Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Vanadium extraction from vanadium-bearing titanomagnetite by selective chlorination using chloride wastes (FeClx)

Vanadium extraction of vanadium-bearing titanomagnetite was investigated by selective chlorination. Thermodynamics analyses on the interactive reactions among related species in the system were made before the experiments. Some fundamental experiments for extracting vanadium by FeClx as chlorinating agent were conducted over the temperature range of 900-1300 K under air or oxygen atmosphere. The results show that vanadium can be extracted by the selective chlorination, using FeClx, based on thermodynamic analysis and experiment. Vanadium extraction ratio first increases with the increase of temperature, and then decreases with the increase of temperature over the range of 900-1300 K under air or oxygen atmosphere. The higher molar ratio of FeCI3 to oxides （nchl：noxd） reacting with FeC13, the higher ratio of vanadium extraction. Under oxygen atmosphere, the vanadium extraction ratio is up to 32% at 1100 K for 2 h by using FeCI3 as chlorinating agent.

Effects of smelting parameters on the slag/metal separation behaviors of Hongge vanadium-bearing titanomagnetite metallized pellets obtained from the gas-based direct reduction process

Smelting separations of Hongge vanadium-bearing titanomagnetite metallized pellets（HVTMP）prepared by gas-based direct reduction were investigated,and the effects of smelting parameters on the slag/metal separation behaviors were analyzed.Relevant mechanisms were elucidated using X-ray diffraction analysis,FACTSAGE 7.0 calculations,and scanning electron microscopy observations.The results show that,when the smelting temperature,time,and C/O ratio are increased,the recoveries of V and Cr of HVTMP in pig iron are improved,the recovery of Fe initially increases and subsequently decreases,and the recovery of Ti O_2 in slag decreases.When the smelting Ca O/Si O_2 ratio is increased,the recoveries of Fe,V,and Cr in pig iron increase and the recovery of Ti O_2 in slag initially increases and subsequently decreases.The appropriate smelting separation parameters for HVTMP are as follows：smelting temperature of 1873 K;smelting time of 30–50 min;C/O ratio of 1.25;and Ca O/Si O_2 ratio of 0.50.With these optimized parameters（smelting time：30 min）,the recoveries of Fe,V,Cr,and Ti O_2 are 99.5%,91.24%,92.41%,and 94.86%,respectively.

A method for recovery of iron,titanium,and vanadium from vanadium-bearing titanomagnetite

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures： low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70 wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.

Biodesulfurization of vanadium-bearing titanomagnetite concentrates and pH control of bioleaching solution

Vanadium-bearing titanomagnetite concentrates were desulfurized with Acidithiobacillus ferrooxidans （A. ferrooxidans）. The sulfur content of the concentrates was reduced from 0.69wt% to 0.14wt% after bioleaching for 15 d with a 10% pulp density at 30℃. Maintaining a stable pH value during biodesulfurization was critical because of high acid consumption, resulting from a combination of nonoxidative and oxidative dissolution of pyrrhotite in acid solution. It is discovered that the citric acid-disodium hydrogen phosphate buffer of pH 2.0 can control the solution pH value smoothly in the optimal range of 2.0-3.0 for A. ferrooxidans growth. Using the buffer in the volume fraction range of 5.0%-15.0% stimulates A. ferooxidans growth and improves the biodesulfurization efficiency. Compared with the buffer-free control case, the maximum increase of biodesulfurization rate is 29.7% using a 10.0vol% buffer. Bioleaching provides an alternative process for desulfurization of vanadium-bearing titanomagnetite ores.

Leaching of vanadium,sodium,and silicon from molten V?Ti-bearing slag obtained from low-grade vanadium-bearing titanomagnetite

The water leaching process of vanadium, sodium, and silicon from molten vanadium-titanium-bearing（V-Ti-bearing） slag obtained from low-grade vanadium-bearing titanomagnetite was investigated systematically. The results show that calcium titanate, sodium aluminosilicate, sodium oxide, silicon dioxide and sodium vanadate are the major components of the molten V-Ti-bearing slag. The experimental results indicate that the liquid-solid（L/S） mass ratio significantly affects the leaching process because of the respective solubilities and diffusion rates of the components. A total of 83.8% of vanadium, 72.8% of sodium, and 16.1% of silicon can be leached out via a triple counter-current leaching process under the optimal conditions of a particle size below 0.074 mm, a temperature of 90°C, a leaching time of 20 min, an L/S mass ratio of 4：1, and a stirring speed of 300 r/min. The kinetics of vanadium leaching is well described by an internal diffusion-controlled model and the apparent activation energy is 11.1 kJ/mol. The leaching mechanism of vanadium was also analyzed.

Development of Intensified Technologies of Vanadium-Bearing Titanomagnetite Smelting

It was very difficult for the smelting of vanadium-bearing titanomagnetite by blast furnace because the content of TiO2 of blast furnace slag could amount to 20%-25%.After long term development and continuous improvement,special intensified smelting technologies for vanadium-bearing titanomagnetite by blast furnace were obtained and improved gradually.With the improvement of beneficiated material level and equipment level,smelting intensity has been increased gradually and the highest comprehensive smelting intensity reached 1.45 t/（m3·d）.Technical-economic indexes of blast furnace have also been increased remarkably.The highest utilization coefficient exceeded 2.7 t/（m3·d）on the condition that the burden grade was only about 50%.

Influences of Technological Parameters on Smelting-separation Process for Metallized Pellets of Vanadium-bearing Titanomagnetite Concentrates

The smelting-separation process for metallized pellets of vanadium-bearing titanomagnetite concentrates was studied.The influences of smelting temperature,smelting time,and the basicity of the metallized pellet on vanadium and iron recovery were investigated.The characteristics of titanium slag were analyzed using X-ray diffraction,energy dispersive spectroscopy,and mineralographic microscopic analysis.The results demonstrate that appropriate increases in smelting temperature and smelting time can improve the vanadium and iron recovery from metallized pellets and are beneficial for the slag-iron separation.Although increasing the basicity of the metallized pellet can considerably improve the vanadium and iron recovery,the TiO;grade of titanium slag was decreased.Under the optimal conditions,90.17% of vanadium and 92.98% of iron in the metallized pellet were recovered,and the TiO;grade of titanium slag was 55.01%.It was found that anosovite,augite,spinel,glassiness,and metallic iron were the main mineral phases of the titanium slag.

Behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized reduction of titanomagnetite

The direct reduction process is an important development direction of low-carbon ironmaking and efficient comprehensive utilization of poly-metallic iron ore,such as titanomagnetite.However,the defluidization of reduced iron particles with a high metallization degree at a high temperature will seriously affect the operation of fluidized bed reduction.Coupling the pre-oxidation enhancing reduction and the particle surface modification of titanomagnetite,the behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized bed reduction of titanomagnetite are systematically studied in this paper.Pre-oxidation treatment of titanomagnetite can significantly lower the critical stable reduction fluidization gas velocity to 0.17 m/s,which is reduced by 56%compared to that of titanomagnetite reduction without pre-oxidation,while achieving a metallization degree of>90%,Corresponding to the different reduction fluidization behaviors,three pre-oxidation operation regions have been divided,taking oxidation degrees of 26%and 86%as the boundaries.Focusing on the particle surface morphology evolution in the pre-oxidation-reduction process,the relationship between the surface morphology of pre-oxidized ore and the reduced iron with fluidization properties is built.The improving method of pre-oxidation on the reduction fluidization provides a novel approach to prevent defluidization by particle surface modification,especially for the fluidized bed reduction of poly-metallic iron ore.

Phase equilibria relations in the V_(2)O_(5)-rich part of the Fe_(2)O_(3-)TiO_(2)-V_(2)O_(5) system at 1200℃ related to converter vanadium-bearing slag

The efficient recycling of vanadium from converter vanadium-bearing slag is highly significant for sustainable development and circular economy.The key to developing novel processes and improving traditional routes lies in the thermodynamic data.In this study,the equilibrium phase relations for the Fe_(2)O_(3)-TiO_(2)-V_(2)O_(5)system at 1200℃in air were investigated using a high-temperature equilibrium-quenching technique,followed by analysis using scanning electron microscopy-energy dispersive X-ray spectrometer and X-ray photoelectron spectroscopy.One liquid-phase region,two two-phase regions(liquid-rutile and liquid-ferropseudobrookite),and one three-phase region(liquid-rutile-ferropseudobrookite)were determined.The variation in the TiO_(2)and V_(2)O_(5)contents with the Fe_(2)O_(3)content was examined for rutile and ferropseudobrookite solid solutions.However,on further comparison with the predictions of FactSage 8.1,significant discrepancies were identified,highlighting that greater attention must be paid to updating the current thermodynamic database related to vanadium-bearing slag systems.

Softening–melting–dripping characteristics and evolution mechanism of vanadium-bearing titanomagnetite carbon composite briquette used as novel blast furnace burden

Vanadium-bearing titanomagnetite carbon composite briquette(VTM-CCB)was proposed as an innovative and promising blast furnace burden to realize low-carbon and high-efficiency ironmaking.To optimize the compositions of VTM-CCB based on its softening–melting–dripping characteristics,the evolution behavior and mechanisms of VTM-CCB in cohesive zone and dripping zone were investigated by conducting softening–melting tests under blast furnace conditions.The results show that the structure evolution of VTM-CCB in softening–melting process is correlated to the molten slag,metallic iron,liquid iron,and residual carbon.With the molar ratio of the fixed carbon to the reducible oxygen in iron oxides(FC/O ratio)ranging from 0.8 to 1.0,the VTM-CCB tends to form dense structure and accelerate the softening and melting.With increasing the FC/O ratio to 1.2 and 1.4,the VTM-CCB tends to form concentric circular structure,which could suppress the collapse of packed bed,shift down the location of core cohesive zone,and improve the gas permeability.Although the appropriate increase in FC/O ratio could improve the softening–melting performance of VTM-CCB,a higher FC/O ratio could also promote the precipitation of Ti(C,N),thereby thickening the molten mixtures and deteriorating the dripping behavior.Fully considering the softening–melting–dripping characteristics and permeability,the appropriate FC/O ratio of VTM-CCB should be controlled in the range of 1.0–1.2.

Influence of phosphorus on iron-based friction material prepared directly vanadium-bearing titanomagnetite concentrates

In situ selective carbothermic reactions and vacuum sintering were used to prepare iron-based friction material directly vanadium-bearing titanomagnetite concentrates.Effects of phosphorus addition(0.05–0.20 wt.%)on the microstructure and properties of iron-based friction material were investigated.The results show that the addition of phosphorus improves the microstructure and properties of the material significantly.When phosphorus addition increases to 0.15 wt.%,the sintering densification is promoted and the number of lamellar pearlites increases.Therefore,the relative density,hardness and tribological properties of the material are greatly enhanced.Particularly,the friction coefficient decreases 0.58 to 0.43,and the wear rate reduces 1.829×10^(–7) to 0.694×10^(–7)cm^(3)J^(-1).The dominant wear mechanism of the material changes severe abrasive wear to mild oxidation wear accordingly.However,when phosphorus addition exceeds 0.15 wt.%,the matrix continuity and tribological properties of the material are deteriorated.Comprehensively,the optimal addition of phosphorus in the iron-based friction material is 0.15 wt.%.

Analysis of Vanadium-Bearing Titanomagnetite Sintering Process by Dissection of Sintering Bed

Many problems appear in the sintering process of vanadium-bearing titanomagnetite, such as high energy consumption and low productivity; simer quality is also very poor for its low tumble strength and high reduction deg- radation. Sinter productivity and quality are dominated by bed permeability and mineralogy structure, which are highly influenced by the thermal state of sintering bed, so the sintering process of titanomagnetite is researched by bed dissection in this work. Temperature evolution curves of sinter materials were measured, and the results show that melting duration, peak temperature duration and sintering temperature of different layers differ greatly from each other; flame front speed and vertical sintering speed of bed lower region are much smaller than those of bed up- per region. Simultaneously, sinter samples were collected from different layers, and their mineralogy characteristics are analyzed; sinters from bed lower region have poor mineralogy structure, and the amounts of perovskite and dieM- cium silicate increase intensively, which are bad for sinter strength and reduction degradation property. Measures are proposed to improve the quality and productivity of titanomagnetite sinter.

Experimental study and industrial demonstration on utilization of Fe,Ti and V from vanadium-bearing titanomagnetite ore sands

In order to achieve highly efficient utilization of three valuable elements Fe,Ti and V simultaneously from vanadium-bearing titanomagnetite ore sands,an improved carbothermic reduction method was proposed and verified in both laboratory scale and industrial test-bed scale.The method combined the process of direct reduction and the process of further reduction and separation.Particularly,pulverized coal injection was introduced.In experimental tests,the effects of parameters such as carbon content in briquette,reduction duration and reduction temperature on the contents of metallic Fe and FeO as well as Fe metallization rate were analyzed.Experimental results indicated that Fe metallization rate in the carbon-containing briquette could reach 75.83%.In the industrial test-bed tests,the effects of carbon content in briquette,reduction duration and reduction temperature were also investigated,respectively.In addition,processes with and without pulverized coal injection were tested.The comparative analysis indicated that the content of TiO2 in titaniferous slag was increased by applying pulverized coal injection,and it can reach 82.5 wt.%.Meanwhile,the energy performance analysis showed that the equivalent electricity consumption of the test-bed dropped significantly to 2071 kWh per ton of slag,about 26.0%less than that of traditional method.Moreover,the investment payback of the test-bed is 3.4 years.Both experiments and industrial test-bed tests demonstrated that the proposed method has the advantages of highly efficient utilization,high energy efficiency as well as good economic performance.

Bioleaching and biosorption behavior of vanadium-bearing stone coal by Bacillus mucilaginosus

The recovery of vanadium(V)from stone coal by bioleaching is a promising method.The bioleaching experiments and the biosorption experiments were carried out,aiming to explore the adsorption characteristics of Bacillus mucilaginosus(B.mucilaginosus)on the surface of vanadium-bearing stone coal,and the related mechanisms have been investigated.After bioleaching at 30℃ for 28 d,the cumulative leaching rate of V reached 60.2%.The biosorption of B.mucilaginosus on stone coal was affected by many factors.When the pH value of leaching system is 5.0,strong electrostatic attraction between bacteria and stone coal promoted biosorption.Bacteria in the logarithmic growth phase had mature and excellent biosorption properties.The initial bacterial concentration of 3.5×10^(8) CFU/mL was conducive to adhesion,with 38.9%adsorption rate and 3.6×10^(7) CFU/g adsorption quantity.The adsorption of B.mucilaginosus on the stone coal conformed to the Freundlich model and the pseudo-second-order kinetic model.Bacterial surface carried functional groups(-CH_(2),-CH_(3),-NH_(2),etc.),which were highly correlated with the adsorption behavior.In addition,biosorption changed the surface properties of stone coal,resulting in the isoelectric point(IEP)approaching the bacteria.The results could provide an effective reference for the adsorption laws of bacteria on minerals.

Effect of Cr2O3 addition on oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets with simulated coke oven gas

The oxidation induration and reduction swelling behavior of chromium-bearing vanadium titanomagnetite pellets(CVTP)with Cr2O3 addition were studied,and the reduction swelling index(RSI)and compressive strength(CS)of the reduced CVTP with simulated coke oven gas(COG)injection were investigated.The results showed that the CS of the CVTP decreases and the porosity of the CVTP increases with increasing amount of Cr2O3 added.The Cr2O3 mainly exists in the form of(Cr,Fe)2O3 solid solution in the CVTP and as Fe-Cr in the reduced CVTP.The CS of the reduced CVTP increases and the RSI of the reduced CVTP decreases with increasing amount of Cr2O3 added.The limited aggregation and diffusion of metallic iron contribute to the formation of dense lamellar crystals,which leads to the slight decrease for reduction swelling behavior of reduced CVTP.This work provides a theoretical and technical basis for the utilization of CVTP and other Cr-bearing ores such as chromite with COG recycling technology.

Effects and mechanisms of fluorite on the co-reduction of blast furnace dust and seaside titanomagnetite

The co-reduction roasting and grinding-magnetic separation of seaside titanomagnetite and blast furnace dust was investigated with and without fluorite addition at a reduction roasting temperature of 1250°C for 60 min, a grinding fineness of-43 μm accounting for 69.02 wt% of the total, and a low-intensity magnetic field strength of 151 kA/m. The mineral composition, microstructure, and state of the roasted products were analyzed, and the concentrations of CO and CO_2 were analyzed in the co-reduction roasting. Better results were achieved with a small fluorite dosage(≤4 wt%) in the process of co-reduction. In addition, F^- was found to reduce the melting point and viscosity of the slag phase because of the high content of aluminate and silicate minerals in the blast furnace dust. The low moisture content of the blast furnace dust and calcic minerals inhibited the hydrolysis of CaF_2 and the loss of F^-. Compared with the blast furnace dust from Chengdeng, the blast furnace dusts from Jiugang and Jinxin inhibited the diffusion of F-when used as reducing agents, leading to weaker effects of fluorite.

Effect of reductant type on the embedding direct reduction of beach titanomagnetite concentrate

Iron and titanium were recovered from beach titanomagnetite(TTM) concentrate by embedding direct reduction and magnetic separation. The reduction products and the effects of the reductant type and reduction temperature on the reduction behavior were investigated. The results showed that the reduction of TTM concentrate was strongly related to the gasification reactivity of the reductant. Bitumite presented a better product index than wheat-straw biochar and coke, mainly because the gasification reactivity of bitumite was better than that of the other reductants. In addition, high temperatures were not beneficial to embedding direct reduction because of the emergence of a molten phase and iron-joined crystals, which in turn reduced the diffusion rate of the reducing gas and impeded the reduction reaction in the central area of the roasted briquette. The use of bitumite as the reductant at a C/Fe molar ratio of 1.4 and a reduction temperature of 1200°C for 120 min resulted in direct-reduction iron powder assaying 90.28 wt% TFe and 0.91 wt% TiO_2 with an iron recovery of 91.83% and titanium concentrate assaying 46.01 wt% TiO_2 with a TiO_2 recovery of 91.19%. Titanium existed mainly in the form of anosovite and ilmenite in the titanium concentrate.

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate(VTC) were investigated. It was found that calcium compounds had great effects on the metallization rate of the reduction product, the order of the metallization rate of reduction product being CaCO3 > no additive > CaSO4 > CaCl2, which indicated that the addition of CaCO3 was more conducive to promoting the reduction of iron than other calcium compounds. Gas analysis showed that there were mainly two processes in the carbothermic reduction of VTC, a solid–solid and a solid–gas reaction. The concentrations of CO and CO2 were highest when CaCO3 was added, while that in a roasting system decreased the most when CaCl2 was added. X-ray diffraction(XRD) analysis showed that calcium compounds could change the reduction process of ilmenite in VTC. The phase compositions of the reduction products were changed from metallic iron(Fe) and anosovite(FeTi2O5) to metallic iron(Fe) and perovekite(CaTiO3) when calcium compounds were added. Additionally, CaSO4 and CaCl2 could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg2TiO4 in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO4.

Effects of the continuous cooling process conditions on the crystallization and liberation characteristics of anosovite in Ti-bearing titanomagnetite smelting slag

This study involved the investigation of the effects of the continuous cooling process conditions on the crystallization and liberation characteristics of anosovite in Ti-bearing titanomagnetite smelting slag. The samples were heated until melting and then the temperature was held at 1650℃ for nearly 0.5 h;subsequently, the samples were cooled at different cooling rates to different temperatures and water-quenched after being held for different times at these temperatures. Last, the obtained crystallized samples were used to analyze the crystallization and liberation characteristics. It was found that, during the continuous cooling process, anosovite particles were found to initially precipitate in the slag at a relatively high crystallization temperature, showing the characteristics of euhedral crystal. The precipitation and growth of anosovite grain is strong and the morphology of anosovite was basically not affected by the continuous cooling conditions. From the morphology perspective, the formed anosovite is an excellent Ti-rich phase to be selective separated. The formation of spinel and diopside is negative for the liberation and selective separation of the anosovite phase. The crystallization diagrams of TiO2-MgO-CaO-SiO2-Al2O3-FeO slag undergoing different continuous cooling processes were constructed to help to determine the optimal continuous cooling–quenching condition for selective separation of anosovite. Moreover, the addition of B2O3 can enlarge the range of the optimal continuous cooling–quenching conditions for selective separation of anosovite.