CaO-SiO2-Al2O3-MgO-FeO渣系FeO活度的计算模型

利用熔渣结构共存理论建立了CaO-SiO2-Al2O3-MgO-FeO渣系FeO活度的计算模型,并分析了1400℃时炉渣碱度、MgO和FeO含量对该渣系FeO活度的影响规律。结果表明：当CaO-SiO2-Al2O3-MgO-FeO渣系三元碱度为1.3,Al2O3含量为12wt%,FeO含量为2wt%条件下,随MgO含量的增加,炉渣FeO活度增大;当二元碱度为1.1,Al2O3含量为12wt%,MgO含量为10wt%时,FeO活度随随渣中FeO含量的增加呈线性增加;当渣中Al2O3、MgO和FeO含量分别为12wt%、10wt%和2wt%固定不变时,随着二元碱度的提高,炉渣FeO活度迅速增加。计算得到的上述规律和实测规律一致,说明了本模型用于分析FeO活度的正确性。     

CaO-SiO_2-FeO-Cr_2O_3-MgO-MnO渣系物相组成的热力学计算

在含铬铁水转炉冶炼过程中,Cr很容易被氧化成Cr_2O_3进入渣中,并与渣中其他成分反应生成高熔点含铬尖晶石。采用FactSage热力学软件计算了CaO-SiO_2-FeO-Cr_2O_3-MgO-MnO转炉渣系在冶炼温度1 300～1 700℃下的物相组成,研究了Cr_2O_3、FeO和碱度对炉渣中尖晶石相含量的影响规律。研究结果表明,温度和渣系成分都会影响炉渣的物相组成。渣系中含有Cr_2O_3时,物相中均含有MgCr_2O_4、FeCr_2O_4和MgFe_2O_4尖晶石相,尖晶石相的总含量随着Cr_2O_3和碱度的增加而增加,随着炉温的升高而减少。温度为1 300～1 500℃时,炉渣中尖晶石含量随着FeO的增加而增加;温度为1 500～1 700℃时,尖晶石含量随着FeO的增加而略有减少。在温度小于1 500℃的转炉冶炼前中期,炉渣物相组成中尖晶石相所占比例较大,易造成化渣不良或者炉渣粘稠,影响转炉冶炼工艺的顺行。     

CaO-SiO2-FeO-Cr2O3-MgO-MnO渣系物相组成的热力学计算

摘要：在含铬铁水转炉冶炼过程中，Cr很容易被氧化成Cr2O3进入渣中，并与渣中其他成分反应生成高熔点含铬尖晶石。采用FactSage热力学软件计算了CaO-SiO2-FeO-Cr2O3-MgO-MnO转炉渣系在冶炼温度1300～1700℃下的物相组成，研究了Cr2O3、FeO和碱度对炉渣中尖晶石相含量的影响规律。研究结果表明，温度和渣系成分都会影响炉渣的物相组成。渣系中含有Cr2O3时，物相中均含有MgCr2O4、FeCr2O4和MgFe2O4尖晶石相，尖晶石相的总含量随着Cr2O3和碱度的增加而增加，随着炉温的升高而减少。温度为1300～1500℃时，炉渣中尖晶石含量随着FeO的增加而增加；温度为1500～1700℃时，尖晶石含量随着FeO的增加而略有减少。在温度小于1500℃的转炉冶炼前中期，炉渣物相组成中尖晶石相所占比例较大，易造成化渣不良或者炉渣粘稠，影响转炉冶炼工艺的顺行。     

FeO、Al2O3和MgO质量分数对高炉初渣黏度的影响

以涟钢7号高炉软熔带炉料滴落形成的初渣为研究对象进行化学成分分析，采用分析纯试剂制备高炉炉渣渣样，探究CaO SiO2 MgO Al2O3 FeO五元渣系中，w(FeO)为3%～8%、w(Al2O3)为9%～13%及w(MgO)为2%～6%对涟钢7号高炉初渣黏度和熔化性温度的影响规律。结果表明，在碱度为1.373时，炉渣黏度随FeO质量分数的增加而减小，且FeO质量分数越大，炉渣的熔化性温度越低；当w(MgO)为7.38%、w(FeO)为5%时，炉渣黏度和熔化性温度都随着Al2O3质量分数的增加而减小；当w(Al2O3)为10.95%、w(FeO)为5%时，随着MgO质量分数的增加，炉渣黏度和熔化性温度都呈现降低趋势。     

超低碳钢BOF渣成分对终点[C]含量影响

采用共存理论、动力学分析和实验验证的方法,研究转炉冶炼超低碳钢吹炼末期炉渣成分对终点[C]含量的影响规律,建立1853-1973 K时终点[C]与炉渣成分和温度的回归模型.结果表明:FeO活度受温度影响较小,主要受炉渣成分的影响;脱碳动力学条件主要受炉渣成分和温度的影响.炉渣碱度增加,终点[C]含量升高;渣中FeO含量增加,终点[C]含量迅速降低,渣中FeO质量分数应控制在12.0%-18.0%之间;渣中MgO质量分数在7.0%-13.0%范围内逐渐增加,钢液中[C]质量分数增加值不足0.01%;随着温度的增加,钢液中[C]含量降低.回归模型对冶炼超低碳钢的转炉终点[C]含量的预判平均误差率为±15.25%,[C]含量误差在±0.01%以内的炉次占69.19%.      

钢包渣改质对锰在渣-钢间分配的影响

试验在LaCrO3高温电阻炉中模拟研究了1 873K时,超低碳铝硅镇静钢冶炼过程中锰元素在钢包渣与钢液间的分配平衡,考察了影响锰在钢包渣与钢液间分配比的因素。试验得出,渣中的FetO含量对锰的分配比有显著影响,FetO的质量分数在0~20%的范围内,随着FetO含量的增加,锰的分配比不断增加。在0.5~5.0的炉渣碱度范围内,当炉渣碱度增加时,锰的分配比先降低后增大。随着渣中Al2O3含量的增加,锰的分配比LMn先降低后增加。为了提高锰合金的收得率,FetO的质量分数应该维持在5%以下,Al2O3的质量分数在20%~25%之间,同时wCaO/wSiO2比值在2.5左右。在所使用的4种改质剂(CaC2+Al2O3,Al+CaC2,Al+CaCO3,Al+CaO)中,Al+CaO改质剂的效果最好,得到的LMn最小。     

基于转炉CaO-SiO2-FeO-10%MgO渣系脱磷行为

 基于CaO-SiO2-FeO-10%MgO渣系,从热力学角度对渣钢界面的脱磷行为进行分析,归纳出磷分配比与钢液温度、碳质量分数以及炉渣成分间的表达式,并在此基础上绘制出了CaO-SiO2-FeO-10%MgO渣系的等磷分配比线,同时分析了转炉终渣氧化性、碱度以及温度对磷分配比的影响情况。研究结果表明,转炉吹炼过程磷分配比是钢液温度、碳质量分数和炉渣成分的函数,通过与实际生产数据进行验证,发现其与实际结果吻合良好。基于该预测公式,在其他条件不变情况下,随着炉渣FeO质量分数增加,磷分配比[LP]先增加后减小,当终渣FeO质量分数为18%左右时达到最大值;随着终渣碱度的增加,渣钢间磷分配比增加,当终渣超过4.0时,磷分配比增加不再明显。     

120 t转炉熔池中硫行为的研究

取样测定了120 t转炉在冶炼过程中熔池中硫的变化情况,通过物料平衡计算研究了熔池中硫的来源,并研究了终点温度、炉渣碱度、渣中(FeO)对硫在渣钢间分配比的影响.结果表明,提高终点温度和炉渣碱度有利于硫分配比的提高,在一定范围内提高渣中(FeO)含量有利于硫分配比的提高,w(FeO)≥18%时,随着(FeO)含量的提高硫分配比减小;减少入炉硫负荷是冶炼低硫钢的基础.     

硫容量模型和在五元渣系CaO SiO2 MgO Al2O3 FetO中的应用

 硫容量和硫平衡分配比是衡量炼钢过程中渣系脱硫能力的重要指标。通过光学碱度模型和KTH模型计算了五元渣系CaO SiO2 MgO Al2O3 FetO的硫容量,并与文献的实验测定值进行了比较。结果表明用KTH模型计算的硫容量比用光学碱度模型计算的硫容量更接近实验值,因此KTH模型可用来预测不同组元渣系的硫容量。还详细研究了硫容量和硫平衡分配比的影响因素,结果表明硫容量随炉渣碱度和温度的增加而增加,硫平衡分配比随着钢液中铝、碳、硅含量的增加而增加。     

半钢炼钢化渣剂的开发和应用

针对半钢在冶炼中具有硅、锰等元素生成的氧化物少,成渣困难,吹炼过程热量少的特点,研究了减少渣量、改造渣系结构、提高炉渣冶金能力的方法,制定出3种渣料配比方案.通过对初期渣形成时间、过程冶炼情况、造渣材料消耗、炉渣脱磷、脱硫效果和改造前后终渣成分的对比,3种化渣剂均能缩短半钢炼钢成渣时间,合理调整炉渣碱度,降低渣中FeO含量,改善渣系结构,提高炉渣冶金效果,是半钢炼钢有效的化渣剂.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

提高炉渣中MnO向钢中传递的试验

 为了提高锰矿直接合金化锰的收得率,根据热力学分析结果确定了降低渣钢间锰分配比的影响因素。分析结果表明,提高温度和碳的活度是降低渣钢间锰分配比的必要条件。由此设计了感应炉试验方案,并进行了试验研究。结果表明,精炼渣在配加还原剂的情况下锰矿直接合金化锰平均收得率为90.8%,碳化硅作为还原剂在配碳量为1.2～1.4时,锰分配比最低;高温、高碳质量分数可以有效降低渣钢间锰分配比,底吹强度、锰矿加入量等工艺参数对锰矿直接合金化的效果有影响,应控制工艺避免锰矿石和还原剂的加入对钢中磷、硫产生的不利影响。     

Parameters affecting manganese oxidation in top blown basic oxygen converter

The data obtained from 84 heats carried out in a 90-t top blown basic oxygen converter were used to study the effects of slag composition and temperature on the activity coefficient and activity of manganous oxide in the slag as well as on the manganate capacity and the manganese distribution between slag and metal. In addition, the dependence of manganese activity in the metal on the concentration of maganese and temperature was also investigated. The present study carried out in wide ranges of temperature, 1350–1690°C, and slag basicity expressed as (CaO)/(SiO₂), 1.4–10.6, clarifies the dependence of MnO activity coefficient mainly on temperature. The activity coefficient of MnO increases by decreasing the temperature. On the other hand, activity of MnO increases by increasing MnO concentration and temperature. Both activity coefficient and activity of MnO in the slag slightly increase by increasing the slag basicity. At constant temperature, the activity of Mn in the molten metal varies linearly with Mn concentration and tends also to increase with increasing temperature at constant Mn concentration. The increase in manganese activity by increasing Mn concentration is much steeper at high temperatures. The manganate capacity as well as manganese distribution ratio decrease with increasing temperature at constant basicity and tend also to slightly decrease with increasing slag basicity at constant temperature. Equations describing the parameters affecting activity coefficient and activity of manganous oxide in the slag, manganese activity in the metal, manganate capacity and manganese distribution ratio have been derived.     

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。     

Effect of BaO,Basicity and Temperature on Manganese Distribution between Slag and Hot Metal in Blast Furnace

Daily average data obtained on the 1033 m³ blast furnace No.3 of the Egyptian Iron and Steel Company (EISCO) were used to investigate the effects of BaO, basicity and temperature on the activity coefficient and activity of MnO in the slag as well as on the manganate capacity and manganese distribution between slag and metal. The activity coefficient was estimated by using the regular ionic solution model. Both activity coefficient and activity increase with increasing basicity and BaO content of the slag. The activity, manganate capacity and manganese distribution ratio are largely dependent on temperature and change only slightly with the basicity. The relative partial molar enthalpy of solution of MnO in the slag is 107 kJ/mol. The relationship between activity and concentration of MnO in the slag is linear over the whole ranges of temperature (1400 to 1450°C) and basicity, (CaO/SiO₂ = 0.61‐0.95). The concentration dependence of manganese activity in hot metal is also linear and the activity coefficient of Mn in hot metal is 0.51. The distribution ratios calculated by using the concept of manganate capacity were correlated with the relevant values obtained from the slag and metal analyses. The calculated partition ratios are in agreement with the observed values. In all cases, empirical equations have been derived.     

Dissolution behaviour of manganese ore in basic oxygen furnace type slag

In order to improve manganese yield during the reduction process of manganese ore in blowing practices employing less slag at BOF, the dissolution behaviour of manganese ore in slag has been studied in an experimental scale. The effect of temperature, slag composition, addition of CaF₂, and pre-treatment of manganese ore was examined for the dissolution behaviour of manganese ore into BOF type slags. The precipitation of (Fe,Mn)O phase in slag was observed during the addition of manganese ore. The dissolution rate of manganese ore into molten slag increased with temperature, and also increased with the initial contents of FeO, MgO and MnO. However, the effect of slag basicity was not evident on the dissolution rate of manganese ore into slag. The addition of CaF₂ and pre-treatment of Mn ore were very effective to promote the dissolution of manganese ore into slag.     

锰浸出渣制备白炭黑的工艺研究

以工业锰浸出渣、氢氧化钠、硫酸为主要原料通过沉淀法制备白炭黑,研究了锰渣与氢氧化钠的配比、氢氧化钠浓度、反应时间、反应温度等因素对白炭黑回收率的影响。获得了制备白炭黑的最佳工艺条件为:反应温度为140℃、氢氧化钠/锰渣的质量比为0.8∶1、反应时间为8 h,白炭黑的回收率达到44%。通过红外光谱、TEM等技术表征了白炭黑的结构,粒径为50nm左右,经测试二氧化硅的含量达到90.5%,达到国家标准。     

Equilibria between liquid Mn-Si alloys and MnO-SiO2-CaO-MgO slags

The activity of silicon in manganese-silicon melts was determined at 1500°C. The results are in general agreement with the thermodynamic data of the iron-silicon system. Equilibria between manganese-silicon melts and slags containing MnO, SiO₂, CaO, and MgO were studied at 1400 and 1500°C in silica and magnesia crucibles. An empirical relationship easy to use in practice was derived, expressing the manganese and silicon distribution ratio between slag and metal as a function of the slag basicity. This relationship describes equilibria pertinent to the silicothermic reduction of manganese oxide and the production of silicomanganese. The present knowledge of the activities in the slag and metal phase is adequate to explain the experimental results. The presence of up to about 10 pct CaF₂ in the slag makes it possible to maintain a higher slag basicity and therefore a lower activity of silica, resulting in lower silicon contents in the metal. Iron contents of up to about 20 pct in the metal cause a slight increase in the silicon content of the metal under otherwise similar conditions. The effect of 1 to 2 pct carbon in the metal on the equilibrium was roughly estimated and found to be almost negligible.