Behavior of vanadium during reduction and smelting of vanadium titanomagnetite metallized pellets

The effects of CaO content,MgO content and smelting temperature on the vanadium behavior during the smelting of vanadium titanomagnetite metallized pellets were investigated.The thermodynamics of reduction and distribution of vanadium was analyzed and the high-temperature smelting experiments were carried out.The thermodynamic calculations show that the distribution ratio of vanadium between the slag and the hot metal decreases with the increments of CaO and MgO content in the slag as well as the increase of the smelting temperature.The smelting experiments demonstrate that the vanadium content in iron and the recovery rate of vanadium in pig iron increase as the CaO content,MgO content and smelting temperature increase,whereas the vanadium distribution ratio between the slag and iron tends to decrease.Moreover,the recovery rate of vanadium in pig iron has a rising trend with increasing the optical basicity of the slag.The addition of MgO in the slag to increase the slag optical basicity can not only improve the vanadium reduction but also promote the formation of magnesium-containing anosovite,which is beneficial to following titanium extraction.

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.

Carbothermic reduction of vanadium titanomagnetite with the assistance of sodium carbonate

The carbothermic reduction of vanadium titanomagnetite concentrate(VTC)with the assistance of Na_(2)CO_(3)was conducted in an argon atmosphere between 1073 and 1473 K.X-ray diffraction and scanning electron microscopy were used to investigate the phase transformations during the reaction.By investigating the reaction between VTC and Na_(2)CO_(3),it was concluded that molten Na_(2)CO_(3)broke the structure of titanomagnetite by combining with the acidic oxides(Fe_(2)O_(3),TiO_(2),Al_(2)O_(3),and SiO_(2))to form a Na-rich melt and release FeO and MgO.Therefore,Na_(2)CO_(3)accelerated the reduction rate.In addition,adding Na_(2)CO_(3)also benefited the agglomeration of iron particles and the slag–metal separation by decreasing the viscosity of the slag.Thus,Na_(2)CO_(3)assisted carbothermic reduction is a promising method for treating VTC at low temperatures.

Appropriate titanium slag composition during smelting of vanadium titanomagnetite metallized pellets

The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis.According to the thermodynamic results,low-melting-point regions and MgTi2O5primary phase area in the phase diagrams,the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of50%TiO2,8%-12%MgO and13%Al2O3(mass fraction)with a binary basicity of0.8-1.2.Finally,the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained.The obtained vanadium-containing molten iron contains0.681%V and0.267%Ti,and the obtained titanium slag contains52.21%TiO2(mass fraction),in which MgTi2O5is the primary phase.The titanium resource in the final titanium slag production could be used to produce TiO2pigment by acid leaching methods.

Formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate by adding CaCO3

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate(VTC)by adding CaCO3 was investigated.Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and Ca CO3 in a reductive atmosphere,where ilmenite is more easily reduced by CO or carbon in the presence of CaCO3.The effects of CaCO3 dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test.Appropriate increase of CaCO3 dosages and reduction temperatures were found to be conducive to the formation of calcium titanate,and the optimum conditions were a CaCO3 dosage of 18 wt%and a reduction temperature of 1400°C.Additionally,scanning electron microscopy–energy dispersive spectrometry(SEM–EDS)analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO3 addition was of higher purity with particle size approximately 50μm.Hence,the separation of calcium titanate and metallic iron will be the focus in the future study.

Effect of B2O3 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 the chromium-bearing vanadium titanomagnetite pellets (CVTP) with B2O3 addition were investigated. Besides, the reduction swelling index (RSI) and compressive strength (CS) of the reduced CVTP were also examined using the simulated coke oven gas (COG). The results suggested that the CS of CVTP was increased from 2448 to 3819.2 N, while the porosity of CVTP was decreased from 14.86% to 10.03% with the increase in B2O3 addition amounts. Moreover, the B2O3 mainly existed in the forms of TiB0.024O2 and Fe3BO5 in both CVTP and the reduced CVTP. Specifically, the CS of the reduced CVTP was elevated from 901 to 956.2 N, while the RSI was reduced from 5.87% to 3.81% as the B2O3 addition amounts were increased. Taken together, B2O3 addition would facilitate the aggregation and diffusion of metallic iron particles, which contributed to reducing the formation of metal iron whiskers and weakening the reduction swelling behavior.

Preparation of titanium mineral from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching

Titanium mineral was prepared from vanadium titanomagnetite concentrates by hydrogen reduction and acid leaching.The leaching behaviors of elements like Fe,V,Mn,Al,Mg,Ca,and Si were highly related to the reduction degree.The phase compositions of the reduced materials and the leached residues were analyzed by XRD to identify the effect of reduction degree on the leaching mechanisms.The results showed that the concentrates were reduced to iron metal and titanomagnetite at 800-1000°C for 0.5 h,and the above elements of Fe and impurities were easily leached.Deeper reduction led to the formation of ilmenite and Mg-Al spinel,which hindered leaching.Mg-bearing anosovite appeared in the further reduced materials,and the leaching rates of impurities became much lower.An upgraded titanium mineral with a normalized TiO_(2) grade of 70.3%was achieved by H_(2) reduction at 850°C for 0.5 h and acid leaching,which is a satisfactory Ti resource for the preparation of titanium oxide by sulfate process.

Effect of Cr_2O_3 addition on the oxidation induration mechanism of Hongge vanadium titanomagnetite pellets

As part of a research project to develop a novel clean smelting process for the comprehensive utilization of Hongge vanadium titanomagnetite（HVTM）, in this study, the effect of Cr2O3 addition on the oxidation induration mechanism of HVTM pellets（HVTMPs） was investigated in detail. The results showed that the compressive strength of the HVTMPs was greatly weakened by the Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe–Cr solid solutions（Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3） embedded in the hematite grains. Moreover, the compact hematite was destroyed by forming a dispersed structure and the hematite recrystallization was hindered during the oxidation induration, which adversely affected the compressive strength. On the basis of these results, a schematic was formulated to describe the oxidation induration mechanism with different amounts of added Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

Effect of nickel oxide additive on smelting mechanism of chromium-bearing vanadium titanomagnetite pellets

The effect of nickel oxide additive on the smelting behaviors of chromium-bearing vanadium titanomagnetite pellets(CVTP)was investigated while analyzing the transfer behavior of nickel in iron and slag.The results show that when NiO added to CVTP increases from 0 to 6 wt.%,softening start temperature increases from 1148 to 1212℃,and the softening end temperature increases from 1280 to 1334℃;the melting start temperature increases from 1318 to 1377℃,and the dripping temperature decreases from 1558 to 1521℃.The pig iron comprises a compound of Fe-Ni-C.The slag structure depolymerizes with increasing nickel addition.The softening-melting behaviors of CVTP,the reduction of nickel into pig iron,and the depolymerization of slag structure indicate the feasibility of producing nickel-iron alloy through the blast furnace process.

Reduction behavior and mechanism of Hongge vanadium titanomagnetite pellets by gas mixture of H2 and CO

Hongge vanadium titanomagnetite（HVTM）pellets were reduced by H2-CO gas mixture for simulating the reduction processes of Midrex and HYL-III shaft furnaces.The influences of reduction temperature,ratio ofφ（H2）toφ（CO）,and pellet size on the reduction of HVTM pellets were evaluated in detail and the reduction reaction kinetics was investigated.The results show that both the reduction degree and reduction rate can be improved with increasing the reduction temperature and the H2 content as well as decreasing the pellet size.The rational reduction parameters are reduction temperature of 1050℃,ratio ofφ（H2）toφ（CO）of 2.5,and pellet diameter in the range of 8-11 mm.Under these conditions（pellet diameter of 11mm）,final reduction degree of 95.51% is achieved.The X-ray diffraction（XRD）pattern shows that the main phases of final reduced pellets under these conditions（pellet diameter of 11 mm）are reduced iron and rutile.The peak intensity of reduced iron increases obviously with the increase in the reduction temperature.Besides,relatively high reduction temperature promotes the migration and coarsening of metallic iron particles and improves the distribution of vanadium and chromium in the reduced iron,which is conducive to subsequent melting separation.At the early stage,the reduction process is controlled by interfacial chemical reaction and the apparent activation energy is 60.78kJ/mol.The reduction process is controlled by both interfacial chemical reaction and internal diffusion at the final stage,and the apparent activation energy is 30.54kJ/mol.

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.

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.

Influence of TiO2 on the melting property and viscosity of Cr-containing high-Ti melting slag

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag(CaO–SiO2–MgO–Al2O3–TiO2–Cr2O3) with TiO2 contents ranging from 38.63 wt% to 42.63 wt% was conducted. The melting properties were investigated with a meltingpoint apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy(SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO2 content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO2 content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO2 content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO2.

Blast furnace ironmaking process with super high TiO_(2) in the slag:Density and surface tension of the slag

Aiming at the process of smelting ultra-high(>80%)or even full vanadium titanomagnetite in blast furnace,we are conducting a series of works on physics character of high TiO_(2) bearing blast furnace slag(BFS)for slag optimization.This work discussed the density and surface tension of high TiO_(2) bearing BFS using the Archimedean principle and the maximum bubble pressure method,respectively.The influence of TiO_(2) content and the MgO/CaO mass ratio on the density and surface tension of CaO-SiO_(2)-TiO_(2)-MgO-Al_(2)O_(3)slags were investigated Results indicated that the density of slags decreased with the TiO_(2) content increasing from 20wt%to 30wt%,but it increased slightly with the MgO/CaO mass ratio increasing from 0.32 to 0.73.In view of silicate network structure,the density and the degree of polymerization(DOP)of network structure have a consistent trend.The addition of TiO_(2) reduced(Q^(3))^(2)/(Q^(2)) ratio(Q^(2) and Q^(3) represent structural unit with bridge oxygen number of 2 and 3,respectively)and then decreased DOP,which led to the decrease of slag density.The surface tension of CaO-SiO_(2)-TiO_(2)-MgO-Al_(2)O_(3) slags decreased dramatically with the TiO_(2) content increasing from 20wt%to 30wt%.Conversely,it increased with the MgO/CaO mass ratio increasing from 0.32 to 0.73.Furthermore,the iso-surface tension lines were obtained under 1723 K using the Tanaka developed model in view of Butler formula.It may be useful for slag optimization of ultra-high proportion(>80%)or even full vanadium titanomagnetite under BF smelting.

Amelioration of the mineral compositions and microstructures of the special ore sinters

Mineral compositions and microstructures of fluorine bearing magnetite concentrate and vanadium titanomagnetite concentrate are studied. The results show that a boride and a catalytic oxidation agent have great effects on ameliorating the mineral compositions and microstructures of these sinters, and the catalytic agent is more effective. Comparing these two kinds of ores, the performance of fluorine bearing magnetite concentrate is better. Addition of 0.01% catalyst into fluorine bearing magnetite concentrate can increase calcium ferrite content from 15% 20% up to 34% 39%, and its microstructure changes from large cavities and thin framework into intermediate cavities and thick framework, and the microcracks disappear.

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.

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.

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.

Infiltration behavior of sintering liquid on nuclei ores during low-titanium ore sintering process

Sinter strength is dependent not only on the self-intensity of the residual rude and bonding phase but also on the bonding degree between them. The infiltration behavior of sintering liquid on nuclei ores influences the bonding degree, which ultimately determines the sinter strength. Infiltration tests were conducted using micro-sinter equipment. The infiltration area index of original liquid（IAO）, infiltration volume index of secondary liquid（IVS）, and sinter body bonding strength（SBS） were proposed to study the melt infiltration behavior. The results show that the IVS first increases and then decreases with increasing TiO2 content in adhering fines, whereas the IAO exhibits the opposite behavior. Compared with the original liquid, the secondary liquid shows lower porosity, smaller pores, and more uniform distribution. The SBS increases first and then decreases with increasing IAO and TiO2 content, and reaches a maximum when the IAO and TiO2 contents are approximately 0.5 and 2.0wt%, respectively. The SBS first increases and then tends to be stable with increasing IVS. The TiO2 content is suggested to be controlled to approximately 2.0wt% in low-titanium ore sintering.

A thermodynamic model for predicting activity of CaO-SiO_(2)-Al_(2)O_(3)-MgO-TiO_(2)-V_(2)O_(3)-FeO slags during electric furnace smelting process

To optimize the comprehensive utilization of vanadium titanomagnetite by direct reduction-smelting processes,it is essential to acquire titanium slag with a higher TiO_(2)content of 45–60 wt.%.A thermodynamic model was developed based on the ion and molecule coexistence theory,specifically targeting the CaO–SiO_(2)–Al_(2)O_(3)–MgO–TiO_(2)–V_(2)O_(3)–FeO slag system.The impact of slag composition on the smelting of vanadium titanomagnetite was assessed,and the thermodynamic model was utilized to identify the optimal high-titanium slag.The results revealed that increasing the basicity,MgO content,and FeO content within the slag effectively suppressed the reduction of titanium and silicon oxides.Furthermore,the calculated activity coefficient of TiO_(2)decreased with higher basicity,MgO,and FeO levels.While an increase in basicity significantly enhanced the reduction of vanadium oxides,the effects of MgO and FeO contents on vanadium oxide reduction were comparatively less significant.Notably,higher basicity and FeO content promoted the formation of calcium titanates,whereas an elevated MgO content favored the formation of magnesium titanates.The smelting results indicated that a lower V_(2)O_(3)content and higher TiO_(2)activity corresponded to a smaller titanium mass fraction in the iron alloy,while the opposite trend was observed for vanadium.