不同类型含钛高炉渣主要冶金性能及物相

根据渣中TiO_2及Al_2O_3质量分数不同对高炉渣进行划分,以钒钛磁铁矿现场高炉渣为基准,采用纯化学试剂配制渣样,在中性气氛下对比研究低、中、高钛型钒钛矿高炉渣及低、中、高铝型钒钛矿高炉渣主要冶金性能。同时,运用XRD物相分析及Factsage 6.4热力学软件对各渣系主要组成物相及其变化进行分析。研究结果表明:低、中、高钛渣熔化性温度逐渐增大,初始黏度和高温黏度降低,渣系热稳定性和化学稳定性先变好后变差,渣中黄长石相骤减,辉石、钙钛矿相数量增多。低、中、高铝渣熔化性温度、初始黏度和高温黏度升高,渣系热稳定性和化学稳定性变差,渣中镁铝尖晶石等高熔点物相数量增多。     

含钛高炉渣高效利用的最新进展

含钛高炉渣是含钛冶金渣中难以处理的一类硅铝酸盐固体废弃物,大量堆积的含钛高炉渣造成了严重的资源浪费和环境污染。因此,开发绿色、高效的含钛高炉渣利用途径是资源节约和环境保护的关键需求。在过去的几十年里,多种途径被用于含钛高炉渣高效利用的研究,并在研究含钛高炉渣的基本特征和开发高效方法等方面取得了重大进展。本文回顾了近年来高效利用含钛高炉渣的各类方法,从用作建筑材料的原料、碳化氯化法提钛、钛合金的制备、酸法、碱熔煅烧法和高温重结晶–富集等角度全面地介绍了高效利用含钛高炉渣的研究进展。重点讨论了各类方法的反应机制和目前的现状。然而,目前的利用方法在效率和成本上仍与实际应用相差很远。因此,开发清洁、高效、大规模利用含钛高炉渣的新方法仍然是一个重要的目标。要实现这一目标,需要重点研究以下三个方面:(1) 发展新兴的理论方法;(2) 开发全面可靠的热力学性质数据库;(3) 开发先进的表征方法。这一系统和全面的回顾将有利于设计高效和低成本的利用路线。     

碳氮化含钛高炉渣对铁沟捣打料抗氧化性及抗渣性的影响

测定碳氮化处理后含钛高炉渣的熔化特性,并研究在高炉铁沟捣打料中加入碳氮化含钛高炉渣后对材料抗氧化性及抗渣性的影响。结果表明,含钛高炉渣经碳氮化处理后,渣中主要的矿物相为氮化钛或碳氮化钛和钙镁黄长石或钙铝黄长石,渣中相的组成和含量受还原温度影响较大,随着渣的还原温度升高,还原渣的熔点呈上升趋势;将还原渣引入到高炉铁沟捣打料中,部分或完全替代碳化硅原料,可明显提高捣打料的抗氧化性,最佳的渣加入量为7%,过多将会导致捣打料抗氧化性减弱;因Ti(C,N)具有优良的抗渣性能,碳氮化含钛高炉渣的引入不影响高炉铁沟捣打料的抗渣性。     

从含钛电炉熔分渣制备纳米结构六钛酸钾晶须

研究了一种通过水热碱法—酸液回流—煅烧,从含钛电炉熔分渣中分离提取、制备纳米结构六钛酸钾晶须材料的新方法.采用扫描电子显微镜、透射电子显微镜、X射线衍射、X射线荧光光谱等表征手段,详细探讨了煅烧过程中钛钾摩尔比、煅烧温度、保温时间和水浸对最终产物物相和微观形貌的影响.含钛电炉熔分渣在水热温度为200℃,水热反应时间为24 h,碱液浓度达12 mol·L-1时,经酸液回流后所得偏钛酸呈一维单晶纳米棒状结构.随着钛钾摩尔比从1.50增加至1.75,煅烧温度从800℃升高到1100℃,保温时间从0.5h延长至7h,制备得到的六钛酸钾晶须的纯度、结晶性及长径比逐渐提高.当钛钾摩尔比为1.75,煅烧温度为1100℃,保温5 h,水浸2 h后可制备得到尺寸均一的六钛酸钾纳米晶须.     

MnO对高炉型高钛渣起泡行为的影响

应用X射线装置观测了碳饱和铁水与含MnO的含钛高炉渣反应过程中渣的起泡行为,测定了熔渣的起泡高度、泡沫寿命、孕育期等参数·结果表明:随MnO含量增加,起泡高度下降,泡沫寿命缩短,孕育期增长,温度是影响泡沫渣的重要因素·当渣中w(MnO)为5%、温度为1450℃时,高钛渣将不会产生泡沫现象·     

含钛复合矿选择性提取制备钛合金

采用固体透氧膜（solid oxygen-ion membrane,SOM）熔盐电解法,对含钛复合矿直接脱氧并选择性提取钛合金.经过X-射线衍射（X-ray diffraction, XRD）、扫描电子显微镜（scanning electron microscope, SEM）和能量分数X-射线（energy dispersive X ray, EDX）分析,结果表明：从含钛高炉渣中可以直接提取出Ti5Si3合金粉末,并可有效去除金属杂质Ca,Mg,Al;从钛铁矿中可以直接提取出TiFex合金.最后,对电解脱氧过程进行讨论分析.     

含钛高炉渣活度模型的建立及热力学分析

根据分子离子共存理论,建立了CaO-SiO2-MgO-Al2O3-TiO2含钛高炉渣活度模型,模型计算结果与实验测定结果吻合较好.利用该模型并结合相图计算分析了碱度和w(TiO2)对含钛高炉渣主要组元活度的影响.结果表明,含钛高炉渣中钛的主要赋存相是CaO·TiO2,1500℃时典型含钛高炉渣中CaO·TiO2的活度为0.18.随着碱度和w(TiO2)增加,CaO·TiO2活度先增后减.当碱度区间在1.08~3.08,w(TiO2)在26%~43%的条件下,有利于CaO·TiO2活度的增加,促进钛组分在钙钛矿中富集.CaO·TiO2活度最大值所需碱度随TiO2含量的增加而增加,当含钛高炉渣中w(TiO2)为20%~28%时碱度为1.34~1.63,对促进钛在钙钛矿中的富集是有利的.     

真空碳热还原酸浸含钛高炉渣制备TiC分析

含钛高炉渣中含有20%~30%的TiO_2,是一种附加值较高的二次资源,但在综合利用过程中存在氧化物还原难度大,硅钛难分离,二次污染严重等问题。基于热力学理论基础,采用真空碳热还原联合酸浸工艺处理含钛高炉渣制备TiC。结果表明:真空有助于钛氧化物彻底还原,可实现渣中硅钛彻底分离,减少酸耗量,降低二次污染。真空碳热还原联合酸浸工艺处理含钛高炉渣(TiO_2含量23%左右)制备TiC的最佳条件为:炉渣粒度200目,还原温度1 673K,渣碳质量比100∶38。     

含钛高炉渣吸附水中磷的实验

以含钛高炉渣为主要原料,研究了吸附剂的粒径大小、投加量、溶液pH值、溶液的初始浓度及吸附时间对吸附除磷效果的影响.实验结果表明,在本实验条件下,细高炉渣对磷酸盐的去除率在炉渣粒径大于10μm时,随粒径减小而增大,随高炉渣用量、pH值、反应时间的增加而增加,随磷酸盐的初始浓度的增加而减少.吸附磷的反应进行得很迅速,20~30 min基本可达到吸附饱和.对比吸附前后含钛高炉渣的XRD图和扫描电镜照片,可以看出,吸附反应后,在高炉渣的表面有大量结晶物出现,成块状和片状附着在粉末的表面,部分区域出现了多层附着现象.     

钛氧化物还原与钛渣变稠

采用攀钢高炉现场渣经过还原,获得具有一定钛氧化物还原度的炉渣试样,进一步测定样品的粘度和熔化性温度。随着钛氧化物还原度的提高,炉渣的粘度和熔化性温度总体呈上升趋势。用矿相显微镜研究了炉渣的显微结构前用图象分析仪对渣中TiC、TiN进行了定量研究。结果表明,高钛型高炉渣的变稠还与钛氧化物还原生成的TiC、TiN数量有关。因此高炉冶炼过程中用钛氧化物还原度作为判断和控制钛渣变稠的指标能更准确地反映高炉过程特点。     

Effects of additives on the phase transformation,occurrence state,and the interface of the Ti component in Ti-bearing blast furnace slag

The influences of additives on the phase transformation, occurrence state, and the interface of the Ti component in Ti-bearing blast furnace slag were investigated. After oxidation, most of the Ti component in the slag was enriched into the perovskite phase, which served as the Ti-rich phase during the crystallization process. The phase transformation, occurrence state, and the interface of the Ti component were observed to be affected by the addition of different types of agents. During the oxidation process, titanaugite and Ti-rich diopside phases gradually transformed into non-Ti phases (anorthite: CaMgSi₂O₆ and CaAl₂Si₂O₈) in the form of dendrites or columns, which were observed to be distributed at the surface of the perovskite phase. Several more cracks appeared along the grain boundaries of the perovskite phase after the addition of P₂O₅, facilitating the liberation of the perovskite phase. Composite additives combining both an acid and a base, such as CaO + CaF₂ or P₂O₅ + CaF₂, were used. We observed that the disadvantages of using single additives were successfully overcome.     

用X光透视装置观察钛漳-铁水反应过程

报道了用X光透视装置观察渣铁反应过程。普通渣与铁水反应时渣铁界面清晰,起泡但无泡沫。钛渣与铁反应时,随界面处Ti(CN)的生成、气泡的搅动,铁水逐渐向渣中乳化。重熔乳化了的渣铁样,开始界面清晰、分离良好。渣-铁反应生成的气泡能在渣面形成泡沫,主要由于Ti(CN)微粒起到了稳定剂的作用,但形成的泡沫有限。     

铌钒钛与含钛高强钢的高温变形行为

在Gleeble 2000热模拟实验机及D450实验轧机上进行不同参数的单道次压缩及多道次淬火实验.研究表明,对铌钒钛高强钢,微合金元素铌、钒、钛的碳氮化物能有效抑制奥氏体的高温软化行为,经过6道次变形的奥氏体晶粒细化到8μm左右,其控轧工艺为未再结晶区的控制轧制.对含钛高强钢,微合金元素钛表现出相对较弱的抑制奥氏体再结晶效果,经过6道次变形后的奥氏体晶粒细化到11μm左右,其控轧工艺为再结晶区控制轧制.     

Clogging behavior of submerged entry nozzles for Ti-bearing IF steel

The nozzle clogging behavior of Ti-bearing IF steel was studied by metallographic analysis, scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and X-ray diffraction (XRD). According to the experimental results, nozzle clogging primarily appears three layers. There are a lot of large-sized iron particles in the inner layer and mainly slag phase in the middle and outer layers. The principal clog constituents of the inner layer are loose alumina cluster inclusions and granular shaped alumina inclusions, containing iron particles. The clog constituents of the middle layer are mainly dendrite alumina inclusions. The primary phases existing in nozzle clogging are FeO·TiO₂ and FeO·Al₂O₃ besides α-Al₂O₃ and α-Fe. The FeO·TiO₂ phases among the deposits adhere the deposits together firmly enough to lead to the inferior castability of Ti-bearing ultra low carbon steel compared with that of Ti-free low carbon Al-killed steel.     

Phosphorus partitioning and recovery of low-phosphorus iron-rich compounds through physical separation of Linz-Donawitz slag

The Linz-Donawitz (LD) steelmaking process produces LD slag at a rate of about 125 kg/t. After metallic scrap recovery, the non-metallic LD slag is rejected because its physical/chemical properties are unsuitable for recycling. X-ray diffraction (XRD) studies have indicated that non-metallic LD slag contains a substantial quantity of mineral phases such as di- and tricalcium silicates. The availability of these mineral phases indicates that LD slag can be recycled by iron (Fe)-ore sintering. However, the presence of 1.2wt% phosphorus (P) in the slag renders the material unsuitable for sintering operations. Electron probe microscopic analysis (EPMA) studies indicated concentration of phosphorus in dicalcium silicate phase as calcium phosphate. The Fe-bearing phases (i.e., wustite and dicalcium ferrite) showed comparatively lower concentrations of P compared with other phases in the slag. Attempts were made to lower the P content of LD slag by adopting various beneficiation techniques. Dry high-intensity magnetic separation and jigging were performed on as-received samples with particle sizes of 6 and 3 mm. Spiral separation was conducted using samples ground to sizes of less than 1 and 0.5 mm. Among these studies, grinding to 0.5 mm followed by spiral concentration demonstrated the best results, yielding a concentrate with about 0.75wt% P and 45wt% Fe.     

含钛高炉炉渣微波合成碳化钛及其介电性能测定

The preparation of functional material titanium carbide by the carbothermal reduction of Ti-bearing blast furnace slag with microwave heating is an effective method for valuable metals recovery; it can alleviate the environmental pressure caused by slag stocking. The dynamic dielectric parameters of Ti-bearing blast furnace slag/pulverized coal mixture under high-temperature heating are measured by the cylindrical resonant cavity perturbation method. Combining the transient dipole and large π bond delocalization polarization phenomena, the interaction mechanism of the microwave macroscopic non-thermal effect on the titanium carbide synthesis reaction was revealed. The material thickness range during microwave heating was optimized by the joint analysis of penetration depth and reflection loss, which is of great significance to the design of the microwave reactor for the carbothermal reduction of Ti-bearing blast furnace slag.     

山东某高铁赤泥工艺矿物学研究

采用化学分析、X射线衍射、激光粒度分析、光学显微镜、能谱分析和BPMA等多种分析手段,对山东某高铁赤泥从工艺矿物学角度进行了详细研究.结果表明:赤泥粒度很细,化学成分与矿物(相)组成非常复杂.主要矿物(相)为微粒硅渣、赤铁矿、铁-铝氧化物、褐铁矿,以及微量的硅铝酸钠、铁-钛氧化物、石英、三水铝石、软水铝石、长石、云母等矿物.赤泥中的铁主要赋存于赤铁矿、褐铁矿、铁-铝氧化物和微粒硅渣中.赤泥中微粒硅渣含量较大但其中的矿物(相)粒度很细.充分利用微粒硅渣中的铁、铝、钛、钠是关键.     

改性料中MgO含量对溅渣护炉的影响

通过对溅渣前后炉渣的分析表明，改性料中MgO含量降低后，调渣后渣样中的其余矿物相变化不大，且MgO颗粒消失，这有利于复吹转炉的溅渣护炉。