钒钛磁铁精矿直接还原反应行为及其强化还原研究

通过在钒钛磁铁精矿中添加还原煤粉和少量添加剂,研究了还原温度、还原时间和添加剂等因素对钒钛磁铁精矿金属化率的影响,并对添加剂强化还原机理进行了探讨.结果表明:还原温度、还原时间、碳铁摩尔比及添加剂对金属化率的影响较大.在还原温度1200℃、还原时间120 min的条件下,未添加添加剂时金属化率最高可达84.5%;添加质量分数3.0%Na2CO3或CaF2的条件下,钒钛磁铁精矿的金属化率可以分别达到96.5%和93.3%.     

钒钛磁铁精矿冷固球团催化还原机理

对添加剂催化钒钛磁铁精矿冷固球团直接还原行为进行了详细的研究 ,包括添加剂种类和用量及催化剂催化还原机理 .研究结果表明 :在 1 0 50～ 1 1 0 0℃ ,m(C)∶m(Fe)为 0 .5～ 0 .6 ,还原时间 3h的条件下 ,添加DA 2催化剂与常规的Na2 SO4或Na2 CO3相比 ,钒钛磁铁精矿冷固球团煤基直接还原所得产品的金属化率提高 3 .1 %～ 4 .6 % ;该金属化球团经磨矿磁选进行铁和钒钛分离时 ,所得磁性产品 (直接还原铁粉 )中铁的品位提高 5 .30 %～ 5 .43 % ,非磁性物中TiO2 ,V2 O5 的品位分别提高 2 .76 %～ 3 .87%和 0 .2 7%～ 0 .45 % ,TiO2 ,V2 O5 的回收率分别提高 1 4 .68%～1 3 .0 8%和 4.1 3 %～ 6 .97% .SEM及XPS等微观测试结果表明 :添加剂DA 2的作用机理为加速铁氧化物还原 ,促进铁晶粒的长大 ,降低还原球团中MFe与TiO2 晶粒嵌布的紧密程度 ,从而强化了铁与钒钛的磁选分离     

磁铁精矿球团氧化动力学

推导出了磁铁矿氧化"单界面未反应核"修正模型,并应用该模型研究了凹山磁铁精矿球团的氧化动力学.研究结果表明:在800～950℃时,凹山磁铁精矿球团氧化反应表观活化能为64 kJ/mol,其氧化由化学反应所控制;在1000～1 050℃时,氧化反应的表观活化能为13 kJ/mol,反应为反应产物层的内扩散所控制;在950～1000℃时,氧化反应为混合控制;在较低氧化温度下,加入MgO可以降低化学反应阻力,提高球团的氧化率;在较高氧化温度下,MgO对扩散阻力无明显影响,添加MgO并不提高氧化反应速度,但在任何氧化温度下,添加MgO不改变磁铁矿氧化反应的控制环节.     

铝粉对钒钛磁铁精矿碳热还原及熔分过程的影响

研究了铝粉对钒钛磁铁精矿碳热还原及熔分过程的影响。结果表明：添加铝粉能提高钒钛磁铁精矿碳热还原反应速率。铝粉添加量越大,还原反应越快。在还原反应过程中,铝热还原反应的发生放出了大量热量,并在其反应界面周围形成局部高温,从而强化碳热还原反应过程,同时促进新生金属铁聚集长大。添加1%铝粉可稍微改善渣金分离;当铝粉添加量大于2%时,由于TiC的生成,渣的流动性变差,渣铁分离效果恶化。     

高负压大风量高钛型钒钛磁铁精矿烧结生产实践

本文通过分析风量和负压对烧结产质量的影响关系,找出钒钛磁铁精矿烧结实施高负压大风量的措施。采用高负压大风量转子,以改善透气性指数P为主,合理控制工艺参数。推行厚料层烧结,实行全风烧结,降低抽风系统管网的漏风率,实施低负压点火工艺等烧结技术改进,在一台360m2烧结机成功实现了高负压大风量烧结,当负压由14520Pa提高到15340Pa后,随着负压上升820Pa,料层提高15mm,利用系数上升0.047 t.m-2.h-1,转鼓指数提高0.94%,固体下降0.82 kg/t。     

磁铁精矿的无碳烧结

为了实现磁铁精矿的无碳烧结,从质量、保护气氛（N2）和Fe3O4添加量对磁铁精矿微波烧结的影响3个方面进行了研究．结果表明2采用相同试样碱度（CaO／SiO2=2．5）和微波加热条件（1000W、2．45GHz、20min）,试样中心温度会随着试样质量增加而逐渐降低;在相同的微波加热条件下,采用保护气氛,同无保护气氛相比,同一试样的温度没有提高;相同微波加热条件下加热同碱度（CaO／SiO2=2．5）的磁铁精矿试样100g,试样中Fe3O4添加量越多,微波烧结过程中液相出现得越少,越不利于磁铁精矿的烧结．     

预氧化对钒钛磁铁矿球团矿相及内部结构的影响

以钒钛磁铁矿为原料制备氧化球团,利用XRD和SEM等手段,考察室温至500,700,900,1000,1100,1200,1250℃7种情况下预氧化球团的物相组成和微观结构.结果表明,当预氧化温度低于500℃时,球团内部发生γ-Fe2O3向α-Fe2O3的转变,未发生氧化反应;当预氧化温度高于500℃时,随着预氧化温度的升高,球团内部的TTM和FeTiO3氧化生成TTH和Fe2TiO5,白色物相(含Fe,V,Ti)聚合长大与黑色物相(Mg,Al,Si相)逐渐分离,且晶型由较为分散的颗粒状向紧密互联、结构力强的互联状转变.     

钒钛磁铁精矿直接还原过程中金属铁颗粒长大特性

通过钒钛磁铁矿精矿直接还原实验,研究了不同还原剂和添加剂对还原过程金属铁颗粒长大的影响.提高还原温度能促进还原产物中金属铁颗粒的长大,金属铁颗粒中V含量也显著增加.与用无烟煤和褐煤还原产物相比,用烟煤还原产物中金属铁颗粒明显长大,这是由烟煤中高灰分含量所引起的.金属铁颗粒长大机理的研究表明:Na2CO3和Na2SiO3的熔点较低,且能破坏铁橄榄石和铁尖晶石的结构,并生成一些低熔点物质,而SiO2能与铁橄榄石形成低共熔混合物.这些低熔点物质都有助于改善金属铁相的扩散,从而促进金属铁颗粒长大.     

预氧化在攀枝花钛铁矿固态还原过程中的作用

研究了预氧化对攀枝花钛铁矿还原行为的影响.结果表明:预氧化加快了钛铁矿铁氧化物的还原速率,提高了还原产物铁的金属化率.其作用机理是:钛铁矿在预氧化过程中形成了假金红石、三氧化二铁、金红石和三价铁板钛矿等新的物相,破坏了原有矿物结构,颗粒内部形成了大量孔隙,有利于增大颗粒的比表面积,改善还原过程气体的扩散条件;经预氧化处理的钛铁矿在预氧化过程中形成的新物相将被重新还原,新生钛铁矿活性高,还原产物的显微结构也得到了进一步的改善.     

优化配矿强化西澳超细粒磁铁精矿球团焙烧研究

进行了西澳超细粒磁铁精矿分别配加国产磁铁精矿和巴西赤铁精矿制备氧化球团矿的实验研究.结果表明,以100%西澳超细磁铁精矿为原料制备氧化球团矿时,球团预热及焙烧性能较差,在预热温度为1050℃、预热时间20 min及焙烧温度1300℃、焙烧时间40 min的条件下,预热球团和焙烧球团矿抗压强度分别为每个502和2313 N.西澳超细粒磁铁精矿配加40%国产磁铁精矿或20%巴西赤铁精矿时,球团适宜预热温度由1050℃分别降低到950和975℃,适宜的焙烧温度由1300℃分别降低到1250和1280℃;而且焙烧球团矿的抗压强度分别提高到每个2746 N和每个2630 N.焙烧球团矿的微观结构研究表明:配加国产磁铁精矿后,焙烧球团矿中Fe2 O3晶粒发育优良,晶粒间互联程度提高,晶粒粗大,孔隙率低,固结更加紧密.配加20%巴西赤铁精矿时,焙烧球团矿中Fe2 O3晶粒基本连接成片,Fe2 O3晶体发育良好.优化配矿是改善西澳超细粒磁铁精矿球团矿预热及焙烧性能的有效途径.     

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.     

Biodesulfurization of vanadium-bearing titanomagnetite concentrates and pH control of bioleaching solution

Vanadium-bearing titanomagnetite concentrates were desulfurized with Acidithiobacillus ferrooxidans (A. ferrooxidans). The sulfur content of the concentrates was reduced from 0.69wt% to 0.14wt% after bioleaching for 15 d with a 10% pulp density at 30℃. Maintaining a stable pH value during biodesulfurization was critical because of high acid consumption, resulting from a combination of nonoxidative and oxidative dissolution of pyrrhotite in acid solution. It is discovered that the citric acid-disodium hydrogen phosphate buffer of pH 2.0 can control the solution pH value smoothly in the optimal range of 2.0–3.0 for A. ferrooxidans growth. Using the buffer in the volume fraction range of 5.0%–15.0% stimulates A. ferrooxidans growth and improves the biodesulfurization efficiency. Compared with the buffer-free control case, the maximum increase of biodesulfurization rate is 29.7% using a 10.0vol% buffer. Bioleaching provides an alternative process for desulfurization of vanadium-bearing titanomagnetite ores.     

Non-isothermal reduction kinetics of titanomagnetite by hydrogen

Reduction of titanomagnetite (TTM) powders by H2-Ar gas mixtures was investigated under a non-isothermal condition by using a thermogravimetric analysis system. It was found that non-isothermal reduction of TTM proceeded via a dual-reaction mechanism. The first reaction was reduction of TTM to wüstite and ilmenite, whereas the second one was reduction of wüstite and ilmenite to iron and titanium dioxide. By using a new model for the dual reactions, which was in an analytical form and incorporated different variables, such as time, temperature, particle size, and hydrogen partial pressure, rate-controlling steps for the dual reactions were obtained with the apparent activation energies calculated to be 90–98 and 115–132 kJ/mol for the first and second reactions, respectively.     

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.     

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.     

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite (TTM) ironsand, which contains 11.41wt% TiO₂ and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence: FeO + FeTiO₃ → Fe₂TiO₄ → FeTiO₃ → FeTi₂O₅ → TiO₂. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 kJ·mol-1.     

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.