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℃, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, 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.     

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.     

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.     

钒钛磁铁精矿的预氧化研究

研究了钒钛磁铁精矿在等温预氧化条件下的物相组成及其转变情况,并将钒钛磁铁精矿原矿和预氧化后的样品以煤粉为还原剂进行直接还原,利用XRD和ICP-AES对产物进行物相和成份分析.研究结果表明:预氧化能够加速还原过程,提高金属化率,较为适宜的预氧化条件为:预氧化温度为900℃,预氧化时间为30 min;预氧化矿在1 200℃下还原60 min,比钒钛磁铁精矿原矿金属化率提高了14.0%.其强化还原的机理是:在预氧化过程中Fe3O4被氧化成Fe2O3,FeTiO3被氧化成Fe2O3.FeTiO3固溶体、Fe2O3和TiO2,破坏了钒钛磁铁精矿的结构,矿粉内部形成了大量孔隙,改善了还原反应的动力学条件,加速了还原过程.     

钒钛磁铁精矿直接还原反应行为及其强化还原研究

通过在钒钛磁铁精矿中添加还原煤粉和少量添加剂,研究了还原温度、还原时间和添加剂等因素对钒钛磁铁精矿金属化率的影响,并对添加剂强化还原机理进行了探讨.结果表明:还原温度、还原时间、碳铁摩尔比及添加剂对金属化率的影响较大.在还原温度1200℃、还原时间120 min的条件下,未添加添加剂时金属化率最高可达84.5%;添加质量分数3.0%Na2CO3或CaF2的条件下,钒钛磁铁精矿的金属化率可以分别达到96.5%和93.3%.     

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

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

酸浸法提钒新工艺的研究

研究了用稀硫酸直接浸出—萃取—反萃—氨水沉钒—煅烧的提钒工艺。结果表明,采用稀硫酸直接浸出,原矿渣中总钒的一次浸取率可达95%以上;用萃取-反萃方式净化和浓缩浸出液,同时使用萃取促进剂处理酸浸液,使萃取效率比传统方法有明显提高,萃取级数大大减少;沉钒步骤摒弃了传统的铵盐沉钒工艺,使用氨水直接沉钒,提高了产品的纯度。钒的总回收率达86%以上,比传统提钒工艺效率提高了20%以上,同时由于避免了焙烧从而解决了传统提钒过程中因焙烧等产生的HCl、Cl₂等污染问题。     

硼对钒钛磁铁矿烧结微观结构的影响

为研究硼的含量对钒钛磁铁烧结矿微观结构的影响,利用XRD和扫描电镜对实验样品进行观察,发现添加适量的硼能够对钒钛烧结矿中硅酸盐的生成起抑制作用,并改善钒钛磁铁烧结矿表面结构,提高烧结矿液相生成能力、固相固结性能、抗粉化性同时降低孔隙率。当烧结矿中硼含量达到1.5%~2.5%时实验效果最佳。     

高炉灰为还原剂对海滨钛磁铁矿直接还原焙烧磁选--钛铁分离的影响

对高炉灰在直接还原焙烧-弱磁选工艺中用作印尼某海滨钛磁铁矿还原剂的可行性及其机理进行研究.结果表明,以萤石为添加剂的条件下,高炉灰可代替煤做还原剂,通过高炉灰与萤石的共同作用,可以在直接还原过程中提高还原铁粉中铁的回收率及品位并降低TiO2质量分数,同时回收高炉灰中铁.三种不同产地高炉灰还原效果的比较表明,高炉灰性质对还原效果有影响.在相同用量条件下,津鑫高炉灰( JX)还原效果最好;在JX高炉灰用量30%、萤石用量10%、焙烧温度1250益以及焙烧时间为60 min时,焙烧产物通过两段磨矿和两段磁选,最终得到最佳的还原铁粉中铁品位为91.28%,TiO2质量分数降至0.93%,包括海滨砂矿和高炉灰中铁的铁总回收率达到89.19%.     

Carbothermic reduction of vanadium titanomagnetite with the assistance of sodium carbonate

The carbothermic reduction of vanadium titanomagnetite concentrate (VTC) with the assistance of Na₂CO₃ 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 Na₂CO₃,it was concluded that molten Na₂CO₃ broke the structure of titanomagnetite by combining with th...     

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 CaCO_3 no additive CaSO_4 CaCl_2, which indicated that the addition of CaCO_3 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 CO_2 were highest when CaCO_3 was added, while that in a roasting system decreased the most when CaCl_2 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(FeTi_2O_5) to metallic iron(Fe) and perovekite(CaTiO_3) when calcium compounds were added. Additionally, CaSO_4 and CaCl_2 could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg_2TiO_4 in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO_4.     

钒钛铁精矿内配碳球团高温快速直接还原历程

采用高温实验炉,在1 350℃,氮气保护气氛条件下对钒钛磁铁精矿内配碳球团进行了阶段还原试验,通过TG-DSC、XRD、SEM等检测方法对不同时间内配碳球团还原的组织成分、显微结构等进行研究。结果表明,钒钛铁精矿的还原历程依次为Fe2TiO4和Fe3O4、3(Fe3O4).Fe2TiO4、Fe3O4.Fe2TiO4、Fe2TiO4和FeO、Fe和FeTi2O5;在磁铁矿大量还原生成浮士体的阶段,钛铁矿与新生成的浮士体发生钛铁晶石化,最终还原转变为单质铁和含铁黑钛石。     

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

Smelting separations of Hongge vanadium-bearing titanomagnetite metallized pellets (HVTMP) prepared by gas-based direct reduction were investigated, and the effects of smelting parameters on the slag/metal separation behaviors were analyzed. Relevant mechanisms were elucidated using X-ray diffraction analysis, FACTSAGE 7.0 calculations, and scanning electron microscopy observations. The results show that, when the smelting temperature, time, and C/O ratio are increased, the recoveries of V and Cr of HVTMP in pig iron are improved, the recovery of Fe initially increases and subsequently decreases, and the recovery of TiO₂ in slag decreases. When the smelting CaO/SiO₂ ratio is increased, the recoveries of Fe, V, and Cr in pig iron increase and the recovery of TiO₂ in slag initially increases and subsequently decreases. The appropriate smelting separation parameters for HVTMP are as follows: smelting temperature of 1873 K; smelting time of 30–50 min; C/O ratio of 1.25; and CaO/SiO₂ ratio of 0.50. With these optimized parameters (smelting time: 30 min), the recoveries of Fe, V, Cr, and TiO₂ are 99.5%, 91.24%, 92.41%, and 94.86%, respectively.     

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite (TTM) ironsand, which contains 11.41wt% TiO₂ and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence: FeO + FeTiO₃ → Fe₂TiO₄ → FeTiO₃ → FeTi₂O₅ → TiO₂. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 kJ·mol-1.     

Application of a water cooling treatment and its effect on coal-based reduction of high-chromium vanadium and titanium iron ore

A water cooling treatment was applied in the coal-based reduction of high-chromium vanadium and titanium (V–Ti–Cr) iron ore from the Hongge region of Panzhihua, China. Its effects on the metallization ratio (η), S removal ratio (R_S), and P removal ratio (R_P) were studied and analyzed on the basis of chemical composition determined via inductively coupled plasma optical emission spectroscopy. The metallic iron particle size and the element distribution of Fe, V, Cr, and Ti in a reduced briquette after water cooling treatment at 1350°C were determined and observed via scanning electron microscopy. The results show that the water cooling treatment improved the η, R_S, and R_P in the coal-based reduction of V–Ti–Cr iron ore compared to those obtained with a furnace cooling treatment. Meanwhile, the particle size of metallic iron obtained via the water cooling treatment was smaller than that of metallic iron obtained via the furnace cooling treatment; however, the particle size reached 70 μm at 1350°C, which is substantially larger than the minimum particle size required (20 μm) for magnetic separation. Therefore, the water cooling treatment described in this work is a good method for improving the quality of metallic iron in coal-based reduction and it could be applied in the coal-based reduction of V–Ti–Cr iron ore followed by magnetic separation.     

Formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate by adding CaCO_3

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate(VTC) by adding CaCO_3 was investigated. Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and Ca CO_3 in a reductive atmosphere, where ilmenite is more easily reduced by CO or carbon in the presence of CaCO_3. The effects of CaCO_3 dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test. Appropriate increase of CaCO_3 dosages and reduction temperatures were found to be conducive to the formation of calcium titanate, and the optimum conditions were a CaCO_3 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 CaCO_3 addition was of higher purity with particle size approximately 50 μm. Hence, the separation of calcium titanate and metallic iron will be the focus in the future study.     

熔融还原法镍渣炼铁的热力学与动力学

利用熔融还原法进行了闪速炉水淬镍渣提铁的实验研究,探讨了熔渣二元碱度、反应温度和反应时间对提铁效果的影响.XRD测试结果表明水淬镍渣由正硅酸铁FeO.SiO2和玻璃态物质组成.镍渣中的氧化铁主要以FeO.SiO2的形式存在,通过常规的选矿方法很难实现铁氧化物的富集,故采用熔融还原方法进行镍渣提铁实验.实验结果表明增加配合料中CaO的加入量、提高反应温度以及延长熔制时间都能不同程度地提高镍渣中铁的还原率.通过比较1450～1600℃范围内各反应温度下不同类型还原反应的Gibbs自由能,镍渣熔融还原过程的主要反应形式为(FeO)+C(S)→[Fe]+CO.本实验确定的最佳配方组成为:镍渣100g、CaO34.7g、CaF24.04g和焦炭8.5g;最佳反应条件为1500℃熔制180min.以上条件下的渣铁分离效果较好,铁还原率达到96.32%.     

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 Cr_2O_3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr_2O_3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr_2O_3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe–Cr solid solutions(Fe_(1.2)Cr_(0.8)O_3 and Fe_(0.7)Cr_(1.3)O_3) 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 Cr_2O_3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.     

金川镍弃渣铁资源回收综合利用

针对金川镍弃渣的特点,采用深度还原-磁选工艺,对其进行铁资源回收的综合利用实验研究,获得了铁品位为89.84%,铁回收率达93.21%的铁精矿. 探讨了还原温度、还原时间、二元碱度、磨矿细度和磁场强度等不同实验条件对产品指标和分离效果的影响. 通过X射线衍射分析、光学显微分析、SEM分析、化学分析等手段确定了镍弃渣与铁精矿的物相组成和特点.     

从高炉除尘灰中综合回收碳、铁和锌的试验研究

基于选冶联合工艺,对某厂排放的高炉除尘灰进行综合回收铁、锌、碳的试验研究。先采用浮选-磁选法回收碳和铁,再采用酸浸-除杂-电积湿法回收锌,重点对影响锌浸出的工艺因素和条件进行了考察。结果表明,通过选冶联合工艺处理高炉除尘灰获得较好的选别指标,且可回收碳品位为86.52%和回收率为92.80%的碳精矿、铁品位为54.16%和回收率为45.47%的铁精矿以及纯度为95.2%的锌产品,锌总回收率达到87%以上。