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.     

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 method for recovery of iron,titanium, and vanadium from vanadium-bearing titanomagnetite

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures: low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200°C, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70 wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.     

Metalizing reduction and magnetic separation of vanadium titano-magnetite based on hot briquetting

To achieve high efficiency utilization of Panzhihua vanadium titano-magnetite, a new process of metalizing reduction and magnetic separation based on hot briquetting is proposed, and factors that affect the cold strength of the hot-briquetting products and the efficiency of reduction and magnetic separation are successively investigated through laboratory experiments. The relevant mechanisms are elucidated on the basis of microstructural observations. Experimental results show that the optimal process parameters for hot briquetting include a hot briquetting temperature of 475℃, a carbon ratio of 1.2, ore and coal particle sizes of less than 74 μm. Additionally, with respect to metalizing reduction and magnetic separation, the rational parameters include a magnetic field intensity of 50 mT, a reduction temperature of 1350℃, a reduction time of 60 min, and a carbon ratio of 1.2. Under these above conditions, the crushing strength of the hot-briquetting agglomerates is 1480 N, and the recovery ratios of iron, vanadium, and titanium are as high as 91.19%, 61.82%, and 85.31%, respectively. The new process of metalizing reduction and magnetic separation based on hot briquetting demonstrates the evident technological advantages of high efficiency separation of iron from other valuable elements in the vanadium titano-magnetite.     

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.     

Effect of reductant type on the embedding direct reduction of beach titanomagnetite concentrate

Iron and titanium were recovered from beach titanomagnetite(TTM) concentrate by embedding direct reduction and magnetic separation. The reduction products and the effects of the reductant type and reduction temperature on the reduction behavior were investigated. The results showed that the reduction of TTM concentrate was strongly related to the gasification reactivity of the reductant. Bitumite presented a better product index than wheat-straw biochar and coke, mainly because the gasification reactivity of bitumite was better than that of the other reductants. In addition, high temperatures were not beneficial to embedding direct reduction because of the emergence of a molten phase and iron-joined crystals, which in turn reduced the diffusion rate of the reducing gas and impeded the reduction reaction in the central area of the roasted briquette. The use of bitumite as the reductant at a C/Fe molar ratio of 1.4 and a reduction temperature of 1200°C for 120 min resulted in direct-reduction iron powder assaying 90.28 wt% TFe and 0.91 wt% TiO_2 with an iron recovery of 91.83% and titanium concentrate assaying 46.01 wt% TiO_2 with a TiO_2 recovery of 91.19%. Titanium existed mainly in the form of anosovite and ilmenite in the titanium concentrate.     

Extraction of vanadium from vanadium slag by high pressure oxidative acid leaching

To extract vanadium in an environment friendly manner, this study focuses on the process of leaching vanadium from vanadium slag by high pressure oxidative acid leaching. Characterizations of the raw slag, mineralogy transformation, and the form of leach residues were made by X-ray diffraction, scanning electron microscopy, and energy dispersive X-ray spectroscopy. The result shows that the vanadium slag is composed of major phases of fayalite, titanomagnetite, and spinel. During the high pressure oxidative acid leaching process, the fayalite and spinel phases are gradually decomposed by sulfuric acid, causing the release of vanadium and iron in the solution. Meanwhile, unreacted silicon and titanium are enriched in the leach residues. With the initial concentration of sulfuric acid at 250 g·L-1, a leaching temperature of 140℃, a leaching time of 50 min, a liquid-solid ratio of 10:1 mL·g-1, and oxygen pressure at 0.2 MPa, the leaching rate of vanadium reaches 97.69%.     

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.     

A new process of extracting vanadium from stone coal

A new process of extracting vanadium from the stone coal vanadium ore in Fangshankou, Dunhuang area of Gansu Province, China was introduced. Various leaching experiments were carried out, and the results show that the vanadium ore in Fangshankou is difficult to process due to its high consumption of acid and the high leaching rate of impurities. However, the leaching rate can be up to 80% and the content of V₂O₅ in the residue can be between 0.22%–0.25% in the process of ore fine grinding→oxidation roasting→mixing and ripening→aqueous leaching→P₂O₄ solvent extraction→sulfuric acid stripping→oxidation and precipitation→decomposition by heat. Also, the quality of flaky V₂O₅ produced by this process can meet the requirements of GB3283–87. The total leaching rate of vanadium is 70%. Also, three types of wastes are easy to treat. The vanadium extraction process is better in relation to the aspect of environmental protection than the sodium method.     

钙化合物对钒钛磁铁矿精矿碳热还原的影响

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate (VTC) were investigated. It was found that calcium compounds had great effects on the metallization rate of the reduction product, the order of the metallization rate of reduction product being CaCO₃ > no additive > CaSO₄ > CaCl₂, which indicated that the addition of CaCO₃ was more conducive to promoting the reduction of iron than other calcium compounds. Gas analysis showed that there were mainly two processes in the carbothermic reduction of VTC, a solid–solid and a solid–gas reaction. The concentrations of CO and CO₂ were highest when CaCO₃ was added, while that in a roasting system decreased the most when CaCl₂ was added. X-ray diffraction (XRD) analysis showed that calcium compounds could change the reduction process of ilmenite in VTC. The phase compositions of the reduction products were changed from metallic iron (Fe) and anosovite (FeTi₂O₅) to metallic iron (Fe) and perovekite (CaTiO₃) when calcium compounds were added. Additionally, CaSO₄ and CaCl₂ could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg₂TiO₄ in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO₄.     

钒钛磁铁矿直接还原试验研究

在热力学分析的基础上研究了实验室条件下钒钛磁铁矿配煤直接还原的特点,考察了还原机理及还原温度、反应时间和配碳量对金属化率的影响.结果表明:采用直接还原可使钒钛磁铁矿中铁的氧化物优先还原为金属铁,钛仍以氧化物的形态存在;随着温度升高,球团金属化率呈上升趋势,且上升趋势随之减缓;在xC/xO=0.9∶1时,延长反应时间金属化率增加,但反应时间过长金属铁会被再氧化,反应时间控制在20 min为宜;在xC/xO=1.1∶1时,40 min内未出现再氧化现象;低配碳(xC/xO=0.8∶1)时,球团的金属化率随还原时间、还原温度的增加而增加,1 300℃下还原10 min后金属化率即达到了90%以上.     

以煤泥为还原剂海滨钛磁铁矿直接还原焙烧反应历程

研究以煤泥为还原剂,印尼某海滨钛磁铁矿在直接还原焙烧过程中,不同焙烧温度下矿物组成变化规律. X射线衍射和扫描电镜分析结果表明,随着焙烧温度的升高,钛磁铁矿逐渐被还原. 其中铁矿物经过浮士体( FeO) ,最终被还原成金属铁;而钛则经过钛尖晶石最终生成钛铁矿和少部分的铁板钛矿. 在整个直接还原焙烧过程中,金属铁颗粒在1100℃左右生成,然后不断长大,在1250℃时金属铁颗粒明显增多,在之后的保温过程中,金属铁颗粒不断长大,并在此过程中将金属铁从中分离出来.     

富氧率对钒钛磁铁矿球团还原行为的影响

模拟研究了不同富氧率条件下钛磁铁矿氧化球团的还原过程.通过扫描电镜观察钒钛磁铁矿球团还原过程中的微观结构变化,结合能谱仪研究分析了还原过程中产物的分布变化.结果表明,富氧率的提高对还原度和还原速率提高有明显促进作用.还原过程中钛铁分离伴随着Al元素向高钛矿中迁移富集,最终Al与Ti原子数比为1∶3,Al很可能与钛铁氧化物固溶,形成某种复合化合物并导致球团矿还原难度增加.运用三种不同模型对球团矿还原过程对比分析,发现混合模型可以很好地表征球团矿不同阶段的还原过程.利用混合模型计算得出球团矿还原过程的动力学参数.结果表明,随着富氧率的升高,球团矿还原活化能逐渐降低,从不富氧到富氧79%条件下,活化能由26.5 k J/mol降低到19.68 k J/mol,活化能的降低增加了相同条件下活化分子的数量,提高了反应速率,有利于球团矿在较低还原温度条件下快速反应.     

海砂矿深度还原-磁选分离实验研究

应用化学分析、扫描电镜观察和X射线衍射分析方法研究海砂矿的基础物性. 采用煤基深度还原-磁选工艺,系统考察矿粉中Fe和Ti的还原分离行为,并明确还原温度、还原时间、碳氧比、磁感应强度和磨矿粒度对还原磁选效果的影响规律. 结果表明:海砂矿主要由钛磁铁矿和钛赤铁矿组成;较优的还原分离工艺参数为还原温度1300℃、还原时间30 min、碳氧摩尔比1. 1、磁感应强度50 mT和磨矿细度-0. 074 mm质量分数86. 34%. 在此工艺条件下,可以获得金属化率94. 23%的还原产物,磁选指标分别达到精矿铁品位97. 19%和尾矿钛品位57. 94%,对应的铁、钛回收率为90. 28%和87. 22%,有效地实现海砂矿中铁钛元素的分离富集.     

朝阳钒钛磁铁矿工艺矿物学研究

采用传统工艺矿物学研究方法,结合光学显微镜、X射线衍射、化学分析等分析手段,对朝阳地区钒钛磁铁矿石的化学组成、元素赋存状态、矿物组成、矿物间的嵌布关系及粒度分布进行了详细研究.结果显示:该铁矿石中铁矿物主要为磁铁矿、钛磁铁矿和钒磁铁矿,长石是最主要的脉石矿物.矿石中主要矿物嵌布关系复杂,磁铁矿与钛磁铁矿颗粒结合紧密,大多结合成连生体,不利于铁矿物与钛矿物之间单体解离;主要矿物嵌布粒度粗细不均,磁铁矿嵌布粒度相对较粗,钛磁铁矿和钒磁铁矿嵌布粒度相对较细.该研究为该地区钒钛磁铁矿资源的合理开发利用提供了依据.     

高铬型钒钛磁铁矿配量增加对氧化球团质量的影响

采取“细磨处理高铬型钒钛磁铁矿”和“以粒度较细的廉价欧控矿代替现场生产用矿”两种优化措施，考察了高铬型钒钛磁铁矿配量增加对氧化球团质量的影响，探索了高铬型钒钛矿在球团原料中配量增加的可行性.结果表明:“细磨处理高铬型钒钛磁铁矿”和“以粒度较细的廉价欧控矿代替现场生产用矿”，当高铬型钒钛矿配量40%时，抗压强度分别为2475N·个-1和2005N·个-1，膨胀率为192%和16%，皆满足高炉生产要求，可实现该矿在原料中配量增加，能达到高铬型钒钛矿预期90万t/年的处理目标.     

高钛型高炉渣流变特性模拟实验

高钛型高炉渣流变特性是影响钒钛磁铁矿高炉冶炼的重要因素,其对炉渣的排放、渣铁分离,甚至炉缸的寿命有重要作用.该研究采用高浓度的丙烯腈-丁二烯-苯乙烯共聚物(ABS)悬浮液模拟高钛型高炉渣体系,用NXS-11A型同轴圆筒旋转黏度计测量其表观黏度,研究了温度、颗粒体积分数及颗粒粒度等因素对悬浮液表观黏度的影响.结果表明:温度和颗粒体积分数对悬浮液的表观黏度影响明显,颗粒粒度对悬浮液表观黏度影响较弱.在较宽的颗粒浓度范围内悬浮液符合Bingham塑性体,并得到了表观黏度与温度和体积分数的二元函数关系式.