高磷铁水预处理环保脱磷渣系的相图计算和实验研究

采用FactsageTM软件对以B2O3、K2O、MnO2、TiO2代替CaF2助熔的4种高磷铁水预处理脱磷渣系在1 623 K时的相图进行计算,发现相图中的多数区域都有液态渣出现.根据计算相图制定脱磷实验的配渣方案,实验过程中观察到的化渣情况与计算相图提供的信息基本一致.     

Investigation of the kinetic mechanism of the demanganization reaction between carbon-saturated liquid iron and CaF2-CaO-SiO2-based slags

The demanganization reaction kinetics of carbon-saturated liquid iron with an eight-component slag consisting of CaO-SiO₂-MgO-FeO-MnO-Al₂O₃-TiO₂-CaF₂ was investigated at 1553, 1623, and 1673 K in this study. The rate-controlling step (RCS) for the demanganization reaction with regard to the hot metal pretreatment conditions was studied via kinetics analysis based on the fundamental equation of heterogeneous reaction kinetics. From the temperature dependence of the mass transfer coefficient of a transition-metal oxide (MnO), the apparent activation energy of the demanganization reaction was estimated to be 189.46 kJ·mol-1 in the current study, which indicated that the mass transfer of MnO in the molten slag controlled the overall rate of the demanganization reaction. The calculated apparent activation energy was slightly lower than the values reported in the literature for mass transfer in a slag phase. This difference was attributed to an increase in the "specific reaction interface" (SRI) value, either as a result of turbulence at the reaction interface or a decrease of the absolute amount of slag phase during sampling, and to the addition of calcium fluoride to the slag.     

添加剂对钛精矿固相碳热还原强化作用的比较

利用热重分析法研究了硅铁、硼砂、碳酸钠三种不同添加剂对钛精矿固相碳热还原行为的影响.对这三种添加剂的TG,DTG,DSC曲线进行分析,结果表明硅铁会使钛精矿在还原过程中的失重率减少;而碳酸钠和硼砂会使钛精矿在还原过程中的失重率增加.三种添加剂都可以使达到最大反应速率时的温度降低.碳酸钠和硼砂可以显著提高其最大反应速率,分别提高了013%/min和018%/min;硅铁使最大反应速率降低.其强化还原机理为硅铁为反应提供一定热量,提高了反应体系的温度;硼砂促进还原过程中反应物的传输;碳酸钠可以增强碳的气化反应.     

Distribution behavior of phosphorus in the coal-based reduction of high-phosphorus-content oolitic iron ore

This study focuses on the reduction of phosphorus from high-phosphorus-content oolitic iron ore via coal-based reduction. The distribution behavior of phosphorus (i.e., the phosphorus content and the phosphorus distribution ratio in the metal, slag, and gas phases) during reduction was investigated in detail. Experimental results showed that the distribution behavior of phosphorus was strongly influenced by the reduction temperature, the reduction time, and the C/O molar ratio. A higher temperature and a longer reaction time were more favorable for phosphorus reduction and enrichment in the metal phase. An increase in the C/O ratio improved phosphorus reduction but also hindered the mass transfer of the reduced phosphorus when the C/O ratio exceeded 2.0. According to scanning electron microscopy analysis, the iron ore was transformed from an integral structure to metal and slag fractions during the reduction process. Apatite in the ore was reduced to P, and the reduced P was mainly enriched in the metal phase. These results suggest that the proposed method may enable utilization of high-phosphorus-content oolitic iron ore resources.     

低温低碱度脱磷渣中磷的富集行为

At low basicity and low temperature, the dephosphorization behavior and phosphorus distribution ratio (L_P) between slag and molten steel in the double slag and remaining slag process were studied with a 180 t basic oxygen furnace industrial experiment. The dephosphorization slags with different basicities were quantitatively analyzed. At the lower basicity range of 0.9–2.59, both L_P and dephosphorization ratio were increased as the basicity of dephosphorization slag increased. Dephosphorization slag consisted of dark gray P-rich, light gray liquid slag, and white Fe-rich phases. With increasing basicity, not only did the morphologies of different phases in the dephosphorization slag change greatly, but the area fractions and P₂O₅ content of the P-rich phase also increased. The transfer route of P during dephosphorization can be deduced as hot metal → liquid slag phase + Fe-rich phase → P-rich phase.     

自蔓延法制备铬铁合金

以Cr2O3,Fe2O3,Al为实验原料,采用自蔓延法制备铬铁合金,采用XRD技术对铬铁合金进行表征。研究结果表明:通过热力学计算,反应一经引发能够自我维持进行,加入硝酸钠作发热剂来补充热量,可以使铬铁合金熔体与熔渣更好地分离;制得的合金主要由Cr-Fe,Al2O3和Na2O等相组成。铬铁合金中铬的质量分数≥60%,相应的铁的质量分数≤35%,熔体中的熔渣(Al2O3和Na2O等)质量分数≤5%。     

Dynamic mass variation and multiphase interaction among steel,slag, lining refractory and nonmetallic inclusions: Laboratory experiments and mathematical prediction

The mass transfer among the multiphase interactions among the steel, slag, lining refractory, and nonmetallic inclusions during the refining process of a bearing steel was studied using laboratory experiments and numerical kinetic prediction. Experiments on the system with and without the slag phase were carried out to evaluate the influence of the refractory and the slag on the mass transfer. A mathematical model coupled the ion and molecule coexistence theory, coupled-reaction model, and the surface renewal theory was established to predict the dy-namic mass transfer and composition transformation of the steel, the slag, and nonmetallic inclusions in the steel. During the refining process, Al2O3 inclusions transformed into MgO inclusions owing to the mass transfer of [Mg] at the steel/refractory interface and (MgO) at the slag/re-fractory interface. Most of the aluminum involved in the transport entered the slag and a small part of the aluminum transferred to lining re-fractory, forming the Al2O3 or MgO·Al2O3. The slag had a significant acceleration effect on the mass transfer. The mass transfer rate (or the re-action rate) of the system with the slag was approximately 5 times larger than that of the system without the slag. In the first 20 min of the re-fining, rates of magnesium mass transfer at the steel/inclusion interface, steel/refractory interface, and steel/slag interface were x, 1.1x, and 2.2x, respectively. The composition transformation of inclusions and the mass transfer of magnesium and aluminum in the steel were predicted with an acceptable accuracy using the established kinetic model.     

煤粉-菱镁石混合喷吹对安钢高炉操作的影响

对安钢7号高炉的造渣制度进行了分析,提出从风口添加含MgO物料是改善炉渣性能的有效途径.在安钢7号高炉进行了添加轻烧菱镁石的煤粉喷吹工业试验.结果表明:风口喷煤中添加轻烧菱镁石可以有效地解决w(Al2O3)升高对炉渣冶金性能和高炉冶炼的影响,有利于优化高炉生产指标.对安钢7号高炉,煤粉中添加轻烧菱镁石的适宜比例为3%;炉渣中w(MgO)/w(Al2O3)为0.60～0.65时,高炉铁水物理热明显改善、硫的分配系数有所提高.在实施混合喷吹措施时,应适当调整高炉的热制度、造渣制度、焦炭负荷,控制适宜的高炉"炉缸煤气热量的平衡点"等参数.     

全电子系炉渣热力学在BaO基脱磷渣系中的应用

论述应用电子系炉渣热力学，推导出了磷在渣钢分配比的表示式ＬＰ＝ＫＰｆ［Ｐ］ｐｏ２γ（Ｐ）／ψ（Ｐ），并据此讨论了温度Ｔ，脱磷反应平衡常数ＫＰ，氧分压ｐｏ２，磷在熔渣中的原子活度系数ψ（Ｐ）和磷在钢中的原子活度系数ｆ［Ｐ］对脱磷的影响，得出了实验基本一致的结果。     

转炉铁水预处理脱磷的基础理论分析

通过对转炉铁水预处理脱磷过程中选择性氧化的热力学和动力学分析,并结合首钢京唐公司300 t脱磷转炉的生产数据,研究熔池中铁、硅、锰、碳、磷的氧化过程,讨论影响磷在渣铁间分配比以及脱磷速率的主要因素.研究表明,将转炉铁水预处理温度控制在较低范围内（1 300～1 350 ℃）,选择具有合适碱度（1.7～2.5）和成渣快的造渣工艺,并结合高的底吹搅拌强度（≥0.2 Nm3/(t·min)）,这是实现脱磷保碳、提高脱磷速率、加快生产节奏的有效途径.     

高炉炉缸三维稳态出铁模型

根据热流体力学原理和计算流体力学热焓-多孔介质方法,建立了包含铁水凝固相变的高炉炉缸三维稳态出铁数值计算模型.计算中采用等效对流换热系数的方法对炉缸、炉底的冷却条件进行了合理转化.结合实际高炉炉缸对其流场、温度场和渣皮形貌进行了数值计算和分析.给出了不同高炉容积利用系数和冷却条件下的炉缸铁水流动特征和结渣情况数据,可为现场操作提供技术参考.     

准东煤掺烧油页岩后矿物质的转化迁移研究

研究准东煤和油页岩混合燃料在100 MW锅炉燃烧过程中的矿物质演变规律,解决火力发电厂大比例和大规模掺烧准东煤引起的沾污和结渣问题。对现场试验收集的入炉煤、飞灰和炉渣样品进行化学分步萃取、XRD、灰成分等分析。结果表明,在100 MW机组锅炉燃用准东煤掺混15%油页岩的混合燃料,油页岩灰分中镶嵌或者包裹的可燃物燃烧后,炉渣将形成多孔和酥松形态,从炉渣的结构方面缓解准东煤引起的炉膛结渣问题。掺混15%油页岩后,燃烧过程中碱金属和碱土金属基本不挥发,炉渣中Na_2O、MgO、CaO和SO_3的含量较准东煤分别降低了2.07%、3.42%、15.08%和10.5%;飞灰中Na_2O、MgO、CaO和SO_3的含量也较准东煤明显下降。同时炉渣和飞灰中的钠主要为钠长石,钾在掺烧前后都以KAl_2(Si_3Al)O_(10)(OH)_2存在。在炉膛中碱土金属的碳酸盐和硫酸盐分解后,大部分转化为钙黄长石。油页岩通过降低碱金属和碱土金属含量及改变其存在形态,解决了准东煤引起的炉膛结渣和受热面沾污的问题。     

转炉渣中磷的微观结构行为

为了设计合理的转炉渣成分以达到满意的脱磷效果，根据转炉炼钢过程熔渣成分的变化范围，采用拉曼光谱测定了CaO-SiO₂-Fe_○xO-P₂O₅系熔渣的熔体结构，并解析了磷在熔渣中的存在形式及转变行为.结果表明，熔渣中磷主要以桥氧数为0，1，2的磷氧四面体结构单元存在，并可进入硅氧四面体和铁氧四面体形成Si—O—P和Fe—O—P键.随着渣中CaO和FeO总量的增加，熔渣中聚合程度较低的Q⁰(P)，Q¹(P)和Q⁰(Si)，Q¹(Si)摩尔分数升高，而聚合程度较高的Q²(P)和Q²(Si)，Q³(Si)摩尔分数降低.另外，Fe—O—P和Si—O—P键的含量也逐渐降低，当碱度为2.83时，Si—O—P和Fe—O—P键消失.     

磷在CaO-SiO2-FetO-P2O5与2CaO·SiO2颗粒界面间的传质行为

对2CaO·SiO2(C2S)颗粒与C2S饱和的CaO-SiO2-FetO-P2O5渣在1 500℃下的反应进行了实验研究,采用SEM/EDS观测了C2S颗粒与熔渣界面之间不同位置各成分的含量变化,讨论了磷在C2S颗粒与熔渣界面间的传质行为。结果表明,在C2S颗粒与其周围熔渣形成的固液两相区内生成了n·2CaO·SiO2-3CaO·P2O5(nC2S-C3P)固溶体。随着反应时间的延长,nC2SC3P固溶体层越来越厚,在指向C2S颗粒内部方向,nC2S-C3P固溶体层中的磷含量逐渐降低。了解磷在C2S与熔渣界面间的传质行为,有助于CaO-SiO2-FetO-P2O5中nC2S-C3P固溶体形成机理的研究。     

Na_2O-SiO_2渣系的作用浓度计算模型

根据炉渣结构的共存理论,Na_2O—SiO_2相图和有关的热力学数据,推导了本渣系的作用浓度计算模型。利用此模型计算得的N_(Na_2O)和N_(SiO_2)与实测的~aNa_2O和文献上的~aSiO_2符合甚好。由此证明炉渣结构的共存理论对本渣系也是适用的。     

Effects of additives on the phase transformation,occurrence state,and the interface of the Ti component in Ti-bearing blast furnace slag

The influences of additives on the phase transformation, occurrence state, and the interface of the Ti component in Ti-bearing blast furnace slag were investigated. After oxidation, most of the Ti component in the slag was enriched into the perovskite phase, which served as the Ti-rich phase during the crystallization process. The phase transformation, occurrence state, and the interface of the Ti component were observed to be affected by the addition of different types of agents. During the oxidation process, titanaugite and Ti-rich diopside phases gradually transformed into non-Ti phases (anorthite: CaMgSi₂O₆ and CaAl₂Si₂O₈) in the form of dendrites or columns, which were observed to be distributed at the surface of the perovskite phase. Several more cracks appeared along the grain boundaries of the perovskite phase after the addition of P₂O₅, facilitating the liberation of the perovskite phase. Composite additives combining both an acid and a base, such as CaO + CaF₂ or P₂O₅ + CaF₂, were used. We observed that the disadvantages of using single additives were successfully overcome.     

CaC_2-CaF_2渣系对铁水脱砷的研究

采用CaC_2-CaF_2渣系作为脱砷剂,在实验室范围内进行了铁水还原脱砷的研究。 实验是在钼丝炉内,Ar气氛下,石墨坩埚中进行的。研究了温度、渣成份、渣量、初砷含量和铁水含si量等因素对脱神效率的影响。 通过热力学分析说明了在钢铁溶液中,只能还原脱砷而不能氧化脱砷;用CaO-CaF_2、CaC_2-CaF_2渣系对铁水同时脱硫脱磷脱砷是不可能的。     

Effect of slag composition on the cleanliness of 28MnCr5 gear steel in the refining processes

The equilibrium reaction between CaO—Al₂O₃—SiO₂—MgO slag and 28MnCr5 molten steel was calculated to obtain the suitable slag composition which is effective for decreasing the oxygen content in molten steel. The dissolved oxygen content [O] in molten steel under different top slag conditions was calculated using a thermodynamic model and was measured using an electromotive force method in slag–steel equilibrium experiments at 1873 K. The relations among [O], the total oxygen content (T.O), and the composition of the slag were investigated. The experimental results show that both [O] and T.O decrease with decreasing SiO₂ content of the slag and exhibit different trends with the changes in the CaO/Al₂O₃ mass ratio of the slag. Increasing the CaO/Al₂O₃ mass ratio results in a decrease in [O] and an increase in T.O. To ensure that T.O ≤ 20 ppm and [O] ≤ 10 ppm, the SiO₂ content should be controlled to <5wt%, and the CaO/Al₂O₃ mass ratio should be in the range from 1.2 to 1.6.     

超低碳钢顶渣氧化性对钢液洁净度的影响

为探究降低顶渣氧化性对改善超低碳钢钢液洁净度的影响,在转炉终点至中间包过程中,在多位置取炉渣和钢水试样,分别进行炉渣氧化性、钢液成分和夹杂物分析.实验结果表明:转炉出钢后通过对顶渣改质,渣中T.Fe由转炉终点的19.18％降至RH进站时的4.68％,顶渣氧化性降低明显.渣中T.Fe降低导致钢中[O]的降低,T.Fe较低的炉次平均吹氧量较大,使得铝脱氧前钢中[O]较高.RH结束渣T.Fe与夹杂物数量呈线性关系,T.Fe越低夹杂物数量越少,同时RH结束后夹杂物数量与铝脱氧前钢中[O]无必然关系.顶渣(CaO)/(Al2O3)会影响其吸收Al2O3夹杂物的能力,(CaO)/(Al2 O3)控制不合理的炉次,其夹杂物数量也较多.通过降低顶渣氧化性,热轧板卷缺陷率得到明显降低.     

铁液碱性熔渣脱砷

中国储藏有大量的含砷铁矿。由于目前国内外钢铁生产流程中没有成熟的脱砷工艺。因此,开展钢铁脱砷技术研究对充分利用含砷铁矿资源,提高钢纯净度等有着迫切的现实意义。通过电阻炉上一系列实验研究,结果表明：CaO碱性熔渣对铁水可取得较好的脱砷效果;脱砷炉渣的X射线衍射分析表明CaO基碱性熔渣对铁液脱砷的产物是Ca3As2,脱砷反应为还原反应;脱砷的热力学条件是：W本系的氧位越低,铁注中硫含量越低、脱砷温度越高,熔渣碱度越高,脱砷效果越好。