Preliminary Investigation of Mathematical Modeling of Stainless Steelmaking in an AOD Converter: Application of the Model and Results

The changes in the contents of C, Cr, Si, and Mn in molten steel and the bath temperature during the refining of 304‐grade stainless steel, including both the oxidation (decarburization) and reduction processes, in a side and top combined blowing AOD converter of 120 t capacity have been predicted. The calculations were performed using the mathematical model proposed and presented in Part I of the present work [1] and were based on the designed operational mode of the AOD converter. The model predictions were compared to the referenced values given by the technological design. The results demonstrate that the predictions by the model are in good agreement with the reference values. Not only the competition of oxidation among the elements dissolved in the steel during the oxidative refining process and the corresponding distribution ratios of oxygen, but also the competition of reduction among the oxides during the argon stirring and reductive refining process and the relevant supplied oxygen ratios of the oxides, can all be characterized more comprehensively and determined more reasonably by using the Gibbs free energies of the oxidation and reduction reactions. Corresponding to the top, side, and side and top combined (overall) refining processes of 304‐grade stainless steel in a 120 t AOD converter, the carbon concentrations at the critical rates, i.e. the critical carbon concentrations, after which the decarburization changes to be controlled by the mass transfer of carbon in molten steel, are 1.20, 0.37 and 0.53 mass%, respectively, under the given designed operational mode. The model can offer some useful information for determining the technology of the side and top combined blowing AOD refining process of stainless steel.     

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     

45 t AOD精炼304不锈钢的造渣工艺实践

为降低AOD精炼的渣料和还原剂硅铁用量,对高铬钢液脱碳及还原过程渣碱度控制进行热力学分析,并进行45 t AOD冶炼304不锈钢造渣工艺试验。试生产结果表明,降低AOD精炼304不锈钢脱碳期炉渣碱度可减少钢水铬的氧化,同时有效减少AOD精炼渣料和还原剂消耗;AOD精炼过程石灰加入量平均从104.2 kg/t降至84.2~93.1 kg/t时,脱碳期炉渣碱度由平均13.44降低到10.64,AOD冶炼过程石灰、萤石、硅铁单耗分别平均降低14.7、5.4、4.4 kg/t,钢中Cr收得率、Ni收得率和硫含量分别为99.0%、98.3%和0.0025%。     

Preliminary Investigation of Mathematical Modeling of Stainless Steelmaking in an AOD Converter: Mathematical Model of the Process

Mathematical modeling of stainless steelmaking in an AOD (argon‐oxygen decarburisation) converter with side and top combined blowing has been preliminarily investigated. The actual situations of the side and top combined blowing AOD process were analysed. A mathematical model for the whole refining process of stainless steel has been proposed and developed. The model is based on the assumption that one part of the oxygen blown through a top lance reacts with CO escaping from the bath, another part of the oxygen oxidizes the elements in the molten steel droplets splashed by the oxygen jet, and the remaining oxygen penetrates and dissolves into the molten steel through the pit stroked by the jet. All the oxygen entering into the bath oxidizes C, Cr, Si, and Mn dissolved in the steel and also the Fe of the steel melt, but the FeO generated is also an oxidant of C, Cr, Si, and Mn in the steel. During the process, all possible oxidation‐reduction reactions occur simultaneously and reach their equilibria, respectively their combined equilibrium, in competition at the liquid/bubble and liquid/slag interfaces. In the simple side blowing after the top blowing operation is finished, the possible reactions take place simultaneously and reach a combined equilibrium in competition at the liquid/bubble interfaces. The overall decarburization rate in the refining process is the sum of the contributions of both the top and side blowing processes. It is also assumed that at high carbon concentrations, the oxidation rates of elements are mainly dependent upon the supplied oxygen rate, and at low carbon contents, the rate of decarburisation is primarily related to the mass transfer of carbon from the molten steel bulk to the interface. It is further assumed that the non‐reacting oxygen blown into the bath does not accumulate in the steel and will escape from the bath and react with CO in the atmosphere above the bath. The study presents calculations of the refining rate and the mass and heat balances of the system for the whole process. Additionally, the influences of the operating factors, including addition of slag materials, scrap, and alloy agents, the non‐isothermal conditions, the changes in the amounts of metal and slag during the whole refining process, and others have all been considered.     

邢钢400系低碳易切削不锈钢控碳工艺实践

430F、430FR等低碳易切削不锈钢成品碳含量≤0.035%,由于邢钢采用60 t AOD-LF-CC的低成本生产工艺,其中经常采用造价昂贵的低碳合金和增加末期脱碳时间来保证产品碳合格率,相比同系列的低碳430铁素体不锈钢,吨钢成本升高达100元。通过提高AOD脱碳温度和调整过程碱度,实现出钢[C]≤0.015%。在出钢和精炼工序采用镁钙材质渣线代替镁碳材质渣线的钢包,并调整精炼炉渣氧化性,实现精炼过程平均增碳量≤0.007%。低碳易切削不锈钢整体成品碳含量合格率由76%提高到了≥92%,实现AOD-LF-CC工艺连续生产低碳430系列易切削不锈钢。     

AOD炉精炼不锈钢的微机动态控制

本文介绍了太钢１８ｔＡＯＤ炉休用微机动态控制精炼不锈钢的“工艺模型”及其应用。通过该模型可控制终点碳和温度以及提高的回收率。     

AOD冶炼不锈钢氮合金化控制模型的研究和应用

根据氮在钢中的溶解热力学和脱除动力学理论,建立了AOD精炼氮合金化的控制模型。经45 t AOD装置精炼0Cr19Ni9N不锈钢(%:≤0.08C、18～20Cr、8～11Ni、0.10～0.16N)的应用结果表明,模型计算值与实测值吻合良好,可通过AOD氮气溶解和氩气脱除,精确控制不锈钢的N含量。     

奥氏体不锈钢夹杂物控制工艺技术探讨

奥氏体不锈钢中的夹杂物影响钢材的抗腐蚀性能,对塑性、韧性和抗疲劳性能均有不利的影响。叙述了中航上大高温合金材料有限公司采用EAF+AOD+LF生产奥氏体不锈钢时夹杂物控制的主要工艺,分析了夹杂物的主要来源与产生机理,工艺设计时对冶炼过程夹杂物的控制进行了系统的策划。通过加强原辅材料控制,优化AOD脱氧制度,LF精炼采用钙处理和弱搅拌工艺对夹杂物进行变性处理,模铸浇注采用氩气保护浇注等技术手段,最终实现了钢中各类夹杂物含量的降低和稳定控制,满足了核电、压力容器等高端不锈钢管坯的质量要求。     

Thermodynamic Assessment to Chromium Oxidation in the Production of Stainless Steel

A solution model called ε approach is applied to predict the thermodynamic solution behaviour of Cr in steel melts. The calculated results are supported by the available experimental results. Further predictions on chromium scorification are achieved in view of melting and refining processes for Cr‐containing steels. Chromium reduction from slags after meltdown during EAF melting and AOD or VOD refining treatment is important for the production of Cr‐containing steels. It is thermodynamically predicted that chromium is inevitably oxidized during decarburization process which coincides with the industrial and experimental results. Minimum oxidation of chromium can be reached by lowering the partial pressure of CO gas at high temperatures.     

超纯铁素体不锈钢VOD脱碳模型研究

摘要：为了实现对超纯铁素体不锈钢VOD精炼脱碳过程的动态即时预测及控制,以酒钢宏兴不锈钢分公司100 t VOD炉冶炼超纯铁素体不锈钢的过程为研究对象,从顶吹氧气的分配行为和C Cr的竞争氧化出发,建立基于炉气分析技术的VOD动态脱碳模型,并在Matlab环境下开发相应的应用软件,得到全过程钢液成分、氧气分配比、温度等参数随时间的变化规律,对不同阶段的临界碳浓度给出估计范围。利用VOD出站成分以及精炼过程中CO/CO2的实际变化规律加以检验,与实际值吻合较好,较好地预测了实际变化趋势。     

Effect of Modification Treatment on Inclusions in 430 Stainless Steel by Mg-Al Alloys

 Refining process of 430 stainless steel in AOD (argon oxygen decarburization) was simulated under the experimental condition. Al was chosen as deoxidizer, Mg-Al alloy was added in process of refining, and slag used in oxidation period of AOD was chosen in the experiments. The variation of total oxygen content, the size, morphology and composition of inclusions in refining process and the mechanical properties, pitting corrosion resistance of final samples were studied. The results show that no obvious differences in total oxygen content were observed among all the experiments. Neither chain nor cluster Al2O3 inclusions were found in refining process of experiments treated by Mg-Al alloys, the average size of inclusions in the steel treated by Mg-Al alloys was less than that of inclusions in steel not treated by Mg-Al alloy. 430 stainless steel treated by Mg-Al alloy shows better tensile strength, yield strength, and pitting resistance than that in the contrast experiment.     

缩短AOD炉处理0Cr13C不锈钢的冶炼周期

针对邢钢在铁水预处理＋AOD炉＋LF炉＋连铸机生产0Cr13C不锈钢过程中AOD炉的冶炼周期远大于连铸机浇钢和脱磷站的处理时间,导致整个不锈钢生产线的生产效率受到限制这个问题进行研究。研究入炉冷钢比例、高碳铬铁硅质量分数对AOD炉提枪碳质量分数、提枪温度以及冶炼周期的影响。研究得出,降低AOD炉0Cr13C冶炼周期的思路主要是控制提枪碳质量分数;包含成本在内,当入炉高碳铬铁硅质量分数不小于3.0%、废钢加入量为3.0~3.5t时,可以缩短AOD炉0Cr13C的冶炼周期到77min附近,提枪温度和提枪碳质量分数分别为1682℃和0.49%,并且炉龄和物料消耗等综合指标较好。     

Chromium Recycling from Argon-oxygen Decarburization Dust in Hot Metal Pre-dephosphorization Process

The chromium recycling from the stainless steel dust of an argon-oxygen decarburization (AOD)furnace during a hot metal pretreatment process was investigated.Experiments at different temperatures or with different amounts of AOD dusts were carried out in a laboratory furnace equipped with MoSi2 heating elements and subsequently industri-al experiments were conducted in a stainless steelmaking factory,in order to study the thermodynamic mechanism of C and Si reacted with Cr2 O3 to get Cr from AOD dust.The results showed that the reaction between C and Cr2 O3 occurred below 1 572.18 K.Although its reducing ability was weaker than that of Si,C enabled the Cr in Cr2 O3 in the AOD dust to be recycled using the Si in the slag.By combining the AOD dust added in an earlier stage,the hot metal pretreatment slag added in a later stage could not only recycle Cr from AOD dust but also remove Si,S,and P.Higher hot metal temperatures resulted in higher Cr content and lower remained P concentration in the molten iron.     

Mathematical Modelling of Non‐equilibrium Decarburization Process during Vacuum Circulation Refining of Molten Steel: Application of the Model and Results (I) ‐ Decarburization Process and Influences of Some Technological Factors

A novel three‐dimensional mathematical model proposed and developed for the non‐equilibrium decarburization process during the vacuum circulation (RH) refining of molten steel has been applied to the refining process of molten steel in a 90‐t multifunction RH degasser. The decarburization processes of molten steel in the degasser under the conditions of RH and RH‐KTB operations have been modelled and analysed, respectively, using the model. The results demonstrate that the changes in the carbon and oxygen contents of liquid steel with the treatment time during the RH and RH‐KTB refining processes can be precisely modelled and predicted by use of the model. The distribution patterns of the carbon and oxygen concentrations in the steel are governed by the flow characteristics of molten steel in the whole degasser. When the initial carbon concentration in the steel is higher than 400 · 10⁻⁴ mass%, the top oxygen blowing (KTB) operation can supply the oxygen lacking for the decarburization process, and accelerate the carbon removal, thus reaching a specified carbon level in a shorter time. Moreover, a lower oxygen content is attained at the decarburization endpoint. The average contributions at the up‐snorkel zone, the bath bulk and the free surface with the droplets in the vacuum vessel in the refining process are about 11, 46 and 42% of the overall amount of decarburization, respectively. The decarburization roles at the gas bubble‐molten steel interface in the up‐snorkel and the droplets in the vacuum vessel should not be ignored for the RH and RH‐KTB refining processes. For the refining process in the 90‐t RH degasser, a better efficiency of decarburization can be obtained using an argon blow rate of 417 I(STP)/min, and a further increase in the argon blowing rate cannot obviously improve the effectiveness in the RH refining process of molten steel under the conditions of the present work.     

Theoretical and experimental research of molybdenum oxide alloying for 316L stainless steel smelting process

Thermodynamic studies were carried out to investigate the effects of temperature, molten metal composition on the relationship among MoO3, CaMoO4 and ??Fe??, ??Mn??, ??C??, ??Si??, ??Cr?? during the AOD remelting process. The calculated results show that MoO3 and CaMoO4 can easily be reduced by its reactions with active alloying elements during the refining process of 316L stainless steel. First of all, the feasibility of molybdenum oxide alloying for 316L stainless steel smelting was proved theoretically. Then an industrial test of 316L stainless steel alloyed with molybdenum oxide was performed in a 180t AOD furnace. The results show that the molybdenum oxide has no influence on composition of inclusions in the steel and quality of the cold rolling plate. Above all, molybdenum oxide used as alloying material during AOD of 316L stainless steel is applied in TISCO factory, which can relieve the environmental contamination burden from ferro- molybdenum alloying during the AOD process.     

使用CO2-Ar混合气体悬浮精炼不锈钢

 不锈钢生产成本的降低以及CO2在炼钢过程中的资源化利用是当前冶金工作者研究的热点之一。提出了一种利用电磁悬浮精炼不锈钢脱除其中碳、硫的方法;从动力学的角度分析了碳、硫等元素在悬浮精炼不锈钢熔体状态下脱除的原理。试验结果表明,CO2可以在电磁悬浮状态下代替O2对不锈钢进行精炼,此状态下不锈钢试样组分挥发少,[w(C)]可以脱除到0.04%;脱硫效果与试样中[w(C)]有关,[w(C)]越高,脱硫效果越好;改变气体流速和CO2分压等参数时,试样中的[w(Cr)]几乎保持一个常数,这说明使用CO2悬浮精炼不锈钢时不会伴随着重要元素铬的流失,保铬效果明显。     

不锈钢渣资源化研究现状

不锈钢渣是不锈钢生产过程中产生的有毒废渣,包括初炼渣和精炼渣,其特殊性在于其含有水溶性致癌物质Cr6+,并且在渣的堆放过程中一直持续着Cr3+向Cr6+的转化,严重污染环境。介绍了高温硅铁熔融还原法、湿法及固化法对不锈钢渣脱毒原理,分析了不锈钢渣在烧结、返回炼钢、制备微晶玻璃及烧制水泥等方面的资源化利用现状。     

MTA废气分析在VOD脱碳过程中的应用

为了实现对VOD脱碳终点碳含量进行动态控制,以某钢厂120 t VOD炉冶炼不锈钢的脱碳过程为研究对象,通过MTA（multi task analyzer）废气分析系统分析VOD精炼中CO、CO2等废气成分随时间变化的规律。同时以物质碳平衡为基础,建立了基于废气分析的VOD冶炼碳终点控制的模型,对精炼过程中钢水碳变化情况进行分析。通过对实际值和预测值之间的偏差进行考察,说明了模型能够较好地预测碳含量的总体发展趋势。模型计算VOD脱碳终点碳质量分数误差都在±0.03%之内,模型计算值与实际测量值具有一定的吻合性。     

RH真空精炼过程的动态模拟

建立了描述RH真空精炼装置内钢液动态脱碳（脱气）模型。对RH真空精炼时的脱碳、脱氧、脱氮和脱氢过程进行了动态模拟研究，考察了浸渍管直径、循环流量、吹氩量、氧含量和真空度对脱碳和脱气过程的影响。动态脱碳（脱气）模型考虑了反应机理，认为脱碳是通过上升管中Ar气泡表面、真空室中钢液的自由表面和真空室钢液内部脱碳反应生成的CO气泡表面进行的，并且考虑了精炼处理时的抽真空制度。该模型能全面描述RH精炼过程中不同时刻钢液中碳、氧、氮和氢的含量，能较好预测实际过程，可用于RH真空精炼过程的优化和新工艺开发。