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.     

Contribution to phosphorus behaviour in steelmaking with sponge iron

Experiments were conducted in a 70 t UHP electric arc furnace to study the phosphorus behaviour in steelmaking with sponge iron. The proportion of sponge iron in the metallic feed was varied from 52 to 95.4 wt.%. The results are used to show the effect of the sponge iron proportion in the charge on the phosphorus content of the bath. They are also utilized to illustrate the effects of the composition, temperature and theoretical optical basicity of the slag on the phosphate capacity and to investigate the kinetics of dephosphorization. It is found that both initial and final phosphorus contents of the bath decrease almost linearly with increasing sponge iron proportion in the charge. Using regression analysis, linear equations were obtained which show the change of the phosphate capacity of a slag, at a given temperature, with the total lime content as well as with the theoretical optical basicity. Based on these equations, a functional relationship was derived which shows the effect of simultaneous variation of total lime content and temperature of a slag on its phosphate capacity. A similar equation is given for the influence of simultaneous change of theoretical optical basicity and temperature on the phosphate capacity of a slag. The effect of the compositions of the slag and metal on the phosphorus distribution ratio is expressed by an equation. The kinetics of dephosphorization are investigated, assuming that the mass transfer of phosphorus in the metal is the rate controlling step. In the present investigation the activation energy of dephosphorization is equal to 38 kJ/mol and the mass transfer coefficient of phosphorus at 1600°C is 0.0135 cm/s.     

RH脱碳过程中极低氧钢水的碳氧反应机理

BOF+LF+RH+CC工艺路线生产IF钢,在RH脱碳前,钢水经脱氧和LF精炼后,钢中自由氧达到极低水平.根据表观脱碳速率常数的不同,这种极低氧钢水的RH脱碳可以划分为四个阶段.与传统三个阶段的RH脱碳不同的是在低速脱碳阶段和快速脱碳阶段存在一个脱碳速率介于两者之间的过渡阶段.在正规溶液模型的基础上,建立了能够准确预报钢液氧含量及顶渣FeO含量的RH脱碳模型.结果表明:在RH吹氧前,极低氧含量的钢液与顶渣之间基本不传氧;吹氧之后,钢液氧含量呈线性增加,当钢液氧势大于顶渣氧势后,钢液向顶渣传氧,渣中FeO含量上升;RH处理结束FeO含量较处理初始有所回升,但是仍处于极低水平,能够有效降低顶渣对钢液的二次氧化.     

Decomposition,Reduction and Dissolution Mechanism of Calcium Sulfate in Iron Oxide Dust Pellet

Iron oxide dust generated during oxygen blowing in the BOF process contains a high content of iron. This iron oxide dust can be used as a material of iron source in the BOF slag reduction process or as de‐siliconisation flux or dephosphorization flux of hot metal pretreatment. One of the most practical uses of iron oxide dust is recycling as a form of pellets in the BOF considering easy application and the amount that can be recycled. In the process of making iron dust pellets cement is used as a binder that contains a lot of calcium sulfate. This calcium sulfate is reduced and dissolved in the molten metal during refining in the BOF. If the oxygen content in slag and molten steel is high enough, the reduced sulfate cannot be dissolved into molten metal and it can be removed as SO_x gas. The behaviour of calcium sulfate has been studied using of 50kg high frequency induction furnace and industrial‐scale plant tests were carried out at a 300ton BOF. The results show that for low carbon steels the evaporation of decomposed sulfate increases with increasing oxygen content in the slag while for high carbon steels the decomposed sulfate is reduced into the molten metal.     

碘-乙醇非水体系分离—重铬酸钾滴定法测定炉渣中金属铁与氧化亚铁

对炉渣中的金属铁与氧化亚铁的测定进行了研究。通过考察与金属铁反应而不与氧化亚铁反应的5种弱酸盐溶液(醋酸铅溶液、醋酸铜溶液、三氯化铁-醋酸钠-醋酸溶液、碘-碘化钾溶液、三氯化铁溶液)和非水溶液(碘-乙醇溶液)对金属铁的浸取效果,选取了碘-乙醇溶液作为炉渣中金属铁的浸取剂。实验结果表明,0.200 0 g炉渣样品用50 mL碘-乙醇溶液浸取40min, 采用重铬酸钾滴定法分别测定浸取液中铁量和浸取后残渣中的亚铁量,得到炉渣中金属铁和氧化亚铁量, 金属铁的浸取率在97 %以上,而氧化亚铁不被浸出。与经典的三氯化铁浸取剂相比,本浸取剂对金属铁的浸取效果好,金属铁与氧化亚铁分离完全,避免了用三氯化铁溶液作浸取剂时亚铁与金属铁的酸溶干扰。以碘-乙醇溶液浸取钢渣和脱磷渣后采用重铬酸钾滴定法测定,金属铁的测定结果的相对标准偏差(RSD)分别为4.2%和4.6 %,氧化亚铁测定结果的相对标准偏差(RSD)分别为0.72%和0.62%。     

Results demonstrating techniques for enhancing electrochemical reactions involving iron oxide in slags and C in liquid iron

Two techniques are described for the enhancement of the kinetics of reduction of iron oxide from slags by carbon in molten iron. Laboratory experiments have shown that the rate of iron oxide reduction by carbon-saturated iron can be increased by 5 to 10 times when the reaction is carried out under a reduced-pressure atmosphere. This effect is thought to be the result of the increased volumetric gas evolution through the slag layer and the associated increase in slag stirring. A model is presented, which relates the mass-transfer coefficient for ferrous ions in the slag to its stirring that is controlled by varying the ambient pressure. Additional laboratory experiments examined the electrochemical nature of iron oxide reduction from slag by carbon in liquid iron. Results indicate that the reduction of iron oxide from slag is increased in the presence of an applied electric field. The external circuit allows for the separation of the half-cell reactions associated with iron oxide reduction and decarburization and increases the reaction area available for the individual reactions. These results have significant implications for several important slag metal reactions, which occur during ironmaking and steelmaking operations.     

RH强制脱碳与自然脱碳工艺生产IF钢精炼效果分析

西昌钢钒厂由于转炉热量不足而以转炉—LF精炼—RH精炼—连铸工艺生产IF钢,为探究RH强制脱碳与自然脱碳工艺生产IF钢精炼效果,采用生产数据统计、氧氮分析、夹杂物自动扫描、扫描电镜和能谱分析等手段,对不同脱碳工艺对顶渣氧化性以及钢的洁净度影响进行了详细研究。结果表明:（1）与自然脱碳工艺炉次相比,采用强制脱碳工艺的炉次在转炉结束与RH进站钢中的平均[O]含量更低;（2）两种工艺脱碳结束钢中的[O]含量基本在同一水平;（3）强制脱碳工艺的炉次在RH结束时渣中平均T.Fe的质量分数降低了1.3%。在能满足RH脱碳效果的前提下,尽量提高转炉终点钢液碳含量、降低钢液氧含量,后续在RH精炼时采用强制吹氧脱碳工艺,适当增大吹氧量来弥补钢中氧,可显著降低IF钢顶渣氧化性。自然脱碳工艺与强制脱碳工艺控制热轧板T.O含量均比较理想;与自然脱碳工艺相比,强制脱碳工艺可有效降低IF钢[N]含量,这与强制脱碳工艺真空室内碳氧反应更剧烈所导致的CO气泡更多和气液反应面积更大有关。脱碳工艺对IF钢热轧板中夹杂物类型、尺寸及数量没有明显影响,夹杂物主要由Al₂O₃夹杂、Al₂O₃–TiO_x夹杂与其他类夹杂物组成,以夹杂物的等效圆直径表示夹杂物尺寸,以上三类夹杂物平均尺寸分别为4.5、4.4和6.5 μm,且钢中尺寸在8 μm以下的夹杂物数量占比高于75%。在RH精炼过程中,尽量降低RH脱碳结束钢中[O]含量,有利于提高钢液洁净度。      

LF炉热态钢渣的循环利用技术

LF炉精炼后的钢渣仍含有一定量的硫,有再利用的价值;钢水浇铸后,减少钢包内的浇余可以提高金属收得率。通过对LF炉热态钢渣渣系及硫容量的分析,以Q345B钢为例,分别计算了钢渣循环利用三次时热态钢渣中硫容量和曼内斯曼指数的变化、热态钢渣循环利用对钢水脱硫和钢水升温等的影响。钢渣循环利用后,每炉钢可节约供电时间4～5 min,减少钢水浇余0.5～0.8 t,提高了金属收得率。     

Hot model experiments of the metal bath spraying effect during the decarburization of Fe-C melts through oxygen top blowing

During recent years decarburization has been steadily gaining importance in converter steel metallurgy at the expense of refining reactions for other slag-forming companion elements. Because decarburization is currently a low-slag operation, the phase contact between gas and metal is critical. With the decrease in the amount of slag foam, more attention must be paid to the spraying of iron droplets during oxygen blowing. The experiments were carried out in a hot model reactor with a 50 kg capacity by oxygen top blowing upon Fe-C melts. The resulting spray of iron droplets was collected with the help of a special droplet sampler in the blowing converter. In the metal droplets a pronounced enhanced decarburization was found in comparison to the metal bath. The amount of metal spray was determined with respect to the oxygen blowing pressure, nozzle diameter, and distance between the lance and bath. Depending on the reactor contents, a high circulation rate of the droplets could be observed. At low blowing rates, FeO-slag is formed and sprayed along with the metal.     

Removal of Phosphorous from Steel Produced by Melting Sponge Iron in Induction Furnace

In secondary route of steelmaking, production through induction melting furnace contributes about 31 % of India’s total steel production. The main raw materials used are steel scrap, cast iron and sponge iron. In India, majority of the induction furnaces are operated using acidic lining of silica based ramming mass to produce structural steel where basicity cannot be maintained to remove phosphorous and sulphur. In the present work, efforts are being made to generate the experimental data for refining of steel in 750 kg induction furnace. The basicity is maintained by addition of CaO and MgO in the form of flux. The slag is made oxidizing in nature by addition of sponge iron in the bath. Oxidation potential of the slag is fulfilled by presence of FeO in sponge iron. In every single heat, samples of slag and metal are collected. The degree of dephosphorization obtained is as high as 82 %.     

含铌铁水直接冶炼含铌微合金钢的试验

 含铌铁水通过脱碳保铌探索作为合金化元素回收铁水中铌并直接冶炼为含铌微合金钢的方法。试验在真空碳管炉内进行,铁水温度为1 500 ℃,氧化剂为Fe2O3,真空度为10 Pa,分别进行有SiO2-CaO-Al2O3系造渣剂、无渣真空氧化冶炼研究。结果表明：在无渣条件下,加入Fe2O3铁水中硅、铌和碳同时氧化,不能脱碳保铌;加入造渣剂时,造渣剂的碱度越低,铁水中的硅氧化量越低,碳氧化量越高,碳质量分数最低下降到0.032%,铌质量分数最低值从0.09%下降到0.082%;碱度越高,铁水中硅氧化量越高,铌的氧化量也越高;真空氧化冶炼能够促进碳氧化,减少硅的氧化,抑止铌氧化。在50 kg级真空感应电炉内成功进行了回收铁水中铌直接冶炼为含铌钢试验,为回收含铌铁水中的铌提供新方法,也为工业化直接冶炼含铌钢提供试验依据。     

Oxygen Activity Calculations of Molten Steel: Comparison With Measured Results

This study sets out to find some model/s that could calculate the closest oxygen activity of molten steel to the measured oxygen activity in an ASEA‐SKF ladle furnace. Ten steel heats grade SAE 52100 were chosen, the oxygen activities of the molten steel after vacuum degassing process were measured, then by means of two different equations and one computer programs the theoretical oxygen activities were calculated and compared to the measured results. In order to calculate the activities of Al₂O₃ in the top slag four different models and two different constants were applied. Both Wagner and Turkdogan's equations were found to be useful. It was seen that increasing the wt% Al from 0 up to 0.05 in molten steel, increasing CaO/Al₂O₃ ratio in top slag, and reducing equilibrium temperature of slag‐steel could contribute to reduction of oxygen activity of molten steel. The scanning electron microscope observations revealed that the main types of observed non‐metallic inclusions in these samples were spinels and calcium aluminates and by increasing the CaO content of the inclusions their equivalent circle diameters grew.     

Effect of Direct Reduced Iron on Oxygen Distribution between Slag and Bath in Electric Arc Furnaces

Test charges containing 40 to 95% direct reduced iron (DRI) were melted in two identical electric arc furnaces. Slag and the corresponding metal samples were collected from the furnace in the course of the steelmaking process and from the ladle after deoxidation and composition adjustment. The temperature was measured just before sampling. The activity coefficient and activity of total ferrous oxide in the slag were determined by using the theory of regular ionic solutions. The activity was used to assess the oxygen concentration in the metal. The effect of slag composition on Fe_tO activity coefficient and activity was investigated. The enthalpy of solution of total ferrous oxide in the slag was found to be 78 kJmol^?1. The ratio of activity to concentration of Fe_tO is equal to 0.0138. The effects of DRI proportion and degree of metallization on α^Fe,O were investigated. The activity coefficients of oxygen and carbon in the bath are 0.7243 and 1.0825, respectively. The activity coefficient and activity of oxygen in the metal decrease with increasing carbon concentration, carbon activity coefficient and activity. An “oxide capacity” has been developed which does not need the use of α^Fe,O. It correlates strongly with temperature over the range from 1500 to 1670°C. The basicity has only a small influence compared with the large temperature effect. The oxide capacity increases with growing DRI proportion and decreases with increasing metallization between 93.43 and 95.25%. Oxygen distribution between slag and metal was assessed by using the oxide capacity. Calculated values compare well with the corresponding data obtained from slag and metal analyses. The oxide capacity can be used in monitoring the steelmaking operation.     

400系易切削不锈钢硫铁加入方式优化

邢钢一步法(脱磷站+60t AOD+60t LF)生产400系易切削不锈钢过程中,前期采用硫铁全部在AOD出钢时加入配[S],AOD出钢至上机浇铸过程中钢渣碱度始终处于低碱度范围(R=1.40～1.95),硫铁消耗较大,钢液氧含量偏高,随着冶炼炉数的增加,炉衬侵蚀严重,影响AOD炉龄和钢坯质量,且钢渣较长时间处于低碱度状态,极易造成钢中[C]含量的上升(尤其是430F、430FR低碳类钢种),很难实现多炉连浇。后期通过优化硫铁加入方式,在LF后期加硫铁,AOD炉渣碱度2.0～2.3,LF炉渣碱度1.6～2.0,缩短低碱度渣处理时间,降低[S]损耗和钢液氧含量及对炉衬侵蚀。使易切削不锈钢[S]的收得率由62%提高到75%,吨钢硫铁消耗下降2.12 kg,铸坯皮下气泡等缺陷得到控制。     

真空下钢液脱氮工艺研究

在４０ｋｇ真空感应炉上进行了真空下钢液脱氮工艺的实验研究。实验考察了真空下碳氧反应工艺、表面活性元素控制和脱氮渣系等因素对钢液脱氮动力学的影响。研究结果表明：（１）真空下强烈的碳氧反应能有效地脱除钢中的氮;（２）当钢中硫含量较低时,脱氮速率很快,随着硫含量的逐步增加,脱氮速率相应降低;（３）５０％ＳｉＯ２－４０％Ｂ２Ｏ３－１０％ＴｉＯ２渣系有明显的脱氮效果。     

Dephosphorization stability of hot metal by double slag operation in basic oxygen furnace

Double slag process was adopted to produce low-phosphorus steel from middle-phosphorus hot metal.To achieve a stable dephosphorization operation,conventional process was modified as follows:the blowing time was extended by approximately 1min by reducing the oxygen supply flow rate;calcium ferrite pellets were added to adjust the slag composition and viscosity;the dumping temperature was lowered by 30-50°C by the addition of calcium ferrite pellets during the double slag process to prevent phosphorus in the slag from returning to the molten steel;and the bottom-blown gas flow was increased during the blowing process.For 40 heats of comparative experiments,the rate of dephosphorization reached 91% and ranged between 87% and 95%;the phosphorus,sulfur,manganese,and oxygen contents calculated according to the compositions of molten steel and slag as well as the temperature of molten steel at the end-point of the basic oxygen furnace process were similar to the equilibrium values for the reaction between the slag and the steel.Less free calcium oxide and metallic iron were present in the final slag,and the surface of the slag mineral phase was smooth,clear,and well developed,which showed that the slag exhibited better melting effects than that produced using the conventional slag process.A steady phosphorus capacity in the slag and stable dephosphorization effects were achieved.     

现代电弧炉炼钢过程物理化学行为及应用

本文研究了现代电弧炉炼钢过程的冶金物理化学变化。研究表明钢水中铁、磷、碳与氧枪吹入的氧气发生直接氧化反应,而钢水中的溶解氧无氧化能力、渣中氧化铁无脱磷能力;钢水中碳与氧气的反应最为剧烈,可通过调整配碳量与吹氧强度可对其它各反应进行控制。在实际生产熔炼过程中,通过及时加入碳粉、焦炭或石墨块,还原渣中氧化铁,可以提高钢水收得率。冶炼过程化清后,通过强化吹氧至接近终点氧,减缓升温速度,流渣换渣,可以深度脱磷,并有效抑制“回磷”。     

Mathematical modeling of the argon-oxygen decarburization refining process of stainless steel: Part I. Mathematical model of the process

Some available mathematical models for the argon-oxygen decarburization (AOD) stainless steelmaking process have been reviewed. The actual situations of the AOD process, including the competitive oxidation of the elements dissolved in the molten steel and the changes in the bath composition, as well as the nonisothermal nature of the process, have been analyzed. A new mathematical model for the AOD refining process of stainless steel has been proposed and developed. The model is based on the assumption that the blown oxygen oxidizes C, Cr, Si, and Mn in the steel and Fe as a matrix, but the FeO formed is also an oxidant of C, Cr, Si, and Mn in the steel. All the possible oxidation-reduction reactions take place simultaneously and reach a combined equilibrium in competition at the liquid/bubble interfaces. It is also assumed that at high carbon levels, the oxidation rates of elements are primarily related to the supplied oxygen rate, and at low carbon levels, the rate of decarburization is mainly determined by the mass transfer of carbon from the molten steel bulk to the reaction interfaces. It is further assumed that the nonreacting oxygen blown into the bath does not accumulate in the liquid steel and will escape from the bath into the exhaust gas. The model performs the rate calculations of the refining process and the mass and heat balances of the system. Also, the effects of the operating factors, including adding the slag materials, crop ends, and scrap, and alloy agents; the nonisothermal conditions; the changes in the amounts of metal and slag during the refining; and other factors have all been taken into account. []—metal phase; ()—slag phase; {}—gaseous phase; and 〈〉—solid phase     

100t 转炉留渣双渣法冶炼高硅高磷铁水试验

针对钢厂铁水硅和磷含量较高的特点,采用转炉留渣双渣冶炼工艺以获得稳定的铁水脱磷率。吹炼3 min后加入石灰和污泥球等造渣材料,供氧强度0～3 min时为2.5m³/（t·min）,3～4.5 min时为3.2m³/（t·min）,温度控制在约1320℃。转炉一次倒渣后,继续吹炼,加入后期造渣料,待一氧化碳体积分数稳定时,适当提高氧枪枪位,促进化渣,并进行终点碳控制。试验结果表明:脱磷期铁水平均脱磷率为58.09%,脱碳期钢水平均脱磷率为85.56%;当半钢温度为1320℃炉渣碱度为2.0,炉渣TFe含量为18%时,在脱磷期能获得较好的铁水脱磷效果;当转炉钢水一倒温度为1580℃,终渣碱度为3.5,炉渣TFe含量为20%时,在脱碳期能够获得较好的脱磷效果;转炉终点[P]_e/[P]_r为0.90;试验中得到脱磷期和脱碳期炉渣的岩相组成适合铁水脱磷。     

脱磷炉利用脱碳炉返回渣的试验

为了达到节能降耗的目的,脱磷炉采用回吃脱碳炉返回渣的工艺。主要研究了脱碳炉渣的熔化特性以及作为炉料在脱磷炉中的应用效果。结果表明,通过每炉次加入约3.5t的脱碳炉渣,可平均节约1.01t石灰,4.71kg/t钢铁料消耗,脱磷炉终点炉渣的岩相组成主要由硅酸二钙、RO相、玻璃相和少量的金属铁粒组成。加入返回渣后脱磷炉终点炉渣中硅酸二钙和铁酸二钙含量有所增加,玻璃相含量降低,炉渣碱度有所升高,脱磷炉终点钢水成分控制水平有所提高。由此表明,采用脱碳炉渣返回脱磷炉循环利用减少了石灰等原辅料和钢铁料消耗,同时达到了预期的脱磷效果。