动态氧化条件下含钛高炉熔渣中钙钛矿析出与长大机理

动态氧化不仅有利于含钛高炉熔渣中钛组分富集于设计相(钙钛矿相),同时还会促进钙钛矿相析出与粗化,在自然重力作用下粗化的钙钛矿实现重力富集与沉降分离.本文运用玻璃形成动力学方程,对动态氧化条件下含钛熔渣中钙钛矿相形核速率和晶体生长速率进行分析和研究.结果表明,向熔渣鼓入氧气,低价钛逐渐氧化为四价钛,促进钙钛矿析出反应的进行,提高了钙钛矿晶体生长速率.继续通入氧气则氧化时间过长,熔渣中高熔点TiC和TiN固体颗粒基本消失,黏度降低,异相形核转化为均相形核,析出温度显著降低,析晶温度区间缩短,不利于钙钛矿晶粒粗化和长大.      

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.      

不锈钢粉尘内配煤团块高温自还原过程中金属铁的聚集

用不锈钢生产中的高碱度二次粉尘制备内配煤团块,在高温下自还原获得含铬、镍的金属铁粒.研究影响铁粒聚集长大的因素.研究表明:(1)内配煤团块的渣相碱度(w( CaO)/w( SiO2))小于2.8时,还原产物冷却过程中渣相与金属铁粒才能自然分离.碱度越低,渣量越大,越不利于金属铁聚集长大;(2)提高内配碳比,渣相残碳量明显升高,渣中过量的碳阻碍金属相聚集长大;(3)提高还原温度,直接还原铁的海绵状结构解体,逐渐聚集成颗粒状金属铁.还原温度越高,越有利于金属铁的聚集长大     

刚果(金)某氧化铜精矿还原熔炼渣物化性能研究

针对刚果(金)某氧化铜精矿中高硅、低铁的特性,通过高温马弗炉还原熔炼试验,考察了碱度和FeO对熔渣形貌、熔点、密度、黏度及电导率的影响。结果表明,该体系熔渣主要以硅酸钙的玻璃相存在,Mg、Al及Fe分散在其中。随着碱度从0.2增加到0.6,熔渣熔点先降低后升高,黏度先增大后减小,密度先减少后增大,电导率呈上升趋势;随着FeO含量从6%增加到10%,熔渣熔点和黏度呈下降趋势,密度和电导率呈上升趋势。适合本体系熔渣的碱度为0.5左右,FeO加入量6%,则熔渣熔化温度1 250℃,黏度2Pa·s(1 400℃),密度2.6～3.0g/cm~3。此时,粗铜品位达到96.5%,铜收得率超过98%。     

SiO_2-CaO-Al_2O_3-MgO-FeO熔渣的电解还原行为

电解含有铁氧化物的熔渣是一个潜在的减少甚至消除CO2排放的钢铁冶炼短流程新工艺.本文采用MgO或Y2O3稳定的氧化锆管内装碳饱和铁熔体做阳极,构建可控氧流电池:铁棒|Fe+FeO(slag)|ZrO2(MgO或Y2O3)|[O](Fe+C饱和)|石墨棒.在1723 K高温下通过测定电池开路电压-时间曲线、线性扫描伏安曲线、恒电压电解曲线研究了SiO2-CaO-Al2O3-MgO-FeO熔渣的电解还原行为,并借助扫描电镜与能谱分析了残样的显微结构与成分.结果表明:在本实验条件下,测定获得SiO2-Ca O-Al2O3-MgO-FeO熔渣中FeO的分解电压约为-0.25 V,测定结果位于Fact Sage热力学软件理论计算值范围内,表明采用本实验装置测定熔渣中FeO分解电压是可行的.在外加电压条件下可以从SiO2-CaO-Al2O3-MgO-FeO熔渣中电解还原获得金属铁(或铁合金).可控氧流电解还原电流的大小及FeO还原效果与外加电压、ZrO2稳定剂的种类和ZrO2管(阳极)插入熔渣中的深度等因素有关.     

基于熔渣离子分子共存理论的CaO-MgO-SiO2-FeO-Al2O3熔渣黏度预测模型

研究了含FeO的CaO-MgO-SiO₂-FeO-Al₂O₃五元渣系的黏度预测模型，引入黏度的补偿效应，通过对前人的熔渣共存理论黏度预测模型进行改进，建立含FeO熔渣的黏流活化能和各结构单元之间的关系，模型计算的黏流活化能和拟合得到的数值吻合较好。根据补偿效应，利用模型计算的黏度值与实测值的误差在允许范围内。分析表明，随着渣中混合碱度w(CaO)/w(SiO₂+Al₂O₃)和碱性氧化物(如MgO和FeO)含量的增加，熔渣黏度降低。另外，熔渣黏度随着温度的升高而降低，低温条件下，熔渣组分的变化对熔渣黏度的影响较大。基于本模型计算的参数值可用补偿效应代替前人模型中的Ai参数拟合值，使模型参数值整体减少。     

镍沉降渣深度还原过程中的相变特征

通过化学成分、光学显微镜、X射线衍射、扫描电镜能谱分析等测试手段,分析了镍沉降渣矿物成分和嵌布特点和沉降渣深度还原过程中物相的转变特征,结果表明,渣的物相由铁镁橄榄石和玻璃质组成.渣中主要有用成分铜镍铁硫化物嵌布粒度微细,分布无规律,回收困难.经深度还原,沉降渣逐渐转变为镁黄长石、含镍金属铁、辉石、钙霞石、钠闪石、石英等新的矿物成分,加热至1300℃,还原产物物相组成稳定,镁黄长石和含镍金属铁相对含量最高.还原时间也是影响还原效果重要因素,含镍金属铁相对含量随还原时间的增加而增长,120 min时相对含量最高.热力学分析表明,镍沉降渣深度还原过程中主要发生的反应为铁镁橄榄石与氧化钙作用生成镁黄长石和FeO,FeO被C和CO还原为金属铁.金属硫化物与CaO和C通过氧化还原作用,生成的金属铜和镍溶于金属铁中,产生的CaS与硅酸盐一起析出.      

钛铁矿高效利用新技术研究和开发

 通过研究钛铁矿的还原热力学可知,钛铁矿的还原难度大于普通铁矿。动力学研究表明,通过粉体细化,可以加速钛铁矿的还原速度;用碳还原钛铁矿的最佳温度应选择在900～1100℃。金属铁的渗碳有利于铁的晶粒长大,铁中的渗碳量越高,越有利于金属铁的聚集;外场对铁晶粒长大有明显作用,为金属铁与钛渣的充分分离提供了最佳条件。通过晶粒长大技术将还原后的细微铁晶粒长大到一定粒度,通过简单破碎和磁选,即可得到钛渣和铁产品。开发的钛铁矿高效利用新技术具有反应温度低、无需高温熔分等特点,从而实现高效率、低能耗及低成本生产钛渣和铁产品。     

含钛高炉渣中铁沉降行为研究

针对承钢含钛高炉渣黏度大,渣铁分离较差,炉渣中含金属铁2%左右,给高炉渣利用带来了困难,使生铁成本升高等问题,分析了含钛高炉渣含金属铁的形成原因,研究了含钛高炉渣析铁行为,以及炉渣停留时间、温度、黏度对渣中铁沉降的影响。研究结果表明:渣样的停留时间与渣中含铁量有着复杂的关系,停留时间在20~30min时渣样铁聚合明显,在40~80 min时随着时间的延长铁聚沉量变化不大,但位置下移且粒度变大;温度与渣中含铁量有显著关系,随着炉渣温度的升高,渣样上部含铁量明显减少,温度为1 500℃时,渣样上部含铁量由2.0%减小到0.4%;炉渣的黏度与渣中铁含量关系密切,向高炉渣中添加Ca F2可降低炉渣黏度,提高渣中铁的聚沉程度,Ca F2加入量为1%时可达到较好的聚沉效果。     

攀枝花低硅钛精矿还原试验研究

以攀枝花低硅钛精矿为研究对象,研究氧化温度和时间对钛铁矿物相结构和还原的影响,同时对预氧化钛铁矿不同温度和时间下还原失重率和金属化率变化情况进行分析。研究结果表明:钛精矿的氧化在较短时间内可完成,随着氧化温度的升高,钛精矿主要物相变化过程为FeTiO_3→Fe_2O_3+TiO_2→Fe_2TiO_5+Fe_2O_3+TiO_2;在钛铁矿的还原过程中,还原温度和时间对钛铁矿还原的金属化率影响较大,在还原温度大于1 300℃,时间大于8 h后变化不明显;显微结构分析发现,高温还原后金属铁扩散发生聚集,形成球形和棒状金属铁颗粒,其尺寸大约为10μm。     

Study on recovery of metallic Fe and enrichment behaviour of titanium in Ti bearing blast furnace slag

Abstract

A novel technique to recover metallic Fe droplets from Ti bearing blast furnace slag and, at the same time, to enrich titanium compounds into the perovskite phase by oxidising the slag using injected air with or without injected steel slag additive, was studied and developed. The oxidation treatment enabled >85% of iron droplets in the Ti bearing slag to be agglomerated separated and the dispersed Ti components were selectively enriched into the perovskite phase from 48 to ～95%, so enhancing subsequent separation and recovery.     

Separation of Iron Droplets From Titania Bearing Slag

Owing to smelting vanadium-titanium magnetite ore,the amount of iron entrainment in slag as droplets is far higher than that in conventional BF slag.However,the iron droplets can be easily settled by blowing air into the molten slag.The results show that more than 80% of iron droplets in titania bearing slag can be settled and separated after treatment.The temperature rise of molten slag during the oxidizing process and the decreased viscosity caused by the component change of slag as well as air stirring in slag both accelerate the iron droplets settling.The vanadium content in the settled iron droplets and the original iron droplets was obtained by chemical analysis.The possible reason for the increased vanadium in the settled iron droplets was discussed by thermodynamic principles.     

Coexistence Theory of Slag Structure and Its Application to Calculation of Oxidizing Capability of Slag Melts

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In order to understand the effects of various iron oxides on the properties of melts, viscosity, density as well as sulphide capacities of slag system containing FeOx were summarized and discussed. It is indicated that either thermophysical or thermochemical properties would be modified accordingly with the valence change of iron oxides. Fe2+ and Fe3+ have different functions in slag. Fe2+ existed as a network-breaker, which resulted in the decreasing of viscosity and increasing of sulphide capacities with increasing addition of FeO. However, Fe3+ commonly would occupy the tetrahedron and octahedron positions, and play a network-former role, consequently, cause the viscosity of melts increasing etc. Direct investigations of slag structure or valence state of iron in the melt also support the regular patterns derived indirectly from the various physical-chemical properties. Meanwhile, these patterns of slag system including iron oxides also offer a good reference to the study of other transition melt oxides in slag system.     

Viscosity of SiO2-“FeO”-Al2O3 System in Equilibrium with Metallic Fe

The present study delivered the measurements of viscosities in SiO₂-“FeO”-Al₂O₃ system in equilibrium with metallic Fe. The rotational spindle technique was used in the measurements at the temperature range of 1473 K to 1773 K (1200 °C to 1500 °C). Molybdenum crucibles and spindles were employed in all measurements. The Fe saturation condition was maintained by an iron plate placed at the bottom of the crucible. The equilibrium compositions of the slags were measured by EPMA after the viscosity measurements. The effect of up to 20 mol. pct Al₂O₃ on the viscosity of the SiO₂-“FeO” slag was investigated. The “charge compensation effect” of the Al₂O₃ and FeO association has been discussed. The modified quasi-chemical viscosity model has been optimized in the SiO₂-“FeO”-Al₂O₃ system in equilibrium with metallic Fe to describe the viscosity measurements of the present study.     

The settling of metallic lead from lead blast furnace slag

As a consequence of inadequate working methods, excessive losses of lead can occur in the slags of lead blast furnaces. The settling of metallic lead from a slag containing 20.5 pct SiO₂, 33.4 pct FeO, 16.8 pct CaO, 12.4 pct ZnO, 0.9 pct S, and 6.1 pct Pb has been studied as a function of the temperature (1200 to 1300 °C), composition (addition of CaO, ZnO, and Fe), and time (up to 2 hours). Under these conditions sufficient, although not total, sedimentation of the metal retained is achieved. The best conditions were obtained at 1260 °C with no modification to the composition of the slag. The settled lead was visible macroscopically in a section of the lower part of the melts.     

Reaction of FeO-V2O5 System at High Temperature

 FeO and V2O5 are two main components of the obtained vanadium steel slag, and the reaction of FeO-V2O5 system determines the physical property of the slag. Through thermodynamic calculation and experimental study, it can be found that within the ranges of steel-making temperature, V2O5 is reduced to VO2. As FeO exists in FeO-V2O5 system, VO2 will be reduced to V2O3 further while FeO is oxidized to Fe2O3. In this multi-system, as the content of FeO and temperature increase, the system will have products in turn such as V3O5, V3O4, FeVO4, Fe2VO4 and Fe3O4. The products are mainly V3O5 and Fe2O3 when the content of FeO is 0.58 mol and the temperature is 1100 K, and as the temperature increases, Fe2O3 starts to react with V2O5 and then generates FeVO4; FeVO4 disappears while the content of FeO and the temperature increase at the same time, and then Fe2VO4 is generated by the reaction of FeO, Fe2O3 and V2O3. Iron oxides are also generated such as Fe3O4 and so on.     

电炉冶炼高镁酸溶钛渣的热力学及试验研究

电炉冶炼钛铁矿制备酸溶渣时,为降低冶炼温度、保障渣的流动性,高钛渣中通常保留一定数量的氧化亚铁,导致后续钛白粉生产中产生硫酸亚铁,造成酸耗高等不利影响.针对上述问题,通过采用FactSage热力学分析结合电炉冶炼试验,研究了氧化镁对高钛渣物化性质影响规律及其降低炉渣冶炼温度的可行性.结果表明,提高氧化镁含量、降低氧化亚...     

Confocal Scanning Laser Microscopy Studies of Crystal Growth During Oxidation of a Liquid FeO-CaO-SiO<Subscript>2</Subscript> Slag

The oxidation of FeO in 30 wt pct FeO-35 wt pct CaO-35 wt pct SiO₂ slag was investigated as part of a wider study on the recovery of Fe units through magnetic separation. A confocal scanning laser microscopy (CSLM) technique was used to visualize the oxidation of FeO in the liquid slag. The formation event was observed in situ under the CSLM and the onset of precipitation on a surface of the slag liquid was recorded at various temperatures in an oxidizing atmosphere. A Time-Temperature-Transformation (TTT) diagram was constructed based on the CSLM results. Samples obtained from the CSLM heating chamber were analyzed by a scanning electron microscope (SEM) equipped with an energy-dispersive spectrometer (EDS).