以转底炉技术利用钛资源的基础研究

提出了一种以转底炉煤基直接还原技术利用钛资源的新工艺及两个不同的方案。该工艺以攀枝花钒钛磁铁精矿或钛精矿粉、煤粉和少量添加剂组成的复合球团为原料,在高温加热条件下将含钛矿中的氧化铁还原为铁,经渣铁分离后获得生铁和富集了的钛渣。第一方案以钒钛磁铁精矿配20%钛精矿为原料,还原后渣铁自然分离,得到块铁和品位为50%左右的钛渣;第二方案以钛精矿为原料,还原后经破碎磁选分离得到粒铁和TiO2富集率为～75%的钛渣。对这两种方案均进行了初步试验,确定了合理的工艺条件。     

含钒钛铁矿球团还原过程中微观结构变化

在实验室模拟高炉条件下研究了含钒钛铁矿球团的还原过程,采用X射线衍射仪测定含钒钛铁矿球团在不同还原温度下的物相组成,通过光学显微镜和扫描电镜观察含钒钛铁矿球团还原过程中微观结构变化,并结合能谱分析仪研究氧化物中不同元素的分布状况.含钒钛铁矿球团在还原过程中出现的铁钛分离现象会影响含钒钛铁矿球团的还原性,形成的高钛含量钛铁晶石会增加铁氧化物还原难度.高温时形成的密实金属铁球壳会阻碍内部氧化物的还原,导致还原停滞,从而造成含钒钛铁矿球团高温还原性较差.当内部熔融物滴下时,会提高高炉下部氧势,有利于减少Ti(C,N)的生成.      

Smelting Reduction of Iron Ore‐Coal Composite Pellets

Smelting reduction of iron ore‐coal composite pellets has been carried out in an induction furnace. The pellets, tied with tungsten wire, were immersed into the liquid metal bath. The experiments were carried out in the temperature range of 1713 K to 1733 K. For 16‐18 mm diameter pellets, it was observed that (i) the time required for complete dissolution in liquid metal bath is 83‐90 seconds, (ii) the fraction of reduction for 40 seconds of immersion varied from 0.68‐0.87 for Jharia coal pellets and 0.73‐0.92 for Bhilai coal pellets, and (iii) the fraction of reduction increases with decreasing Fe/C ratio and increasing immersion period. X‐ray diffraction (XRD) of reduced pellets showed that the reduction occurred topochemically. Scanning electron microscopic (SEM) examination of partially reduced pellets evinced the structural changes in pellets. The present investigation aims to assess the effect of Fe/C ratio in pellet, volatile matter in coal, and time of pellet immersion into liquid metal bath on reduction of iron ore‐coal composite pellets.     

The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part III. The simulation of volatile reduction in a multi-layer rotary hearth furnace process

For reduction of iron oxides by volatiles from coal, the major reductant was found to be H₂, and it can affect the overall reduction of iron oxides. In this study, the reduction by actual volatiles of composite pellets at 1000 °C was studied. The volatile reduction of the hand-packed Fe₂O₃/coal composite pellet as it is devolatilizing out of the pellet was found to be negligible. However, the reduction of iron oxide pellets at the top layer by volatiles from the bottom layers of a three-layer pellet geometry was observed to be about 15 pct. From the morphological observations of partially reduced pellets and the computed rates of bulk mass transfer, volatile reduction appears to be controlled by a mixed-controlled mechanism of bulk gas mass transfer and the limited-mixed control reduction kinetics. Using the reduction rate obtained from the single pellet experiments with pure hydrogen and extrapolating this rate to an H₂ partial pressure corresponding to the H₂ from the volatiles, an empirical relationship was obtained to approximately predict the amount of volatile reduction up to 20 pct.     

高钛渣碳热还原—浮选法提取Ti_2CO

通过高温碳热还原分别将高钛渣中的钛和铁还原至富钛相物质Ti2CO和金属铁,并使其中的熔渣相MOx不被还原,然后选用油酸作为捕收剂对Ti2CO/MOx模拟混合原料开展了浮选研究。结果表明,采用该工艺从还原产物中得到了产率79.88%、Ti2CO回收率87.74%的浮选效果。     

微粒嵌布难选金红石矿煤基深度还原热力学

关键词：金红石矿;深度还原;配碳比;KOH;K2CO3     

Solid-phase prereduction of iron-vanadium concentrates and liquid-phase separation of the products of their reduction

The transformations that occur in ore grains during solid-phase carbon reduction of the metals from the iron-vanadium concentrates formed upon the beneficiation of the titanomagnetite ores from Southern Ural deposits are studied. Upon heating to 1000°C, the solid solution in titanomagnetite grains decomposes with the formation of magnetite and ilmenite; the reduction of iron begins in the temperature range 1080–1110°C, and the reduction of titanium begins at above 1215°C. The reaction mixture should be held at 1250°C for 45 min to ensure almost complete iron reduction and the minimum degree of titanium reduction. For rapid separation melting, this procedure results in vanadium-containing cast iron (0.43–0.5% V) with <0.15% Ti and a slag with 42–43% titanium oxides.     

含碳球团直接还原熔分机理

为了探究含碳球团还原熔分机理,将分析纯的Fe₂O₃、氧化物和不同还原剂固结成球并进行等温还原实验,研究了温度、还原时间、配碳量、还原剂种类等条件对球团还原熔分行为的影响.进一步采用X射线衍射、扫描电子显微镜等手段表征了含碳球团在不同还原时间的微观结构及物相变化.实验结果表明:焙烧温度过低或过高含碳球团都不能良好熔分,配碳量增加可以提高球团还原和熔分速率,适宜的温度、碳氧摩尔比、还原剂分别是1400℃、1.2和煤粉.含碳球团还原熔分包括直接还原反应、间接还原反应、碳的气化反应、渗碳反应和铁的熔化反应,最后实现渣铁分离.      

Effect of alumina on slag–metal separation during iron nugget formation from high alumina Indian iron ore fines

Abstract

Iron nuggets can be obtained from ore–coal composite pellets by high temperature reduction. Alumina in the ore plays a vital role in slag–metal separation during nugget formation, as it increases the liquidus temperature of the slag. In this study, the effect of carbon content, reduction temperature and lime addition on slag–metal separation and nugget formation of varying alumina iron ore fines were studied by means of thermodynamic modelling. The results were validated by conducting experiments using iron ore fines with alumina levels ranging from 1·85 to 6·15%. Results showed that increase in reduction temperature enhances slag metal separation, whereas increasing alumina and carbon content beyond the optimum level adversely affects separation. Carbon below the required amount decreases the metal recovery, and carbon above the required amount reduces the silica and alters the slag chemistry. Optimum conditions were established to produce iron nuggets with complete slag–metal separation using iron ore–coal composite pellets made from high alumina iron ore fines. These were reduction temperature of 1400°C, reduction time minimum of 15 min, carbon input of 80% of theoretical requirement and CaO input of 2·3, 3·0 and 4·2 wt-% for 1·85, 4·0 and 6·15 wt-% alumina ores respectively.     

高铝铁矿和高锰铁矿共还原行为的研究

高铝铁矿和高锰铁矿是两种储量丰富但又极难分选的铁矿资源,实现铁、锰、铝的高效综合利用具有重要意义.本文研究了这两种铁矿石工艺矿物学,考查了单矿种及两者的混合矿种的直接还原行为及还原过程中的矿物组成演变,揭示了相应的还原机理.结果表明:高铝铁矿难还原,其机理为经还原后仅部分铁氧化物转化为金属铁,其余的铁与铝、硅矿物形成难还原的铁橄榄石和铁尖晶石;高锰铁矿易还原,其中的铁氧化物大部分被还原成金属铁,锰氧化物与铝、硅矿物结合形成锰尖晶石和锰橄榄石,促进了铁氧化物的还原.而且在相同还原条件下,高锰铁矿球团金属化率比高铝铁矿高30个百分点,前者还原性明显优于后者.两种矿进行共还原,当高锰铁矿配比达到60%时,球团金属化率就可大于90%.锰氧化物的存在对高铝铁矿石中铁氧化物的还原具有显著的促进作用.     

Hydrogen-Based Direct Reduction of Iron Oxides Pellets Modeling

The present study deals with the analyses of the direct reduction kinetics during the hydrogen reduction of industrial iron oxide pellets. Various types of pellets with different percentage of total iron content and metal oxides are examined. They are reduced at different temperatures and pressure (700–1100 °C and 1–6 bar) in hydrogen atmosphere. The reduction behavior is described in terms of time to reduction, rate of reduction, and kinetics constant. All the obtained results are analyzed through the employment of a commercial multiobjective optimization tool to precisely define the weight that each single parameter has on the reduction behavior. It is shown that from the point of view of the processing conditions, temperature is the main factor influencing the time to total reduction. From the point of view of the pellets properties, it is mainly influenced by the total iron percentage and then by porosity and basicity index. Also, the kinetics behavior is largely influenced by the reduction temperature even if it is mainly governed by the porosity and pores size from the point of view of the reduced pellets. The reduction rate is also mainly influenced by temperature and then by iron percentage, gas pressure, basicity index, and porosity.     

钒钛磁铁矿加工利用研究现状及发展趋势

摘要：钒钛磁铁矿作为一种富含铁、钒、钛的特色矿产资源,综合利用价值高。从钒钛磁铁矿的选矿富集和钒钛磁铁精矿的冶金分离层面,论述了钒钛磁铁矿的加工利用研究现状。在选矿富集方面,开发新型选矿设备和药剂、优化选矿工艺,能够获得合格的钒钛磁铁精矿,并阐述了选矿指标难以进一步提高的原因。在冶金分离方面,通过分析对比各工艺的研究现状及优缺点,解释了各类非高炉工艺无法推行工业化生产的原因,并提出流态化预还原-电炉熔分法是未来实现钒钛磁铁精矿高效利用的重要研究方向。     

钒钛铁精矿内配碳球团的高温快速还原

 钒钛铁精矿是一种铁、钒、钛等多元素共生的复合矿,具有很高的综合利用价值。通过采用实验室转底炉对钒钛铁精矿内配碳球团进行了高温快速还原的可行性研究,分别考察了配碳比、还原温度、添加剂、还原时间等参数对球团金属化率的影响。结果表明,配碳比（1.5：1）、还原温度（1350℃）、添加剂（2%）、还原时间（20min）时金属化率可以达到88%以上。对原料、还原样品进行x射线衍射分析表明,钒钛铁精矿粉中的磁铁矿、钛磁铁矿和钛铁矿通过还原转变为单质铁、含铁黑钛石。     

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Isothermal reduction experiments of the pellets from Wuhan Iron and Steel Corporation (WISCO) were performed with the thermogravimetry technique in the temperature range from 900?? to 1100?? and under the atmosphere of CO of 100% (volume fraction). The apparent activation energy, reduction rate constant and diffusion coefficient were calculated in terms of the Arrhenius plots and the unreacted core model, respectively, and the rate controlling steps were ascertained accordingly. The microstructure and forms of iron oxides of the pellets at the different reduction stages were observed by FESEM and EDS techniques and the reduction reaction mechanism of the pellets was analyzed accordingly. The results show that the controlling step of the reduction reaction of the pellets is the interfacial chemical reaction during most of the time from the initial stage through the middle and later stage, and it shifts to the solid diffusion at the final stage, and that the pellets reduction proceed in the order from higher oxides to lower oxides of iron and the application of the unreacted core model to the kinetic analysis is appropriate.     

煤粉燃料球团生产中链篦机结渣物成因分析

对以煤粉为燃料的链篦机-回转窑法铁矿球团生产中链篦机预热段生成的结渣物进行了XRD、显微结构及扫描电镜能谱分析,发现其矿相组成主要是铁氧化物以及少量含镁铝固溶体。为查明链篦机结渣物形成机理,开展了温度及煤灰残碳量对结渣物形成影响的模拟焙烧试验。结果表明,焙烧物的物相中有含残碳的煤灰,其物相组成、显微结构与实际结渣物组成物相类似,证实链篦机喷煤补热燃烧过程中煤灰中的残碳可使结渣混合物体系生成含亚铁相的硅铝酸盐类低熔点化合物,是导致链篦机结渣物形成的主要原因。     

煤粉含碳球团炼铁半工业试验

作者提出一种以非焦煤和含煤球团为原料,用煤粉化铁炉连续生产铁水的方法。该工艺由煤粉,空气在前炉中旋转燃烧供热,燃烧产生的高温煤气经过火道进入竖炉,逆流预热预还原冷固结含煤球团,预还原后的球团在竖炉下部和火道中熔化,过热并进行终还原,最后流入前炉完成渣—铁分离。在已完成的半工业试验中,冶炼耗煤量为916 kg/t铁水,耗电量为80 kwh/t铁水,生产率为6 t铁水/(m~3·d)。本工艺可发展成一种只用非焦煤和铁精矿粉生产铁水的生产工艺。     

CHARACTERIZATION OF PROPERTIES AND REDUCTION BEHAVIOR OF IRON ORES FOR APPLICATION IN SPONGE IRONMAKING

Studies on the chemical and physical properties, and the reduction behavior (in coal) of hematite iron ores procured from 10 different mines of Orissa, were undertaken to provide information for the iron and steel industries (sponge iron plants in particular). The majority of the iron ores were found to have high iron and low alumina and silica contents. All these iron ores were free from the deleterious elements (S, P, As, Pb, alkalies, etc.). The results indicated lower values of shatter and abrasion indices, and higher values of tumbler index in all the iron ore lumps except Serazuddin (previous) and Khanda Bandha OMC Ltd. For all the fired iron ore pellets, the degree of reduction in coal was more intense in the first 30 min, after which it became small. Slow heating led to higher degree of reduction in fired pellets than rapid heating. All the iron ores exhibited more than a 90% reduction in their fired pellets in 2-h time interval at a temperature of 900°C. Iron ore lumps showed a lower degree of reduction than the corresponding fired pellets.     

Effect of temperature on magnetizing reduction of agbaja iron ore

Agbaja oolitic iron ore, which has not been responsive to such beneficiation processes as froth flotation, gravity concentration, magnetic separation, and electrostatic separation, has been concentrated to 60 pct Fe grade and 87.3 pet Fe recovery (starting from a crude assaying 45.6 pct Fe) by the magnetizing reduction technique. The main parameter investigated was the effect of temperature on the magnetizing reduction process, and 600 °C was established as the optimum temperature for the reduction step. X-ray diffraction studies of the reduction products showed that the iron oxides were converted to magnetite, to wustite, or to metallic iron, depending on the temperature of reduction. The results from the subsequent magnetic concentration step were, in the main, dependent on the observed reduction products.     

Effect of temperature on magnetizing reduction of agbaja iron ore

Agbaja oolitic iron ore, which has not been responsive to such beneficiation processes as froth flotation, gravity concentration, magnetic separation, and electrostatic separation, has been concentrated to 60 pct Fe grade and 87.3 pet Fe recovery (starting from a crude assaying 45.6 pct Fe) by the magnetizing reduction technique. The main parameter investigated was the effect of temperature on the magnetizing reduction process, and 600 °C was established as the optimum temperature for the reduction step. X-ray diffraction studies of the reduction products showed that the iron oxides were converted to magnetite, to wustite, or to metallic iron, depending on the temperature of reduction. The results from the subsequent magnetic concentration step were, in the main, dependent on the observed reduction products.     

煤中氢对含碳球团还原的影响

针对含碳球团还原过程中的煤种选择问题,研究了烟煤和无烟煤挥发分中氢对含碳球团还原的作用以及温度、加热速度对氢还原过程的影响。结果表明,含碳球团中煤热解产生的氢对铁氧化物有还原作用。由于煤中挥发分的热解析出温度与氢还原铁氧化物的还原温度不一致,氢在还原初期迅速放出,导致氢的还原作用率低;提高温度和加热速度可提高煤中氢的还原作用率和挥发分的利用率。综合考虑,含碳球团实际生产选择煤种时,应选择反应性好的无烟煤。