Selective enrichment of TiO2 and precipitation behavior of perovskite phase in titania bearing slag

1 Introduction China is rich in mineral resources of titanium, 92.4% of which is vanadium-titanium bearing magnetite, deposited mostly around the southwestern part. About 53% titanium is in the iron concentrate after mineral processing, after smelting pro…     

Kinetics of non-isothermal precipitation process of perovskite phase in oxidized Ti-bearing blast furnace slag

Kinetics of non-isothermal precipitation process and crystal growth of perovskite phase in oxidized Ti-bearing slag were investigated. The oxidized slag was obtained by blowing the air into the molten Ti-bearing blast furnace slag through a lance. The experimental results show that the cooling rate has important effect on precipitation and growth of perovskite phase in oxidized slag; the lower cooling rate is in favor of not only the increase of the volume fraction of perovskite phase, but also the growth of perovskite phase grain sizes. The particle coarsening in non-isothermal process has important effect on the crystal growth of perovskite phase. The relative volume fraction of perovskite phase could be approximately described by JMAK equation, and the experiential expression of the average crystal radius of perovskite phase was also obtained.     

含钛高炉渣中钛组分选择性富集及钙钛矿结晶行为

攀钢含钛高炉渣工艺矿物学分析结果表明 ,钙钛矿是主要的富钛相。采用CaO和Fe2 O3对原高炉渣进行改性处理 ,不仅提高了钙钛矿的析出温度 ,而且使另外两种主要含钛矿物攀钛透辉石和富钛透辉石析出的温度显著降低。在适当热处理条件下 ,近 80 %的钛组分进入钙钛矿相中 ,而且钙钛矿的平均晶体尺寸达 90 μm ,实现了熔渣中钛组分的选择性富集并为选矿分离创造了条件。     

铝热还原酸溶性钛渣制备TiAl基多元合金

对含高钛的酸溶性钛渣进行铝热还原制备钛铝基多元合金。为了控制并了解合金的制备,讨论了铝和氧化钙的添加和温度的影响。通过考虑材料的配比计算,可以成功地使合金与渣合金分离。大多数还原元素的回收率表现为高值,在所有实验条件下均为95%。铝的添加主要影响合金的成分,而氧化钙的添加则通过改变渣系成分来影响渣金分离。此外,系统的温度可以提高大部分还原元素的回收率和分配比。     

Decomposition of acid dissolved titanium slag from Australia by sodium hydroxide

The kinetics of the decomposition of acid dissolved titanium slag with a sodium hydroxide system under atmospheric pressure was studied. The effect of reaction temperature, particle size and NaOH-to-slag mass ratio on titanium extraction was investigated. The results show that temperature and particle size have significant influence on titanium extraction. The experimental data of titanium extraction show that the shrinking core model with chemical reaction controlled process is most applicable for the decomposition of slag, with an apparent activation energy of 62.4 kJ·mol⁻¹. Approximately 85 wt.%−90 wt.% of the titanium can be extracted from the slag under the optimal conditions. In addition, the purity of titanium dioxide obtained in the product is up to 98.5 wt.%.     

高钛渣还原的氢化钛合金粉一步烧结制备高强钛合金（英文）

提出一种直接利用高钛渣制备高强钛合金的方法。先用镁粉还原高钛渣制备氧含量为1.3%(质量分数)的合金粉末,再将合金粉末在600 MPa压力下压制成小圆柱体,最后在氩气下烧结成钛合金产品。对还原粉末进行表征,研究烧结温度对烧结合金的烧后密度、抗压强度、显微组织和硬度的影响。结果表明,随着烧结温度由900℃升高至1200℃,钛合金的密度增加,孔隙率降低,实现较好的烧结致密化(1100℃为98.65%,1200℃为99.41%),在1100℃时硬度达到HV 655.7,压缩强度为1563 MPa。     

Effect of oxidization on enrichment behavior of TiO2 in titanium-bearing slag

1. Introduction There are around 50 million tons of titanium slag piled up in China. Such slag usually contains about 20%-22% TiO2 and cannot be discarded, so this quantity is still increasing at a rate of 3 million tons per year. However, owing to the dispersed distribu-tion of titanium component in various mineral phases, and very fine grains (<10 μm) and complex interfacial combination, it is very difficult to recover titanium component from the slag by conventional separating technique. …     

Post-mortem analysis of high alumina brick attacked by vanadium and titanium bearing slag after service in torpedo ladle

Abstract

High alumina brick after service in a torpedo ladle was analysed by means of atomic emission spectroscopy, X-ray diffraction, electron probe microanalysis and themochemical analysis in order to determine the corrosion mechanism during industrial application in a steel works. The results showed that slag containing vanadium and titanium oxide is more corrosive than common silica slags, and that this facilitates corrosion and penetration into the high alumina brick. Mineralogical observation confirmed that V₂O₅, TiO₂, MnO and FeO and MgO in the slag reacted with native phases presented in high alumina brick to form complex spinel, corundum and anorthite solid solution, etc. The dissolved content of V₂O₅ in the spinel decreased from 6·08 to 2·78 wt-% from the working face to the inner area. However, the FeO and MnO content in the spinel varied little with a slight increase in the TiO₂ content. The expansion coefficient mismatch between the penetrated zone and cold face zones, which results in densification spalling and increased porosity, play a key role in the failure of the high alumina brick.     

Appropriate titanium slag composition during smelting of vanadium titanomagnetite metallized pellets

The suitable titanium slag composition with high titanium content for electric furnace smelting of vanadium titanomagnetite was investigated through thermodynamics and related phase diagram analysis. According to the thermodynamic results, low-melting-point regions and MgTi₂O₅ primary phase area in the phase diagrams, the suggested titanium slag composition for the present vanadium titanomagnetite metallized pellets should consist of 50% TiO₂, 8%–12% MgO and 13% Al₂O₃ (mass fraction) with a binary basicity of 0.8–1.2. Finally, the verified smelting experiments were conducted and successful separation of the molten iron from the titanium slag is obtained. The obtained vanadium-containing molten iron contains 0.681% V and 0.267% Ti, and the obtained titanium slag contains 52.21% TiO₂ (mass fraction), in which MgTi₂O₅ is the primary phase. The titanium resource in the final titanium slag production could be used to produce TiO₂ pigment by acid leaching methods.     

Phase conversion and removal of impurities during oxygen-rich alkali conversion of high titanium slag

In order to achieve high-efficiency alkali conversion and impurity removal of high titanium slag under the condition of low alkali concentration, a new way of oxygen-rich alkali conversion in KOH solution was proposed. The conversion law of element occurrence state and the influence of the conversion conditions on the titanium conversion rate and removal rate of silicon and aluminum were studied. The results showed that the KOH solution converted the titanium oxide in high titanium slag into whisker-like potassium titanate. Silicon and aluminum elements were dissolved into the solution. Under the following conditions, KOH concentration of 6 mol/L, conversion temperature of 260 °C, initial oxygen partial pressure of 2 MPa, liquid?solid ratio of 35 mL/g, conversion time of 4 h, and high titanium slag particle size of 48?74 μm, the conversion rate of titanium was 97.0%, and the removal rates of silicon and aluminum were 90.2% and 76.2%, respectively. Oxygen-rich alkali conversion product was converted to rutile with a TiO₂ grade of 99.1% by acid hydrolysis conversion.     

钙热还原二氧化钛的钛粉制备及其中间产物CaTiO3的成因

通过热力学计算以及XRD、SEM和EDS等测试手段,研究TiO2钙热还原制备钛粉过程中钛酸钙(CaTiO3)的形成原因。热力学计算表明:当温度高于800 K时,添加剂CaCl2水解产物CaO与TiO2生成CaTiO3的反应以及还原副产物CaO与TiO2生成CaTiO3的反应均满足反应发生的热力学条件。实验研究表明:CaTiO3的生成主要是由添加剂CaCl2水解生成的CaO与TiO2烧结反应所致,CaTiO3的量随着CaCl2添加量的增加而增加,且CaTiO3更容易被还原为金属钛。当CaCl2与TiO2的质量比约为1:4时、在1 273 K下还原时间为6 h时,反应过程中的CaTiO3被完全还原为金属钛粉,该粉末具有不规则外形,颗粒粒径为8~15μm。经EDS分析,金属钛粉中钛的质量分数达到99.55%。     

钛渣中TiO2作晶核剂对玻璃晶化的影响

制备了以钛渣和铁尾矿为主要原料,以钛渣兼作晶核剂的微晶玻璃材料,研究了Ｔｉ２含量变化对玻璃晶化的影响。采用ＤＴＡ,ＳＥＭ,ＸＲＤ等技术对该体系的晶化机理进行探讨。结果表明,当ＴｉＯ２含量小于１０％时仅产生表面晶化。而当ＴｉＯ２含量为１０％时可发生整体晶化,其活化能为１９０．６ｋｊ．ｍｏｌ＾－１,动力学参数ｍ＝３,晶体从晶界面呈三维生长。ＴｉＯ２、Ｆｅ２Ｏ３能共同促进晶化,晶体从相界面处生长,析出的     

密闭直流电弧炉冶炼钛渣热量平衡研究

密闭直流电弧炉冶炼生产钛渣利用输入电能进行加热,在高温情况下,钛精矿中的FeO和TiO2发生还原反应.反应进行程度影响熔池内渣的粘度,进而影响炉壁挂渣层的厚度和排渣排铁的难易程度,故还原反应过程必须控制输入能量使DC炉系统达到热量平衡；输入能量过高会使熔池内的渣过热,挂渣层变薄,造成炉壁腐蚀；输入能量过低,会导致渣的粘度明显增大,造成排渣困难,并产生泡沫渣.根据理论计算,每冶炼1t钛精矿需要消耗约911.55kWh的能量,云南某公司加料速率为5t钛精矿/h,钛精矿碳热还原,理论上需要消耗约4557.734kWh的电耗.能量支出方面有物料带走的物理热、炉壁和炉顶冷却水热损失、炉底风冷热损失、电力设备热损失以及少量未预见热损失,钛精矿冶炼过程中,能量的输出和输入是基本相等的,热量处于平衡状态.     

Ti-B19钛合金的β→α＋β等温相变动力学

利用原位电阻法、同步X射线衍射等技术较为系统地研究了亚稳β钛合金Tj-B19的β→α＋β等温相变动力学。结果表明，在试验温度范围内，Ti-B19合金的等温相变为长程扩散控制的形核与长大过程，可以用JMA方程进行描述。在试验温度范围，500℃等温时效时相转变完成所需时间最短，相转变速度最快，当温度大于500℃时，随温度升高，相转变速度降低，这与相转变驱动力不足有关。当温度低于500℃时，由于受溶质扩散速度的影响，完成相转变所需时间更长。α相的数量是温度的函数，在500℃等温时，α相的数量最多，为57．7％，然后随温度的升高，α相的数量减少。根据试验结果，绘制了合金的时间-温度-转变量图（TTT图），其“鼻温”在500℃-550℃之间。     

界面非平衡氧传递过程动力学的解析

将氧通过界面反应在两相间的传递过程简化为界面化学反应和扩散传质两个步骤,对此过程的动力学进行了数学解析,得到了一个新的动力学模型.同时显示,反应过程中界面氧浓度随反应过程的进行不断发生变化,这表明该界面反应是一个非平衡过程.应用得到的动力学模型对几个体系的动力学实验数据进行了拟合,符合很好,根据拟合的参数可以很好地解释实验现象.初步讨论了模型参数的意义和对动力学过程的影响.     

Preparation of Ti-rich material from titanium slag by activation roasting followed by acid leaching

A method of activation roasting followed by acid leaching using titanium slag was introduced to prepare Ti-rich material. The effects of H₃PO₄ dosage, roasting temperature, and roasting time on TiO₂ grade were investigated. A Ti-rich material containing 88.54% TiO₂, 0.42% (CaO+MgO) was obtained when finely ground titanium slag was roasted with 7.5% H₃PO₄ at 1000 °C for 2 h, followed by a two-stage leaching in boiling dilute sulfuric acid for 2 h. The XRD patterns show that the product is titanium dioxide with a rutile structure. Mechanism studies show that structures of anosovite solid solution and silicate minerals are destroyed in the roasting process. As a result, titanium components in titanium slag are transformed into TiO₂ (rutile) while impurities are transformed into acid-soluble phosphate and quartz.     

Oxidization mechanism in CaO-FeOx-SiO2 slag with high iron content

Oxidization mechanism in CaO-FeOx-SiO2 slag with high iron content was investigated by blowing oxygen into molten slag so as to oxidize Fe（ Ⅱ）. The relationship between Fe（ Ⅱ ） content and oxidizing time at different temperatures was obtained by chemical analysis. Microstructure of slag was observed by metallographic microscope and SEM. Phases compositions were ascertained by EDXS and XRD. Grain size and crystallizing quantity of magnetite（Fe3O4 ） were determined by image analyzer. The oxidizing kinetic equations were deduced. Confirmed by graphical construction method, Fe（ Ⅱ ） oxidizing reaction in CaO-FeOx-SiO2 slag system is of first order, and the reaction apparent energy Eo is 296. 67 kJ/mol in the pure oxygen and 340. 30 kJ/mol in air. The enrichment and crystal growth mechanism of magnetite（Fe3O4 ） phases were investigated. In oxidizing process, content of fayalite declines, while that of magnetite（Fe3O4 ） increases, and iron resources enrich into magnetite（Fe3O4 ） phase. All these provide a theoretical base for compressive utilizing of those slags.     

微波作用下铝酸钙炉渣非等温浸出动力学

研究了微波作用下铝酸钙炉渣非等温浸出动力学，考察了不同微波辐射功率对炉渣中氧化铝浸出率的影响以及相应微波功率下反应体系温度随时间的变化规律。结果表明：该浸出动力学过程的控制步骤为界面化学反应控制，表观反应活化能为40kJ／mol左右；微波作用可改变反应的频率因子，对反应活化能影响不明显；随着微波辐射功率的增大，频率因子增加，宏观表现出微波功率的增加对反应有促进作用。     

制钛过程中阴极钙钛矿的形成与阳极溢出气体间的关系

采用FFC剑桥工艺在熔融CaCl₂中电解二氧化钛时,钙钛矿是阴极上不可避免形成的相。本文研究了在制备钛的过程中,阴极钙钛矿的形成与阳极释放气体的关系。结果表明,阴极上相的形成主要有三个阶段,包括钙钛矿的形成、钙钛矿的脱氧及钛的低价氧化物脱氧为TiO、和TiO到Ti的脱氧。尽管分解电压低于CaCl₂,但阴极形成的钙钛矿与从阳极释放的气体密切相关。由于短时间内钙钛矿的形成造成过电压,因而阳极释放出氯气,氯气的量取决于TiO₂和电解过程中产生的不同低价钛的量。当钛的低价氧化物介于Ti₃O₅和TiO₂之间时,在第一脱氧阶段TiO₂和氯的质量比为9：2到46：2。在氯气释放的过程中阳极没有明显的消耗。钙钛矿的形成和Ti₂O的脱氧是在熔融CaCl₂中电解制备钛的主要限制性环节。从TiO₂到Ti的总电流效率是24.07％。目前第一阶段的电流效率在22.37％~44.74％之间,第二阶段在30.18％~37.72％之间。