partial dissolution of Al and slight dissolution of Cr, Mn and Ti.     

Leaching of niobium and tantalum from a low-grade ore using a KOH roast–water leach system

A new process is proposed for the leaching and recovery of niobium and tantalum from a low-grade refractory niobium–tantalum ore after adding pure Nb₂O₅ to adjust the niobium to tantalum ratio. The ore was roasted and decomposed with KOH then leached with water. Experiments were carried out to study the effect of the Nb₂O₅-to-Ta₂O₅ mass ratio, decomposition temperature, alkali-to-ore mass ratio and decomposition time on the leaching of niobium and tantalum, as well as the associated impurity elements, such as titanium, iron, manganese, silicon and tin. The optimal conditions were determined to be: Nb₂O₅-to-Ta₂O₅ mass ratio 2.33:1; KOH-to-ore mass ratio 2:1; reacting for 60 min at 400 °C. Leaching with water extracted ~ 95% Nb and 94% Ta together with about 80% Si and Sn, 50% Ti and < 20% Fe and Mn. The niobium and tantalum was recovered as high purity (Nb,Ta)₂O₅ (99.3%) through evaporation, crystallization and phase transformation processes.     

Thermal physical properties and dephosphorisation kinetics of rare earth oxides containing slags

ABSTRACT

The melting properties and viscosity of CaO–SiO₂–MnO–La₂O₃–CeO₂ slags, with mass ratios of 0.97 and 1.05 between CaO and SiO₂, were measured using the hot stage microscopy method and rotating cylinder method, respectively. In addition, the dephosphorisation kinetics of rare earth (RE) oxides containing slags was studied. For increasing mass contents of the RE oxides, La₂O₃ and CeO₂ (0, 3, 6, 9, and 12?wt.%), in the slag, the melting temperature initially decreases and then increases. Minimum values appeared for mass contents of 6?wt.%. RE oxide concentrations below 9?wt.% are beneficial to the decrease in viscosity, which increases significantly with the mass fraction of RE oxides in molten slags with a basicity of 1.05. In slags with a basicity of 0.97, the RE oxides favour the decrease in viscosity, which does not change noticeably as their mass fraction is increased above 6?wt.%. Finally, it was found that the rate-limiting step of the dephosphorisation process is the diffusion of phosphorus.