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.

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 Cr2O3 addition, mainly because of a substantial increase in the porosity of the HVTMPs. The Cr2O3 addition marginally affected the phase composition but greatly affected the microstructural changes of the HVTMPs. Increased amounts of Cr2O3 resulted in a decrease in the uniform distribution of the hematite grains and in an increase in the Fe–Cr solid solutions（Fe1.2Cr0.8O3 and Fe0.7Cr1.3O3） 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 Cr2O3. This study provides theoretical and technical foundations for the effective production of HVTMPs and a reference for chromium-bearing minerals.

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.

Reduction behavior and mechanism of Hongge vanadium titanomagnetite pellets by gas mixture of H2 and CO

Hongge vanadium titanomagnetite（HVTM）pellets were reduced by H2-CO gas mixture for simulating the reduction processes of Midrex and HYL-III shaft furnaces.The influences of reduction temperature,ratio ofφ（H2）toφ（CO）,and pellet size on the reduction of HVTM pellets were evaluated in detail and the reduction reaction kinetics was investigated.The results show that both the reduction degree and reduction rate can be improved with increasing the reduction temperature and the H2 content as well as decreasing the pellet size.The rational reduction parameters are reduction temperature of 1050℃,ratio ofφ（H2）toφ（CO）of 2.5,and pellet diameter in the range of 8-11 mm.Under these conditions（pellet diameter of 11mm）,final reduction degree of 95.51% is achieved.The X-ray diffraction（XRD）pattern shows that the main phases of final reduced pellets under these conditions（pellet diameter of 11 mm）are reduced iron and rutile.The peak intensity of reduced iron increases obviously with the increase in the reduction temperature.Besides,relatively high reduction temperature promotes the migration and coarsening of metallic iron particles and improves the distribution of vanadium and chromium in the reduced iron,which is conducive to subsequent melting separation.At the early stage,the reduction process is controlled by interfacial chemical reaction and the apparent activation energy is 60.78kJ/mol.The reduction process is controlled by both interfacial chemical reaction and internal diffusion at the final stage,and the apparent activation energy is 30.54kJ/mol.

Reduction Kinetics of Vanadium Titano-Magnetite Carbon Composite Pellets Adding Catalysts Under High Temperature

Experiments were carried out by adding CaF2 and NaF as catalysts in an Ar atmosphere to study the isothermal reduction kinetics of vanadium titano-magnetite carbon composite pellets under high temperature in the range from 1 473 to 1 673 K. The scanning electron microscope （SEM） was used to characterize the microstructure of product. By analyzing reduction mechanism, it was found that the rate controlling step was gas diffusion, and the activation energy was 178.39 kJ/mol without adding any catalysts. Adding CaF2 or NaF of 3% to vanadium titano-magnetite carbon composite pellets can decrease the apparent activation energy of reduction, and the decrease extent was 14.95 and 15.79 kJ/mol, respectively. In addition, temperature was an important factor influencing on reaction rate.

Influence of Coating MgO on Sticking and Functional Mechanism during Fluidized Bed Reduction of Vanadium Titano-magnetite

The vanadium titano-magnetite （VTM） iron ore fines of 110--150/xm in diameter were reduced in a trans- parent quartz fluidized bed by 70 %CO-30 % H2 （volume fraction） mixtures. MgO powders served as coating agent to solve sticking problem. Two coating methods were introduced in this experiment： high temperature injection method and briquetting→oxidizing roast→crushing method. According to the experimental results, the minimum effective coating amount of MgO was 0. 1 mass%. The metallization ratio （MR） of the product rose from around 58% to above 90% with the above treatments. To investigate the sticking mechanism of fine ore, the morphology evolution was in- vestigated. Instead of iron whiskers, an interlaced fibrous porous surface formed. The ulvospinel （2FeO ： TiO2 ） in VTM is more difficult to be reduced than FeO according to thermodynamic calculation. XRD results showed that MgO diffused into Fe203 lattice before forming pleonaste （MgO · Fe2O3 ） during oxidizing roast at 1273 K. The melting point of the pleonaste is 1986 K and that made contribution to prevent the sticking problem.

Formation of Hearth Sediment during Vanadium Titano-magnetite Smelting in Blast Furnace No.7 of Chengde Iron and Steel Company

The large quantity of sediment produced in the hearth during vanadium titano-magnetite smelting in a blast furnace（BF） affects the stability of the blast furnace operation. Testing and analysis of the sediment in the hearth of Chengde Iron and Steel Company？s BF No.7 revealed that it was mainly concentrated in the location below the tuyere and above the iron notch. Notably, some of the bonding material（sediment） consisted of greater than 50% pig iron, and the pig iron distributed in the slag was granular. It is proposed that a large quantity of Ti C and Ti（C,N） are deposited on the surface of the pig iron. These high melting point materials mix with iron drops, preventing the slag from flowing freely, thus leading to the formation of bonding materials. In addition, the viscosity and melting temperature of the slag in the tuyere areas fluctuate greatly, and thus the properties of the slag are unstable. Moreover, the slag contains large quantities of carbon, which results in the reduction of Ti O2. The resultant precipitation of Ti is followed by the formation of Ti C in the slag, which also leads to an increase in the viscosity of the slag and difficulty in achieving separation of the slag-iron. In fact, all of these factors interact with each other, and as a result, sediment is formed when the operating conditions in the hearth fluctuate.

红格地区钒钛磁铁矿地质特征及地球物理找矿的探讨

攀西红格钒钛磁铁矿是我国大型的钢铁生产基地。攀西红格钒钛磁铁矿床赋存于层状基性和超基性的辉石岩和辉长岩岩体中,仅限于攀西裂谷的古隆起带分布,含矿岩体沿安宁河深断裂、昔格达-元谋断裂、攀枝花大断裂侵入。含矿岩体在时间上仅限于华里西期时段的基性-超基性岩。"三位一体"(基性-超基性岩、灯影组白云质灰岩、峨眉山玄武岩)的岩性组合,是形成大型、超大型矿床的必要条件。攀枝花含矿岩体的一级韵律层由岩体上部的辉长岩、中部暗色层状辉长岩、下部中粗粒暗色辉长岩夹橄辉岩和橄榄型矿层组成。准确把握攀西钒钛磁铁的矿床特征,是寻找该矿床的有效途径,目前已利用地球物理方法在红格钒钛磁铁矿及外围发现了多处矿点,为这次整装勘查提出了进一步找矿的新思路。

红格矿深还原—熔分过程及钒、铬走向的研究

深还原—熔分固相还原后的金属化球团生产钒铬生铁是利用红格矿的途径之一.由于V2O5与Cr2O3的赋存、分布以及冶炼过程中的走向基本一致,综合回收利用二者可一起考虑.为了提高钒、铬回收率,实现钛和铁的有效分离,通过单因素试验考察了在氩气保护下,配料的碱度、深还原—熔分温度和配碳量对熔分过程和钒、铬走向的影响.结果表明,当熔渣碱度为1.2,配碳量为0.5%,熔分时间为15 min,熔分温度为1 610℃时,渣铁的分离效果较好,且有利于钒、铬熔于铁相.

攀西红格矿区钒钛磁铁矿开发利用探讨

攀西红格矿区是四川地区较为重要的钒钛磁铁矿资源基地,目前已经进入开发的成熟期。在红格矿区钒钛磁铁矿开发利用过程中,存在矿物成份复杂,现有技术难以满足选矿需求,相关保障措施不健全等一系列问题。建议:(1)开展选矿新技术研究,进一步加强"选择性解离-强化分选"工艺流程,提升选矿效率和成效;(2)加强相关保障措施建设,制定可操作性的政策文件,为推动野外科研基地的建设提供助力,适应时代发展,鼓励开放和资源共享。

攀西红格矿区橄辉岩型钒钛磁铁矿矿石性质研究及对选矿工艺的影响

本文利用矿相显微镜、电感耦合等离子体发射光谱(ICP-AES)、扫描电子显微镜(SEM)、X射线能谱探针(EDS)等手段对红格矿区橄辉岩型钒钛磁铁矿进行了详细的工艺矿物学研究。原矿化学分析结果表明矿石为高钛型钒钛磁铁矿贫矿;矿物定量结果表明:含钛磁铁矿25.5%、钛铁矿11.5%、辉石45.8%、橄榄石10.5%、斜长石1%。样品为稀疏—中等浸染状矿石,普遍发育海绵陨铁结构,工艺粒度整体较粗。结合选矿试验情况以及同其他矿区的比较,本文指出红格矿区矿石性质发生了重大转变:①橄辉岩型钒钛磁铁矿中非磁性矿物斜长石含量大大降低,导致各矿物间磁性差异缩小;②辉石和橄榄石易蚀变泥化,内部普遍含有磁性包裹体,如赤铁矿和磁铁矿,磁性增强。矿石性质的转变对传统选铁和浮钛作业形成了严重挑战,新的选矿工艺呼之欲出。

基于突变理论的红格钒钛磁铁矿区矿山地质环境评价

利用高分一号遥感影像与实地调查数据,结合地理、地质和气象等数据,采用突变理论综合评价方法建立了矿山地质环境评价指标体系,并将其应用于研究区内红格铁矿、马鞍山铁矿、潘家田铁矿、百草铁矿、小黑箐铁矿、阳雀箐铁矿和秀水河铁矿等7个典型矿山的地质环境评价中。结果表明,应用该方法的评价结果和矿山的实地调查结果吻合,与应用较广泛的模糊数学综合评价结果一致。与其它评价方法相比,突变理论综合评价法人为干预较少、不用确定指标权重、计算简单且可以适用于大范围的矿山地质环境评价,为矿山地质环境综合评价提供了新方法。

红格钒钛磁铁矿氧化物相转变及非等温氧化动力学

在对红格钒钛磁铁矿基础特性研究基础上,探讨了其球团氧化过程物相的存在形式和转变过程,并通过热分析法研究了红格矿非等温氧化动力学.结果表明:红格钒钛磁铁矿属于高铬型钒钛磁铁矿,Cr_2O_3的质量分数为1.48%,连晶强度为625 N;主要物相组成为磁铁矿、钛磁铁矿、钒磁铁矿、铬铁矿;温度低于300℃时其氧化速率缓慢;球团氧化过程有价组元物相迁移变化历程为:Fe_3O_4→Fe_2O_3;Fe_2VO_4→(Cr_(0.15)V_(0.85))_2O_3;Fe_(2.75)Ti_(0.25)O_4→FeTiO_3→Fe_9TiO_(15);FeCr_2O_4→(Fe_(0.6)Cr_(0.4))_2O_4,Fe_(0.7)Cr_(1.3)O_3,(Cr_(0.15)V_(0.85))_2O_3.红格矿非等温氧化动力学研究表明:当升温速率为10℃/min时,温度在220~380℃,380~500℃和500~800℃时,反应活化能分别为47.02,14.95和30.36 kJ·mol^(-1).

四川盐边县红格钒钛磁铁矿矿石矿物及化学成分分布特征

红格矿区是我国目前最大的钒钛磁铁矿资源基地,其矿产资源储量丰富,伴生钒、钪、镓、铬、钴、镍、铜、硫等有用元素,具有较高的经济价值。通过系统分析矿区有益元素的赋存状态及分布规律表明:矿石中各种元素的相对含量以及含量的波动幅度,与矿石TFe、岩性和岩石组合高度相关。

四川攀西红格钒钛磁铁矿床地质特征及找矿预测地质模型

红格铁矿位于四川攀西地区钒钛磁铁矿整装勘查区,地处川西南山地南部龙帚山脉南端大黑山西侧斜坡地带。红格矿区沿边、延深找矿取得重大突破,一跃成为全世界最大的钒钛磁铁矿区。基于红格矿区的最新找矿勘探成果,在总结矿床地质特征的基础上,对地层、构造、岩浆岩等成矿地质条件及基性—超基性岩的岩浆演化及成矿机制进行分析,构建红格矿床的找矿预测地质模型。

攀枝花红格钒钛磁铁矿区深部及外围找矿方法分析

红格矿区是我国目前最大的钒钛磁铁矿资源基地,红格基性—超基性含矿岩体主要受区域的三级控岩构造控制。由于大黑山玄武岩浆的喷溢及正长岩体、花岗岩体的破坏,以及后期构造运动的影响,使该区第三级控岩构造转化为以南北向的挤压构造为主。并把原来可能系一个完整大岩体分割成了现在的大小不等、岩相带不全、剥蚀程度不同的十余个岩体(块)组成的岩体(块)群。研究红格岩盆分布特征拓展找矿空间取得外围找矿突破;利用“攀西杂岩层状韵律旋回模式”就矿找矿、预测深部矿体,探边摸底;最后以地磁异常加深部钻孔验证定位深部矿体,是红格矿区深部及外围勘查取得重大进展的有效找矿方法组合。

红格钒钛磁铁矿选铁精矿工艺矿物学特征探析

红格钒钛磁铁矿中含有大量的橄辉石和其蚀变矿物,因而导致矿石的结构构造和嵌布特征较为复杂,直接增加了选矿的难度。在此背景下,深入探析选铁精矿工艺矿物学特征,基于具体的工艺流程,从铁精矿的物质成分和矿物学特征入手,展开相应的实验分析,为铁精矿的选冶工艺和综合利用提供参考。

Coextraction of vanadium and manganese from highmanganese containing vanadium wastewater by a solvent extraction-precipitation process

High-manganese containing vanadium waste-water(HMVW)is commonly produced during the vanadium extraction process from vanadium titano-magnetite.HMVW cannot be reused and discharged directly,and is harmful to the environment and affect product quality due to heavy metals in the wastewater.The wastewater is usually treated by lime neutralization,but valuable metals(especially V and Mn)cannot be recovered.In this study,an efficient and environmentally friendly method was developed to recover valuable metals by using a solvent extraction-precipitation process.In the solvent extraction process,98.15%of vanadium was recovered,and the V2Os product,with a purity of 98.60%,was obtained under optimal conditions.For the precipitation process,91.05%of manganese was recovered as MnCO3 which meets the III grade standard of HG/T 2836-2011.Thermodynamic simulation analysis indicated that MnCO3 was selectively precipitated at pH 6.5 while Mg and Ca could hardly be precipitated.The results of X-ray diffraction and scanning electron microscopy demonstrated that the obtained V2Os and MnCO3 displayed a good degree of crystallinity.The treated wastewater can be returned for leaching,and resources(V and Mn)in the wastewater were utilized efficiently in an environmentally friendly way.Therefore,this study provides a novel method for the coextraction of V and Mn from HMVW.

红格钒钛磁铁矿中铁、铬的赋存状态研究

通过化学多元素分析、物相分析、X射线衍射分析、光学显微镜和MLA等多种现代测试手段对攀枝花红格高铬型钒钛磁铁矿的化学组成、矿物种类及含量、含铬矿物的能谱微区成分分析-平衡概算-产出形式、钛磁铁矿的粒度及解离度等方面进行详细研究,查清了铬的分布状态及其富集趋势和铁精矿的理论指标,综合分析了磨矿细度及其对应铁精矿的理想指标,明确了影响选矿效果的主要矿物学因素,为综合开发利用红格钒钛磁铁矿提供了详细的科学依据。