Sintering behaviors and consolidation mechanism of high-chromium vanadium and titanium magnetite fines

To achieve high efficiency utilization of high-chromium vanadium-titanium magnetite （V-Ti-Cr） fines, an investigation of V Ti42r fines was conducted using a sinter pot. The chemical composition, particle parameters, and granulation of V-Ti-Cr mixtures were analyzed, and the effects of sintering parameters on the sintering behaviors were investigated. The results indicated that the optimum quicklime dosage, mixture moisture, wetting time, and granulation time for V-Ti-Cr fines are 5wt%, 7.5wt%, 10 min, and 5-8 min, respectively. Meanwhile, the vertical sintering speed, yield, tumbler strength, and productivity gains were shown to be 21.28 mm/min, 60.50wt% , 58.26wt%, and 1.36 t·m^-2·h^-1, respectively. Furthermore, the consolidation mechanism of V-Ti-Cr fines was clarified, revealing that the consolidation of a V-Ti-Cr sinter requires an approximately 14vo1% calcium ferrite liquid-state, an approximately 15vo1% silicate liq- uid-state, a solid-state reaction, and the recrystallization of magnetite. Compared to an ordinary sinter, calcium ferrite content in a V-Ti-Cr sinter is lower, while the perovskite content is higher, possibly resulting in unsatisfactory sinter outcomes.

A novel process for the recovery of iron,titanium,and vanadium from vanadium-bearing titanomagnetite:sodium modification–direct reduction coupled process

A sodium modification–direct reduction coupled process was proposed for the simultaneous extraction of V and Fe from vanadium- bearing titanomagnetite. The sodium oxidation of vanadium oxides to water-soluble sodium vanadate and the transformation of iron oxides to metallic iron were accomplished in a single-step high-temperature process. The increase in roasting temperature favors the reduction of iron oxides but disfavors the oxidation of vanadium oxides. The recoveries of vanadium, iron, and titanium reached 84.52%, 89.37%, and 95.59%, respectively. Moreover, the acid decomposition efficiency of titanium slag reached 96.45%. Compared with traditional processes, the novel process provides several advantages, including a shorter flow, a lower energy consumption, and a higher utilization efficiency of vanadium-bearing titanomagnetite resources. © 2017, University of Science and Technology Beijing and Springer-Verlag Berlin Heidelberg.

Effect of diboron trioxide on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets

The effect of diboron trioxide(B_2O_3) on the crushing strength and smelting mechanism of high-chromium vanadium–titanium magnetite pellets was investigated in this work. The main characterization methods were X-ray fluorescence, inductively coupled plasma–atomic emission spectroscopy, mercury injection porosimetry, X-ray diffraction, metallographic microscopy, and scanning electron microscopy–energy-dispersive X-ray spectroscopy. The results showed that the crushing strength increased greatly with increasing B_2O_3 content and that the increase in crushing strength was strongly correlated with a decrease in porosity, the formation of liquid phases, and the growth and recrystallization consolidation of hematite crystalline grains. The smelting properties were measured under simulated blast furnace conditions; the results showed that the smelting properties within a certain B_2O_3 content range were improved and optimized except in the softening stage. The valuable element B was easily transformed to the slag, and this phenomenon became increasingly evident with increasing B_2O_3 content. The formation of Ti(C,N) was mostly avoided, and the slag and melted iron were separated well during smelting with the addition of B_2O_3. The size increase of the melted iron was consistent with the gradual optimization of the dripping characteristics with increasing B_2O_3 content.

Three-liquid-phase extraction and separation of V(V) and Cr(VI) from acidic leach solutions of high-chromium vanadium–titanium magnetite

A new method by liquid-liquid-liquid three phase system, consisting of acidified primary amine N1923 （abbreviated as A-N1923）, poly（ethylene glycol） （PEG） and （NH4）2S04 aqueous solution, was suggested for the separation and simultaneous extraction of Ⅴ（Ⅴ） and Cr（Ⅵ） from the acidic leach solutions of high- chromium vanadium-titanium magnetite. Experimental results indicated that Ⅴ（Ⅴ） and Cr（Ⅵ） could be selectively enriched into the A-N1923 organic top phase and PEG-rich middle phase, respectively, while AI（Ⅲ） and other co-existing impurity ions, such as Si（Ⅳ）, Fe（Ⅲ）, Ti（Ⅳ）, Mg（Ⅱ） and Ca（Ⅱ） in acidic leach solutions, could be enriched in the （NH4）2SO4 bottom aqueous phase. During the process for extraction and separation of Ⅴ（Ⅴ） and Cr（Ⅵ）, almost all of impurity ions could be removed. The separation factors between Ⅴ （Ⅴ） and Cr（Ⅵ） could reach 630 and 908, respectively in the organic top phase and PEG middle phase, and yields of recovered Ⅴ（Ⅴ） and Cr（Ⅵ） in the top phase and middle phase respectively were all above 90%. Various effects including aqueous pH, A-N1923 concentration, PEG added amount and （NH4）2SO4 concentration on three-phase partitioning of Ⅴ（Ⅴ） and Cr（Ⅵ） were discussed. It was found that the partition of Cr（Ⅵ） into the PEG-rich middle phase was driven by hydrophobic interaction, while extraction of Ⅴ（Ⅴ） by A-N1923 resulted of anion exchange between NO; and H2V10O4-28. Stripping of Ⅴ（Ⅴ） and Cr（Ⅵ） from the top organic phase and the middle PEG-rich phase were achieved by mixing respectively with NANO3 aqueous solutions and NaOH-（NH4）2SO4 solutions. The present work highlights a new approach for the extraction and purification of V and Cr from the complex multi-metal co-existing acidic leach solutions of high-chromium vanadium-titanium magnetite.

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.

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.

Influence of Coke Content on Sintering Process of Chromium-containing Vanadium-titanium Magnetite

The sintering of chromium-containing vanadium-titanium magnetite using different coke contents was studied through the sintering pot tests, X-ray diffraction analysis and mineralogical phase analysis. Results showed that, as the coke content increased from 3.2% to 4.4%, the liquid phase and combustion zone thickness increased while the vertical sintering rate and ratio of sintered product decreased. In addition, the combustion ratio of exhaust gas also increased with increasing the coke content, indicating that combustion zone temperature also increased, and the excessive the coke content in the sintering process of vanadiumtitanium magnetite is harmful. As the coke content increased, the magnetite, silicates, and perovskite contents of the sintered ore increased while the contents of hematite and calcium ferrite of sintered ore decreased; drum strength decreased, and reduction degradation properties increased while reduction ability decreased. We found that the appropriate coke content for the sintering process is 3.6 wt%.

STUDY OF SMELTING REDUCTION RATE FOR VANADIUM TITANIUM MAGNETITE

A comparative study was made of the reduction kinetics for high temperature smelting of vadium-titanium-containing magnetite,together with Hainan iron ore,using iron bath method.Three peaks were revealed on the reduction rate curves for the magnetite,while one peak only for Hainan ore.Under the same conditions,the smelting reduction rate of the magnetite was found to be lower than that of Hainan ore.The rate increases evidently with the increase of the bath volume.The expressions of smelting reduction rate were suggested for the reduction with and without iron bath respectively.

Mineralogy and carbothermal reduction behaviour of vanadium-bearing titaniferous magnetite ore in Eastern India

Vanadium-beaxing titaniferous magnetite bands hosted by Precambrian gabbro-norite-anorthositic rocks or their metamorphic equivalents were discovered in some parts of Eastern Indian Shield, containing 48%-49% Fe （total）, 10%-25% TiO2, and 0.3%-2.20% V2O5 by mass. Mineralogical and petrological study, composition, and characterization of the vanadium-bearing titaniferous magnetite ore were carried out by scanning electron microscopy-energy dispersive X-ray （SEM-EDX）, wave length X-ray florescence （WDXRF）, inductively coupled plasma-atomic emission spectroscopy （ICP-AES）, X-ray diffraction （XRD）, etc. Chemical beneficiation for valuable metals, such as Fe, Ti, andV, was performed by reduction roasting. The direct and indirect reduction were investigated by mixing the lump ore with solid activated charcoal in a closed reactor and purging the reducing gas mixture in standard reducibility index apparatus at different temperatures and time intervals. The reduction roasting parameters were optimized. Finally, the reduced samples were crushed and upgraded by magnetic separation. The results show that, the maximum mass fractions of magnetic and nonmagnetic parts achieved axe 69.36% and 30.64%, respectively, which contain 10.6% TiO2 and 0.84% V205 in the magnetic part and 36.5% TiO2 and 0.22% V205 in the nonmagnetic part.

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.

Selective leaching of vanadium from V-Ti magnetite concentrates by pellet calcification roasting-H_(2)SO_(4) leaching process

A novel method of pellet calcification roasting-H_(2)SO_(4) leaching was proposed to efficiently separate and extract vanadium(V)from vanadium-titanium(V-Ti)magnetite concentrates.The leaching rate of V is as high as 88.98%,while the leaching rate of impurity iron is only 1.79%.Moreover,the leached pellets can be used as raw materials for blast furnace ironmaking after secondary roasting.X-ray photoelectron spectroscopy(XPS)and scanning electron microscopy with energy dispersive X-ray spectrometry(SEMEDS)analyses showed that V^(3+)was oxidized to V^(5+)after roasting at 1200℃,and V^(5+)was then leached by H_(2)SO_(4).X-ray diffraction(XRD)analyses and single factor experiment revealed a minimal amount of dissolved Fe_(2)O_(3) during H_(2)SO_(4) leaching.Therefore,a high separation degree of V and iron(Fe)from V-Ti magnetite concentrate was achieved through H_(2)SO_(4) leaching.Compared with the traditional roastingleaching process,this process can achieve a high selectivity of V and Fe,and has excellent prospects for industrial production.

Thermodynamic studies on gas-based reduction of vanadium titano-magnetite pellets

Numerous studies have focused on the reduction thermodynamics of ordinary iron ore;by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed atmospheres of H2, CO, H2O, CO2, and N2. In this paper, thermodynamic studies on the reduction of oxidized VTM pellets were systematically conducted in an atmosphere of a C–H–O system as a reducing agent. The results indicate that VTM of an equivalent valence state is more difficult to reduce than ordinary iron ore. A reduction equilibrium diagram using the C–H–O system as a reducing agent was obtained;it clearly describes the reduction process. Experiments were performed to investigate the effects of the reduction temperature, the gas composition, and two types of iron ores on the reduction of oxidized VTM pellets. The results show that the final reduction degree increases with increasing reduction temperature, increasing molar ratio of H2/(H2 + CO), and decreasing H2O, CO2, and N2 contents. In addition, the reduction processes under various conditions are discussed. All of the results of the reduction experiments are consistent with those of theoretical thermodynamic analysis. This study is expected to provide valuable thermodynamic theory on the industrial applications of VTM.

Influence of microwave treatment on grinding and dissociation characteristics of vanadium titano-magnetite

The effect of microwave treatment on the grinding and dissociation characteristics of vanadium titano-magnetite(VTM) ore were investigated using scanning electron microscopy(SEM), nitrogen absorption measurements, particle size distribution measurements, X-ray diffraction(XRD) analysis, Fourier transform infrared(FT-IR) spectroscopic analysis, and magnetic separation. SEM analysis showed that microfractures appeared in the microwave-treated VTM, which is attributed to the microwaves' selective heating characteristic and the differential expansion between minerals and gangues. Nitrogen absorption showed that the microfractures were more pronounced when the microwave heating time was increased. Particle size distribution analysis showed that microwave treatment could improve the grindability of the VTM, thus increasing the weight percent of the fine-ground product. The increase in grindability was more significant with prolonged heating time. Moreover, the particle size distribution of the fine-ground product changed only slightly after the microwave treatment. XRD analysis showed that the crystallinity of the microwave-treated VTM increased with increasing microwave heating time. The magnetic separation tests revealed that the separation efficiency increased as a result of the intergranular fractures generated by microwave treatment. The Fe grade of the magnetic fraction of microwave-treated VTM was 1.72% higher than that of the raw ore. We concluded that the microwave treatment was beneficial, especially for the mineral processing characteristics.

Vanadium recovery from Na_(2)SO_(4)-added V-Ti magnetite concentrate via grate-kiln process

Pilot experiments on Na;SO;-roasting of V-Ti magnetite(VTM) concentrate pellets were performed to activate vanadium with simulated grate-kiln machines. Combined with thermodynamic calculation, X-ray diffraction(XRD), scanning electron microscopy with energy-dispersive X-ray spectroscopy(SEM-EDS), and inductively coupled plasma-atomic emission spectrometry(ICP-AES) analyses, process parameters of pellet making were optimized, and the enhancement of vanadium oxidation and conversion was realized. The results show that, in balling stage, adding Na;SO;can promote the thermal decrepitation resistance of green pellets;in the drying stage, higher wind temperature can improve the dispersion of sodium salt in pellets;in preheating stage, using O;-rich hot gas can promote more thorough oxidation of vanadium;in roasting stage, the effect of vanadium conversion to sodium vanadate is better when the liquid amount is 15.5%-22.5%. Based on the above measures, the vanadium conversion rate achieved in the roasted pellets is 85.6%, proving the feasibility of vanadium recovery using an existing pellet production line.

Influence and mechanism of Indonesia vanadium titano-magnetite on metallurgical properties of iron ore sinter

In order to provide a reliable reference for utilizing Indonesia vanadium titano-magnetite(VTM) in blast furnace(BF) economically, metallurgical properties of iron ore sinter with addition of Indonesia VTM in mixed sintering materials were investigated, including low-temperature reduction degradation index(RDI), reducibility index(RI), and softening/melting properties. Additionally, influenced mechanism of Indonesia VTM on metallurgical properties of sinter was studied. It is found that adding Indonesia VTM in sintering process quickly increases the RDI of sinters, and decreases the RI from 78.02% to 68.43%. Moreover, both beginning temperature(T_4) and final temperature(TD) of softening/melting increase gradually, and cohesive zone temperature range(T_D–T_4) enlarges from 219 oC to 315 oC. As a result, the permeability of cohesive zone gets worse, which is proven by the higher maximum pressure drop(δPmax) in softening/melting experiments. It is concluded that, after comprehensively considering all metallurgical properties mentioned above, the proper proportion of Indonesia VTM in sintering process is proposed in the new raw materials conditions.

φ-pH diagram of V-Ti-H_2O system during pressure acid leaching of converter slag containing vanadium and titanium

To analyze the thermodynamic characteristics of leaching process of converter slag, φ-pH diagram of V-Ti-H2O system at oxygen partial pressure of 0.5 MPa, ionic mass concentration of 0.1 mol/kg and temperatures ranging from 60 to 200 ℃ was obtained by recently published critically assessed standard Gibbs energies and activity coefficients of various species. When pH2, stable regions of V3＋, VO2＋ and VO2＋ exist in the stable region of TiO2. The pH values of stable regions of vanadium and titanium decrease and redox potentials become more positive with the temperature increasing. Vanadium and titanium could be separated by one-step leaching based on thermodynamics. The experiment results of pressure acid leaching of converter slag show that leaching rates of vanadium and titanium are 96.87% and 8.76% respectively, at 140 ℃ of temperature, 0.5 MPa of oxygen partial pressure, 0.055-0.075mm of particle size, 15：1 of liquid to solid ratio, 120 min of leaching time, 500 r/min of stirring speed and 200 g/L of initial acid concentration. Vanadium and titanium could be selectively separated in the pressure acid leaching process, and the experiment result is in agreement with thermodynamic calculation result.

Review on the latest developments in modified vanadium-titanium-based SCR catalysts

Vanadium-titanium-based catalysts are the most widely used industrial materials for NO_x removal from coal-fired power plants. Owing to their relatively poor low-temperature deNO_x activity, low thermal stability, insufficient Hg^0 oxidation activity, SO_2 oxidation, ammonia slip, and other disadvantages,modifications to traditional vanadium-titanium-based selective catalytic reduction（SCR）catalysts have been attempted by many researchers to promote their relevant performance. This article reviewed the research progress of modified vanadium-titanium-based SCR catalysts from seven aspects, namely,（1） improving low-temperature deNO_x efficiency,（2） enhancing thermal stability,（3） improving Hg^0 oxidation efficiency,（4） oxidizing slip ammonia,（5） reducing SO_2 oxidation,（6） increasing alkali resistance, and（7） others. Their catalytic performance and the influence mechanisms have been discussed in detail. These catalysts were also divided into different categories according to their modified components such as noble metals（e.g., silver, ruthenium）, transition metals（e.g., manganese, iron, copper, zirconium, etc.）, rare earth metals（e.g., cerium, praseodymium）,and other metal chlorides（e.g., calcium chloride, copper chloride） and non-metals（fluorine,sulfur, silicon, nitrogen, etc.）. The advantages and disadvantages of these catalysts were summarized.Based on previous studies and the author＇s point of view, doping the appropriate modified components is beneficial to further improve the overall performance of vanadium-titanium-based SCR catalysts. This has enormous development potential and is a promising way to realize the control of multiple pollutants on the basis of the existing flue gas treatment system.

Reduction behavior and kinetics of vanadium–titanium sinters under high potential oxygen enriched pulverized coal injection

In this work, the reduction behavior of vanadium–titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2contents. Meanwhile, with the increase in CO and H2contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol. © 2017, The Author(s).

Two-stage cyclic ammonium sulfate roasting and leaching of extracting vanadium and titanium from vanadium slag

Compared with traditional sodium or calcification roasting process for vanadium extraction from raw vanadium slag(V-slag),ammonium sulfate(AS)roasting could reduce about 470℃ roasting temperature and avoid Cl_(2),HCl,sodium-containing waste-water and waste gypsum discharging.To reduce the amount of AS added in vanadium extraction process,an efficient AS two-stage cyclic roasting and acid leaching process was proposed.The result of TG analysis indicates V-slag could be decomposed in 275-380℃ using AS roasting process.Using 2.03:1 total mass ratio of AS to V-slag,90.86%V and 80.54%Ti could be extracted after 380℃ roasting for 30 min and 8%initial concentration of H_(2)SO_(4) leaching at 70℃ for 100 min.XRD analysis indicates V-containing spinel phase in the 1st stage leaching residue would be efficiently decomposed by the cyclic two-stage roasting and leaching process.Furthermore,the valence of V(Ⅲ)in raw V-slag was not changed after the 1st AS roasting stage,but a part of V(Ⅲ)in the 1st leaching residue was oxidized to V(V)after 2nd roasting process.

Effect of purification pretreatment on the recovery of magnetite from waste ferrous sulfate

The present study was conducted to elucidate the influence of impurities in waste ferrous sulfate on its recovery of magnetite. Ferrous sulfate solution was purified by the addition of Na OH solution to precipitate impurities, and magnetite was recovered from ferrous sulfate solution without and with purification pretreatment. Calcium hydroxide was added to the solution of ferrous sulfate as a precipitator. A mixed product of magnetite and gypsum was subsequently obtained by air oxidation and heating. Wet-milling was performed prior to magnetic separation to recover magnetite from the mixed products. The results show that with the purification pretreatment, the grade of iron in magnetite concentrate increased from 62.05% to 65.58% and the recovery rate of iron decreased from 85.35% to 80.35%. The purification pretreatment reduced the conglutination between magnetite and gypsum, which favors their subsequent magnetic separation. In summary, a higher-grade magnetite with a better crystallinity and a larger particle size of 2.35 μm was obtained with the purification pretreatment.