Mathematical simulation of direct reduction process in zinc-bearing pellets

A one-dimensional unsteady mathematical model was established to describe direct reduction in a composite pellet made of metallurgical dust. The model considered heat transfer, mass transfer, and chemical reactions including iron oxide reductions, zinc oxide reduction and carbon gasification, and it was numerically solved by the tridiagonal matrix algorithm (TDMA). In order to verify the model, an experiment was performed, in which the profiles of temperature and zinc removal rate were measured during the reduction process. Results calculated by the mathematical model were in fairly good agreement with experimental data. Finally, the effects of furnace temperature, pellet size, and carbon content were investigated by model calculations. It is found that the pellet temperature curve can be divided into four parts according to heating rate. Also, the zinc removal rate increases with the increase of furnace temperature and the decrease of pellet size, and carbon content in the pellet has little influence on the zinc removal rate.     

不同还原度铁氧化物球团在微波场中的升温及还原行为

为深入了解氧化球团在微波竖炉中的升温以及煤基直接还原行为,实验采用铁精矿氧化球团作为基础原料,在气体还原剂条件下进行预还原,通过控制还原时间得到不同还原度铁氧化物球团,并从不同还原度铁氧化物球团的结构以及性能出发,研究它们在微波场中的升温性能及其还原变化.电磁性能测试结果表明,球团中的铁及其氧化物在微波场中的升温速度从快到慢依次为:Fe3O4,Fe2O3,Fe,FeO.微波加热还原结果分析及矿相结构观察显示,Fe2O3的深还原时间较长,物相多重转变,造成过程温度和还原气氛跟不上氧化物的还原反应速度;Fe3O4阶段升温速度快,结构松散,有助于进一步的还原,但进入浮士体(FeO的固溶体)阶段后孔隙率降低,升温速度骤降,造成还原的困难;在还原度达到66.90％时,表层以金属铁相为主,孔洞发达,吸波性能强,在气化反应有效进行的条件下,球团将会实现快速还原.     

铁酸锌气体还原的热力学分析

根据热力学原理,计算并分析了含锌冶金粉尘中的重要成分ZnFe2 O4在CO- CO2气体还原过程中的热力学行为. ZnFe2 O4的气体还原遵循逐级还原规律,且ZnFe2 O4很容易被CO还原到ZnO和Fe3 O4.较高温度条件下,ZnO的气体还原易于FeO的还原.随着反应温度升高,锌完全反应和挥发所需要的CO含量不断降低,当反应温度从1100 K升高到1400 K时所需的CO体积分数由0.4降低到0.01以下.要达到还原分离金属锌的目的,不必将铁氧化物还原到金属铁,而只需将铁氧化物还原到Fe3 O4或FeO,同时满足锌的还原条件即可.在高炉炉身中上部,由于发生锌的还原反应和内部循环,给高炉生产带来危害,因此应减少和控制高炉的锌负荷.     

铁精矿冷固球团矿在工业性回转窑内的还原行为

研究了铁精矿冷固球团矿在工业性回转窑内的还原行为。研究结果表明：由于复合粘结剂集粘结、催化和还原诸功能于一体，使冷固球团矿按均质反应模型还原；铁氧化物催化作用及粘结剂的热致聚合效应，使还原反应前期固体桥键得到强化，在还原反应中期粘结剂促进金属桥键形成和长大，从而使冷固球团矿具有良好的还原性及还原过程中具有足够的机械强度，消除了低温还原粉化，是一种优质的直接还原炉料。     

Numerical simulation of the direct reduction of pellets in a rotary hearth furnace for zinc-containing metallurgical dust treatment

A mathematical model was established to describe the direct reduction of pellets in a rotary hearth furnace (RHF). In the model, heat transfer, mass transfer, and gas-solid chemical reactions were taken into account. The behaviors of iron metallization and dezincification were analyzed by the numerical method, which was validated by experimental data of the direct reduction of pellets in a Si-Mo furnace. The simulation results show that if the production targets of iron metallization and dezincification are up to 80% and 90%, respectively, the furnace temperature for high-temperature sections must be set higher than 1300℃. Moreover, an undersupply of secondary air by 20% will lead to a decline in iron metallization rate of discharged pellets by 10% and a decrease in dezincing rate by 13%. In addition, if the residence time of pellets in the furnace is over 20 min, its further extension will hardly lead to an obvious increase in production indexes under the same furnace temperature curve.     

富氧率对钒钛磁铁矿球团还原行为的影响

模拟研究了不同富氧率条件下钛磁铁矿氧化球团的还原过程.通过扫描电镜观察钒钛磁铁矿球团还原过程中的微观结构变化,结合能谱仪研究分析了还原过程中产物的分布变化.结果表明,富氧率的提高对还原度和还原速率提高有明显促进作用.还原过程中钛铁分离伴随着Al元素向高钛矿中迁移富集,最终Al与Ti原子数比为1∶3,Al很可能与钛铁氧化物固溶,形成某种复合化合物并导致球团矿还原难度增加.运用三种不同模型对球团矿还原过程对比分析,发现混合模型可以很好地表征球团矿不同阶段的还原过程.利用混合模型计算得出球团矿还原过程的动力学参数.结果表明,随着富氧率的升高,球团矿还原活化能逐渐降低,从不富氧到富氧79%条件下,活化能由26.5 k J/mol降低到19.68 k J/mol,活化能的降低增加了相同条件下活化分子的数量,提高了反应速率,有利于球团矿在较低还原温度条件下快速反应.     

钢带烧结料层的干燥氧化过程仿真

针对钢带烧结机内铬铁球团的干燥氧化过程，建立一套多尺度的欧拉-欧拉双流体数学模型. 基于收缩核模型计算单个球团的物理化学反应，模型预测结果与现场数据吻合.结果发现生球层的干燥可以分为两阶段:不均匀升速干燥阶段和降速干燥阶段. 在生球层底部，第二干燥阶段会出现干燥速率又升高的现象，此时湿核表面温度为383K. 而当湿核半径小于4.75mm后干燥速率又开始下降. 过湿区的最大水分质量分数为10.2%，比初始值高7.4%. 当铬铁球团的温度达到焦炭的燃点后，焦炭的氧化优先于磁铁矿. 生球层在烧结区出口的平均温度达到1698K，满足生产需求.     

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.     

含碳球团的还原性和还原冷却后的强度

在 １２７３～１５７３ Ｋ条件下研究了不同煤种、木炭和石墨与不同种类矿石制成含碳球团 的还原速度;进而讨论了温度、配碳比（Ｃ／Ｏ）、挥发分含量等因素对含碳球团还原所需时间和 金属化率的影响．通过测定含碳球团还原冷却后的强度,对影响强度因素进行了分析．还原冷 却后的强度在温度 １２７３ Ｋ时较低,配入含挥发分较高的气煤,可以使还原冷却后的强度提高, 加快反应速度．     

New pyrometallurgical process of EAF dust treatment with CaO addition

The non-carbothermic zinc pyrometallurgical processing of electric arc furnace (EAF) dust was investigated on a laboratory scale. The main objective of this process was to convert highly stable zinc ferrite (ZnFe₂O₄), which accounts for more than half of total zinc in the EAF dust, into ZnO and Ca₂Fe₂O₅ by CaO addition. The EAF dust was mixed with CaO powder in various ratios, pressed into pellets, and heated in a muffle furnace in air at temperatures ranging from 700 to 1100℃ for a predetermined holding time. All ZnFe₂O₄ was transformed into ZnO and Ca₂Fe₂O₅ at a minimum temperature of 900℃ within 1 h when sufficient CaO to achieve a Ca/Fe molar ratio of 1.1 was added. However, at higher temperatures, excess CaO beyond the stoichiometric ratio was required because it was consumed by reactions leading to the formation of compounds other than ZnFe₂O₄. The evaporation of halides and heavy metals in the EAF dust was also studied. These components could be preferentially volatilized into the gas phase at 1100℃ when CaO was added.     

预还原球团吸波性能及其微波加热煤基直接还原

研究预还原球团在微波场中的升温特性,考察预还原球团微波加热中对直接还原的影响,分析铁氧化物煤基微波加热的还原行为.研究结果表明:预还原程度越高,球团中的Fe3O4含量逐渐减少,浮氏体和金属铁含量逐渐增多,对微波的吸收性能逐渐减弱,但是仍然具有较好的吸波能力.预还原球团金属化率越高,得到的海绵铁金属化率越高,在预还原球团金属化率为42.85％(质量分数),温度为1 000℃,还原时间为48 min,碳氧质量比为1.75:1时,海绵铁金属化率达到97.29％.随着还原反应的进行,铁氧化物的成分不断改变,金属铁颗粒呈星点状分布于浮氏体之间,但并不会形成致密金属壳,为还原反应中的气体交换创造良好的动力学条件.     

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.     

高炉灰为还原剂对海滨钛磁铁矿直接还原焙烧磁选--钛铁分离的影响

对高炉灰在直接还原焙烧-弱磁选工艺中用作印尼某海滨钛磁铁矿还原剂的可行性及其机理进行研究.结果表明,以萤石为添加剂的条件下,高炉灰可代替煤做还原剂,通过高炉灰与萤石的共同作用,可以在直接还原过程中提高还原铁粉中铁的回收率及品位并降低TiO2质量分数,同时回收高炉灰中铁.三种不同产地高炉灰还原效果的比较表明,高炉灰性质对还原效果有影响.在相同用量条件下,津鑫高炉灰( JX)还原效果最好;在JX高炉灰用量30%、萤石用量10%、焙烧温度1250益以及焙烧时间为60 min时,焙烧产物通过两段磨矿和两段磁选,最终得到最佳的还原铁粉中铁品位为91.28%,TiO2质量分数降至0.93%,包括海滨砂矿和高炉灰中铁的铁总回收率达到89.19%.     

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.     

含铁尘泥高碱度内配碳球团自还原过程中脱硫和脱磷研究

在竖式碳管炉中进行含铁尘泥高碱度内配碳球团的还原试验,并通过改变温度、配碳比和碱度对含铁尘泥还原过程中的脱硫和脱磷进行研究。结果表明,高碱度内配碳球团在高温下快速还原制备金属铁粒的脱硫率高于97%,铁粒中硫含量最低达到0.007%,而脱磷率一般为25%~35%,最高达到38.52%。随着温度和配碳比的升高,铁粒的脱硫率和脱磷率均增加;而随着碱度的增加,铁粒的脱硫率和脱磷率均先增大后减小。     

含铁炉料在高炉各区的冶炼特性

为了掌握不同含铁炉料在高炉冶炼过程的行为特性以及炉料之间的相互反应性,通过模拟高炉各区的温度和气氛条件,系统研究不同含铁炉料(烧结矿、球团矿和块矿)及综合炉料的冶炼特性,分析综合炉料冶金性能与单一炉料冶炼特性的关系.研究结果表明:烧结矿的低温还原粉化性能较差,球团矿较好,粒径大于3.15 mm的球团矿还原指数达到92%以上;烧结矿的还原性较好,还原度都在80%以上,球团矿的还原性次之,块矿的还原性较差;综合含铁炉料的还原性和低温还原粉化性能存在叠加性,综合炉料的高温软熔性能不存在叠加性;高炉炉料结构的合理性由含铁炉料的自身性能和炉料间反应性决定.     

有机结合剂对硬质磁铁矿球团活化及性能的影响

In the ironmaking process, the addition of an organic binder to replace a portion of bentonite has the potential to improve the performance of pellets. The interaction between original bentonite (OB) and organic binder was investigated. Results indicated that the micromorphology of organic composite bentonite (OCB) became porous and the infrared difference spectrum exhibited a curved shape. In addition, the residual burning rates of OB and organic binder were determined to be 82.72% and 2.30%, respectively. Finally, the influence of OCB on the properties of pellets was investigated. The compressive strength of OCB-added green pellets (14.7 N per pellet) was better than that of OB-added pellets (10.3 N per pellet). Moreover, the range of melting temperature of OCB-added green pellets (173°C) was narrower than that of OB-added pellets (198°C). The compressive strength of OCB-added green pellets increased from 2156 to 3156 N per pellet with the increase in roasting temperature from 1200 to 1250°C.     

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.     

电弧炉粉尘直接还原炉渣氧化和脱硫能力计算热力学

电孤炉炼钢粉尘中含有多种重金属，若填埋弃置会对环境造成污染．将粉尘与还原剂碳粉混合制粒后返回电弧炉，并补充硅铁还原粉尘中难还原的金属，有价金属还原后回收于钢液中，不仅能生产不锈钢或特种钢，而且能保护环境．制粒时使用木质磺酸钙作为粘结剂，而木质磺酸钙中含有硫，可能影响钢材质量，影响程度取决于冶炼过程中炉渣的条件．经改变初始熔铁、球团、硅铁和石灰加入的量比关系进行实验，采用X射线荧光分析仪检测炉渣成分进行计算热力学研究，确定了1550℃时CaO-MgO-FeO-Fe     

MHA黏结剂在钒钛磁铁矿氧化球团制备中的应用

应用已发明的MHA黏结剂替代膨润土制备钒钛磁铁矿氧化球团,获得质量优良的高炉冶炼原料。研究表明:当MHA用量为0.25%,在预热温度950℃,预热时间10 min,焙烧温度1 250℃,焙烧时间10 min的条件下,获得的预热球团抗压强度为522 N/个,焙烧球团抗压强度为3 702 N/个。与2.0%膨润土球团矿比较,MHA成品球团的抗压强度略低,而TFe品位明显提高1.11%。2种黏结剂球团矿的还原性能指标接近。MHA球团黏结剂在氧化球团矿生产中具有良好的应用前景。