Review on desulfurization in electroslag remelting

Electroslag remelting(ESR) gives a combination of liquid metal refining and solidification structure control.One of the typical aspects of liquid metal refining during ESR for the advanced steel and alloy production is desulfurization.It involves two patterns, i.e., slag–metal reaction and gas–slag reaction(gasifying desulfurization).In this paper, the advances in desulfurization practices of ESR are reviewed.The effects of processing parameters, including the initial sulfur level of consumable electrode, remelting atmosphere, deoxidation schemes of ESR,slag composition, melting rate, and electrical parameters on the desulfurization in ESR are assessed.The interrelation between desulfurization and sulfide inclusion evolution during ESR is discussed, and advancements in the production of sulfur-bearing steel at a high-sulfur level during ESR are described.The remaining challenges for future work are also proposed.     

含锰钢液在真空有渣精炼过程中的锰蒸发和脱氮行为研究

Considering the precise composition control on the vacuum refining of high-Mn steel, the behaviors of both Mn evaporation and nitrogen removal from molten Mn steel were investigated via vacuum slag refining in a vacuum induction furnace. It was found that the reaction interfaces of denitrification and Mn evaporation tend to migrate from the surface of slag layer to the surface of molten steel with the gradual exposure of molten steel during the vacuum slag refining process. Significantly, compared with the experimental group without slag addition, the addition of slag into steel can result in a lower Mn evaporation rate constant of 0.0192 cm·min?1 at 370 Pa, while the denitrification rate is almost not affected. Besides, the slag has a stronger inhibitory effect on Mn evaporation than the reduced vacuum pressure. Moreover, the inhibitory effect of the slag layer on Mn evaporation can be weakened with the increase of the initial Mn content in molten steel. The slag layer can work as an inhibitory layer to reduce the Mn evaporation from molten steel, the evaporation reaction of Mn mainly proceeds on the surface of the molten steel. This may be attributed to the Mn mass transfer coefficient for one of reaction at steel/slag interface, mass transfer in molten slag, and evaporation reaction at slag/gas interface is lower than that of evaporation reaction at steel/gas interface. The introduction of slag is proposed for both denitrification and manganese control during the vacuum refining process of Mn steels.     

Mn evaporation and denitrification behaviors of molten Mn steel in the vacuum refining with slag process

Considering the precise composition control on the vacuum refining of high-Mn steel, the behaviors of both Mn evaporation and nitrogen removal from molten Mn steel were investigated via vacuum slag refining in a vacuum induction furnace. It was found that the reaction interfaces of denitrification and Mn evaporation tend to migrate from the surface of slag layer to the surface of molten steel with the gradual exposure of molten steel during the vacuum slag refining process. Significantly, compared with the experimental group without slag addition, the addition of slag into steel can result in a lower Mn evaporation rate constant of 0.0192 cm·min~(-1) at 370 Pa, while the denitrification rate is almost not affected. Besides, the slag has a stronger inhibitory effect on Mn evaporation than the reduced vacuum pressure. Moreover, the inhibitory effect of the slag layer on Mn evaporation can be weakened with the increase of the initial Mn content in molten steel. The slag layer can work as an inhibitory layer to reduce the Mn evaporation from molten steel, the evaporation reaction of Mn mainly proceeds on the surface of the molten steel. This may be attributed to the Mn mass transfer coefficient for one of reaction at steel/slag interface, mass transfer in molten slag, and evaporation reaction at slag/gas interface is lower than that of evaporation reaction at steel/gas interface. The introduction of slag is proposed for both denitrification and manganese control during the vacuum refining process of Mn steels.     

Direct Current Electric Arc-Electroslag Ladle Furnace

In order to solve the high consumption problem of small capacity ladle furnace (LF), the operation principle and control method of the DC are and electroslag heating ladle furnace are introduced. With only one arcing electrode, the distance between the are and the wall of ladle is enlarged, and consequently the consumption of the ladle refractory is decreased. In the invention, a signal electrode is embedded in the refractory lining of the ladle, which contacts directly with the liquid steel and the ladle shell. Two graphite anode ends are submerged in the slag layer. The signal electrode is used as voltage reference during refining process. The electroslag voltage between anode end and liquid steel is applied to control the depth of anode end in the slag layer during the refining process with this ladle furnace.     

Characteristics of inclusions in high-Al steel during electroslag remelting process

The characteristics of inclusions in high-Al steel refined by electroslag remelting (ESR) were investigated by image analysis, scanning electron microscopy (SEM), and energy-dispersive spectrometry (EDS). The results show that the size of almost all the inclusions observed in ESR ingots is less than 5 μm. Inclusions smaller than 3 μm take nearly 75% of the total inclusions observed in each ingot. Inclusions observed in ESR ingots are pure AlN as dominating precipitates and some fine spherical Al₂O₃ inclusions with a size of 1 μm or less. It is also found that protective gas operation and slag deoxidation treatment during ESR process have significant effects on the number of inclusions smaller than 2 μm but little effects on that of inclusions larger than 2 μm. Thermodynamic calculations show that AlN inclusions are unable to precipitate in the liquid metal pool under the present experimental conditions, while the precipitation of AlN inclusions could take place at the solidifying front due to the microsegregation of Al and N in liquid steel during solidification.     

Desulfurization ability of refining slag with medium basicity

The desulfurization ability of refining slag with relative lower basicity (B) and Al₂O₃ content (B = 3.5–5.0; 20wt%–25wt% Al₂O₃) was studied. Firstly, the component activities and sulfide capacity (C_S) of the slag were calculated. Then slag-metal equilibrium experiments were carried out to measure the equilibrium sulfur distribution (L_S). Based on the laboratorial experiments, slag composition was optimized for a better desulfurization ability, which was verified by industrial trials in a steel plant. The obtained results indicated that an MgO-saturated CaO-Al₂O₃-SiO₂-MgO system with the basicity of about 3.5–5.0 and the Al₂O₃ content in the range of 20wt%–25wt% has high activity of CaO (a_CaO), with no deterioration of C_S compared with conventional desulfurization slag. The measured L_S between high-strength low-alloyed (HSLA) steel and slag with a basicity of about 3.5 and an Al₂O₃ content of about 20wt% and between HSLA steel and slag with a basicity of about 5.0 and an Al₂O₃ content of about 25wt% is 350 and 275, respectively. The new slag with a basicity of about 3.5–5.0 and an Al₂O₃ content of about 20wt% has strong desulfurization ability. In particular, the key for high-efficiency desulfurization is to keep oxygen potential in the reaction system as low as possible, which was also verified by industrial trials.     

Experimental study on sulfur removal from ladle furnace refining slag in hot state by blowing air

In view of the present problem of sulfur enrichment in the metallurgical recycling process of ladle furnace (LF) refining slag, a simple and efficient method of removing sulfur from this slag was proposed. The proposed method is compatible with current steelmaking processes. Sulfur removal from LF refining slag for SPHC steel (manufactured at a certain steel plant in China) by blowing air in the hot state was studied by using hot-state experiments in a laboratory. The FactSage software, a carbon/sulfur analyzer, and scanning electron microscopy in conjunction with energy-dispersive X-ray spectroscopy were used to test and analyze the sulfur removal effect and to investigate factors influencing sulfur removal rate. The results show that sulfur ions in LF refining slag can be oxidized into SO₂ by O₂ at high temperature by blowing air into molten slag; SO₂ production was observed to reach a maximum with a small amount of blown O₂ when the temperature exceeded 1350℃. At 1370℃ and 1400℃, experimental LF refining slag is in the liquid state and exhibits good fluidity; under these conditions, the sulfur removal effect by blowing air is greater than 90wt% after 60 min. High temperature and large air flow rate are beneficial for removing sulfur from LF refining slag; compared with air flow rate, temperature has a greater strongly influences on the sulfur removal.     

Reaction mechanisms between molten CaF2-based slags and molten 9CrMoCoB steel

Investigating the reaction mechanism between slag and 9CrMoCoB steel is important to develop the proper slag and produce qualified ingots in the electroslag remelting(ESR) process. Equilibrium reaction experiments between molten 9CrMoCoB steel and the slags of 55 wt%CaF2–20 wt%CaO–3 wt%MgO–22 wt%Al2O3–xwt%B2O3(x = 0.0, 0.5, 1.0, 1.5, 2.0, 3.0) were conducted. The reaction mechanisms between molten 9 CrMoCoB steel and the slags with different B2O3 contents were deduced based on the composition of the steel and slag samples at different reaction times. Results show that B content in the steel can be controlled within the target range when the B2O3 content is 0.5 wt% and the FeO content ranges from 0.18 wt% to 0.22 wt% in the slag. When the B2O3 content is ≥1 wt%, the reaction between Si and B2O3 leads to the increase of the B content of steel. The additions of SiO2 and B2O3 to the slag should accord to the mass ratio of [B]/[Si] in the electrode, and SiO2 addition inhibits the reaction between Si and Al2O3.     

Activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag and their application to the recycling of Ni–Co–Fe-based end-of-life superalloys via remelting

To design optimal pyrometallurgical processes for nickel and cobalt recycling, and more particularly for the end-of-life process of Ni–Co–Fe-based end-of-life(EoL) superalloys, knowledge of their activity coefficients in slags is essential. In this study, the activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag, a candidate slag used for the EoL superalloy remelting process, were measured using gas/slag/metal equilibrium experiments. These activity coefficients were then used to consider the recycling efficiency of nickel and cobalt by remelting EoL superalloys using CaO–Al_2O_3–SiO_2 slag. The activity coefficients of NiO and CoO in CaO–Al_2O_3–SiO_2 slag both show a positive deviation from Raoult's law, with values that vary from 1 to 5 depending on the change in basicity. The activity coefficients of NiO and CoO peak in the slag with a composition near B =(%CaO)/(%SiO_2) = 1, where B is the basicity. We observed that controlling the slag composition at approximately B = 1 effectively reduces the cobalt and nickel oxidation losses and promotes the oxidation removal of iron during the remelting process of EoL superalloys.     

Reaction mechanisms between molten CaF_2-based slags and molten 9CrMoCoB steel

Investigating the reaction mechanism between slag and 9CrMoCoB steel is important to develop the proper slag and produce qualified ingots in the electroslag remelting(ESR) process. Equilibrium reaction experiments between molten 9CrMoCoB steel and the slags of 55 wt%CaF_2–20 wt%CaO–3 wt%MgO–22 wt%Al_2O_3–xwt%B_2O_3(x = 0.0, 0.5, 1.0, 1.5, 2.0, 3.0) were conducted. The reaction mechanisms between molten 9 CrMoCoB steel and the slags with different B_2O_3 contents were deduced based on the composition of the steel and slag samples at different reaction times. Results show that B content in the steel can be controlled within the target range when the B_2O_3 content is 0.5 wt% and the FeO content ranges from 0.18 wt% to 0.22 wt% in the slag. When the B_2O_3 content is ≥1 wt%, the reaction between Si and B_2O_3 leads to the increase of the B content of steel. The additions of SiO_2 and B_2O_3 to the slag should accord to the mass ratio of [B]/[Si] in the electrode, and SiO_2 addition inhibits the reaction between Si and Al_2O_3.     

LF炉冶炼超低硫钢的工艺条件

提出了采用热力学计算分析确定LF炉冶炼超低硫钢工艺条件的方法·分析表明,可通过提高炉渣碱度、强化渣钢脱氧、控制渣钢原始硫质量分数和渣质量,来实现超低硫钢的冶炼·150tLF炉生产实践表明,在原始钢水硫平均为00146%条件下,通过控制规定的工艺条件,经LF处理后的钢水硫质量分数平均可达00044%·再经VD处理后,可实现成品硫质量分数为00027%的超低硫钢生产·在上述条件基础上,将原始硫质量分数控制在00058%以下或保证渣金硫的分配比在250以上或采用双渣操作,LF炉可精炼0002%以下极低硫钢     

新型精炼合成渣的高效脱硫研究

本文开发了一种预熔型精炼合成渣,具有高碱度低熔点的特性,实验室条件下,平均脱硫率为84.5%.在工业实验中,根据钢种出钢要求,设计了分钢种的加料方案.实验结果表明,本精炼渣可以达到100%出钢化渣率,精炼时间缩短了11min.与原工业渣系相比,使用本精炼渣后,VD前钢中氧和氮含量分别降低了7×10-6和12×10-6,VD后钢中氧和氮含量分别降低了5×10-6和15×10-6.脱硫率也得到了大幅提高,从电炉出钢至VD后吊包的脱硫率为92%,最低硫含量达到30×10-6.     

含钛高炉渣脱硫的动力学研究

在实验室条件下对承钢含钛高炉渣进行了脱硫过程的动力学研究,确定其脱硫的相关动力学参数。结果发现：在温度一定时,铁水中脱硫量和时间的延长而降低。由于铁水的脱硫反应属于二级反应,硫在熔渣中的扩散成了脱硫过程的限制性环节,熔渣的脱硫能力与炉温成正比,并且在试验中的到硫在熔渣中的扩散活化能为 ED =127.04kJ/ mol。     

电渣重熔系统渣温对输入功率的响应

本文通过渣池的能量平衡,建立了渣温对输入功率的响应关系。给出了确定系统参数的实验方案,并在0.5t电渣炉上进行了实验,结果表明,渣温对输入功率的响应是一个一阶线性系统,理论分析与实验结果相符。对三种工艺下的渣温、熔速进行了讨论并得到如下结果:恒功率重熔——渣温、熔速随锭高线性增加;恒熔速重熔——渣温,熔速在过程中保持恒定;恒熔池深度重熔——渣温、熔速随过程降低。     

Variation and optimization of acid-dissolved aluminum content in stainless steel

As a key step in secondary refining, the deoxidation process in clean stainless steel production is widely researched by many scholars. In this study, vacuum oxygen decarburization (VOD) deoxidation refining in a 40-t electric arc furnace + VOD + ingot casting process was analyzed and optimized on the basis of Al deoxidation of stainless steel and thermodynamic equilibrium reactions between the slag and steel. Under good stirring conditions in VOD, the deoxidation reaction reaches equilibrium rapidly, and the oxygen activity in the bulk steel is controlled by the slag composition and Al content. A basicity of 3–5 and an Al content greater than 0.015wt% in the melt resulted in an oxygen content less than 0.0006wt%. In addition, the dissolved oxygen content decreased slightly when the Al content in the steel was greater than 0.02wt%. Because of the equilibrium of the Si–O reaction between the slag and steel, the activity of SiO₂ will increase while the Si content increases; thus, the Si content should be lowered to enable the formation of a high-basicity slag. A high-basicity, low-Al₂O₃ slag and an increased Si content will reduce the Al consumption caused by SiO₂ reduction.     

用热重法分析电石渣的固硫性能

用热重法建立一种分析电石渣固硫性能的方法.通过分析电石渣的固硫机理,利用煤燃烧、电石渣热分解和电石渣与煤混合试样的TG曲线计算生成电石渣固硫反应TG曲线,同时通过各试样残留质量间的关系计算出了不同钙硫摩尔比电石渣的固硫效率.结果表明:三种实验条件下,钙硫摩尔比为1.5时,电石渣固硫效果最好.     

连铸结晶器内钢液弯月面行为的研究

在自行设计的可以实现振动、水冷及拉坯的连铸模拟装置上，用低熔点的Ｐｂ－Ｓｎ－Ｂｉ合金模拟钢液，用硅油似保护渣对弯月面行为进行了研究，结果表明，增加过热度使得弯月面与结昌器壁的接触角变小，弯月面的高度降低；在弯月面区域加上电磁场时，变月面变结晶器中心拱起，其拱起程序随着电磁强度和磁场的增加相应增大，但液态金属高的过热度会弱电磁场的作用效果，结晶器振幅增大及拉速提高均会使弯月面处液态金属的波动程度增大     

柴油水蒸气催化脱硫精制的动力学研究

建立了可以用于预测水蒸气催化脱硫精制柴油实验结果的四集总反应动力学模型。该模型能够给定原料柴油的脱硫转化率、柴油的收率和汽油的收率，并能选取最佳操作条件。通过对实验数据的处理，得到了该模型的反应级数、速率常数、表观活化能以及催化剂失活因子等参数。结果表明，在温度不是太高的情况下，预测值与实验值有良好的吻合；不同性质的柴油应具有不同的模型参数；高温阶段预测的结果外推能力较差。     

低碳含铝钢20Mn2精炼渣系CaO-SiO2-Al2O3-MgO-CaF2的优化

通过对低碳含铝钢20Mn2精炼过程的取样分析,得出精炼渣的熔化温度偏高,渣中存在大量固相CaO,并导致钢中含有CaO类夹杂物,精炼渣吸附夹杂物能力差. 利用FactSage热力学计算,从渣的低熔点区域控制和渣-钢反应这两个方面对渣系进行研究与优化. 结果表明,CaO/Al2 O3 质量比在1. 5左右添加质量分数为3% CaF2 可以有效降低渣的熔化温度,渣的熔化温度随着CaF2 含量的升高呈现先降低后升高的趋势,MgO的质量分数控制5%左右低熔点区域面积达到最大. 在SiO2 质量分数大于30%区域,钢中氧含量大体上随着CaO/Al2 O3 质量比的增加而降低,在SiO2 的质量分数低于30%区域随着CaO含量的升高而降低,钢中酸溶铝含量在SiO2 含量高的区域随着Al2 O3/SiO2 质量比的增加而升高,在SiO2 含量低的区域随着CaO/SiO2 质量比的增加而增加. 根据热力学分析结果得出合理的渣系范围:CaO 50% ~60%, Al2 O3 20% ~35%, SiO2 5% ~10%, MgO 5% ~8%, CaF2 0~5%. 优化渣系的实验结果表明,优化后渣系熔化温度降低,钢中夹杂物数量、面积和平均尺寸均有明显下降.