Phase Equilibrium for the CaO-SiO₂-FeO-P₂O₅ System at 1673K for Dephosphorization With Multi Phase Flux

Development of the efficient hot metal dephosphorization processes during steelmaking process is one of the most essential topics for the production of high grade clean steels. Since the formation of solid solution composed of tricalcium phosphate and dicalcium silicate could obtain a considerable mass transfer of phosphorus from liquid slag into solid phase during hot metal dephosphorization, itcould obviously sustain a high phosphatecapacityof theliquid slag without huge consumption of lime or addition of fluxes, such as fluorite. The above outlines are the main idea of multi phase flux dephosphorization. For the last few decades, many studies have been done towards the scientific principles and the commercial utilization of this technique. However, the reaction mechanism by using multi phase fluxes remains unclear even by now due tolack of evidence. Based on those previous works, providing a reliable and available phase diagram for the fundamental understanding of the reaction mechanism of multi phase flux dephosphorization has become the main purpose of present research. As well known, the CaO-SiO2-FeO-P2O5 slag is the main component of current steelmaking process. Hence the CaO-SiO2-FeO-P2O5 system at equilibrium has been studied at 1673K with low oxygen partial pressure. The solid phase coexisting with liquid flux is approved to be the solid solution composed of CaO, SiO2 and P2O5. Phosphorus distributes mainly in solid solution rather than liquid phase.     

Effect of change of slag phase on dephosphorization of ��double- slag+slag- remaining�� steelmaking technology

The microstructure and phase constituent of dephosphorization slag of ??double- slag+slag- remaining?? steelmaking technology were observed and analyzed by SEM, part of the slag were heat treatment, and the effect of the change of slag phase on dephosphorization was studied. The research results show that the phase of dephosphorization slag A1-A3 with high dephosphorization rate are composed of calcium ferrite, complex liquid silicate phase (Ca3TiFeSi3O12, Ca54MgAl2Si16O9) and 2CaO??SiO2(C2S) solid phase solution with calcium phosphate (2Ca2SiO4??Ca3(PO4)2, Ca7(PO)4(SiO4)2), the main phase of dephosphorization slag A4 with low dephosphorization rate is liquid phase, the main phases of dephosphorization slag A5 are MnFe2O4, MnV2O4, Ca12Al14O33, little phosphorus rich calcium silicate solid phase is found in both dephosphorization slag A4 and A5; the phase of dephosphorization slag A3 changes little before and after heat treatment, but the phase of dephosphorization slag A4 changes greatly after heat treatment, which changing to liquid phase and white branches like RO phase; the dephosphorization slag of ??double- slag+slag- remaining?? steelmaking technology contain many un- dissolved CaO, but little is found in decarburization slag, the formation of C2S solid phase in dephosphorization slag plays an important role to accelerate the dephosphorization reaction.     

转炉脱磷渣物相结构对脱磷的影响

通过采用热力学软件 Factsage 6.4、SEM、EDS、XRD,并结合红外和拉曼实验手段分析研究了一次倒渣和终点炉渣物相结构.结果表明：一倒渣和终渣的黏度均随着温度的升高而降低.温度相同时,一倒渣的黏度较高,但熔点低于终渣.低温时形成的液相较多,更有利于脱磷反应的进行.炉渣 Si、Ca、P 元素富集的区域,形成的矿相主要为2CaO?SiO2-3CaO?P2 O5固溶体相,对脱磷较为有利;而 Fe、Mn、Mg 和 O 元素富集的区域,形成的物相主要为铁氧化物和RO相,炉渣脱磷能力脱磷较差.红外和拉曼分析结果表明：一倒渣和终渣都形成SiO4四面体单元,一倒渣主要以Si-O-Si键为主,而终渣主要以P-O-P键为主.硅酸盐网状结构单元结构越多,对脱磷越有利.     

不锈钢不同脱磷渣系性能的测试和分析

对不锈钢4种主要脱磷渣系的熔化和失重性能进行了测试和分析，结果得出,BaO-BaCl2渣更适合于低温脱磷，BaO-CaO复合渣应作为不锈钢脱磷的主要渣系。     

磷在多相脱磷转炉渣中的分布

 为了研究碱度、TFe含量对炉渣物相以及磷在不同物相中分布的影响,对3种不同成分脱磷转炉渣的微观结构进行形貌和成分分析对比。当炉渣中FeO含量较高、碱度中等时,炉渣在冶炼过程高温状态下处于液态,在取样空冷条件下析出FeO含量高的枝状晶体结构和CaO-SiO₂-(FeO)基体相,基体相中P₂O₅质量分数约为6.5%。当炉渣中FeO含量较低、碱度较低时,炉渣在冶炼过程高温状态下处于液态,在取样空冷条件下析出相和炉渣总成分相差不大。当炉渣的碱度中等、TFe含量控制合适的情况下,炉渣在冶炼过程高温状态下处于固液共存区域,形成液相和2CaO·SiO₂-3CaO·P₂O₅固溶体,固溶体中P₂O₅质量分数为30%～40%。当炉渣处于C₂S和液相渣的共存区域时,2CaO·SiO₂-3CaO·P₂O₅固溶体的析出使得炉渣液相中P₂O₅活度降低,使得铁水中磷向液相渣中传递,脱磷反应程度更高,脱磷效果较好。     

低碳铝镇静钢转炉炼钢低温脱磷工艺

对转炉脱磷进行热力学与动力学分析,介绍了低碳铝镇静钢转炉低温脱磷生产工艺,对该生产工艺过程参数进行了统计分析,并对过程炉渣进行了SEM、EDS、XRD分析.结果表明:通过降低平均出钢温度至1 617 ℃,碱度控制在2.4～3.0,TFe质量分数控制在12％～15％,转炉后期脱磷效率大大加强,冶炼后期调渣后TSC阶段渣钢...     

转炉熔渣气化脱磷时磷迁移规律研究

气化脱磷能够有效地去除熔渣中部分P2O5,扩大其磷容量.在实验室进行了焦炭还原转炉渣气化脱磷热态试验,热力学计算研究结果表明,在1540℃下焦炭会优先还原P2 O5,还原产物为可能的P2,而P2 O5的实际还原率与理论计算值基本一致.通过SEM-EDS对还原前后炉渣形貌进行分析,转炉终渣主要由C2 S相、RO相、钙铁橄...     

转炉炼钢渣磷元素的富集及影响因素

为了研究炼钢过程中出现的低碳低磷钢冶炼困难以及转炉终点补吹回磷的现象,以转炉炼钢渣相为研究对象,利用扫描电镜测量分析了渣相的微观组成与C_2S(2CaO·SiO_2)富磷相在渣中的比例。研究结果表明,转炉脱磷由"氧化脱磷"+"固磷"两个环节组成;渣中SiO_2通过影响C_2S量的多少对脱磷产生影响,渣中FeO质量分数高,会分解C_2S相进而导致钢水回磷;温度高导致固磷相分解,研究结果表明,通过控制转炉终渣固磷相熔点高于钢水温度,可实现低温出钢。     

钢液二次精炼用CaO基熔剂的脱磷能力

根据CaO基熔渣和钢液之间在1853K脱磷平衡实验结果，利用CaO-Fe2O3-CaF2和CaO-BaO-Fe2O3-CaF2熔剂对钢液进行二次精炼脱磷试验，试验发现，采用优化组成的CaO基熔剂，可得到大于90%的脱磷率，能将钢液磷含量从0.05%降低到0.005%以下。     

CaO-SiO_2-FeO-P_2O_5渣系脱磷影响因素的研究

为了提高转炉渣中CaO的利用率,降低转炉渣的碱度,通过试验研究了CaO粒度、粒状CaO的加入比例、温度和保温时间对含磷富集相的影响。结果表明,适当增大CaO的粒度有利于2CaO·SiO2-3CaO·P2O5固溶体的形成;当渣中粒状CaO的含量较低时,增加粒状CaO的加入比例,可促进渣中大颗粒固溶体的形成并减少渣中磷的含量,但当粒状CaO的含量较高时,2CaO·SiO2-3CaO·P2O5固溶体生成量减少;适当提高温度有利于脱磷反应的进行;随反应时间的延长,2CaO·SiO2-3CaO·P2O5固溶体的粒径增大,而且固溶体中磷的含量也不断增加。     

Dephosphorization and Desulphurization Pretreatment of Liquid Iron using CaF2‐free Fluxes containing BOF Slags

In order to examine the possibility of recycling BOF slags as dephosphorization and desulphurization fluxes, experiments were performed in a system with liquid iron and artificially prepared fluxes comprising BOF slags, lime and/or sinter ore in a Al₂O₃ crucible at 1623 and 1673K. The phosphorus and sulphur content in liquid iron were expressed as a function of reaction time in the form of exponential decay of first order. CaF₂‐free fluxes comprising BOF slags, lime and/or sinter ore showed very high capacities of dephosphorization and desulphurization, which means that BOF slags could largely be recycled in the hot metal pretreatment processes.     

低氧分压条件下CaO-SiO_2-P_2O_5(10%)-FeO体系热力学性质的研究

以促进2CaO·SiO_2-3CaO·P_2O_5固溶体生成的非均相脱磷工艺被视为未来实现转炉少渣冶炼的重要手段,但目前相关渣系热力学性质的研究较少,不能为合理解释非均相渣脱磷的机理提供理论依据.为此,本文利用FactSage热力学软件绘制了低氧分压(1mPa)条件下CaO-SiO_2-P_2O_5(10%)-FeO体系及其子体系的热力学相图,分析了不同温度下相平衡关系及液相线的变化规律.研究结果表明:升高温度可使体系中液相区及Ca_3(PO_4)_2初晶区的范围扩大,但会导致α'-Ca_2SiO_4的初晶区缩小以及Ca_2Fe_2O_5等物相的消失;降低氧分压可使体系的液相区缩小,并向高FeO的方向收缩;CaO-SiO_2-P_2O_5(10%)-FeO体系中存在较大的α'-Ca_2SiO_4与Ca_3(PO_4)_2共存区,尤其是α'-Ca_2SiO_4,Ca_3(PO_4)_2与Ca_2Fe_2O_5的三相共存区可极大地促进2CaO·SiO_2-3CaO·P_2O_5固溶体的生成.     

基于高FeO转炉渣的钢液脱磷行为

 为了研究在转炉冶炼中高FeO转炉渣条件下钢液的脱磷行为,采用双联法在某钢厂300 t脱磷转炉上展开高氧化性转炉渣脱磷工业试验。通过理论分析并结合XRD、拉曼光谱分析等手段,研究了脱磷温度、转炉渣矿相结构以及终渣成分等因素对高FeO转炉渣条件下钢液的脱磷的影响。通过热力学公式计算发现,脱磷转炉最佳理论脱磷温度约为1 675 K。对比分析了不同脱磷效果的转炉渣的矿相结构,结果表明,2CaO·SiO₂和3CaO·P₂O₅矿相结构有利于脱磷反应的进行,3CaO·SiO₂对脱磷效果的影响不明显;Si—O—Si键和[FeO₄]键特征峰面积越大,Q0和Q2单元特征峰面积越小,脱磷效果越好。最后研究了脱磷炉钢液脱磷率≥60%时终渣成分的最佳控制工艺参数,碱度R为1.05～1.30,w([FeO])为33%～37%,w([MgO])≤3.0%,w([MnO])为4.3%～5.4%。本研究可以为钢铁企业采用双联法开发超低磷钢提供理论依据和技术指导。     

转炉脱磷工艺的最新进展

转炉脱磷工艺利用了转炉容积大的特点,可以实现转炉前期快速高效低碱度脱磷.脱碳渣的循环利用降低了石灰等辅料消耗和渣量.在低温低碱度转炉脱磷的条件下,低温在热力学上有利于脱磷,但温度过低会使渣过于粘稠而影响动力学条件并使倒渣困难;适当提高碱度,脱磷效果较好.随着渣中氧化铁含量的上升,脱磷效果先上升后下降.转炉脱磷渣中固液两...     

Utilization of Multiphase Fluxes for the Dephosphorization of Hot Metal

Although steelmaking slags have been usually treated and studied as homogeneous liquids, they are actually mixtures of a liquid and solids in practical processes. CaO‐based refining flux that does not contain fluxing agents such as CaF₂ inevitably forms a heterogeneous slag in normal cases, and hence, it is defined as a “multiphase flux.” Efficient utilization of this type of flux would decrease the consumption of resources and the emission of CO₂, and thus, would reduce the load on the environment. Metallurgical studies on multiphase fluxes are limited, however, the physical chemistry and reaction kinetics of the same are important for the development of advanced refining processes. The reaction mechanism of dephosphorization using a multiphase flux at hot metal temperatures was investigated in this study. The reaction of a P₂O₅‐containing slag with solid CaO was studied by immersing a CaO disc in the slag. A CaO‐FeO layer was formed near the interface, and a solid solution of Ca₂SiO₄‐Ca₃P₂O₈ was observed in this layer. The Fe‐P‐Si alloy reacted with calcium ferrites at 1673 K, and the samples were analysed by XMA. The same solid solution (Ca₂SiO₄‐Ca₃P₂O₈) was observed near the slag‐metal interface, which suggests that the phosphorus removed from the metal gets concentrated in the solid phase. The experimental results were reproduced with a kinetic simulation model. The simulation program was also applied to the reaction of the CaO‐FeO droplet in a hot‐metal bath.     

CaO-SiO2-Al2O3-Fe2O3渣系脱磷行为

利用Factsage软件计算了Al2O3含量对CaO-SiO2-Al2O3-Fe2O3四元渣系熔点和黏度的影响,并通过实验研究了在1 400℃时,CaO-SiO2-Al2O3-Fe2O3四元渣系对高磷铁水脱磷行为的影响.结果表明:渣中Al2O3的质量分数在3％～6％之间时,随着A12O3含量的增加,渣系的熔化温度迅速降低,进一步增加渣中的A12O3含量,渣系的熔化温度逐渐增加;Al2O3对CaO-SiO2-Al2O3-Fe2O3渣系的黏度影响不大;渣中Al2O3的质量分数在3％～6％之间变化时,渣系脱磷能力变化不是很大,脱磷率维持在91％左右,进一步增加渣系中A12O3的量,脱磷率逐渐下降;Al2O3对脱磷率产生影响可能是其改变了炉渣中液相所占比例,进而影响磷从铁水中向液相渣的传质过程.     

液渣成分和硅酸二钙颗粒含量对铁水预处理非均相脱磷剂脱磷能力的影响简

 高磷铁水预处理脱磷的难题是脱磷剂用量太大、温降太多，急需研究脱磷能力强的脱磷剂。含有固体颗粒和液渣的非均相脱磷剂比仅含液渣的均相脱磷剂的脱磷能力强很多。为此，针对磷的质量分数为0. 5%的高磷铁水，应用FactSageTM热力学软件优选出脱磷能力强的3种液渣，添加不同数量的硅酸二钙颗粒配制非均相脱磷剂试样，脱磷剂和熔铁在1560℃下反应6h，测定熔铁中的平衡磷含量，用以评价其脱磷能力，然后在1400℃下进行了铁水脱磷预处理试验。研究结果表明，随着硅酸二钙颗粒含量的增加，非均相脱磷剂的脱磷能力明显改善；采用非均相脱磷剂有助于减少渣量和控制反应器内衬的侵蚀；采用非均相脱磷剂对铁水脱磷，仍然需要控制较高的渣铁界面FetO浓度。     

Kinetic Model of Hot Metal Dephosphorization by Liquid and Solid Coexisting Slags

In most cases, hot metal dephosphorization slag is saturated with dicalcium silicate, and the partition ratio of phosphorus between dicalcium silicate and liquid slag is high. These results indicate the important role of solid dicalcium silicate in dephosphorization. In order to understand the reaction kinetics and obtain an optimum treatment method, it is very important to know the influence of solid phases in the slag. In this study, a new reaction model for hot metal dephosphorization considering the effects of dicalcium silicate and dissolution rate of lime is proposed. In the new dephosphorization model, in addition to the reaction rate between liquid slag and metal, the partition between dicalcium silicate and liquid slag and the dissolution rate of lime are also considered. The dephosphorization reaction of hot metal by the liquid slag phase was calculated by using the coupled reaction model. The calculated results demonstrated the importance of dicalcium silicate in dephosphorization. Also, in some cases, the dissolution rate of lime affected the dephosphorization behaviour.     

CaO-SiO2-Fe2O3-MnO2-MgO-P2O5系熔剂对钢液脱磷、回磷的实验研究

在１８５３Ｋ的温度下,利用ＣａＯ－ＳｉＯ２－ＦｅＯ３－ＭｎＯ２－ＭｇＯ－Ｐ２Ｏ５系熔剂,对钢液进行脱磷、回磷实验,研究熔剂碱度ＣａＯ／ＳｉＯ２和氧化性（Ｆｅ２Ｏ３＋ＭｎＯ２）对钢液脱磷、回磷的影响,研究得出,防止钢液回磷的先决条件是：控制熔剂碱度和氧化性大于其临界值。实验发现,用适量ＢａＯ取代ＣａＯ基熔剂中的ＣａＯ,可有效控制钢液的回磷。     

环保型高磷铁水预处理脱磷剂的试验研究

为开发高效环保的高磷铁水预脱磷剂,利用FactsageTM软件绘制了Fe3O4-CaO-B2O3和Fe3O4-CaO-K2O三元相图,根据相图确定出B2O3系和K2O系脱磷剂成分的质量分数,然后在实验室进行脱磷试验,并与以CaF2为助熔剂的高磷铁水预脱磷试验结果进行了比较。结果表明:B2O3能够完全替代CaF2作为助熔剂进行高磷铁水的脱磷预处理,控制w(P)<0.1%,此时w(B2O3)/w(CaO)=0.16,用此种脱磷剂进行脱磷时,化渣良好且不产生泡沫渣,脱磷率也最高。而K2O系脱磷剂的脱磷效果较差。