浅议转炉出钢过程的脱硫

本文通过对脱硫反应的热力学及动力学条件分析，及以实际生产为例，阐述了出钢过程脱硫的可行性及重要性。     

从钙处理到凝固钢中夹杂物改性及析出热力学研究

钙处理是使钢中氧化物和硫化物夹杂转化成对钢的性能有利的无害夹杂很好的方法。通过钙使固体Al2O3串状物转化成液体铝酸钙，从而避免铝脱氧钢连铸期间水口堵塞。钙处理也是改进钢的机械加工性的一种重要方法，增加硫含量可进一步改进机械加工性。然而，加硫钢由于缺乏氧化物的改性以及形成容易堵塞水口的固体硫化钙而出现浇注问题。[第一段]     

钢中夹杂物含量及其形态对钢力学性能的影响

在实验室１６ｋｇ真空感应炉上对铝镇静钢水用ＣａＯ－ＣａＦ２－Ａｌ和ＣａＯ－ＣａＦ２－Ａｌ－Ｃａ进行精炼处理，降低了钢中硫含量和总氧含量，研究了钢中氧化物和硫化物夹杂的含理及其形态对钢力学性能，尤其是冲击韧性的影响。钢水经钙处理后，钢中硫含量和总氧含量都可降低到１０ｐｐｍ以下，且钢中Ａｌ２Ｏ３和ＭｎＳ夹杂物能完全转变成硫化钙和铝酸钙，钢的转变温度低于－６０℃，而且钢的各向异性消失。     

高锰高强IF钢转炉-连铸过程中夹杂物演变与控制

为了摸索高锰高强IF钢钢液洁净度及夹杂物演变规律,采用Thermofisher Explorer 4全自动夹杂物分析仪对转炉-连铸过程中夹杂物进行分析和研究。结果表明：高锰高强IF钢RH结束、中间包和铸坯中全氧含量依次降低,铸坯全氧随着宽度方向由边部向中心位置移动而逐渐增加。高锰高强IF钢RH进站时主要夹杂物为椭球状或球状含有P₂O₅的FeO-MnO夹杂,加铝脱氧后主要夹杂物转变为Al₂O₃夹杂,RH结束、中间包Al₂O₃主要类型为小型块状和不规则形状。铸坯中主要夹杂物为块状、棒状、不规则形状Al₂O₃,尺寸多在10μm以下,边部位置TiN、MnS析出物较少,中心位置MnS析出物进一步增加,也存在少量TiN析出。热力学计算普通IF钢、高锰高强IF钢TiN析出温度分别为1 745、1 589 K,MnS析出温度分别为1 450、1 675 K。通过增加铝钛间隔时间、降低脱氧前氧、进行钢包渣改质,高锰高强IF钢钢液洁...     

BOF-LF-VD-CC过程35MnB钢中夹杂物的演变分析

夹杂物对高品质特殊钢的服役性能有显著影响,但国内外对冶炼过程35MnB钢中夹杂物的演变行为尚不明晰。通过采用扫描电镜和FactSage热力学计算等方法和手段,对Al粒+SiC扩散脱氧(1号工艺)和SiC扩散脱氧(2号工艺)生产的35MnB钢冶炼过程钢成分、渣成分及钢中夹杂物的演变行为进行研究。结果表明,1号工艺精炼过程会出现钢水增硅,不同扩散脱氧工艺铸坯中的全氧和氮质量分数差别不大,全氧质量分数分别为11.9×10^-6和11.6×10^-6。35MnB钢中主要存在尺寸小于5μm的氧化物、硫化物或TiN夹杂物。夹杂物种类主要受沉淀脱氧工艺影响,受扩散脱氧工艺影响较小。冶炼过程夹杂物的演变规律为:Al₂O₃(氩站)→CaO-MgO-Al₂O₃(LF精炼)→CaO-MgO-Al₂O₃-CaS(软吹)→CaO-MgO-Al₂O₃-CaS或CaO-Al₂O₃-CaS(铸坯),夹杂物演变规律与热力学计算结果相符。     

高级别船板钢生产过程中夹杂物的演变规律

 通过采用扫描电镜对船板钢F40中的夹杂物进行全流程系统分析，研究了冶炼过程中夹杂物的形成和演变规律，并采用夹杂物的弹性模量概念对其在轧制过程中的变形机理进行解释。结果表明，LF出站后钢中的主要夹杂物为MgO-Al2O3复合夹杂，在钙处理后夹杂物逐渐向低熔点的CaO-Al2O3-MgO-CaS系夹杂转变。在轧制过程中，高弹性模量的夹杂物，在轧制中相对塑性变形低。热力学计算表明，当船板钢中的w（[Als]）为0.02%～0.04%时，为使夹杂物改性完全，钙处理后钢液中的w（[Ca]）应控制在0.001 8%～0.002 8%。为避免钙处理后生成CaS，可通过控制w（[S]）在0.002 1%以内，减小其对浇注过程和钢性能的不利影响。     

转炉出钢过程"渣洗"脱硫工艺研究

理论计算和工业试验效果表明，在南钢现有生产条件下，采用转炉出钢过程“渣洗”脱硫工艺具有比较好的脱硫效果。在进一步优化工艺参数后，可以成为有效的脱硫手段，降低品种钢在冶炼过程的生产成本。     

从钙处理到凝固钢中夹杂物改性及析出热力学研究

钙处理是使钢中氧化物和硫化物夹杂转化成对钢的性能有利的无害夹杂很好的方法。通过钙使固体AlO2半状物转化成液体铝酸钙，从而避免铝脱氧钢连铸期间水口堵塞。钙处理也是改进钢的机械加工性的一种重要方法，增加硫含量可进一步改进机械加工性。然而，加硫钢由于缺乏氧化物的改性以及形成容易堵塞水口的固体硫化钙而出现学浇注问题。     

南钢DF钢夹杂物分析研究

对南钢转炉厂生产DF钢中的夹杂物进行了研究，结果表明现有工艺制度下吹氩精炼效果不明显，氩后钢中的夹杂物含量为865．78mg／kg；大于300μm的夹杂物，主要成分为Si—Al，或Si—Al—Mn；80～300μm夹杂物，主要成分为Si—Al-Mn，且Si较高，Mn较低；小于80μm的夹杂物，主要成分为Si—Al—Mn，并且含Mn较高：改变钢液脱氧制度及控制吹氩搅拌，可使氩后钢中及铸坯中的夹杂物含量分别降低到203．38mg/kg、59．8mg／kg。     

Optimisation of Inclusion Chemistry by Improved Steel Cleanliness and Optimum Calcium Treatment

SMSII, Bokaro Steel Plant produces ~ 2.0 million tons of low carbon aluminium killed (LCAK) steels per annum. Calcium treatment is done regularly at the end of ladle treatment to avoid clogging of submerged entry nozzles (SEN). With calcium consumption of 0.23 kg/t, inconsistent calcium in steel, SEN clogging and slide gate erosions were reported. Nozzle clogging during casting of LCAK steels was primarily caused by deposition of complex oxide and sulfide inclusions and slide gate erosion by excess calcium in steel. Optimum calcium in steel was essential to achieve desired inclusion composition conducive to smooth casting and eliminate slide gate or SEN erosion effectively. With calcium consumption of 0.12kg/ton optimum calcium content in steel could be achieved through i) improved steel cleanliness, ii) restricted CaS formation and iii) optimum aluminium content in steel. Process optimisation resulted in reduction in aluminium consumption by 1.0 kg/t and improvement in steel cleanliness with consistent total oxygen level of ≤ 42 ppm. Desired inclusion characteristics conducive to longer sequence length was achieved and evidenced through EPMA. Erosion of slide gate plates could be eliminated completely.     

X70管线钢钙处理研究

在X70管线钢LF精炼后期分别以100 m/min和200 m/min速度向钢中喂入300~500 m硅钙线或添加硅钙钡铁,对钢中夹杂物进行变性处理。喂钙后钢样、结晶器钢样和铸坯样中的CaTot和夹杂物分析表明:钙处理后钢中钙含量在不断下降;夹杂物的组成、形貌和尺寸也在不断变化。根据钢中夹杂物的变化、夹杂物对高级别管线钢性能和连铸顺行的影响,提出了高级别管线钢生产中夹杂物变性控制策略。     

管线钢硫化物夹杂及钙处理效果研究

系统分析了硫化物夹杂形貌、组成,并采用氧化物变性指标及硫化物变性指标对管线钢钙处理效果进行了全面评价,分析结果表明:管线钢经过钙处理后,没有发现沿晶界分布的MnS塑性夹杂,少量的硫化物夹杂由(Ca,Mn)S夹杂、CaS均匀分布的CaO-Al2O3-CaS复合夹杂和内核为CaO-A12O3外壳为CaS的复合夹杂组成,这对于提高钢板抗HIC性能非常有利;在现有工艺条件下,硅钙线加入量为0.7kg/t时夹杂物变性效果不理想,应适当增加硅钙线的加入量.     

Effect of Calcium Treatment on Non-Metallic Inclusions in Ultra-Low Oxygen Steel Refined by High Basicity High Al2O3 Slag

 The influence of calcium treatment on non-metallic inclusions had been studied when control technology of refining top slag in ladle furnace was used in ultra-low oxygen steelmaking. A sufficient amount aluminium was added to experimental heats for final deoxidizing during BOF tapping, and the refining top slag with strong reducibility, high basicity and high Al2O3 in ladle furnace was used to produce ultra-low oxygen steel and the transformation of non-metallic inclusions in molten steel was compared by calcium treatment and no calcium treatment. The results show that the transformation of Al2O3→MgO·Al2O3 spinel→CaO-MgO-Al2O3 complex inclusions has been completed for aluminum deoxidation products and calcium treatment to molten steel is unnecessary when using the control technology of ladle furnace refining top slag to produce ultra-low oxygen steel, and the complex inclusions are liquid at the temperature of steelmaking and easily removable to obtain very high cleanliness steel by flotation. Furthermore, the problems of nozzle clogging in casting operations do not happen and the remaining oxide inclusions in steel are the relatively lower melting point complex inclusions.     

钙处理对钢水浇铸性能的影响

为了改善浇铸性能，应向钢中加入适量的钙，形成液态的铝酸钙。分析钙处理对钢水浇铸性能的影响，钙处理不当时不仅影响钢水的浇铸性能，而且还会影响钢水在结晶器内的凝固行为。     

钙处理钢水中非金属夹杂物的形态

通过理论计算和在真空感应炉中钢水钙处理试验,研究了钙处理对钢中非金属夹杂物形态的影响。试验结果与理论计算基本一致。     

Investigations of Inclusion Modification in High Grade Pipeline Steel

SiCa line was injected into liquid pipeline steel at the end of LF refining as calcium treatment, and samples were taken from liquid steel in ladles before and after calcium treatment, liquid steel in mould, and slabs. Results show that Ca content in steel decreased obviously after calcium treatment with production, and the compositions, morphologies and sizes of inclusions in steel also varied with time; Al2O3 inclusions turned to be fine irregular CaS-CaO-Al2O3 compound inclusions after calcium treatment, and then to be fine globular CaO-Al2O3 inclusions in mould, and finally changed to be a few larger irregular CaS-CaO-Al2O3 complex inclusions in slabs; reoxidation of molten steel treated by Ca deteriorates effect of calcium treatment. Thermodynamic study revealed that inclusion variations were related with preferential reactions among Ca, Al2O3 and S and precipitation of S in high sulfur capacity CaO-Al2O3 inclusions. New calcium treatment controlling rules were put forward according to the inclusion variations and requirements of pipeline on inclusion controlling.     

钙处理技术在钢水精炼中的应用

钢水精炼过程中进行钙处理,对于硅还原的钢种,向钢液中喂入硅钙线,有利于钢水进行深脱氧,去除钢液中残余氧及金属氧化物,提高钢水纯净度;对于硅、铝还原的钢种,向钢液中喂入硅钙线,能够改变高熔点的铝氧化物夹杂的形态,形成低熔点的钙-铝化合物,有利于铝氧化物的去除,提高钢水清洁度,改善钢液的浇铸性能,减轻中间包水口堵塞问题,保证连铸顺利进行,改善钢的质量,提高合金收得率。降低生产成本。