转炉四元熔渣中锰矿含碳球团熔化行为模拟研究

采用实验模拟与数值模拟相结合的方法,对锰矿含碳球团在转炉4元熔渣(51CaO-16SiO_2-10MgO-23FeO)中的熔化行为进行研究。结果表明,锰矿含碳球团在熔渣中还原时生成了固态产物层,减少固态产物层的厚度和存在时间,能加快球团在熔渣中的还原速度;基于一维非稳态导热微分方程建立了含碳球团熔化过程的数值模型,模型计算与实验结果能较好吻合;采取不同条件进行模拟计算发现,当熔渣温度为1 600℃时,假设固态产物层不存在,球团还原时间可缩短35%左右;对锰矿含碳球团进行预热、适当缩小球团直径及降低还原产物熔点均能减少固态产物层存在时间,从而提高球团还原速度。     

不锈钢粉尘含碳球团还原机理的探讨

为研究不锈钢粉尘含碳球团的还原机理,比较了含碳球团熔化速度和其中金属还原速度的相对大小,结果表明球团的还原速率大于熔化速率,渣对还原和熔化速度都有促进作用,含碳球团在AOD炉的第一个还原阶段末期加入时,金属的还原率最高。通过分析碳在渣和钢液间的迁移规律确定了碳有向渣中迁移的趋势;并估算了渣的粘度约为0.254Pa.s,渣钢间界面张力约为490mN/m。     

铬矿还原速度的研究

用热失重法及通过渣-金界面反应研究了含碳铬矿球团及熔渣中铬氧化物的还原速度。含碳铬矿球团还原速度的限制环节为CO在铬矿表面上的析碳反应和碳通过产物层向内部的扩散,通过动力学分析及实验结果得出还原速度与温度和球团矿粉粒度的关系式。在1200～1300℃,求得碳的扩散系数为10~(-12)～10~(-11)cm~2/s,析碳反应速度常数为10~(-7)～10~(-6)cm/s。球团中添加CaCl_2或CaF_2能提高球团的还原速度。铬氧化物在MgO-Al_2O_3-SiO_2-CaO渣中与碳饱和铁液中溶解碳反应,其还原速度与渣中CrO活度的一次方成正比。还原速度的限制环节为CrO由渣中向渣-金界面的传递,在1600～1670℃,得传递系数数为10~(-5)～10~(-4)mol/min·cm~2。还原速度随熔渣的CaO/SiO_2比值提高及渣中GaF_2含量的增加而加快。     

钒钛磁铁矿含碳球团高温还原研究

本文通过实验,研究了钒钛磁铁矿含碳球团在高温还原过程中的还原速度及熔体膨胀高度。讨论了钒钛磁铁矿含碳球团碳含量及球团碱度对还原速度及熔体膨胀高度的影响。     

从赤泥中联合提取铁和氧化铝试验

 赤泥是从铝土矿中浸出氧化铝后产生的固态废渣,含有一定量的铁、氧化铝以及其他有价金属元素。为了综合回收赤泥中铁和氧化铝,开发了赤泥配碳制备成含碳球团,含碳球团直接还原-熔分生产金属铁,熔渣自粉化浸出氧化铝的方法。试验研究了不同工艺参数对赤泥中铁和氧化铝提取结果的影响,得到的最佳工艺条件为：碳氧比为1.8,还原温度为1 250 ℃,还原时间为60 min,熔分温度为1 500 ℃,熔分时间为20 min,熔渣冷却速度小于20 ℃/min,钙铝比为1.6。在最佳工艺参数下,得到的生铁磷、硫质量分数分别为0.047%和0.017%,熔渣中[w(FeO)]为1.26%,熔渣自粉化完全,自粉化渣中Al2O3浸出率可以达到86.65%。     

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.      

粘结剂对含碳球团还原的影响

水玻璃已被证明是用于含碳球团的理想粘结剂，作研究了在９００～１２００℃、氮气氛中粘结剂（水玻璃）对含碳球团还原的影响。对实验数据进行了动力学分析，给出了理论解释，并指出了其在生产中的应用。结果表明：水玻璃可促进含碳球团还原。该还原反应由球团内矿粒层中的气相内扩散控制，加入水玻璃并没有改变这一限制环节，但可减少该环节的阻力。     

褐铁矿含碳球团的爆裂特性研究

根据褐铁矿含碳球团转底炉还原熔分生产粒铁的技术思想,对褐铁矿含碳球团的爆裂特性进行了实验研究.实验结果表明,褐铁矿含碳球团的爆裂与结晶水的解离有关,结晶水解离速度较快,在950℃下90s内球团中的结晶水基本上全部解离,褐铁矿含碳球团的爆裂温度约为900℃,与不含煤粉的褐铁矿球团相比约高100℃,含碳球团有利于减弱爆裂,因此,褐铁矿含碳球团的入炉温度要低于900℃.在爆裂温度以下,褐铁矿含碳球团的预热温度越低,预热时间越短,到1 300℃急速加热时,球团爆裂越严重.因此,在本实验条件下,球团最佳入炉温度约为850℃.     

CO/CO2气氛下含碳球团还原动力学模型及其应用

分析了ＣＯ／ＣＯ２气氛下含碳球团的还原步骤,以此为基础建立了含碳球团还原动力学的微分方程组,并编制了相应的计算机程序,在验证了该数学模型准确性的基础,对ＣＯ／ＣＯ２气氛中含碳球团的还原行为进行计算机模拟,该模型全面考虑了ＦＡＳＴＭＥＴ工艺条件下还原过程中的各种影响因素,模拟计算结果与献「１」的实测结果相符合,证明了用此模型可以优化含碳球团的直接还原工艺条件。     

钒钛铁精矿非自然碱度含碳球团高温固态还原试验

为了研究钒钛铁精矿非自然碱度含碳球团高温固态还原规律,以钒钛铁精矿为原料,在实验室条件下,探索了还原温度、还原时间、碱度和配煤比对钒钛铁精矿非自然碱度含碳球团高温固态还原的影响,采用X射线衍射仪测定了金属化球团的物相组成。研究结果表明,适当提高还原温度、延长还原时间、提高碱度和配煤比均可促使球团的金属化率提高;对于钒钛铁精矿金属化球团物相组成,在还原温度高于1 400℃时,金属化球团中出现大量碳氮化钛,碱度的提高有利于抑制还原产物中碳氮化钛的生成,配煤比的增加促进了碳氮化钛的生成。从后续熔分工序对钒钛铁精矿金属化球团质量要求的角度来说,高温固态还原的适宜条件,还原温度为1 350℃,碱度为1.0,还原时间为30 min,配煤比为1.3,在此条件下,球团的金属化率为93.72%,金属化球团碳质量分数为6.08%,主要物相为黑钛石和金属铁。     

Experimental study on preparation of manganese rich slag by direct reduction melting separation of low manganese high iron ore

In this experiment, low manganese high iron ore with manganese grade of 27.7% and iron grade of 18.1% was used as the research object to reduce and prepare manganese rich slag. The obtained manganese rich slag can be used for smelting silicon manganese alloy to achieve the purpose of efficient utilization of low grade manganese ore. According to the results of composition analysis, XRD analysis and particle size analysis of the ore, the reduction melting separation method was used to prepare manganese rich slag from low manganese ore. The experimental results show that each parameter has a greater impact on the mass fraction of manganese and iron in the reduction melting separation slag of low manganese high iron ore and the recovery rate of manganese under the single factor test. At the same time, combined with the Box Behnke principle design scheme, three experimental factors including temperature, alkalinity and carbon content were selected. The influence of each factor on the recovery rate of manganese was studied by response surface method. The experimental results were analyzed to establish the corresponding polynomial model, and the optimal process conditions were as follows: reduction temperature of 1402℃, alkalinity of 0.10, carbon content of 10.04%, and the recovery rate of manganese was 97%. A verification test was conducted under the optimal conditions; the recovery rate of manganese was 95.80%, and the error was 1.24%, which proved that the response surface method was a reliable and accurate prediction model. At the same time, the results are instructive for the application of low manganese and high iron ore.     

低锰高铁矿直接还原-熔分制备富锰渣试验研究

摘要：试验以锰品位27.7%,铁品位18.1%的低锰高铁矿为研究对象还原制备富锰渣,生产得到的富锰渣可用于冶炼硅锰合金,以达到高效利用低品位锰矿的目的。根据该矿的成分分析、XRD分析和粒度检测分析结果,采用还原 熔分法对低锰矿进行还原制备富锰渣试验,试验结果表明：单因素试验下各参数对低锰高铁矿的还原-熔分后渣中Mn、Fe元素的含量和Mn元素的回收率均有较大影响,同时结合Box-Behnke原理设计方案,选取温度、碱度以及配碳量3个试验因素,通过响应曲面法研究各因素交互作用下对Mn元素回收率的影响规律,对试验因素进行优化分析,建立相应的多项式模型。模拟优化得到最优的工艺条件为：还原温度1402℃,碱度0.10,配碳量10.04%,Mn元素回收率为97%。在最佳条件下做验证试验得出Mn元素回收率为95.80%,误差1.24%,证明响应曲面法预测模型具有可靠性,同时对低锰高铁矿的应用有重要指导意义。     

转炉终点渣钢间锰平衡状况分析

为了推广锰矿直接还原技术在转炉内的使用,对转炉终点条件下锰矿的热分解、熔融还原和渣钢间平衡状态进行了分析。利用热力学分析方法讨论了国内外转炉锰矿直接合金化锰的平衡状态。结果表明,在转炉终点时刻,锰矿以MnO形式存在于渣中;锰在渣钢间的平衡主要以铁、锰竞争氧化的形式存在;理论计算锰分配比和实践生产数据有相同的趋势,且计算值大于实践生产数据;高温、高碱度、高w([C])、低w((TFe))可以降低锰分配比;渣量越小,锰收得率越高。此外,讨论了进一步提高转炉锰收得率的控制工艺。     

Strength and high temperature behaviour of carbon composite pellets containing BOF fine dust

Abstract

Steel plants produce significant amounts of dust and sludge during iron and steel production. These wastes contain valuable elements, such as Fe, Cr, Ni, C, K and Na and should be handled properly to prevent them from polluting the environment. In order to utilise the BOF fine dust, the effects of the dust on cold bonded pelletising, solid state reduction and reduction melting behaviours of composite pellets made from iron ore and anthracite with added BOF fine dust were investigated at laboratory scale. The BOF dust was found to improve the cold compressive strength of the wet green carbon composite pellet, and increased with increasing dust content. Almost four times the amount of dust was needed to get the same effect on the strength of the pellet when it was used to replace bentonite. The carbothermic reduction of the composite pellet proceeded effectively at temperatures above 1200°C. The BOF dust had a positive effect on the reduction rate of the pellet, and the rate increased with increased dust content. The reduction of iron oxide was topochemical and conformed to a shrinking core kinetic model. The dust was found to improve the iron and slag melting separation rate of reduced pellets at 1400°C when its content was less than 23·11 wt-%. The liquidus temperature of the slag would decrease with the content of BOF dust increasing from zero to ～30 wt-% and then increase if the content continued to become more in the experiment. Utilising the BOF dust as the binder and flux to adjust the composition of the slag system can potentially reduce the slag ratio and production cost compared with using bentonite and limestone. This work can help to find a new process for the effective utilisation of BOF dust in a more appropriate and environmentally friendly way.     

Ore Melting and Reduction in Silicomanganese Production

The charge for silicomangansese production consists of manganese ore (often mixed with ferromanganese slag) dolomite or calcite, quartz, and in some cases, other additions. These materials have different melting properties, which have a strong effect on reduction and smelting reactions in the production of a silicomanganese alloy. This article discusses properties of Assman, Gabonese, and Companhia Vale do Rio Doce (CVRD) ores, CVRD sinter and high-carbon ferromanganese (HC FeMn) slag, and their change during silicomanganese production. The melting and reduction temperatures of these manganese sources were measured in a carbon monoxide atmosphere, using the sessile drop method and a differential thermal analysis/thermogravimetric analysis. Equilibrium phases were analyzed using FACTSage (CRCT, Montreal, Canada and GTT, Aachen, Germany) software. Experimental investigations and an analysis of equilibrium phases revealed significant differences in the melting behavior and reduction of different manganese sources. The difference in smelting of CVRD ore and CVRD sinter was attributed to a faster reduction of sinter by the graphite substrate and carbon monoxide. The calculation of equilibrium phases in the reduction process of manganese ores using FACTSage correctly reflects the trends in the production of manganese alloys. The temperature at which the manganese oxide concentration in the slag was reduced below 10 wt pct can be assigned to the top of the coke bed in the silicomanganese furnace. This temperature was in the range 1823 K to 1883 K (1550 °C to 1610 °C).     

Self-reduction of Manganese-rich Slag Briquette Containing Carbon

The self-reduction experiment of manganese-rich slag briquette containing carbon was carried out in a hightemperature carbon tube furnace.The main factors affecting the reduction rate were analyzed,and the kinetic model of reduction was established.The results show that the increase of basicity of briquette has an obvious effect on improving reduction rate.When the carbon ratio of briquettes is 1.2and its basicity is 1.0,the reduction rate can reach90%.It can accelerate reduction process and decrease reduction time when the appropriate flux CaF2 is added to the briquette.The apparent activation energy of chemical reaction is 24.07kJ/mol,and the apparent activation energy of internal diffusion is 107.55kJ/mol by calculation.Therefore,the reduction rate of briquette is determined by the mass transfer of CO in the product layer.     

Reduction kinetics of manganese oxide in basic oxygen furnace type slag

In order to improve manganese yield during the reduction of manganese ore, the reduction kinetics of manganese oxide in BOF type slag has been investigated on an experimental scale. The reduction rate of (MnO) was promoted for the slag of low basicity and high contents of (FeO). The maximum reduction rate of (MnO) has been found for an iron melt with carbon mass contents of 1.9 %. The silicon in metal may accelerate the reduction of manganese oxide in slag. The kinetic model for the reduction rate of (MnO) has been formulated based on the assumption that the reduction of (MnO) was controlled by the mass transfer through the metal and slag boundary layers at the metal/slag interface. The result calculated by the kinetic model showed a good agreement with the experimental one. The reduction behaviour of (MnO) can be described by the present model.     

云铜铜渣还原熔分试验分析

为了合理利用云铜渣,采用ITmk3工艺获得高质量粒铁,在实验室条件下进行了一系列的基础研究。通过比较试样全铁质量和熔分得到的粒铁质量,得到了金属铁的收得率,结合化学分析方法,分别得到了试样还原后的金属化率以及熔分后金属铁中的碳质量分数,研究了各个因素对以上指标的影响规律,形成了对云铜渣合理还原熔分的工艺路线,得到如下结论:渣熔化是形成粒铁的必要条件,铁的聚合程度取决于渣铁分离熔化之前铁的渗碳质量分数。渣中SiO_2的存在是渣相低熔点的根本原因,碱度改变时云铜渣的熔化区间会发生变化,但对熔化开始温度的影响不显著。当碱度大于0.4后,添加CaO能显著地提高云铜渣的还原性能。     

转炉锰矿熔融还原工业试验研究

为打通转炉炼钢过程锰矿熔融还原技术路径,提高锰的收得率,对锰矿熔融还原过程和提高锰收得率的工艺参数进行了热力学探讨,并在某钢厂200 t转炉上开展了工业试验研究。研究结果表明:高效稳定的铁水“三脱”预处理技术是锰矿熔融还原技术成功的基本前提;通过理论计算,在炉渣中的(MnO)质量分数为5%～10%,终点[C]质量分数控制在0.13%～0.36%时,终点钢液[Mn]质量分数可控制在0.3%以上。工业试验主要通过采用双渣法冶炼操作,在确保前期铁水低磷的条件下尽可能控制少渣量、降低炉渣中氧化铁,从而实现加入锰矿后提高锰收得率;并在现有工艺控制条件下,锰矿加入10 kg·t?1以内时,工业试验可使锰矿还原过程锰收得率超过40%,平均为51.40%;为进一步提高锰收得率,建议严格将锰矿熔融还原渣料总量控制在40～60 kg·t?以内,石灰加入量控制在10～15 kg·t?1以内;研究结果为锰矿熔融还原技术的开发和应用提供重要参考。      

Direct Reduction Experiment on Iron-Bearing Waste Slag

 A lot of iron-bearing slags were produced, and whose grade is much more than that of industrial iron ore grade. Chemical analysis and phase identification shows that the iron-bearing slag is amorphous, has fayalite main phase, iron grade is 36. 10%, and is difficult to recover iron from the slag. Thermodynamic calculation indicates that CO cannot reduce fayalite at high temperature and carbon direct reduction can be effective. Moreover, the reaction begins at 770 ℃ and the temperature can be reduced down to 500℃ when CaO is added. On this basis, a method is put forward to making direct enrichment of iron by taking carbon contained pellets to realize the rapid reduction of fayalite, and the direct reduction process were studied in this paper. Experiments show that xC/xO should be less than 1. 5 for the need of reduction and carburization, and CaO and Al2O3 can spur the reduction of fayalite. On conditions that xC/xO is 1. 2, metallization rate can be 77% when temperature is 1250 ℃ and only carbon is added, and metallization rate can be 74% when temperature is 1200 ℃ and only CaO is added. Moreover the addition of Al2O3 can get a higher metallization rate (10% or so) than usual as R is between 0. 4 and 1. 0. Under the optimized condition of R equals to 0. 6, temperature of 1250 ℃, slag melting point of 1320 ℃, and time of 30 min, the metallization rate can reach 88. 43%.