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.

Preparation of TiCl4 with the Titanium Slag Containing Magnesia and Calcia in a Combined Fluidized Bed

This paper describes a new method for producing TiCl4 by chloridizing materials of high content CaO and MgO, in which a combined fluidized bed is used as a reactor to avoid agglomeration between particles caused by molten CaCl2 and MgCl2. The combined fluidized bed consists of at least a riser tube and a semi-circulating fluidized bed. Two kinds of high titanium slag, in which the total mass content of CaO and MgO is 2.03% and 9.09% respectively, are employed to examine the anti-agglomeration effect and the conversion of the materials when the temperature ranges are between 923.15K and 1073.15K, gas apparent velocity 0.7--1.1m.s-1, and inlet amount of solid materials is 4.6-7.0kg·h^-1. It is found that the anti-agglomeration effect in the combined fluidized bed is satisfactory and the new method can achieve a TiCl4 production capacity of 14.0-75.4t·m^-2·d^-1 in relation to 25.0-- 40.0t·m^-2·d^-1 from the conventional bubble bed. Furthermore, low-temperature chloridization, for example, at 923K or 973K, can also be used to produce TiCl4 and avoid agglomeration.

Indirect mineral carbonation of titanium-bearing blast furnace slag coupled with recovery of TiO_2 and Al_2O_3

Large quantities of CO2 and blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial CO2 emission reduction and comprehensive utilization of the solid waste. This paper describes a novel route for indirect mineral carbonation of titanium-bearing blast furnace （TBBF） slag, in which the TBBF slag is roasted with recyclable （NH4）2SO4 （AS） at low temperatures and converted into the sulphates of various valuable metals, including calcium, magnesium, aluminium and titanium. High value added Ti-and Al-rich products can be obtained through stepwise precipitation of the leaching solution from the roasted slag. The NH3 produced during the roasting is used to capture CO2 from flue gases. The NH4HCO3 and （NH4）2CO3 thus obtained are used to carbonate the CaSO4-containing leaching residue and MgSO4-rich leaching solution, respectively. In this study, the process parameters and efficiency for the roasting, carbonation and Ti and Al recovery were investigated in detail. The results showed that the sulfation ratios of calcium, magnesium, titanium and aluminium reached 92.6%, 87% and 84.4%, respectively, after roasting at an AS-to-TBBF slag mass ratio of 2：1 and 350℃ for 2 h. The leaching solution was subjected to hydrolysis at 102℃ for 4 h with a Ti hydrolysis ratio of 95.7%and the purity of TiO2 in the calcined hydrolysate reached 98 wt%. 99.7% of aluminium in the Ti-depleted leaching solution was precipitated by using NH3. The carbonation products of Ca and Mg were CaCO3 and （NH4）2Mg（CO3）2·4H2O, respectively. The latter can be decomposed into MgCO3 at 100-200℃ with simultaneous recovery of the NH3 for reuse. In this process, approximately 82.1% of Ca and 84.2% of Mg in the TBBF slag were transformed into stable carbonates and the total CO2 sequestration capacity per ton of TBBF slag reached up to 239.7 kg. The TiO2 obtained can be used directly as an end product, while the Al-rich precipitate and the two carbonation products can act, respectively, as raw materials for electrolytic aluminium, cement and light magnesium carbonate production for the replacement of natural resources.

Research and prospect on extraction of vanadium from vanadium slag by liquid oxidation technologies

A series of innovative green metallurgical processes using novel reaction media including the NaOH/KOH sub-molten salt media and the NaOH-NaNO3 binary molten salt medium, for the extraction of vanadium and chromium from the vanadium slag have been developed. In comparison with the traditional sodium salt roasting technology, which operates at 850 ℃, the operation temperatures of these new processes drop to 200-400 ℃. Further, the extraction rates of vanadium and chromium utilizing the new approaches could reach 95% and 90%, respectively, significantly higher than those in the traditional roasting process, which are 75% and approximate zero, respectively. Besides, no hazardous gases and toxic tailings are discharged during the extraction process. Compared with the conventional roasting method, these new technologies show obvious advantages in terms of energy, environments, and the mineral resource utilization efficiency, providing an attractive alternative for the green technology upgrade of the vanadium production industries.

Extraction of vanadium from molten vanadium bearing slag by oxidation with pure oxygen in the presence of CaO

A novel process of vanadium extraction from vanadium slag in its molten state was conducted at the laboratory scale by oxidation with pure oxygen in the presence of CaO. The effect of mass ratio of CaO to V2O5 on the recovery of vanadium was studied. The sintered samples were leached by H2SO4 solution and characterized by XRD, XPS, SEM and EDS techniques. Compared with the roasting process, the energy saving effect of the proposed process was also discussed. The results showed that vanadium-rich phases were formed and vanadium mainly existed in the forms of CaV2O5 and Ca2V2O7. The formation mechanism of calcium vanadates in the molten vanadium bearing slag was explained. The XRD and XPS results implied that there was a limit to the oxidation reaction of V(IV) to V(V) under the high temperatures even though oxygen-supply was sufficient. An increase in the CaO content led to an increase in the formation of Ca2V2O7. About 90%of the vanadium recovery was obtained under optimal experiment conditions (mass ratio of CaO to V2O5 of 0.6, particle size 120 to 150μm, leaching temperature 90 °C, leaching time 2 h, H2SO4 concentration 20%, liquid to solid ratio 5:1 mL/g, stirring speed 500 r/min). The energy of 1.85×106 kJ could be saved in every 1000 kg of vanadium bearing slag using the proposed process from the theoretical calculation results. Recovery of vanadium from the molten vanadium bearing slag and utilisation of its heat energy are important not only for saving metal resources, but also for energy saving and emission reduction.

Removal of magnesium and calcium from electric furnace titanium slag by H_3PO_4 oxidation roasting-leaching process

H3PO4 oxidation roasting followed by HCl acid leaching was proposed to remove magnesium and calcium from electric furnace titanium slag containing 3.12% MgO and 0.86% CaO. XRF, XRD and SEM techniques were used to characterize the composition, mineral phase component and microstructure of the titanium slag. The H3PO4 oxidation thermodynamic, mineral phase transformation, microstructure, element distribution in titanium slag during H3PO4 oxidation process and leaching process were investigated. The thermodynamic analysis indicated that H3PO4 could promote the decomposition of MgTi2O5 and CaSiO3. The results indicated that H3PO4 could effectively promote the transformation of titanium-bearing mineral to rutile and enrich the impurities in MxTi（3-x）O5 into phosphate which could be removed by acid leaching process. Under the studied conditions, the leaching rates of magnesium and calcium reached 94.68% and 87.19%, respectively. The acid leached slag containing 0.19% MgO and 0.13% CaO（mass fraction） was obtained.

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.

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.

Effects of MgO and TiO_2 on the viscous behaviors and phase compositions of titanium-bearing slag

The effects of MgO and TiO_2 on the viscosity, activation energy for viscous flow, and break-point temperature of titanium-bearing slag were studied. The correlation between viscosity and slag structure was analyzed by Fourier transform infrared（FTIR） spectroscopy. Subsequently, main phases in the slag and their content changes were investigated by X-ray diffraction and Factsage 6.4 software package. The results show that the viscosity decreases when the MgO content increases from 10.00wt% to 14.00wt%. Moreover, the break-point temperature increases, and the activation energy for viscous flow initially increases and subsequently decreases. In addition, with increasing TiO_2 content from 5.00wt% to 9.00wt%, the viscosity decreases, and the break-point temperature and activation energy for viscous flow initially decrease and subsequently increase. FTIR analyses reveal that the polymerization degree of complex viscous units in titanium-bearing slag decreases with increasing MgO and TiO_2 contents. The mechanism of viscosity variation was elucidated. The basic phase in experimental slags is melilite. Besides, as the MgO content increases, the amount of magnesia–alumina spinel in the slag increases. Similarly, the sum of pyroxene and perovskite phases in the slag increases with increasing TiO_2 content.

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.

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.

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.

A novel method for extracting vanadium by low temperature sodium roasting from converter vanadium slag

Long-term high temperature in conventional vanadium extraction process would cause particles to be sintered and wrapped, thus reducing extraction efficiency of vanadium. Based on the purpose of directional conversion and process intensification, this work proposed a combination of low temperature sodium roasting and high efficiency selective oxidation leaching in vanadium extraction. The investigation of the reaction mechanism suggested that the structure of vanadium slag was changed by roasting, which also caused the fracture of spinel.The addition of MnO2 promoted the directional oxidation of low-valent vanadium into high valence. It also found that Na2S2O8 could oxidize low-valent vanadium effectively in leaching. The leaching efficiency of vanadium reached 87.74% under the optimum conditions, including a roasting temperature of 650 ℃, a roasting time of 2.0 h, a molar ratio of sodium-to-vanadium of 0.6, a MnO2(roasting additive) dosage of 5 wt% and a Na2S2O8(leaching oxidant) dosage of 5 wt%. This percentage is 7.18% higher than that of direct roasting-andleaching under the same conditions.

Effect of oxidization on enrichment behavior of TiO_2 in titanium-bearing slag

Due to the dispersed distribution of the titanium component in various mineral phases and very fine grain size, it is difficult to recover the titanium component from the slag. In order to utilize titanium resources, selective enriching and selective growing of the titanium component from the molten slag is expected. In this paper, the selection of the best titanium enrichment phase and the effect of oxidization on the enrichment of titanium by blowing air into the molten slag were studied. The results showed that through oxidizing the slag, the content of the perovskite phase increases while that of the other titanium-bearing mineral phases decreases until they disappear. Most titania resources were enriched into the perovskite phase and increase in size. The process of enrichment and growth is easily carried out.

Removal Hg⁰from Flue Gas with Modified VTSS by KBr and KI

Vanadium titanium steel slag (VTSS) containing transition metal can promote the adsorption of Hg0. The method of KBr and KI impregnation was applied to modify VTSS and the properties of the adsorbents were tested. The Hg0 removal tests were carried out with a fixed bed under different conditions. The results showed that the Hg0 adsorption capacity increase with the increasing temperature. The efficiency was highest with KI(3)/VTSS at 20。C and adsorption capacity was 163.4 ug/g after 3 h. The highest Hg0 removal efficiency were 90.6% for KI(3)/VTSS, 73.5% for KBr(10)/VTSS/ VTSS at 120。C, respectively.

Influence of desulfurization slag containing oxides of vanadium and titanium on semi-steel pre-desulfurization

The desulfurization and resulfurization of slag containing oxides of vanadium and titanium(CaO–SiO_(2)–MgO–Al_(2)O_(3)–V_(2)O_(3)–TiO_(2)–FeO)in the pretreatment of semi-steel desulfurization at 1623 K were investigated.Based on the ionic structure theory of slag,it could be concluded that V_(2)O_(3) and TiO_(2) combined with(O_(2)–)to form complex anions including VO_(3)^(3–),TiO_(4)^(4–),etc.,which reduced the activity of(O_(2)–)and decreased the sulfur partition ratio(LS).And FeO enhanced the activity of[O]at the slag–metal interface,which decreased the desulfurization capacity of the slag.Compared to the binary basicity,the presented basicity expression containing V_(2)O_(3) and TiO_(2) described the relationship between LS and basicity more accurately.Considering the problems of dilute slag,a large amount of residual slag and much resulfurization in the slagging-off process after pretreatment,the effect of CaO+C-based slag modifier on the resulfurization,melting point and viscosity of the desulfurization slag was investigated.It was proposed that adding 5%–10%of the slag modifier to the desulfurization slag after desulfurization decreased the resulfurization effectively.And the added modifier adjusted the slag viscosity well,which helped to reduce iron loss and residual slag.

Preparation of narrow band gap V_2O_5/TiO_2 composite films by micro-arc oxidation

V2Os/TiO2 composite films were prepared on pure titanium substmtes via micro-arc oxidation （MAO） in electrolytes consisting of NaVO3. Their morphology and dements were characterized by scanning electron microscopy （SEM） and energy-dispersive X-ray （EDX） analysis. Phase composition and valence states of species in the films were characterized by X-ray diffraction （XRD） and X-ray photoelec- tron spectroscopy （XPS）. Ultraviolet-visible diffuse reflectance spectra （UV-Vis DRS） were also employed to evaluate the photophysical property of the films. The VEOs/TiO2 composite films show a sheet-like morphology. Not only V205 phase appears in the films when the NaVO3 concentration of the electrolyte is higher than 6,10 g/L and is loaded at the surface of anatase, but also V4＋ is incorporated into the crystal lattice of anatase. In comparison with pure TiO2 films the V2Os/TiO2 composite films exhibit significantly narrow band gap energy. The film prepared in an electrolyte consisting of NaVO3 with a concentration of 8.54 g/L exhibits the narrowest band gap energy, which is approximately 1.89 eV. The V2Os/TiO2 composite films also have the significantly enhanced visible light photocatalytic activity. The film prepared in an electrolyte consisting of NaVO3 with a concentration of 8.54 g/L exhibits the best photocatalytic activity and about 93% of rhodamine is degraded after 14 h visible light radiation.

Corrosion Resistance of MgO-C Based Refractory to Slag Containing Titania

The interaction between the slag containing titanium oxides(TiO2of 2.0 %-20.0%)and a MgO-C based refractory was investigated by immersion test.The relationship between TiO2 content in slag and corrosion rate of the refractory was studied.The microstructure and compositions of the corroded refractory were analyzed by SEM and X-ray diffraction.The corrosion mechanism of MgO-C based refractory in the slag containing titanium was proposed,and the effects of TiO2 content,slag basicity(ωCaO/ωSiO2)and temperature in molten bath on the corrosion rate of the refractory were obtained.

高钛钢连铸保护渣对Al_(2)O_(3)夹杂物吸收性的研究

针对高钛钢连铸保护渣钢渣反应及吸收夹杂物的变性问题,采用热力学计算、保护渣性能测试和旋转柱法等方法,对高钛钢钢液内夹杂物的生成种类和不同温度下的生成量进行了计算,根据夹杂物的生成情况对比了传统CaO-SiO_(2)系和新开发的低反应性BaO-Al_(2)O_(3)-SiO_(2)-TiO_(2)系保护渣吸收夹杂物的性能变化,并对比了两种保护渣对夹杂物的吸收速率。热力学计算表明,研究的高钛钢中铝质量分数为0.03%、钛质量分数为0.40%,钢液中生成的夹杂物为Al_(2)O_(3),而实际生产中由于钢液局部成分差异可能有钛氧化物的生成;从保护渣吸收夹杂物前后的性能对比可知,两种保护渣的黏度和熔点均随其吸收Al_(2)O_(3)含量的增加而增加,但新开发的低反应性保护渣相对于CaO-SiO_(2)系渣的性能变化更小,其性能更稳定;由旋转柱试验可知,CaO-SiO_(2)系和BaO-Al_(2)O_(3)-SiO_(2)-TiO_(2)系保护渣对氧化铝棒的吸收速率分别在(8~12)×10^(-3) g/(cm^(2)·min)和(10~13)×10^(-3) g/(cm^(2)·min),后者对夹杂物的吸收能力更强。因此,新开发的BaO-Al_(2)O_(3)-SiO_(2)-TiO_(2)系低反应性保护渣有潜力用于更高钛含量的钢种浇铸。