The kinetics of dephosphorization of carbon-saturated iron using an oxidizing slag

The kinetics of dephosphorization of carbon-saturated iron by oxidizing slags were studied at 1330 °C. Nine slag compositions were investigated in the systems CaO-Fe₂O₃-SiO₂-CaF₂ and CaO-Fe₂O₃-SiO₂-CaCl₂. Increasing Fe₂O₃ up to 50 pct was found to increase the rate and extent of dephosphorization, whereas further increases were found to decrease the rate and extent of dephosphorization. This was explained in terms of two competing effects on the driving force, where increased levels of iron oxide increase the oxygen potential for dephosphorization, hence the driving force, but simultaneously dilute the basic components in the slag, lowering the driving force for dephosphorization. CaF₂ and CaCl₂ were found to decrease the rate and extent of dephosphorization at levels higher than 12 pct. The rate of dephosphorization was found to be first order with respect to phosphorous in the metal and was controlled by mass transport in the slag. The oxygen potential at the slag/metal interface was controlled by the FeO activity in the slag. When the kinetic results were analyzed to take account of different driving forces, Fe₂O₃, CaF₂ and CaCl₂ were all found to increase the mass transfer coefficient of phosphorous in the slag, and a quantitative relationship has been demonstrated between these mass transfer coefficients and the slag viscosity for each system studied.     

Dynamics of the hot metal dephosphorization with Na2O slags

Dephosphorization reaction of hot metal by Na₂CO₃ has been studied experimentally to determine the reaction mechanism and thermodynamics. Most of the experiments were carried out at 1300 °C using Fe-C_sat.-Si-P-S alloys. The results indicate that the CO₂ gas released from Na₂CO₃ is important in the dephosphorization reaction as an oxidizer and increasing mass transfer by stirring the slag and metal. As the initial Si content in hot metal is increased, the degree of dephosphorization decreases significantly and the rephosphorization takes place earlier. The primary reason for the rephosphorization is that the activity of PO_2.5 increases in the slag because of the evaporation of Na₂O from the slag. The loss of Na₂O increases the activity coefficient of PO_2.5 and decreases the slag volume. At the later stage of Na₂CO₃ treatment, the reactions reach equilibrium with respect to phosphorus and sulfur, and the oxygen potential,P _o2, at the slag-metal interface is determined by the C-CO equilibrium (a _c=1 and 1 atm CO). The presence of sulfur in the metal increases the rate of the dephosphorization because of the electrochemical nature of the reaction; sulfur transfer to the slag accepts the electrons from phosphorus transfer.     

Simulation of Steel Refining Process in Converter

Steel refining is a complex phenomenon which depends on numerous variables, so, a kinetic approach is necessary for precise understanding of the refining process. In this study, based on a previously proposed model for hot metal dephosphorization, a new simulation model for the steel refining process in BOF is presented. In most cases, steelmaking slag is saturated with dicalcium‐silicate (C₂S) and it is well known that C₂S forms solid solution with tricalcium‐phosphate (C₃P) in a wide composition range and the partition ratio of phosphorus between C₂S and liquid slag is large. On the other hand, C₂S formed around the lime surface is known as a barrier to lime dissolution into liquid slag. In this simulation model not only the effect of solid phase in slag is considered but also the effects of temperature dependence of variables as well as top and bottom blowing and scrap melting are taken into account. The calculation results are compared with industrial data and the good agreement between experimental and simulation results evidence the validity of this kinetic approach to steel refining process in BOF. Moreover, by using this model the influence of various parameters on the reaction efficiency is discussed.     

Studies on the removal of phosphorus and sulfur from Fe-C and Fe-C-Mn melts at 1350°C

Laboratory studies have been performed on simultaneous dephosphorization and desulfurization of Si-free Fe-4.5 % C melts with [P]_o = 0.11 wt.% and [S]_o = 0.04 wt.% in MF induction furnaces at 1 350°C. In these investigations, CaO- or Na₂CO₃-based fluxes were used and the techniques of powder injection or single top slag addition were applied. The following results have been obtained:

• – The effectiveness of lime and soda-based fluxes with regard to dephosphorization is practically the same. But a lower sulfur level is attained when Na₂CO₃-based fluxes are used.
• – In the injection experiments, efficiencies of η_P = 80% for dephosphorization and η_s = 90% for desulfurization are easily reached at a powder consumption of 50 to 60 g/kg. But a further increase of the η values requires a remarkable increase in the amount of injected powder. Top slag addition instead of powder injection is less effective, in general.
• – Apparent rate constants k_[P] and k_[S] from 0.05 to 0.3 min^?1 have been determined in the initial stage of injection depending on the relative amount of injected flux. In the top slag experiments, the k_[P] and k_[S] values were practically constant at a level of 0.1 min^?1.

Furthermore, dephosphorization of molten Fe-C-Mn alloys at 1 350°C has been studied at variable Mn content. It is predicted from thermodynamic data and confirmed by experiments that dephosphorization lessens with increasing Mn content in the range from 0 to 15 wt.%.     

Dephosphorization of complexly alloyed nickel melts under vacuum induction melting conditions: II. Experimental results and their interpretation

The activities of the components of BaO-BaF₂-BaCl₂-NiO and CaO-CaF₂-CaCl₂-NiO slags systems, which were considered as a phase having a collective electron system, are calculated, and it is shown that the barium, calcium, and oxygen activities at 1600°C are maximal in the BaO- and CaO-based systems depending on the main oxide content. The dephosphorization of three types of nickel-based melts by slags of 14 compositions in crucibles made of Al₂O₃, MgO, and MgO-Al₂O₃ (80-20 wt %) is experimentally studied, and the degree of dephosphorization is shown to depend on the phosphorus content in a metal, the slag composition, and the crucible material (degree of dephosphorization is maximal in Al₂O₃ crucibles). The forming slag is assimilated by Al₂O₃ and MgO-Al₂O₃ ceramics with a porosity of about 30%. If 4–10 wt % NiO are present in a slag, the wettability of the Al₂O₃ ceramic is significantly higher than that of the MgO-based ceramic.     

Thermodynamics of chromium oxides in CaO-SiO2-CaF2 slag

The distribution ratio of chromium between a CaO-SiO₂-CaF₂ slag and liquid silver under the oxygen partial pressure used in practical hot-metal dephosphorization treatment was measured at 1623 K. The distribution ratio was minimal when the basicity index of a slag, wt pct CaO/wt pct SiO₂, was about 2. The redox equilibrium between CrO (Cr²⁺) and CrO_1.5 (Cr³⁺) in the slag was also measured as a function of slag composition. The calculated activity coefficient of CrO had a maximum value at wt pct CaO/wt pct SiO₂=2, whereas that of CrO_1.5 decreased monotonously with the increase in slag basicity.     

Thermodynamic Behaviors of Nb and P in Dephosphorization of Niobium-bearing Hot Metal with BaO-based Slag

The Bayan Obo iron ore contains valuable metallic elements such as niobium and rare earth elements. However, developing appropriate metallurgical processes to achieve effective dephosphorization of Nb-bearing hot metal meanwhile retaining Nb in the steel products remains a challenge. We carried out a thermodynamic study on dephosphorization of Nb bearing hot metal and investigated the effects of the initial [C] content and the dephosphorization temperature on oxidation behaviors of [Nb] and [P]. In particular, we focused on thermodynamic analysis of dephosphorization of Nb-bearing hot metal with highly basic BaO-based slag. The results showed that the highly basic BaO-based slag system is more suitable for dephosphorization under oxidative conditions, and increasing the [C] content favors dephosphorization of Nb-bearing hot metal without oxidizing [Nb]. Moreover, the values of equilibrium oxygen activity for oxidation reactions of [Nb] and [P] are increased as the dephosphorization temperature increases. Considering the hot metal containing 0.02% of [Nb] in Baotou Steel, thermodynamic calculations indicated that the content of [P] can be reduced to 0.02%–0.05% and [Nb] remains unoxidized when dephosphorization occurs at the cconditions of T=1573–1673 K, [C]=4.0%, [Nb]=0.02%, a_P2O5 =10⁻²⁴, a_Nb2O5 =10⁻¹⁰.     

Dephosphorization and desulfurization of molten Fe-Cr-C alloys

Thermodynamic calculation of phosphorus-chromium and sulfur-chromium relationships in molten Fe-Cr-P-C and Fe-Cr-S-C alloys at 0 to 18 wt. % Cr and 0 to 6 wt. % C. Experiments to prove the potentiality of dephosphorization and desulfurization of Fe-Cr alloys at 18 wt. % Cr and elevated carbon contents using highly basic FeO_n-CaO-CaF₂-BaF₂ slag.     

The composition and temperature dependence of the sulfide capacity of metallurgical slags

The concept of optical basicity and its applicability as a means of correlating the available data on the sulfide capacity of metallurgical slags has been reviewed. An excellent correlation based on very extensive data at 1500 °C, which was discussed in a previous paper, is combined with good correlations based on considerably less data at 1550 °C and 1650 °C to quantify the effect of temperature on the sulfide capacity of slags. The combined effects of slag composition and temperature have been expressed in the equation, logC _s = [(22690 – 54640A)/7] + 43.6A − 25.2. Use of this equation permits the calculation of the sulfide capacity of a slag at any temperature between 1400 °C and 1700 °C simply from a knowledge of its chemical composition, and can be employed for virtually any oxide slag of interest in the field of iron and steelmaking. This, in turn, permits calculation of the equilibrium distribution of sulfur between this slag and iron or steel, provided that the oxygen potential is known or can be calculated from the degree of deoxidation applied.     

Desiliconization and decarburization behavior of molten Fe-C-Si(-S) alloy with CO<Subscript>2</Subscript> and O<Subscript>2</Subscript>

One of the most important problems in the steelmaking process is an increase of the disposal slag mainly discharged from the dephosphorization process. In order to reduce the quantity of the disposal slag, the complete removal of silicon from molten pig iron is considered very effective before the dephosphorization in the pretreatment process. From this point of view, the desiliconization and the decarburization behavior of Fe-C-Si alloy with CO₂ and O₂ has been investigated in the present work. It is thermodynamically calculated that silicon should be oxidized in preference to carbon over 0.60 mass pct Si under the condition of s_SiO2=a _C=1 at 1573 K and is experimentally confirmed that silicon is only oxidized under the condition in actual. Even under the competitive region of desiliconizing and decarbonizing, under 0.60 mass pct Si, silicon is found to be oxidized down to about 0.1 mass pct Si in preference. The overall rate constants for the desiliconization and the decarburization are derived, and the value for the desiliconization is one order of magnitude larger than that for the decarburization. The influence of sulfur is also examined, and the retarding effect is not observed on the oxidation reactions.     

脱磷炉利用脱碳炉返回渣的试验

为了达到节能降耗的目的,脱磷炉采用回吃脱碳炉返回渣的工艺。主要研究了脱碳炉渣的熔化特性以及作为炉料在脱磷炉中的应用效果。结果表明,通过每炉次加入约3.5t的脱碳炉渣,可平均节约1.01t石灰,4.71kg/t钢铁料消耗,脱磷炉终点炉渣的岩相组成主要由硅酸二钙、RO相、玻璃相和少量的金属铁粒组成。加入返回渣后脱磷炉终点炉渣中硅酸二钙和铁酸二钙含量有所增加,玻璃相含量降低,炉渣碱度有所升高,脱磷炉终点钢水成分控制水平有所提高。由此表明,采用脱碳炉渣返回脱磷炉循环利用减少了石灰等原辅料和钢铁料消耗,同时达到了预期的脱磷效果。     

Effects of Mn ore on the Dephosphorization and Desulphurization in Hot Metal Pretreatment

In order to examine the possibility of utilizing Mn ore in the pretreatment process of liquid iron, experiments were carried out in a system with liquid iron and CaO‐SiO₂‐MgO‐Al₂O₃‐FeO slag with additives (Mn ore and Fe₂O₃+MnO₂) in a magnesia crucible at 1673K. When Mn ore was added to the pretreatment slag, decarburization, desiliconization, dephosphorization and desulphurization proceeded simultaneously with the reduction of Mn ore. The reduction rate of MnO and the Mn concentration in the melt increased with increasing initial Si content. The maximum dephosphorization was obtained when the additive consisted of 66.6 mass% Fe₂O₃ and 33.4 mass% MnO₂. The desulphurization ratio increased with increasing the relative amount of MnO₂ in the additives. The amount of additives comprising Fe₂O₃ and MnO₂ required for a targeted manganese content could be predicted using the mass balance. Effects of the additives on dephosphorization were also estimated.     

Dephosphorization of Mn-based alloys

The critical oxygen partial potential of dephosphorization in liquid Mn-base alloys under oxidizing or reducing conditions has been determined by thermodynamic analysis. Under oxidizing conditions, thermodynamic conditions to achieve dephosphorization and avoid manganese oxidizing were given. The results of thermodynamic analysis show that BaO-base slag can be an effective dephosphorization agent for Mn-base alloys. Under reducing conditions, the high degree of dephosphorization in Mn-base alloys can be obtained based on thermodynamic analysis. In experimental work, BaCO₃ was added to remove phosphorus from Mn–Fe–C melts. The time needed for equilibration of the dephosphorization reaction of Mn–Fe–C melts was determined at 1573, 1623 and 1673 K. The refining results were experienced as dephosphorization efficiency ≠_p = (%[P]₀ ? %[P])/%[P]₀. Moreover, the effect of the initial content of Si and C on ≠_p was investigated. ≠_p in the Mn–Fe–C melts was also given as a function of temperature. Dephosphorization reaction in Mn–Fe–C melts is of first order.     

大型复吹转炉造渣工艺工业试验

通过工业试验对迁钢210 t复吹转炉冶炼过程钢样成分、渣样成分和炉渣岩相进行分析,研究了两种造渣工艺(方案A和方案B)的成渣过程及脱磷状况。对比两种造渣工艺的工业试验效果表明高枪位的造渣工艺方案B优于方案A;转炉冶炼前期化渣速度快,冶炼前、中期脱磷率高12.6%;高熔点矿相少,炉渣流动性较好;成渣路线更加平稳;方案B较方案A石灰消耗少11.5 kg/t,Lp高5.42,转炉平均脱磷率高2.7%。     

脱磷转炉内成渣路线的理论研究

以CaO-SiO2-FeO三元渣系为基，利用正规溶液模型计算了不同碱度、炉渣组分对于脱磷转炉内磷分配比和终点磷含量的影响规律；同时，采用Factsage软件计算了不同脱磷渣系的液相线温度，考察了添加不同炉渣组元对于渣系液相线温度的影响规律。综合理论计算结果，得到脱磷转炉适宜的成渣路线为铁质成渣路线，脱磷初渣成分为15%CaO-44%SiO2-41%FeO，中期渣成分为53%CaO-25.5%SiO2-21.5%FeO,后期固磷渣成分为63.6%CaO-30.3%SiO2-6.1%FeO。可为脱磷转炉的生产操作提供参考。     

Double Slag Operation Dephosphorization in BOF for Producing Low Phosphorus Steel

A study on the production of low phosphorus steel by double slag operation in 210 t converter was carried out. A phosphorus content of less than 0.005% (mass percent) was obtained before tapping. About 80% phosphorus could be removed by the first slag after 5 min. High Fe³⁺ content and high basicity in the first slag were in favor of dephosphorization. On the other hand, Fe³⁺ content had less effect on dephosphorization during second slag treatment. In the second slag period, the fraction of dephosphorization increased with the increase of basicity up to a basicity of 6. Further increase of basicity of the second slag had very little effect on dephosphorization. The tapping temperature had great impact on dephosphorization. It was impossible to get phosphorus less that 0. 005% when the tapping temperature was higher than 1 943 K. The optimum operation conditions were suggested. On the basis of these conditions, the amount of the second slag and the effect of the remaining first slag were estimated.     

LF炉精炼渣用于铁水预处理脱磷剂的可行性分析

基于对铁水脱磷热力学条件及常用铁水脱磷剂组成的分析,对比LF炉精炼渣和脱磷剂的成分和理化性质,认为LF炉精炼渣经过部分处理和合理配料后,可以作为铁水预处理的脱磷剂使用;LF炉精炼渣可替代脱磷剂中的固定剂和部分助溶剂,应用于铁水预处理能够满足生产要求,减少造渣材料消耗和炉渣外排,达到清洁生产的目的。     

Lead solubility in FeO x -CaO-SiO2 slags at iron saturation

Experiments have been carried out to determine the equilibria between FeO _x -CaO-SiO₂ slag and lead metal in iron crucibles at temperatures ranging from 1473 to 1573 K. It has been found that the highest lead solubilities are observed in the silica-saturated iron silicate slags, while the lowest solubilities are observed in the CaO-saturated calcium ferrite slags. The activity coefficient of PbO varies from 0.15 to 3, depending on the slag composition. Changes in temperature do not have a significant impact on the activity coefficient. The activity of FeO and pct Fe³⁺/pct Fe²⁺ ratios have been determined as a function of slag composition. These new experimental data have been incorporated into an optimized thermodynamic slag model using the computer package FACT.     

Application of equilibrium investigations to operational practice of adjusting lowest phosphorus contents

Operational investigations of dephosphorization in BOF were carried out. By means of a controlled slag steering during the entire blowing time in order to adjust a good fluid slag with low P₂O₅ content, saturated both with lime and lime silikates, a good approach to equilibrium state can be achieved. The thus incurred high expenditure, however, must be opposed to an appropriate expense profit ratio.     

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.