Sulphide Capacities of CaO‐SiO2‐Al2O3‐MgO Slags

In Japanese steelworks, hot metal is now being produced by a scrap melting process. With this process, removals of sulphur is very much handicapped because of very high sulphur levels (0.04‐ to 0.09‐ pct by weight) and relatively low tapping temperatures (1623 to 1723 K). In order to overcome such handicaps, the authors explored on the respective phase diagrams. These explorations revealed that {CaO‐SiO₂‐Al₂O₃‐MgO} slags with Al₂O₃ contents of 30‐ to 35‐pct by weight would be good candidates as reagents for sulphur removal from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, sulphide capacities were determined through gas/slag equilibrium technique. The experimental results suggest that there would be, at least, a “window” to remove sulphur from high sulphur hot metal as relatively low temperatures.     

Thermodynamics of Phosphorus and Sulphur Removal during Basic Oxygen Steelmaking

Removal of impurity elements from hot metal is essential in basic oxygen steelmaking. Oxidation of phosphorus from hot metal has been studied by several authors since the early days of steelmaking. Influence of different parameters on the distribution of phosphorus, seen during the recent work of the authors, differs somewhat from that reported earlier. On the other hand, removal of sulphur during steelmaking has drawn much less attention. This may be due to the magnitude of desulphurisation in oxygen steelmaking being relatively low and desulphurisation during hot metal pre‐treatment or in the ladle furnace offering better commercial viability. Further, it is normally accepted that sulphur is removed to steelmaking slag in the form of sulphide only. However, recent investigations have indicated that a significant amount of sulphur removed during basic oxygen steelmaking can exist in the form of sulphate in the slag under oxidising conditions. The distribution of sulphur during steelmaking becomes more important in the event of carry‐over of sulphur‐rich blast‐furnace slag, which increases sulphur load in the BOF. The chemical nature of sulphur in this slag undergoes a gradual transition from sulphide to sulphate as the oxidative refining progresses.     

The Activities of FexO in {CaO‐SiO2‐Al2O3‐MgO‐FexO} Slags at 1723 K

In Japanese steelworks, hot metal is now produced by scrap melting process. With this process removal of sulphur is very much handicapped because of very high sulphur levels (0.04 to 0.09 pct by weight) and relatively low tapping temperatures (1623 to 1723 K). In order to overcome such disadvantages, the authors explored on the phase diagrams of {CaO‐SiO₂‐Al₂O₃‐MgO} slags, and this research revealed that those slags at 35 wt%‐Al₂O₃ would be good candidates as reagents for the removal of sulphur from high sulphur hot metal at relatively low temperatures. For better understanding of the thermodynamic properties of the candidate slags, in this study, activities of Fe_xO were determined by using solid‐state electrochemical cells incorporating MgO‐stabilized zirconia and Mo + MoO₂ reference electrode.     

Manganese Distribution between FeO‐MnO‐SiO2–CaO–MgO‐Al2O3 Slags and Molten Iron

Pretreatment of high manganese hot metal is suggested to produce hot metal suitable for further processing to steel in conventional LD converter and rich manganese slags satisfy the requirements for the production of silicomanganese alloys. Manganese distribution between slag and iron represents the efficiency of manganese oxidation from hot metal. The present study has been done to investigate the effect of temperature, slag basicity and composition of oxidizer mixture on the distribution coefficient of manganese between slag and iron. Ferrous oxide activity was determined in molten synthetic slag mixtures of FeO‐MnO‐SiO₂–CaO–MgO‐Al₂O₃. The investigated slags had chemical compositions similar to either oxidizer mixture or slags expected to result from the treatment of high manganese hot metal. The technique used to measure the ferrous oxide activity in the investigated slag systems was the well established one of gas‐slag‐metal equilibration in which molten slags contained in armco iron crucibles are exposed to a flowing gas mixture with a known oxygen potential until equilibrium has been attained. After equilibration, the final chemical analysis of the slags gave compositions having a particular ferrous oxide activity corresponding to the oxygen potential of the gas mixture. The determined values of ferrous oxide activity were used to calculate the equilibrium distribution of manganese between slag and iron. Higher manganese distribution between slag and iron was found to be obtained by using oxidizer containing high active iron oxide under acidic slag and relatively low temperature of about 1350°C.     

Sulphur partition between hot metal and high alumina blast furnace slag

Abstract

The sulphur partition ratio between hot metal and high alumina blast furnace slag (>18% alumina) has been examined on cast by cast basis for G blast furnace of Tata Steel. Equilibrium sulphur partition ratio was calculated from sulphide capacity with the help of oxygen activity in the melt. Oxygen activity was calculated from SiO₂/Si, MnO/Mn and CO/C equilibria. The equilibrium sulphur distribution calculated by considering the reaction [C]+[O]=(CO)_g in equilibrium for estimation of oxygen activity was very close to measured sulphur distribution ratio on cast by cast basis. Use of MnO/Mn pairs gives very high oxygen activity compared with SiO₂/Si and CO/C pairs.     

Evaluation of Desulphurization Flux in CaO‐Al2O3‐BaO‐CeO2‐MgO System

The flux of the CaO‐Al₂0₃‐BaO‐CeO₂‐MgO system as a desulphurization flux containing no fluorine for the secondary metallurgy process was evaluated in this study. The flux composition was designed using the eutectic compositions of the binary systems. The melting and desulphurization abilities of the fluxes were evaluated by measuring their liquidus temperatures and the distribution ratios of sulphur between the fluxes and the carbon‐saturated iron or stainless steel. The lowest liquidus temperature of 1325°C was obtained by adding 5.7 mass% MgO to the 80mass%A‐20mass%B flux. (A: 12CaO‐7Al₂O₃, B: BaCeO₃+12mass%Al₂O₃). The distribution ratios of sulphur and sulphide capacities of the fluxes in this study were higher than those of the commercial product of calcium aluminate flux. This means that the CaO‐Al₂O₃‐BaO‐CeO₂‐MgO fluxes developed in this study have higher desulphurization and melting abilities compared with the commercial product of calcium aluminate flux.     

Hot metal pretreatment by powder injection of lime‐based reagents

A mathematical model earlier proposed has been improved to predict the kinetics of multicomponent reactions in the hot metal pretreatment through the injection of reactive fluxes. It is assumed that there are two reaction zones along the flux injection operation: a transitory reaction between the rising particles and the bulk metal, and the permanent reaction between the metal and the top slag. A criterion to estimate the fraction of solids which will react with molten iron in a three‐phase jet (gas‐solid‐liquid) was considered; this fraction of solids carries out the transitory reaction. The model also takes into account the thermodynamic changes produced in the metal and slag due to the chemical reactions. Calculated results of the model are in good agreement with experimental results for the desulfurization of hot metal through the injection of CaO‐SiO₂‐CaF₂‐FeO‐Na₂O reagents at 1400 ‐ 1450 °C. Two kinds of hot metal were tested, one with a low carbon mass content of 3 % and the other with a high carbon mass content of 4.5 %.     

On sulphur behaviour in steelmaking with sponge iron in an electric arc furnace

The sulphur behaviour in steelmaking by melting of charges containing from 38.7 to 95.4 wt.% sponge iron in the metallic input in a 70 t UHP electric arc furnace is investigated. The effect of both slag composition and temperature on the sulphide capacity of the slag and on the sulphur distribution ratio between slag and metal is studied. The kinetics of desulphurization are also treated. Regression analysis shows that the logarithm of sulphide capacity varies linearly with total lime equivalent, theoretical optical basicity and logarithm of slag basicity. Equations relating the sulphide capacity to these parameters as well as to the temperature are given. Based on these equations, functional relationships for the calculation of sulphur distribution between slag and metal are derived. Metallurgical reactions for metal desulphurization by slag and equilibrium relationships are given from which the slag-metal sulphur partition ratio can be calculated. In all cases, the results of the calculations are in line with the experimental data. The rate of desulphurization is expressed by an equation based on the boundary layer diffusion theory. Under the conditions of the present investigation, the activation energy of desulphurization is found to be 39 kJ/mol and the mass transfer coefficient of sulphur at 1600°C is equal to 0.014 cm/s.     

降低生铁含硫量途径的探讨

随着对钢材性能要求的提高和超低硫钢产量的增加,对炼铁生产过程中的脱硫提出了越来越高的要求,本文通过对影响安钢水冶高炉生铁含硫量各因素的分析,探讨了降低水冶生铁含硫量和提高生铁质量的各种措施。提出了降低含硫量的措施。     

Sulphidation studies of Fe—15Cr—4Al alloy in H2—H2S environment at 850°C

The sulphidation behaviour of Fe—15Cr—4Al alloy has been investigated under low sulphur vapour pressure of 10^?9 to 10^?3 atm in the temperature range of 700–1000°C. Distinct changes in sulphide scale morphology were observed with the increase of partial vapour pressure of sulphur (ps₂). Triplex and duplex sulphide layers were observed at higher and lower ps₂ respectively. Parabolic rate constants of sulphidation of this alloy are strongly dependent on ps₂ and activation energies of the order of 83,6 kJ/mole suggesting diffusion of iron as a rate controlling step.     

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.     

A Study of Some Elemental Distributions Between Slag and Hot Metal During Tapping of the Blast Furnace

This paper investigates the distribution of elements between slag and hot metal from a blast furnace through calculation of distribution coefficients from actual production data. First, samples of slag and hot metal tapped from a commercial blast furnace were taken continually at 10‐minute intervals for a production period of 68 hours. Distribution coefficients of manganese, silicon, sulphur and vanadium were then calculated from the results of the sample analyses. A major conclusion drawn from examination of the results was that the behaviour of the studied elements was as could be expected when approaching the equilibrium reactions from thermodynamic theory. The distributions of the elements in the slag‐metal system showed clear tendencies which did not appear to be influenced by the operational conditions of the furnace. For example, for manganese, vanadium and sulphur, it was found that a higher basicity led to a decreased distribution coefficient L_Mn and L_V, but an increased L_S, which is according to theory. Another observed relationship was that slag basicity increased with an increased carbon content in the hot metal, which indicated that SiO₂ was reduced to [Si] when the oxygen potential decreased. Furthermore, it was found that sulphur and silica behaviour likened that of acidic slag components, while the manganese oxide and vanadium oxide behaviour was similar to that of basic slag components.     

Steel Desulphurisation and Sulphur Bonding in Solidified Ladle Slags

It was investigated in which form sulphur is bonded in ladle slags. For this purpose, the mineralogical phases of the ladle slags were qualitatively and quantitatively evaluated by means of a microprobe. This slag characterisation allowed reconstructing the bonding of sulphur into the phases of the ladle slag. Moreover, the reaction process with regard to the ionic theory as well as the structural formula for the mechanism of sulphur bonding were discussed. The bonding of sulphur into calcium aluminate slags is determined by the sulphide ion content in the slag as well as by the ratio of (CaO)/(Al₂O₃). Calcium sulphide separates only if the slag contains a large number of sulphide ions. When Ca₁₂Al₁₄O₃₃ is separated the sulphide ion is successively integrated into the lattice. The crystal lattice of Ca₁₂Al₁₄O₃₃ is characterised by an open, three‐dimensional anionic network composed of aluminium‐oxygen tetrahedrons linking the edges. In this network, large interstitial spaces are formed, which may be filled with calcium ions on the one hand and statistically with a free oxygen or sulphide ion on the other hand.     

Micro‐scale Strain Distribution in Hot‐worked Duplex Stainless Steel

A modified microgrid technique has been applied to a laboratory‐made duplex stainless steel, to experimentally simulate the local state of deformation of the austenite‐ferrite microstructure of low‐alloy steels subject to intercritical deformation. A sample containing such a microgrid was deformed by plane strain compression at high temperature under conditions representative of hot rolling processes. The distortion of the microgrid after hot deformation revealed, in a quantifiable manner, the plastic flow of both phases and different deformation features. The micro‐strain distributions measured can be used to validate the models predicting the hot deformation of low alloyed C‐Mn steels during intercritical rolling.     

Leaching behaviour of rock material and slag used in road construction ‐ amineralogical interpretation

Rock materials used in road construction contain heavy metal elements bound in minerals that are more or less soluble. There are no requirements for investigations of leaching behaviour before use of rock materials in Sweden, which is the case regarding other materials as, e.g., slags. This implies that there is a lack of data to be used when other materials are evaluated. Seven rock materials and two gravels representing non‐weathered material for use in base or sub‐base course from three counties in Sweden have been investigated regarding mineral composition in order to explain the leaching behaviour. Microscopic studies of the mineral composition, acid‐base‐accounting and pH‐measurements have been used to explain the leaching results achieved with the availability test. The identified transparent minerals were the expected silicate minerals for the sampled rock‐forming materials. Overall, the content of identified opaque minerals was low. How an element is bound in the mineral is decisive for the dissolution of the heavy metal elements. Sulphide bound elements have a notably high fraction that is soluble, especially under oxidising conditions. Chromium and vanadium present as substituted ions in the crystal lattice of oxides are not dissolved. The dissolution of the buffering rock forming silicates is much slower than the dissolution of the acid‐producing sulphides. The results have been compared to similar leaching tests of metallurgical slag used in road construction. The dissolution of the major phase, the solubility of the heavy metal mineral and secondary reactions are factors influencing the dissolved amounts of heavy metal elements. Compared to the crystalline rock materials, the amorphous fuming slag from a copper smelter has very low solubility, while blast furnace slag is easily dissolved due to hydrolysis. The soluble amounts of sulphide bound elements in rock material is higher compared to blast furnace slag. The kinetics of the acid‐producing and acid‐consuming reactions of the rock materials needs to be further investigated. The blast furnace slag and the fuming slag can be used in road construction without any risk of harmful environmental impact due to heavy metal leaching.     

高炉铁水含硅量和含硫量动力学预报研究

把平行工序调整为顺序工序是网络计划图优化调整的中心问题之一。根据网络的特点，本文引入了准值与最小值的概念，彻底解决了从四个平行工序中选择三个工序组成最佳顺序链的优化方法。     

鞍钢260t铁水脱硫扒渣生产实践

对鞍钢260 t铁水脱硫站的铁水温度条件、脱硫喷粉速率、脱硫喷枪插入深度以及扒渣工艺进行了优化,对铁水脱硫的控制方法及控制目标进行了介绍。采用镁基复合喷粉脱硫工艺,入转炉铁水硫可以达到0.002%～0.030%目标要求。通过铁水脱硫工艺与LF钢包精炼炉进行系统脱硫工艺控制,满足了中薄板坯连铸机的浇注要求,实现了全量钢水成品硫0.015%以下的低硫浇注,为稳定铸坯质量提供了保证。     

低硫铁水在转炉冶炼过程中回硫的控制

通过对脱硫铁水在转炉冶炼过程中回硫的各种因素进行分析,得出影响回硫的主要原因是铁水硫含量、转炉留渣、及石灰硫含量等,提出了冶炼低硫钢减少回硫的主要措施,通过工艺改善,降低了转炉终点硫含量.     

LF(VD)精炼工艺对控制28MnCr5齿轮钢中硫和硫化物的影响

试验了45 t LF精炼渣的碱度、喂硫线和脱氧工艺对28MnCr5钢(％:0.25～0.30C、0.60～0.80Mn、0.020～0.035S、0.80～1.00Cr)硫含量的控制、氧化物含量和钢中硫化物的影响。结果表明,LF精炼渣碱度控制在2.8～5.1喂硫线,VD后硫的回收率达80％～90％;钢中氧化物级别≤1.5级;精炼结束喂适量CaSi线可改善钢中硫化物的形貌。     

铁水预脱硫过程的新概念分析

铁水炉外脱硫是炼钢过程中的一个重要工序，它不仅是产品质量品种要求基本保证，也是生产流程物流调控的“柔性”活套之一，从新的角度讨论了现代钢铁制造流程的铁水脱硫问题，对降低入炉铁水铁含水量，脱硫剂组成，脱硫处理时间，脱硫率和物流调控以及它们之间的相互关系的一些新的概念进行了分析，着重强调了铁水炉外预处理的“柔性”活套功能。