Effect of carbon species on the reduction and melting behavior of boron-bearing iron concentrate/carbon composite pellets

Iron nugget and boron-rich slag can be obtained in a short time through high-temperature reduction of boronbearing iron concentrate by carbonaceous material, both of which are agglomerated together as a carbon composite pellet. This is a novel flow sheet for the comprehensive utilization of boron-bearing iron concentrate to produce a new kind of man-made boron ore. The effect of reducing agent species (i.e., carbon species) on the reduction and melting process of the composite pellet was investigated at a laboratory scale in the present work. The results show that, the reduction rate of the composite pellet increases from bituminite, anthracite, to coke at temperatures ranging from 950 to 1300℃. Reduction temperature has an important effect on the microstructure of reduced pellets. Carbon species also affects the behavior of reduced metallic iron particles. The anthracite-bearing composite pellet melts faster than the bituminitebearing composite pellet, and the coke-bearing composite pellet cannot melt due to the high fusion point of coke ash. With anthracite as the reducing agent, the recovery rates of iron and boron are 96.5% and 95.7%, respectively. This work can help us get a further understanding of the new process mechanism.     

Innovative method for boron extraction from iron ore containing boron

A novel process for boron enrichment and extraction from ludwigite based on iron nugget technology was proposed. The key steps of this novel process, which include boron and iron separation, crystallization of boron-rich slag, and elucidation of the boron extraction behavior of boron-rich slag by acid leaching, were performed at the laboratory. The results indicated that 95.7% of the total boron could be enriched into the slag phase, thereby forming a boron-rich slag during the iron and slag melting separation process. Suanite and kotoite were observed to be the boron-containing crystalline phases, and the boron extraction properties of the boron-rich slag depended on the amounts and grain sizes of these minerals. When the boron-rich slag was slowly cooled to 1100℃, the slag crystallized well and the efficiency of extraction of boron (EEB) of the slag was the highest observed in the present study. The boron extraction property of the slow-cooled boron-rich slag obtained in this study was much better than that of szaibelyite ore under the conditions of 80% of theoretical sulfuric acid amount, leaching time of 30 min, leaching temperature of 40℃, and liquid-to-solid ratio of 8 mL/g.     

基于气基直接还原-熔分的硼铁矿高效利用新工艺

实验室条件下,以含硼铁精矿为原料制备氧化球团,对含硼铁精矿气基竖炉直接还原-电炉熔分新工艺进行了研究.结果表明,含硼铁精矿是良好的造球原料,1 200℃下焙烧20 min后,成品球团抗压强度可达2 500 N以上,满足气基竖炉直接还原工艺要求.在H2与CO体积比大于2/5且温度在850~1 000℃条件下,含硼铁精矿氧化球团还原率达到95%的时间为15~60 min,还原膨胀率不高于15%.在高温下电热熔化DRI后硼和铁可以高效分离,硼、铁收得率均可达到98%以上,富硼渣中B2O3的质量分数在21%以上,活性可达89%左右,是"一步法"生产硼酸的优良原料.含硼铁精矿气基竖炉直接还原电炉熔分新工艺可以实现硼铁高效分离和清洁利用.     

含硼铁精矿用于巴润精矿氧化球团生产的实验研究

在实验室条件下,研究了含硼铁精矿对巴润精矿氧化球团制备工艺及冶金性能的影响.研究表明:球团原料中外配5.0%的含硼铁精矿,可将混合料中的巴润精矿配比(质量分数)提高到40%,制备的氧化球团满足高炉冶炼要求;含硼铁精矿可增加巴润精矿氧化球团的抗压强度和降低还原膨胀率,并可降低球团的焙烧温度;当含硼铁精矿配加量(质量分数)从0增加到7.5%时,球团抗压强度从2 630 N·个-1上升到3 709 N·个-1,还原膨胀率从25.69%降低到15.53%;外配质量分数为7.5%的含硼铁精矿时,球团的焙烧温度可从1 200℃降低至1 150℃,巴润精矿氧化球团满足高炉生产要求.     

含碳球团的低温熔分

根据低nC/nO含碳球团直接还原-低温熔分工艺制备粒铁的技术思想,进行了低nC/nO含碳球团低温条件下的熔分实验研究.实验结果表明,1 300℃,nC/nO为0.8的含碳球团,还原熔分时间为55 min时,得到的铁粒中存有少量熔渣2FeO.SiO2;60 min时渣铁则完全分离,铁粒中几乎没有熔渣存在.nC/nO为0.8和0.85的含碳球团还原后渣相FeO质量分数较高,熔点较低,易于渣铁熔化分离.nC/nO为0.9的含碳球团渣相FeO的质量分数较低,熔点较高,需要较长时间或在较高温度下才能进行渣铁分离.在1 320℃,nC/nO为0.8,还原熔分时间为60 min时,铁的收得率可达86.1%以...     

Carbothermic reduction characteristics of ludwigite and boron-iron magnetic separation

Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization of ludwigite. In the present work, the reduction mechanism of ludwigite was investigated. The thermogravimetry and differential scanning calorimetry analysis and isothermal reduction of ludwigite/coal composite pellet were performed. Ludwigite yielded a lower reduction starting temperature and a higher final reduction degree compared with the traditional iron concentrates. Higher specific surface area and more fine cracks might be the main reasons for the better reducibility of ludwigite. Reducing temperature highly affected the reaction fraction and microstructure of the reduced pellets, which are closely related to the separation degree of boron and iron. Increasing reducing temperature benefited the boron and iron magnetic separation. Optimum magnetic separation results could be obtained when the pellet was reduced at 1300℃. The separated boron-rich non-magnetic concentrate presented poor crystalline structure, and its extraction efficiency for boron reached 64.3%. The obtained experimental results can provide reference for the determination of the comprehensive utilization flow sheet of ludwigite.     

硼铁精矿的碳热还原动力学

为了揭示硼铁精矿的碳热还原机理,以高纯石墨为还原剂,进行硼铁精矿含碳球团等温还原实验,并采用积分法进行动力学分析.还原温度分别设定为1000、1050、1100、1150、1200、1250和1300益,配碳量即C/O摩尔比=1.0.当还原度为0.1<α<0.8时,温度对活化能和速率控制环节有重要影响：还原温度≤1100益时,平均活化能为202.6 kJ·mol-1,还原反应的速率控制环节为碳的气化反应;还原温度>1100益时,平均活化能为116.7 kJ·mol-1,为碳气化反应和FeO还原反应共同控制.当还原度α≥0.8时(还原温度>1100益),可能的速率控制环节为碳原子在金属铁中的扩散.碳气化反应是含碳球团还原过程中主要速率控制环节,原因在于硼铁精矿中硼元素对碳气化反应具有较强烈的化学抑制作用.     

低配碳比含碳球团直接还原的实验研究

根据低配碳比含碳球团还原熔分工艺制备粒铁的技术思想,对低配碳比含碳球团的直接还原进行实验研究.结果表明,这种低配碳比的含碳球团还原速度较快,还原反应进行了10 min时表观还原度为84%,20min时表观还原度可达88%;继续延长反应时间,球团表层还原得到的少量金属铁会再次被氧化成FeO.还原反应结束后,球团内仍存在少量尚未还原的FeO,它们与脉石中的SiO2形成低熔点的铁橄榄石,有利于工艺后期渣铁的熔化及分离.     

Recovery of iron from high phosphorus oolitic iron ore using coal-based reduction followed by magnetic separation

Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.     

熔分过程中铌、磷在渣铁两相间的分配比

以白云鄂博铌精矿经预还原后在电炉内熔分所形成的渣铁体系为研究对象,通过实验考察了熔分过程中铌、磷在渣铁两相间分配比的变化规律.结果表明,在本实验条件下,铌、磷的分配比随铁液中碳质量分数的增加而减小,当碳达到饱和时,铌氧化物会在渣铁界面处被还原为碳化铌,熔分终点w［C］应控制在342%以下;铌、磷的分配比随温度升高而减小,熔分温度可控制在1450℃左右;铌、磷的分配比随渣中FeO质量分数的增加而增大,熔分终点w(FeO)应控制在585%左右;铌、磷的分配比随熔渣光学碱度的升高而增大,添加MgO可明显降低磷的分配比.     

辽宁凤城地区硼铁矿石适宜选矿工艺

根据硼铁矿石性质和冶炼、化工对含硼铁精矿、硼精矿的要求，研究出适宜的选矿工艺，试验结果表明，含硼铁精矿和硼精矿分别满足了冶炼和化工的需要，使开发利用硼铁矿资源成可能。     

红土矿半熔融态还原渣金界面分离的影响因素

红土矿半熔融态还原工艺中金属与渣相的界面分离及液渣从耐火材料表面的脱除是该工艺能否工程化的核心问题.针对该问题,考察了CaO和体系温度对渣铁分离行为的影响规律,同时实验研究了炉渣在不同耐火材料上的界面铺展行为.实验结果表明:不添加CaO时,1440℃金属聚集效果较好,磁选后“精矿”金属质量分数为61%;随着CaO质量分数的增加,液态金属易于团聚与长大,精矿金属的质量分数增加显著,在1400℃,15%CaO时可达937%;熔渣与Al2O3质耐火材料较易润湿,与碳质耐材较难润湿,在实验范围内随着炉渣碱度的增加其与耐材的润湿性变差.     

添加硅铁对钛精矿直接还原-渣铁分离的影响

利用碳热还原方法研究了硅铁添加对钛精矿还原及渣铁分离效果的影响.结界表明:硅铁可提高还原反应速率和铁的金属化率,在1 380℃还原30 min的金属化率达到84.5%.添加硅铁还可明显缩短还原球团冶炼周期,降低渣中金属铁含量,提高渣铁分离效率及钛渣品位(Ti O2的质量分数为84.75%).同时运用Fact Sage软件对钛渣液相线及黏度进行了理论计算,结果表明:添加硅铁对钛渣黏度影响不大,但可增大钛渣的液相区域,从而有利于金属铁的聚集长大及分离.理论计算很好地解释了实验结果.     

硼铁矿应用于高铬型钒钛矿烧结优化的实验研究

实验室条件下,研究了硼铁矿对高铬型钒钛矿烧结工艺及冶金性能的影响.研究表明:随着硼铁矿质量配比的升高,垂直烧结速度、成品率、转鼓指数、烧结杯利用系数、综合指标及低温还原粉化性能均呈先升高后降低的趋势,在硼铁矿质量配比为5.0%时,以上各指数均达到最高值,分别为28.84 mm·min-1,86.02%,61.2%,1.919 t·(m2·h)-1,363及90.76%,均优于未配加硼铁矿时的烧结矿性能.因此,烧结矿性能得以优化,可以为高炉冶炼提供更为优质的高铬型钒钛烧结矿.     

TiO2对含铬高钛熔分渣熔化性能和黏度的影响

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag (CaO–SiO₂–MgO–Al₂O₃–TiO₂–Cr₂O₃) with TiO₂ contents ranging from 38.63wt% to 42.63wt% was conducted. The melting properties were investigated with a melting-point apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy (SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO₂ content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO₂ content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO₂ content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO₂.     

MOE法炼铁工艺的可行性

采用MOE法处理高炉冶炼用的铁精矿粉原料,对电解过程中的理论分解电压、吨铁所消耗的铁精矿粉量、CaO量及产生的渣量进行了分析。同时,对MOE法炼铁工艺及高炉炼铁工艺的能耗进行了分析。实验结果表明,MOE法在电解过程中阳极只有Fe3+铁离子的还原,因此可得到不含碳的纯铁。MOE法需要排渣及添加CaO过程,以维持其体系碱度在1.1左右。根据热力学方法计算出单纯的电解炼铁热耗标准煤为310.67 kg/t,远低于传统高炉炼铁部分能耗。     

A method for recovery of iron,titanium, and vanadium from vanadium-bearing titanomagnetite

An innovative method for recovering valuable elements from vanadium-bearing titanomagnetite is proposed. This method involves two procedures:low-temperature roasting of vanadium-bearing titanomagnetite and water leaching of roasting slag. During the roasting process, the reduction of iron oxides to metallic iron, the sodium oxidation of vanadium oxides to water-soluble sodium vanadate, and the smelting separation of metallic iron and slag were accomplished simultaneously. Optimal roasting conditions for iron/slag separation were achieved with a mixture thickness of 42.5 mm, a roasting temperature of 1200℃, a residence time of 2 h, a molar ratio of C/O of 1.7, and a sodium carbonate addition of 70wt%, as well as with the use of anthracite as a reductant. Under the optimal conditions, 93.67% iron from the raw ore was recovered in the form of iron nugget with 95.44% iron grade. After a water leaching process, 85.61% of the vanadium from the roasting slag was leached, confirming the sodium oxidation of most of the vanadium oxides to water-soluble sodium vanadate during the roasting process. The total recoveries of iron, vanadium, and titanium were 93.67%, 72.68%, and 99.72%, respectively.     

富硼渣冷却速率与活性的关系

以硼铁矿13 m3高炉分离生产的富硼渣为原料进行了缓冷试验.通过改变富硼渣熔体的冷却条件,在1500~1 200℃区间控制冷却速率从0.76℃/min到20℃/min,在1200~900℃区间,冷却速率应小于2℃/min.富硼渣活性可由40.05%增加到83.72%.冷却速率越高,富硼渣的活性越大.这一试验结果与实验室研究结果相符合.试验结果表明现场可以实现两段式冷却提高活性,并为今后冷却装置设计指明了方向.     

Effects of MgO and TiO<Subscript>2</Subscript> on the viscous behaviors and phase compositions of titanium-bearing slag

The effects of MgO and TiO₂ on the viscosity, activation energy for viscous flow, and break-point temperature of titanium-bearing slag were studied. The correlation between viscosity and slag structure was analyzed by Fourier transform infrared (FTIR) spectroscopy. Subsequently, main phases in the slag and their content changes were investigated by X-ray diffraction and Factsage 6.4 software package. The results show that the viscosity decreases when the MgO content increases from 10.00wt% to 14.00wt%. Moreover, the break-point temperature increases, and the activation energy for viscous flow initially increases and subsequently decreases. In addition, with increasing TiO₂ content from 5.00wt% to 9.00wt%, the viscosity decreases, and the break-point temperature and activation energy for viscous flow initially decrease and subsequently increase. FTIR analyses reveal that the polymerization degree of complex viscous units in titanium-bearing slag decreases with increasing MgO and TiO₂ contents. The mechanism of viscosity variation was elucidated. The basic phase in experimental slags is melilite. Besides, as the MgO content increases, the amount of magnesia–alumina spinel in the slag increases. Similarly, the sum of pyroxene and perovskite phases in the slag increases with increasing TiO₂ content.     

A novel process for Fe recovery and Zn,Pb removal from a low-grade pyrite cinder with high Zn and Pb contents

Comprehensive utilization of pyrite cinders is increasingly important because of their huge annual outputs and potential valuable metals recovery to cope with the gradual depletion of high-grade mineral resources. In this work, a new process, i.e., a high-temperature chlorination-magnetizing roasting-magnetic separation process, was proposed for recovering Fe and removing Zn, Pb from a low-grade pyrite cinder containing 49.90wt% Fe, 1.23wt% Zn, and 0.29wt% Pb. Various parameters, including the chlorinating conditions (dosage of CaCl₂, temperature, and time) and the magnetization roasting conditions (amount of coal, temperature, and time) were investigated. The results indicate that the proposed process is effective for Fe recovery and Zn, Pb removal from the pyrite cinder. Through this process, 97.06% Zn, 96.82% Pb, and approximately 90% S can be removed, and 89.74% Fe is recovered as magnetite into the final product under optimal conditions. A purified magnetite concentrate containing 63.07wt% Fe, 0.16wt% P, 0.26wt% S, and trace amounts of nonferrous metals (0.005wt% Cu, 0.013wt% Pb, and 0.051wt% Zn) was obtained. The concentrate can be potentially used as a high-quality feed material for producing oxidized pellets by blending with other high-grade iron ore concentrates.