High-chromium vanadium-titanium magnetite all-pellet integrated burden optimization and softening-melting behavior based on flux pellets

High-chromium vanadium-titanium magnetite(HVTM)is a crucial polymetallic-associated resource to be developed.The allpellet operation is a blast furnace trend that aims to reduce carbon dioxide emissions in the future.By referencing the production data of vanadium-titanium magnetite blast furnaces,this study explored the softening-melting behavior of high-chromium vanadium-titanium magnetite and obtained the optimal integrated burden based on flux pellets.The results show that the burden with a composition of 70wt%flux pellets and 30wt%acid pellets exhibits the best softening-melting properties.In comparison to that of the single burden,the softening-melting characteristic temperature of this burden composition was higher.The melting interval first increased from 307 to 362℃and then decreased to 282℃.The maximum pressure drop(ΔPmax)decreased from 26.76 to 19.01 kPa.The permeability index(S)dropped from 4643.5 to 2446.8 kPa·℃.The softening-melting properties of the integrated burden were apparently improved.The acid pellets played a role in withstanding load during the softening process.The flux pellets in the integrated burden exhibited a higher slag melting point,which increased the melting temperature during the melting process.The slag homogeneity and the TiC produced by over-reduction led to the gas permeability deterioration of the single burden.The segregation of the flux and acid pellets in the HVTM proportion and basicity mainly led to the better softening-melting properties of the integrated burden.

Effect of basicity on sintering behavior of low-titanium vanadium-titanium magnetite

Basicity has an important effect on the sinter quality, especially for low-titanium vanadium-titanium sinter. The effect of basieity on sintering behavior of low-titanium vanadium-titanium mixture, and the transference and distribution of element in sintering process were researched by sinter pot test, mineralogical analysis, scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS） analysis. The results show that CaO preferentially reacts with TiO2, generating pervoskite, so that the total liquid phase content of the sinter is low. There is an increase in the perovskite concentration of the sinter with the basicity ranging from 1.9：1 to 2.7：1. With increasing the basicity, the calcium ferrite content increases slightly and then rises rapidly, while the silicate content decreases and the metallurgical property of the sinter is improved. As for the distribution of these elements in the sinter, Ti occurs mainly in perovskite, V occurs mainly in silicate, and Fe occurs mainly in magnetite and hematite. The most abundant occurrence of Ca and Si occurs in silicate and perovskite. With increasing the basicity, the contents of A1 and Mg increase in calcium ferrite, while they decrease in other minerals.

Solid-state reduction kinetics and mechanism of pre-oxidized vanadium-titanium magnetite concentrate

The solid-state reduction kinetics of pre-oxidized vanadium-titanium magnetite concentrate was studied. The phase and microstructure of the reduction product were characterized by XRD, SEM and EDS methods, based on which the mechanism of the solid-state reduction was investigated. The results showed that using coal as reductant at 950-1100 °C, the solid-state reduction of the pre-oxidized vanadium-titanium magnetite concentrate was controlled by interface chemical reaction and the apparent activation energy was 67.719 k J/mol. The mineral phase transformation during the reduction process can be described as follows： pre-oxidized vanadium-titanium magnetite concentrate → ulvospinel → ilmenite → Fe Ti2O5 →（FenTi1-n）Ti2O5. M3O5-type（M can be Fe, Ti, Mg, Mn, etc） solid solutions would be formed during the reduction process of the pre-oxidized vanadium-titanium magnetite concentrate at 1050 °C for 60 min. The poor reducibility of iron in M3O5 solid solutions is the main reason to limit the reduction property of pre-oxidized vanadium-titanium magnetite concentrate.

Effects of basicity and temperature on mineralogy and reduction behaviors of high-chromium vanadium-titanium magnetite sinters

The effects of basicity and temperature on the reduction process of Hongge high-chromium vanadium-titanium magnetite(HCVTM)sinter were investigated in this work.The main characterization methods of X-ray fluorescence(XRF),X-ray diffraction(XRD),scanning electron microscope(SEM),and metallographic microscope were employed in this study.In this work,the reduction of HCVTM sinter with different temperature and basicity were experimented.The Fe,FeO,and TiO in reductive samples increase with increasing basicity and temperatures.The increase of basicity and temperature is favorable to the reduction of HCVTM sinter.The Fe phase has out-migration tendency to the surface of sinter while the perovskite and silicate phases have in-migration tendency to the inside of sinter.The reduction degradation index(RDI)decreases while the reduction index(RI)increases with increasing basicity.The RI increases from 67.14%to 82.09%with increasing temperature from 1073 K to 1373 K.

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%.

Effect and function mechanism of sinter basicity on softening-melting behaviors of mixed burden made from chromium-bearing vanadium-titanium magnetite

The effect of sinter basicity on softening-melting behaviors of mixed burden made from chromium-bearing vanadium-titanium magnetite(Cr-V-Ti magnetite) was investigated and the function mechanism was simultaneously analyzed.The results show that with increasing sinter basicity from 1.71 to 2.36,the softening interval tends to increase from 149.3 ℃ to 181.7 ℃while the melting interval tends to decrease from 178.0 ℃ to 136.7 ℃.The location of cohesive zone moves downwards firstly and then ascends slightly,but the cohesive zone becomes thinner.The softening-melting characteristic value becomes small,which indicates that the permeability of burden column is improved.The dripping ratio of mixed burden tends to increase firstly and then decrease,which comes to the highest value of 74.50%when the sinter basicity is 2.13.The content and the recovery of V and Cr in dripping iron are all increased.The generation amount of components with high melting point in slag becomes little with the increase of sinter basicity,which could improve the permeability of mixed burden.Taking softening-melting behaviors of mixed burden and recovery of valuable elements into account,the proper sinter basicity is no less than 2.13 for smelting mixed burden made from Cr-V-Ti magnetite in blast furnace.

Wettability and corrosion behavior between alkaline slag from sodium smelting of vanadium-titanium magnetite and refractory substrates

The sodium smelting of vanadium-titanium magnetite can achieve the comprehensive utilization of Fe,V,and Ti.However,the generation of alkaline slag during this process may cause damage to refractory materials.The wettability and corrosion behavior of alkaline slag on three types of refractory(MgO-C,SiC,and high alumina refractory)substrates were investigated at temperatures up to 1200℃.The effects of duration on the wettability of molten slag on SiC substrates were also investigated.Results showed that the high alumina refractory exhibited better wettability with the molten slag than the others,and thus,it is easier to be corroded.The results of scanning electron microscopy coupled with energy dispersive spectroscopy showed that MgO-C and high alumina refractory substrates were severely eroded.There was a visible and regular interfacial reaction layer between the slag and SiC refractory substrate,which was produced by the redox reaction between the metal oxides in the slag and the SiC refractory substrate.With the increase in holding time,the interface layer expands and silico-ferrite phases are generated at the interface.The redox reaction between Fe_(2)O_(3) and SiC substrate is the main reason for the corrosion.By comparing the differences in wettability and corrosion behavior between the alkaline slag from sodium smelting of vanadium-titanium magnetite and MgO-C,SiC and high alumina refractories,it is concluded that SiC refractory has good corrosion resistance to the slag.Iron oxides in the slag accelerate the oxidation rate of SiC refractory.

Enrichment and reconfiguration of titanium-bearing phase in vortex smelting reduction process of vanadium-titanium magnetite

To comprehensively utilize the low-iron high-vanadium-titanium magnetite,a new method of vortex smelting reduction of vanadium-titanium magnetite was proposed,and the enrichment and reconstitution regularity of Ti-bearing phases in the slag was investigated through X-ray fluorescence spectrometry,X-ray photoelectron spectroscopy,X-ray diffraction analysis,and optical microscopy.The phase diagram revealed that the preferential crystallization of MgTi_(2)O_(5) can be achieved by adjusting the CaO,MgO,and TiO_(2) contents of slag.The predominant Ti-bearing phases in the slag obtained from the reduction process are MgxTi_(3_x)O_(5)(0≤x≤1)and CaTiO_(3).FeTiO_(3) is present at carbon-iron ratio(CR)=1.3,while MgTi_(2)O4 and TiC are formed at CR=1.3.The enrichment of TiO_(2) in the slag increases first and then decreases as the CR increases,and at CR=1.1,the enrichment of TiO_(2) in the slag reaches 51.3 wt.%.Additionally,the concentrations of MgxTi_(3_x)O_(5)(0≤x≤1)and CaTiO_(3) in the slag,along with the grain width of MgxTi_(3_x)O_(5)(0≤x≤1),decrease with the increase in CR.

Optimization of BF Slag for High Cr_2O_3 Vanadium-titanium Magnetite

In order to clarify the slag system of high Cr2O3 vanadium-titanium magnetite smelting in BF （blast furnace）, the melting properties of slag samples prepared by analytically pure reagents were measured. By means of orthogonal test synthetic weighted score method, the optimal slag for high Cr2O3 vanadium-titanium magnetite was obtained, which contained 10% MgO, 8% TiO2 and 15% Al2O3, with the binary basicity being 1.15. In addition, the effects of basicity, MgO, TiO2 and A12 03 on slag melting properties were investigated by single factor test, and the results showed that, with increasing the basicity or TiO2 content, melting temperature （Tin） increased, whereas initial vis- cosity （r/0） and high temperature viscosity （r/h） decreased. With increasing the MgO content, Tm decreased firstly and then increased. With increasing the Al2 O3 content, Tm increased, and η0 and r/h decreased firstly and then increased.

Oxidation Kinetics,Structural Changes and Element Migration during Oxidation Process of Vanadium-titanium Magnetite Ore

The oxidation kinetics, structural changes, and elements migration during the oxidation process of the va- nadium-titanium magnetite （VTM） ore were analyzed. Kinetics analysis indicated that the oxidation process was con- trolled by diffusion control and could be divided into interface diffusion and lattice diffusion with apparent activation energy of 99.69 kJ/mol and 144.08 kJ/mol in the range of 800--1000℃, respectively. The surface structure changed with the oxidization temperature as follows： dense surface→nano sized sheets→submicron particles→molten particles. The compact structure changed into porous one because of the elements migration and enrichment. Both Fe and Ti elements migrated in the opposite direction during the oxidation process. The V etement in the raw ore stably existed in the form of V^5＋ state, some vanadium migrated and occupied the tetrahedral sites of the hematite during the oxidation process.

Carbothermic Reduction Mechanism of Vanadium-titanium Magnetite

To achieve the high-efficiency utilization of vanadium-titanium magnetite（ VTM）,reduction experiments were conducted to determine the carbothermic reduction mechanism of VTM. Effects of volatile matter,temperature,time,and carbon ratio（ molar ratio of fixed carbon in coal to oxygen in iron oxides of VTM） on reduction degree were investigated.Results show that reduction degree increases with increasing volatile matter in coal,temperature,time,and carbon ratio.Phase transformation,microstructure,and reduction path were analyzed by X-ray diffraction,scanning electron microscopy,energy-dispersive X-ray spectroscopy,and Fact Sage 6. 0. The thermoravimetry-differential scanning calorimetry-quadrupole mass spectrometer method was used for kinetic analysis of the main reduction process. Results indicate that the kinetic mechanism follows the principle of random nucleation and growth（ n = 4）,and the activation energy values at 600-900 and 900-1 350 ℃ are 88. 7 and 295. 5 kJ / mol,respectively.

Kinetics and mechanism of coal-based direct reduction of highchromium vanadium-titanium magnetite

High-chromium vanadium-titanium magnetite(HCVTM)is a valuable resource containing metal elements such as iron,vanadium,titanium,and chromium.To recycle these elements,direct reduction is an efficient way.The mechanism and reaction kinetic parameters for the direct reduction of HCVTM were studied.Experimental results show that the reduction degree increases obviously when the C/O ratio and temperature increase.Thermodynamic analysis showed a dramatic mass loss in the direct reduction of HCVTM in the temperature range of 985-1160℃.From 1200 to 1350℃,the reduction curves for the isothermal reduction of HCVTM followed the same trend,with a sharp increase in the initial reaction zone and a slight increase in the reduction rate with increasing time,and finally,the isothermal reduction process of HCVTM was divided into several limiting stages with varying degrees,with inconsistent limiting factors for the reaction rate at different stages.The results also show that the activation energy decreases slightly at larger degrees of reduction.Also,the apparent rate constant k(T)increased with increasing reduction temperature,with lnk(T)showing a good linear relationship with temperature.

A promising method to recover spent V_(2)O_(5)-WO_(3)/TiO_(2) catalyst: treatment by vanadium-titanium magnetite sintering process

A large number of spent selective catalytic reduction(SCR)denitration catalysts are produced after the ultra-low emission transformation of coal-fired power plants in China.According to the China’s“Directory of National Hazardous Wastes(Version 2021)”,these spent vanadium-tungsten-titanium catalysts are classified as“HW50”hazardous waste,and their disposal and utilization processes have been strictly controlled.Thus,an effective and low-cost technique was developed to treat and utilize these spent SCR catalysts by the vanadium-titanium magnetite sintering process.Effects of adding spent SCR catalysts on the sintering production process and product quality indexes of sinter were studied.The results showed that adding spent SCR catalysts can improve the sintering granulation and green feed permeability,thereby increasing the productivity and flame front speed.When the addition proportion of spent SCR catalysts is less than 1 wt.%,the performance indexes of the finished sinter are basically equal to those of the finished sinter without adding spent SCR catalysts.Further increasing the proportion of spent SCR catalysts to 2.0 wt.%results in a decrease in product quality indexes,which could be attributed to the increase in perovskite content in the finished sinter.

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.

Conversion of ferric oxide to magnetite by hydrothermal reduction in Bayer digestion process

Digesting aluminum-bearing minerals and converting ferric oxide to magnetite simultaneously in Bayer digestion process is crucially important to deal with high-iron diasporic bauxite economically for alumina production.The reaction behaviors of hydrothermal reduction of ferric oxide in alkali solution were studied by both thermodynamic calculation and experimental investigation.The thermodynamic calculation indicates that Fe3O4 can be formed by the conversion of Fe2O3 at proper redox potentials in alkaline solution.The experimental results show that the formation ratio of Fe3O4 either through the reaction of Fe and Fe2O3 or through the reaction of Fe and H2O in alkaline aqueous solution increases remarkably with raising the temperature and alkali concentration,suggesting that Fe（OH）3- and Fe（OH）4- form by dissolving Fe and Fe2O3,respectively,in alkaline aqueous solution and further react to form Fe3O4.Moreover,aluminate ions have little influence on the hydrothermal reduction of Fe2O3 in alkaline aqueous solution,and converting iron minerals to magnetite can be realized in the Bayer digestion process of diasporic bauxite.

Effect of MgO content in sinter on the softening–melting behavior of mixed burden made from chromium-bearing vanadium–titanium magnetite

The effect of sinter with different MgO contents on the softening-melting behavior of mixed burden made from chro- mium-bearing vanadium-titanium magnetite was investigated. The results show that with increasing MgO content in the sinter, the softening interval and melting interval increased and the location of the cohesive zone shifted downward slightly and became moderately thicker. The softening-melting characteristic value was less pronounced when the MgO content in the sinter was 2.98wt%-3.40wt%. Increasing MgO content in the sinter reduced the content and recovery of V and Cr in the dripped iron. In addition, greater MgO contents in the sinter resulted in the generation of greater amounts of high-melting-point components, which adversely affected the permeability of the mixed burden. When the softening-melting behavior of the mixed burden and the recovery of valuable elements were taken into account, proper MgO con- tents in the sinter and slag ranged from 2.98wt% to 3.40wt% and from 11.46wt% to 12.72wt%, respectively, for the smelting of burden made from chromium-bearing vanadium-titanium magnetite in a blast furnace.

Exsolutions of Diopside and Magnetite in Olivine from Mantle Dunite,Luobusa Ophiolite,Tibet,China

The exsolutious of diopside and magnetite occur as intergrowth and orient within olivine from the mantle dunite, Luobusa ophiolite, Tibet. The dunite is very fresh with a mineral assemblage of olivine （〉95%） ＋ chromite （1%-4%） ＋ diopside （〈1%）. Two types of olivine are found in thin sections： one （Fo = 94） is coarse-grained, elongated with development of kink bands, wavy extinction and irregular margins; and the other （Fo = 96） is fine-grained and poly-angied. Some of the olivine grains contain minor Ca, Cr and Ni. Besides the exsolutions in olivine, three micron-size inclusions are also discovered. Analyzed through energy dispersive system （EDS） with unitary analytical method, the average compositions of the inclusions are： Na20, 3.12%-3.84%; MgO, 19.51%-23.79%; Al2O3, 9.33%-11.31%; SiO2, 44.89%-46.29%; CaO, 11.46%-12.90%; Cr2O3, 0.74%-2.29%; FeO, 4.26%- 5.27%, which is quite similar to those of amphibole. Diopside is anhedral f＇dling between olivines, or as micro-inclusions oriented in olivines. Chromite appears euhedral distributed between olivines, sometimes with apparent compositional zone. From core to rim of the chromite, Fe content increases and Cr decreases; and A! and Mg drop greatly on the rim. There is always incomplete magnetite zone around the chromite. Compared with the nodular chromite in the same section, the euhedral chromite has higher Fe3O4 and lower MgCr2O4 and MgAI2O4 end member contents, which means it formed under higher oxygen fugacity environment. With a geothermometer estimation, the equilibrium crystalline temperature is 820℃-960℃ for olivine and nodular chromite, 630℃-770℃ for olivine and euhedral chromite, and 350℃-550℃ for olivine and exsoluted magnetite, showing that the exsolutions occurred late at low temperature. Thus we propose that previously depleted mantle harzburgite reacted with the melt containing Na, Al and Ca, and produced an olivine solid solution added with Na^＋, Al^3＋, Ca^2＋, Fe^3＋, Cr^3＋. With temperature decreasing, the olivine solid solution decomposed; and Fe^3＋, Cr^3＋ diffused into magnetite and Ca^2＋ and Na^＋ into clinopyroxene, both of which formed intergrowth textures. A few Fe^3＋ and Cr^3＋ entered interstitial chromite. Through later tectonism, the peridotite recrystallized and formed deformational coarse grained olivine, fine grained and poly-angled olivine, and euhedral grained chromite. Due to the fast cooling rate of the rock or rapid tectonic emplacement, the exsolution textures in olivine and compositional zones of chromite are preserved.

Some basic properties of granules from ore blends consisting of ultrafine magnetite and hematite ores

Some basic properties of granules,including the granule size distribution,packed-bed permeability,and chemical composition of the adhering layer,were investigated in this study for four iron ore blends consisting of 5wt%,25wt%,and 45wt%ultrafine magnetite and 25wt%ultrafine hematite concentrates.The effects of varying the sinter basicity(CaO/SiO2 mass ratio=1.4 to 2.2)and adding ultrafine concentrates on the variation of the adhering-layer composition and granule microstructure were studied.Moreover,the effect of adhering-layer compositional changes on sintering reactions was discussed in combination with pot sintering results of ore blends.Increasing sinter basicity led to an increase in the basicities of both the adhering layer and the fine part of the sinter mix,which were higher than the overall sinter basicity.When the sinter chemistry was fixed and fine Si-bearing materials(e.g.,quartz sand)were used,increasing the amount of ultrafine ores in the ore blends tended to reduce the adhering-layer basicity and increase the SiO2 content in both the adhering layer and the fine part of the sinter mix,which will induce the formation of low-strength bonding phases and the deterioration of sinter strength.The adhering-layer composition in granules can be estimated in advance from the compositions of the-1 mm fractions of the raw materials.

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.

Oxidation behavior of artificial magnetite pellets

The oxidation behavior of artificial magnetite pellets was investigated through measurements of the oxidation degree and mineralogical analysis. The results show that artificial magnetite pellets are much easier to oxidize than natural magnetite. The oxidation is controlled through two different reaction mechanisms. The oxidation of artificial magnetite is dominated by internal diffusion, with an activation energy of 8.40 kJ/mol, at temperatures less than 800°C, whereas it is controlled by chemical reaction, with a reaction activation energy of 67.79 kJ/mol, at temperatures greater than 800°C. In addition, factors such as the oxygen volume fraction and the pellet diameter strongly influence the oxidation of artificial magnetite: a larger oxygen volume fraction and a smaller pellet diameter result in a much faster oxidation process.