Kinetics of solid-state reduction of chromite overburden

The demand for alternative low-grade iron ores is on the rise due to the rapid depletion of high-grade natural iron ore resources and the increased need for steel usage in daily life.However,the use of low-grade iron ores is a constant clinical task for industry metallurgists.Direct smelting of low-grade ores consumes a substantial amount of energy due to the large volume of slag generated.This condition can be avoided by direct reduction followed by magnetic separation(to separate the high amount of gangue or refractory and metal parts)and smelting.Chromite overburden(COB)is a mine waste generated in chromite ore processing,and it mainly consists of iron,chromium,and nickel(<1wt%).In the present work,the isothermal and non-isothermal kinetics of the solid-state reduction of self-reduced pellets prepared using low-grade iron ore(COB)were thoroughly investigated via thermal analysis.The results showed that the reduction of pellets followed a firstorder autocatalytic reaction control mechanism in the temperature range of 900-1100℃.The autocatalytic nature of the reduction reaction was due to the presence of nickel in the COB.The apparent activation energy obtained from the kinetics results showed that the solid-state reactions between COB and carbon were the rate-determining step in iron oxide reduction.

Petrogenesis of the Neoarchean zincian chromite within ultramafic xenoliths,Bastar Craton,India

The present study reports and discusses the genesis of zincian chromite in the ultramafic xenoliths from the Dongripali area,Bastar craton,Central India.The zincian chromite is in the ultramafic xenoliths of Bengpal supracrustal rock hosted by Neoarchaean Bundeli gneisses.Compositionally zincian chromite shows a range of Cr_(2)O_(3)(39.69 to 51.66 wt%),Al_(2)O_(3)(05.30 wt%to 08.71 wt%),FeO(21.74 wt%to 27.51 wt%),Fe_(2)O_(3)(10.19 wt%to 19.36wt%)with higher ZnO content ranging from 1.73 wt%to 4.08 wt%.Accordingly,their Cr#[Cr/(Cr+Al)]varies in a narrow range from 0.83 to 0.85.Its calculated melt composition supports metamorphic or post-magmatic nature rather than common occurrences such as inclusion in diamonds,meteorites,and association with any sulfide-rich mineralised belt.This reveals that the post-magmatic processes play a vital role in transforming chromite to zincian chromite.The empirical thermometric calculation from chromite,amphibole,and pyroxene support their metamorphic origin and formed during low-P and high-T amphibolite grade facies of metamorphism(~700℃).The Neoarchaean granitic magmatism has a significant role in generating and transferring the heat during contact metamorphism with hydration of ultramafic xenoliths and further alteration,i.e.,serpentinisation.The olivine is a major repository for Mn,Zn,and Co in peridotite/ultramafic;these elements get mobilised during the metamorphism and serpentinisation.This is a possible reason for the mobilisation of zinc and incorporation in the chromite within altered ultramafic.As a result,chromiterich ultramafic xenolith subjected to metamorphic process gets enrichment of Zn and Fe due to elemental exchange.It converts common chromite into zincian chromite,as reported in altered ultramafics elsewhere.

New Data on the Mineralogy of Chromite from the Nuggihalli Schist Belt,Western Dharwar Craton,Karnataka,India:Petrogenetic Implications

The occurrence of rhythmic layering of chromite and host serpentinites in the deformed layered igneous complexes has been noticed in the Nuggihalli schist belt （NSB） in the western Dharwar craton, Karnataka, South India. For this study, the chromitite rock samples were collected from Jambur, Tagadur, Bhakatarhalli, Ranganbetta and Byrapur in the NSB. Petrography and ore microscopic studies on chromite show intense cataclasis and alteration to ferritchromite. The ferritchromite compositions are characterized by higher Cr number （Cr/[Cr＋AI]） （0.68-0.98） and lower Mg number （Mg/[Mg＋Fe]） （0.33-0.82） ratios in ferritchromite compared to that of parent chromite. The formation process for the ferritchromite is thought to be related to the exchange of Mg, AI, Cr, and Fe between the chromite, surrounding silicates （serpentines, chlorites）, and fluid during serpentinization.

Origin of Listwanite in the Luobusa Ophiolite,Tibet,Implications for Chromite Stability in Hydrothermal Systems

Listwanite from the Luobusa ophiolite, Tibet, forms a narrow, discontinuous band along the eastern part of the southern boundary fault. We undertook a detailed petrographic and geochemical study to understand the mineral transformation processes and the behaviour of major and trace elements during listwanite formation. Three alteration zones characterized by distinct mineral components and texture are recognized and, in order of increasing degree of alteration, these are： zonem is rich in serpentine minerals; zonen is rich in talc and carbonates; and zone_Ⅰ is mainly composed of carbonates and quartz. Geochemical data for the three alteration zones show significant modification of some major and trace elements in the protolith, although some oxides show linear correlations with MgO. Gold mineralization is recognized in the Luobusa listwanite and may signify an important target for future mineral exploration. Gold enrichment occurs in both zone_Ⅰ and zone_Ⅱ and is up to 0.91 g/t in one sample from zonei. We show that CO_2-rich hydrothermal fluids can modify both the occurrence and composition of chromite grains, indicating some degree of chromite mobility. Low-Cr anhedral grains are more easily altered than high-Cr varieties. The compositions of chromite and olivine grains in the listwanite suggest a dunite protolith.

Thermodynamics of chromite ore oxidative roasting process

To explicate the thermodynamics of the chromite ore lime-free roasting process, the thermodynamics of reactions involved in this process was calculated and the phrases of sinter with different roasting times were studied. The thermodynamics calculation shows that all the standard Gibbs free energy changes of the reactions to form Na2CrO4, Na2O-Fe2O3, Na2O·Al2O3 and Na2O3 SiO2 via chromite ore and Na2CO3 are negative, and the standard Gibbs free energy changes of the reactions between MgO, Fe2O3 and SiO2 released from chromite spinel to form MgO-Fe2O3 and MgO·SiO2 are also negative at the oxidative roasting temperatures （1 173 1 473 K）. The phrase analysis of the sinter in lime-free roasting process shows that Na2O·Fe2O3, Na2O·Al2O3 and Na2O·SiO2 can be formed in the first 20 min, but they decrease in contents and finally disappear with the increase of roasting time. The final phase compositions of the sinter are Na2CrO4, MgO·Fe2O3, MgO·SiO2 and MgO. The results indicate that Na2CrO4 can be formed easily via the reaction ofNa2CO3 with chromite ore. Na2O·Fe2O3, Na2O-Al2O3 and Na2O·SiO2 can be formed as intermediate compounds in the roasting process and they can further react with chromite ore to form Na2CrO4. MgO released from chromite ore may react with iron oxides and silicon oxide to form stable compounds of MgO·Fe2O3 and MgO·SiO2, respectively.

Carbothermic reduction of chromite fluxed with aluminum spent potlining

Aluminum spent potlining (SPL) was employed as both the fluxing agent and a source of carbonaceous reductant for the carbothermic reduction of chromite, aiming to allow effective separation of alloy from the slag component. The experimental results show that the carbonaceous component of the SPL is more reactive towards chromite reduction compared to graphite. The formation of refractory spinel (MgAl2O4) on chromite particles hinders further reduction and alloy growth. The slag-making components of the SPL (e.g. nepheline and NaF) form molten slags at low temperatures (~1300℃) and partly dissolve the refractory spinel as well as the chromite. Destruction of the spinel layer with enhanced mass transfer greatly improves the alloy growth, which can be further promoted by reduction at a higher temperature (e.g. 1500℃). Ferrochrome alloy particles grow large enough at 1500℃ in the presence of SPL, allowing effective separation from the slag component using elutriation separation.

Leaching kinetics of acid-soluble Cr(Ⅵ) from chromite ore processing residue with hydrofluoric acid

Leaching kinetics of acid-soluble Cr（VI） in chromite ore processing residue （COPR） using hydrofluoric （HF） acid solution as a leaching agent was investigated for potential remediation of COPR with industrial waste water containing HF. The results show that HF can effectively destabilize the Cr（VI）-bearing minerals, resulting in the mobilization of Cr（VI） from COPR into the leachate. Particle size significantly influences the leaching of acid-soluble Cr（VI） from COPR, followed by leaching time, whereas the effects of HF concentration and leaching temperature are slight and the influence of stirring rate is negligible. The leaching process of acid-soluble Cr（VI） from COPR is controlled by the diffusion through the product layer. The apparent activation energy is 8.696 kJ/mol and the reaction orders with respect to HF concentration and particle size is 0.493 8 and -2.013 3, respectively.

Effect of mechanical activation on alkali leaching of chromite ore

Mechanical activation was used to improve the extraction of chromium in molten NaOH.It is observed that the extraction ratio reaches 97% after leaching for 200 min when chromite ore is mechanically activated for 10 min,but only 34% if not activated.Mechanical activation can decrease the particle size,increase the surface area,and enhance the lattice distortion.Further,the mechanisms for mechanical activation were exposed.The results show that the mechanical activation mainly focuses on chromite ore particle size decrease and the lattice distortion.The formation of aggregation weakens the strengthening effect of mechanical activation for releasing high surface energy.

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.

Distribution Characteristics of Minerals and Elements in Chromite Ore Processing Residue

In this paper, environmental scanning electron microscopy （ESEM） is applied to characterizing the mineral and element distribution of chromite ore processing residue （COPR）. The test results show that Cr-bearing brownmillerite occurs in the rim of COPR particle, while hydroandradite with Cr （Ⅵ） in its structure presents inside the COPR particle. Periclase and calcite occur in the interstitial area. Element analyses show that Ca, Fe and Al are distributed throughout the COPR particle, and Mg exists mostly in the interstitial area or on the particle surface. A lower content of Cr is evenly distributed in the COPR particle, while slightly higher concentration of Cr occurs inside the particle. It is suggested that it will take a relatively longer time for Cr to migrate out of COPR, especially fbr hexavalent chromium, so the leaching time and the particle size may be two important factors to affect the release of Cr （Ⅵ）.

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.

Microbial extraction of nickel from chromite overburdens in the presence of surfactant

The effect of surfactant polyoxyethylenesorbitan monolaurate （Tween-20） on the nickel bioleaching from pre-treated chromite overburden （COB）, Sukinda with fungal strain Aspergillus niger, was examined in shake flasks. Along with the nickel recovery from COB by the fungal bioleaching, the effect of surfactant on the growth of the A. niger was also investigated. Results show that the addition of surfactant in low concentration was favorable for the recovery of nickel from pre-treated COB. Normally, the carbon source （sucrose） in the culture medium was utilized by the A. niger for its cellular metabolism and organic metabolites （bio acids） were produced, which were responsible for the bioleaching of minerals. However, the addition of surfactant （Tween-20） accelerated the rate of sucrose consumption by the fungi, and thus enhancing the extraction of nickel from pre-treated COB. During the study, around 39% nickel extraction was achieved in A. niger mediated bioleaching performed at 2% pulp density of pre-treated COB at 30 °C, in the presence of surfactant whereas only 24% nickel was extracted without surfactant.

Analysis and assessment of nickel and chromium pollution in soils around Baghejar Chromite Mine of Sabzevar Ophiolite Belt,Northeastern Iran

The key objective of this research was to estimate the Ni and Cr contents of soil around the Baghjar Chromite Mine（BCM）of Sabzevar Ophiolite Belt,Northeastern Iran,and assess the degree of soil pollution using the pollution indices.Soil samples（0-20 cm depth） were collected at various distances from the BCM.In the present research,heavy metals（Cr and Ni） in soil samples were analyzed by atomic absorption spectrometry to detect their concentrations and contour maps were produced to explain the metal spatial distribution.Also,the degree of metal pollution was quantified.The results indicate that the soils in the studied area are contaminated by Cr and Ni.The corresponding concentrations for Cr and Ni are（156.19±24.45） and（321.7±133.27） mg/kg,respectively,which exceed the corresponding maximum allowable concentrations in soils.The different indices demonstrate that soils around chromite mine are significantly contaminated with Cr and Ni,suggesting several times higher levels of toxic metals than normal ranges.The above results revealed that the heavy metal concentrations increase with increasing the distance from the mine and mining pollutants can be transported to long distances from their sources.

Geochemistry and mineralogy of platinum-group elements(PGE)in chromites from CentralnoyeⅠ,Polar Urals,Russia

The Polar Urals region of northern Russia is well known for large chromium （Cr）-bearing massifs with major chromite orebodies, including the Centralnoye I deposit in the Ray-Iz ultramafic massif of the Ural ophiolite belt. New data on platinum （Pt）-group elements （PGE）, geochemistry and mineralogy of the host dunite shows that the deposit has anomalous iridium （Ir） values. These values indicate the predominance of ruthenium--osmium--iridium （Ru--Os--Ir）-bearing phases among the platinum-group mineral （PGM） assemblage that is typical of mantle-hosted chromite ores. Low Pt values in chromites and increased Pt values in host dunites might reflect the presence of cumulus PGM grains. The most abundant PGM found in the chromite is erlichmanite （up to 15 μm）. Less common are cuproiridsite （up to 5 μm）, irarsite （up to 4--5 μm）, and laurite （up to 4 μm）. The predominant sulfide is heazlewoodite, in intergrowth with Ni--Fe alloys, sporadically with pentlandite, and rarely with pure nickel. Based on the average PGE values and esti- mated Cr-ore resources, the Centralnoye I deposit can be considered as an important resource of PGE.

Leaching of chromite ore in concentrated KOH by catalytic oxidation using CuO as catalyst

CuO was used as a catalyst in the concentrated KOH solution to enhance the leaching of chromium from the chromite ore.The impacts of temperature,KOH-to-chromite ore mass ratio,CuO-to-chromite ore mass ratio,and gas flow rate on the chromiumleaching rate were investigated.The results indicated that CuO played an important role in improving the chromium leaching rate.The leaching rate reached98%after leaching for6h when CuO was applied,whereas it was only60.8%without CuO under thesame reaction conditions:temperature230°C,KOH-to-ore mass ratio6:1,stirring speed700r/min,gas flow rate1L/min.Accordingto the kinetics study,the catalytic oxidation was controlled by surface chemical reaction and the activation energy was calculated tobe15.79kJ/mol when the temperature was above230°C.In contrast,without CuO,the rate-determining step was external diffusionand the apparent activation energy was38.01kJ/mol.

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.

Processing of chromite ultra-fines in a water only cyclone

In the present investigation, an attempt is made to examine the interdependencies among the operating parameters and their interactional effect on the separation performance of a water-only cyclone for treating ferruginous chromite fines. Statistically designed experiments are carried out, and empirical models are developed for the critical response parameters, i,e., yield(%) to underflow, grade(%Cr_2O_3 and%SiO_2)and Cr:Fe ratio of the underflow stream. Further, using these empirical models, operating regime of the process parameters is optimized to obtain the peak performance of water-only cyclone. Also, efforts are made to validate the prediction models with the experimental results.

Evaluation of Chromite Recovery from Shaking Table Tailings by Magnetic Separation Method

This study aimed to evaluate the chromite recovery from shaking table tailings of Forumad plant by a dry high-intensity magnetic separation. The average feed grade of chromium trioxide (Cr2O3) was 7.62% by XRF. Also, different mineral phases were determined by XRD, identifying the presence of Chrysotile, Augite, Albite, Chlorite and Chromite. Although the Forumad plant usually applies gravity methods utilizing the specific gravity difference between chromite and other gangue minerals, this study applied magnetic separation utilizing the paramagnetic nature of chromite crystals to recover chromite from tailings. 27 tests for 3 factors in 3 levels designed by the Taguchi method with design expert 12 software to determine the optimum conditions for the grade and recovery. Finally, the best condition was identified at 10,000 gauss (or 1 tesla) in the magnetic field intensity, 1 kg/min feeding rate, and 40 rpm drum rotating speed which produced a concentrate with 34.65% Cr2O3 and 59.42% recovery.

Recovery of Chromite Values from Plant Tailings by Gravity Concentration

Large tonnages of chromite tailing were discarded during processing of chromite ore in the conventional circuit. A typical chromite plant tailing was treated in wilfley table for the recovery of chromite values. Optimisation study was carried out for the process parameters of wilfley table using empirical models, developed from the experimental data. It was found that grade and recovery (% Cr2O3) in the concentrate fraction majorly depended on the variation of deck tilt angle. To achieve high grade (>45%) with acceptable recovery (>40%), set of optimisation condition of parameters have derived which resulted large quantity of wash water (>5lpm of flow rate) is necessary. Validation of the empirical models were done with set of tests which resulted good agreement with the predict values (R2 is 0.96 and 0.99 for the grade and recovery respectively).

Microbial leaching of chromite overburden from Sukinda mines,Orissa,India using Aspergillus niger

Leaching of nickel and cobalt from two physical grades （S1, 125-190 μm, coarser and S3, 53-75 μm, finer） of chromite overburden was achieved by treating the overburden （2% pulp density） with 21-d culture filtrate of an Aspergillus niger strain grown in sucrose medium. Metal dissolution increases with ore roasting at 600℃ and decreasing particle size due to the alteration of microstructural properties involving the conversion of goethite to hematite and the increase in surface area and porosity as evident from X-ray diffraction （XRD）, thermogravimetry-differential thermal analysis （DT- TGA）, and field emission scanning electron microscopy （FESEM）. About 65% Ni and 59% Co were recovered from the roasted S3 ore employing bioleaching against 26.87% Ni and 31.3% Co using an equivalent amount of synthetic oxalic acid under identical conditions. The results suggest that other fungal metabolites in the culture filtrate played a positive role in the bioleaching process, making it an efficient green approach in Ni and Co recovery from lateritic chromite overburden.