Thermodynamic and kinetic aspects of the desulphurisation reaction in secondary metallurgy

The desulphurisation of liquid steels with a refining ladle top slag is one of the most important processes of secondary metallurgy. But the process control is even now based on empirical rules. Deviations from the sulphur contents aimed at can often be observed in practice. An improvement of the process control supported by knowledge of the thermodynamics and kinetics of the desulphurisation reaction is of great importance, especially for the production of steels with very low sulphur contents. To investigate the removal of sulphur, operational trials were carried out in 185 t steel ladles. In the trials the stirring gas flow rate, the pressure on the bath surface and the steel composition were varied as process parameters. The obtained results show that ladle slags saturated with lime have a high sulphide capacity. The desulphurisation rate of steel melts increases if the specific stirring energy is enhanced by increasing the gas flow rate or reducing the pressure on the bath surface. In the case of production of Al/Si‐killed steel melts, a desulphurisation degree above 90 % can be obtained by a vacuum treatment within 10 minutes.     

Emulsification of Top Slags during Argon Stirring through a Porous Plug in the Ladle of Si Deoxidised Carbon Steels

Intensive experiments with 170‐t heats of carbon steels in the LD steel plant of Saarstahl AG were performed to study the emulsification of an acid top slag during different stirring conditions in this research project. During ladle treatment samples were taken from steel for the analysis of the composition of the inclusions together with the top slag. Within these investigations gas flow rates and stirring times were systematically varied in order to study their influence on the entrapment of top slag in the steel melt. At the same time a model was developed for the evaluation of the performance of the porous plug with regard to gas flow rate and gas pressure or finally for blockades and leakages. According to the experiments of this project the following results were established. Small top slag particles are discovered nearly in all steel samples together with endogenous SiO₂‐Al₂O₃ deoxidation products. But emulsified phases or parts of the top slag generating larger inclusions with a size of 30 – 60 μm show the low melting eutectic composition. On the other hand, this emulsification process leads simultaneously to CaO depletion and SiO₂ accumulation of the top slag particularly when a longer stirring period is applied as shown during these experimental trials. The whole process requires low melting top slags and low melting emulsified inclusions in combination with a low viscosity level. To meet the emulsification requirements the gas flow is characterised by high gas flow rates in the order of 30 – 40 STP m³/h and high pressures with 8 – 12 bar indicating a blockade of the porous plug and the existence of a gas jet.     

Numerical modelling of fluid flow and desulphurisation kinetics in an argon-stirred ladle furnace

A full-scale, three-dimensional, transient CFD modelling approach capable of predicting the three-phase fluid-flow characteristics and desulphurisation behaviour in an argon-stirred ladle was developed. The model can accurately predict the molten steel flow and slag eye behaviour. The predicted sulphur content in ladle as a function of time agrees well with the experimental data. The effects of the initial sulphur content, the gas flow rate and the slag layer thickness on the desulphurisation efficiency were also investigated. The predicted results show that the desulphurisation efficiency improves with the increase of the initial sulphur content, the gas flow rate and the slag layer thickness. Higher gas flow rate can improve the slag–steel interaction, which, in turn, helps improving the desulphurisation rate. The thinner the slag layer, the larger the slag eyes and the smaller the interfacial area between the slag and steel phases. The consequence is the decrease in the desulphurisation rate.     

Carburization and desulphurisation of the semi‐steel during plasma heating

Experiments were carried out on the carburisation, desulphurisation and temperature rise of the semi‐steel in a plasma induction furnace. Influences of many factors, such as power supply, structure and positioning of the plasma torch and bottom‐blown‐gas stirring, on heating efficiency and melt temperature distribution were studied. During carburisation of the semi‐steel, plasma heating could effectively control the melt temperature, consequently, the carbon mass content of semi‐steel increased from 1.92 to 4.58 % with the utilisation efficiency of carbon reached up to 61.57 %, and the desulphurisation ratio could be beyond 66.58 %.     

Emulsification and mass transfer in ladle metallurgy

Measurements of slag emulsification in gas-stirred ladles were carried out in cold-model systems of different geometric sizes. Detaching of slag droplets – necessary for efficient emulsification – only takes place if the flow velocity at the slag/metal interface exceeds a certain level. The use of a centric nozzle leads at high gas flow rates to considerably larger degrees of emulsification than eccentric stirring. The reason of this phenomenon is that the recirculation flow during centric gas injection transports larger amounts of emulsified droplets into deeper regions of the melt while during eccentric stirring there is more time for reseparation of slag droplets into the top slag. Comparing emulsification results with mass-transfer measurements, the dependence between rate constants as well as degrees of emulsification and Froude number shows similar behaviour.     

Theoretical model of steel desulphurisation with gaseous calcium

A model of desulphurisation of steel with gaseous calcium bubbles based on a population balance equation is presented. The equation is a basis of the quantitative approach to the phenomena observed in the dispersive systems. The course of reaction of the calcium bubbles with the oxygen and sulphur during the Stokes float-out was studied for various model parameters. The effect of the following factors on the refining process efficiency was considered: interval of bubble sizes, distribution of bubble sizes and participation of a carrier gas. It was found that the refining process is affected mainly by the global bubble surface and the residence time of bubbles in the steel. It means that the bubble size interval and size distribution of the bubbles for the calcium mass is a decisive factor for the desulphurisation efficiency. Any increase in the carrier gas content, in fact, increases the bubble surface, yet, simultaneously accelerates the float-out of the not reacting bubbles. Thus, for the Stokes model the effect of a carrier gas on the desulphurisation efficiency is small. The comparison of the calculated and experimental results for different blowing depths and different amounts of calcium is presented.     

Preliminary Investigation of Mathematical Modeling of Stainless Steelmaking in an AOD Converter: Application of the Model and Results

The changes in the contents of C, Cr, Si, and Mn in molten steel and the bath temperature during the refining of 304‐grade stainless steel, including both the oxidation (decarburization) and reduction processes, in a side and top combined blowing AOD converter of 120 t capacity have been predicted. The calculations were performed using the mathematical model proposed and presented in Part I of the present work [1] and were based on the designed operational mode of the AOD converter. The model predictions were compared to the referenced values given by the technological design. The results demonstrate that the predictions by the model are in good agreement with the reference values. Not only the competition of oxidation among the elements dissolved in the steel during the oxidative refining process and the corresponding distribution ratios of oxygen, but also the competition of reduction among the oxides during the argon stirring and reductive refining process and the relevant supplied oxygen ratios of the oxides, can all be characterized more comprehensively and determined more reasonably by using the Gibbs free energies of the oxidation and reduction reactions. Corresponding to the top, side, and side and top combined (overall) refining processes of 304‐grade stainless steel in a 120 t AOD converter, the carbon concentrations at the critical rates, i.e. the critical carbon concentrations, after which the decarburization changes to be controlled by the mass transfer of carbon in molten steel, are 1.20, 0.37 and 0.53 mass%, respectively, under the given designed operational mode. The model can offer some useful information for determining the technology of the side and top combined blowing AOD refining process of stainless steel.     

Mathematical Modeling of Fluid Flow in Bath during Combined Side and Top Blowing AOD Refining Process of Stainless Steel: Mathematical Model of the Fluid Flow

Considering that the liquid flow field under the conditions of the combined side and top blowing would be a combined result from the common action of the side blowing gas streams and a gas top blowing jet, as the first attempt, the three‐dimensional mathematical models for the flows of molten steel in an AOD converter bath during the simple side and top blowing processes have been proposed and developed, respectively. And the mathematical model of the flow in the bath during the combined blowing AOD refining process of stainless steel has been given by the composition and superposition of the two models. In the composed model, the gas‐liquid two‐phase flow is described and treated in terms of the two‐fluid (Eulerian‐Eulerian) model. The especially modified two‐equation k?ε model for the turbulence in the liquid phase is employed. And, the surface of the sunken pit formed by impact of the gas jet blown from a top lance at the central location of the bath liquid surface is regarded as a revolution paraboloid. The related details of the composed model are shown.     

Cold model investigations of fluid flows and mixing within top and combined blowing in metallurgical processes

Cold model investigations were performed during top and combined blowing in metallurgical processes. The investigations include 2- and 3-phase systems with gas, water and oil phase. The results of top blowing tests can be used to arrange and optimise the fluid flow. Further, conclusions can be drawn for the spraying and emulsification process, if the slag thickness is known. Under combined blowing conditions a small amount of stirring gas injected from the bottom has a great influence on mixing. According to the slag thickness, in combination with the power of the top blowing momentum, the fluid flow is dominated by top or bottom blowing. If bottom blowing is added as a stirring mechanism, a better mixing can not be guaranteed by this means. The bottom blowing conditions have to be adapted to the top blowing conditions and to the reactor geometry.     

Development of a numerical model simulating the desulphurisation of liquid steel

A comprehensive numerical model is developed simulating the batch process of liquid steel desulphurisation. Special emphasis is placed on the exact figuring of real process engineering conditions. The model includes time dependent intensive parameters such as the aluminium content and the oxygen content of the liquid steel as well as the temporal course of the CaO-, CaS, Al₂O₃-component activities in the refining top slag. Mass transfer coefficients are derived from practical experience. The computations prove the outstanding influence of the stirring intensity on the rate of the refining reaction. Its progress is delayed by the dissolution of the lime charge at the beginning of the stirring treatment. The simulation model can also be applied to optimize the desulphurisation process with respect to stirring time, state of deoxidation and amount of refining slag.     

Influence of the Stirring Gas in a 170‐t Ladle on Mixing Phenomena – Formation and On‐line Control of Open‐Eye at an Industrial LD Steel Plant

3D calculations with Computational Fluid Dynamics were carried out to evaluate the flow pattern under industrial conditions with different gas flow rates at the steel plant of Saarstahl AG. The generated flow pattern consists of a circulating loop characterised by an upward flow driven by the argon gas and a downward flow close to the wall on the opposite side of the porous plug in the case of a gas flow rate of 27 STP m³/h. When this high gas flow rate is used, the gas bubbles are taking a straight way from the inlet, but further up the momentum from the circulating steel is affecting the path of the gas bubbles followed by a breakthrough zone at the top surface. Intensive experiments with the 170‐t ladle of Saarstahl AG revealed typical open‐eyes. Large open‐eyes coupled with turbulences in the surface were generated in the case of gas flow rates between 20 and 30 STP m³/h. Intensive turbulences and even smoke formation were identified when a gas flow rate of > 30 STP m³/h was applied. For the investigation of the influence of gas stirring processes on the mixing phenomena samples were taken from the melt immediately after alloying. It could be seen that the analyses of Al, C, Mn and Si increased to the target analyses due to alloying and introduction of Ar through the porous plug. The total time for complete alloying depended on the elements within these experiments. It seemed to be that the alloying time increased in the order of Al, C, Mn and Si. For on‐line control and analysis of open‐eyes in the melt surface during ladle stirring, a BFI image processing system was installed at the steel plant of Saarstahl. It consisted of a conventional digital camera equipped with an infrared filter and coupled to an image processing software. Primary tests showed a slight influence of the open‐eye diameter at the end of the ladle treatment on inclusion densities in the liquid steel and oxidic K0 values of the finished wire rod. Additional experiments were performed but only a small correlation existed between the stirring energy at the end of ladle treatment and the inclusion length index of the applied blue brittle tests. But as soon as an open‐eye came into existence, the inclusion length was higher compared to those heats produced under a closed top slag.     

Numerical Simulation of Fluid Flow and Interfacial Behavior in Three‐phase Argon‐Stirred Ladles with One Plug and Dual Plugs

A numerical investigation is performed to describe the quasi‐steady fluid flow and interfacial behavior in a three‐phase argon gas‐stirred ladle with off‐centered bottom Ar injection through a plug and two plugs placed in 180° and 90°configurations, respectively. The flow of the fluid phase is solved in an Eulerian frame of reference together with the motion of every individually injected Ar bubble, tracked in its own Lagrangian frame. Volume of fluid (VOF) model is used to track any interface between two or more immiscible phases, which include slag/metal, slag/gas and metal/gas. The characteristics of fluid flow in a gas‐stirred ladle with one plug or two plugs configuration are described when the slag layer and the top gas are presented. The slag layer deformation and slag open‐eye formation at different Ar gas flow rates for three types of plug arrangements are given. The comparison of the mixing time, the deformation of slag layer and the behavior of slag/steel interface between one‐plug and two‐plug system is made. Several implications for ladle operational issues during a gas‐stirred ladle refining cycle are discussed. It is found that the proper selection of Ar gas flow rate and plug arrangements during a ladle refining cycle is required for different refining purposes considering the mixing and metallurgical reaction in a three‐phase ladle system.     

Metallurgical Development in Steel‐plant‐internal Multi‐injection Hot Metal Desulphurisation

The use of thermodynamic, statistical, and light and electron‐optical microscopic methods has made it possible to analyse the course of reactions during steel‐plant‐internal hot metal desulphurisation. The theoretical dependence between oxygen and sulphur activity has been used to develop an EMF‐measurement‐based technique for determining the sulphur content as the hot metal is desulphurised. The absence of magnesium sulphide from the collection of phases in the final slag because of the greater stability and secondary formation of calcium sulphide has been explained with the aid of thermo‐chemical calculations.     

Study of Open Eye Formation in an Argon Stirred Ladle

Two cold models were employed to simulate the formation of open‐eyes in a gas stirred ladle. In the first model, water and silicon oils were employed to simulate liquid steel and slag respectively. In the second one, liquid Ga‐In‐Sn alloy was used to simulate liquid steel, while 12% hydrochloric acid simulated the top slag. The experimental results indicated that the gas flow rate, height of the lower liquid and height of the top liquid had a strong impact on the open‐eye size. On the other hand, the viscosity of the top liquid and the interfacial tension between the two liquids had only little effect on the open‐eye size. A semi‐empirical model was developed to describe the size of open‐eye as a function of the heights of the two liquids and the gas flow rate. The two sets of parameters obtained for the water and Ga‐In‐Sn models were very different. Industrial trials were also conducted to examine the applicability of the models. The model developed based on the Ga‐In‐Sn model could well predict the formation of an open‐eye during ladle treatment. The model could be adopted by the industry to estimate the real gas flow rate by measuring the size of the open‐eye online. On the other hand, the mathematical model based on water model experiments was unsatisfactory when applied to the industrial ladle process.     

AOD/CLU process modelling: optimum mixed reductants addition

Abstract

To increase the productivity of the AOD/CLU converter process in stainless steelmaking, single slag practice, i.e. simultaneous top slag reduction and desulphurisation, is an attractive alternative. Furthermore, if the combined addition of reductants FeSi and Al is used, desulphurisation can be optimised. A model approach to calculating the additions of FeSi, Al, and fluxes to recover the valuable elements of the slag and to reach the aim sulphur level is presented. The paper also describes an online verification of the model, where model calculations recommended additions to a 75 t AOD converter. Finally, some aspects of model prediction are given. It was found that it is possible to obtain a sulphur content lower than 20 ppm by utilising single slag practice based on a mixed reductant addition and on the observation that the AOD converter appears to be close to thermodynamic equilibrium from a sulphur point of view after the refining operations. However, a successful operation requires strict control with respect to electric arc furnace slag carryover and crude steel silicon content.     

Prediction of gas‐liquid two‐phase mixture flow in a vertical pipe with a sudden expansion in diameter

The principle of gas‐lift pumps is applied to vacuum‐decarburization with the RH (Ruhrstahl Heraeus) process to circulate molten steel. Gas‐lift pumps are also applicable to the transportation of molten iron/steel between different refining processes. This paper treats theoretical analysis of steady‐state flow characteristics of gas‐liquid two‐phase mixtures rising in a vertical pipe with an abrupt expansion of its diameter. The system of governing equations is based upon a one‐dimensional multi‐fluid model. Flow pattern transitions are taken into consideration. A new numerical procedure to predict the flow characteristics at the sudden expansion has been proposed. Experiments have also been performed for several conditions to confirm the applicability as well as the validity of the present numerical model. It has been found that the predictions agree reasonably well with the experimental data. Next, the effect of the sudden expansion of pipe diameter on the pump performance was investigated numerically. As a result, it has been confirmed that the sudden expansion of pipe diameter contributes to improve the pump efficiency.     

Study on the Formation of Open‐Eye and Slag Entrainment in Gas Stirred Ladle

Laboratory experiments were carried out to study the phenomena related to open‐eye formation in ladle treatment. Ga‐In‐Sn alloy with a melting temperature of 283 K was used to simulate the liquid steel, while MgCI₂‐Glycerol(87%) solution as well as HCl solution were used to simulate the ladle slag. No open‐eye was formed at lower gas flow rates, but, occurred when gas flow reached a critical rate. This critical gas flow rate was found to depend significantly on the height of the top liquid. No noticeable amount of top liquid was observed in any of the samples taken from the metal bulk during gas stirring. To confirm this aspect, samples of slag‐metal interface were taken around the open‐eye in an industrial gas stirred steel ladle. No entrapped slag droplet was found in the solidified steel within the region between the interface and 2 cm from the interface. The accordance of the laboratory and industrial results suggests that the entrainment of slag into the steel bulk around the open‐eye cannot be considered as the major contribution to inclusion formation.     

Kinetic model of desulphurisation by powder injection and blowing in RH refining of molten steel

Abstract

The desulphurisation by powder injection and blowing in the RH refining of molten steel and its mechanism have been considered and analysed. Based on the two-resistance mass transfer theory and the mass balance of sulphur in the system, a kinetic model for the process has been developed. The related parameters of the model, including the mass transfer coefficients and the effective amount of powder in the molten steel being treated for desulphurisation, have been reasonably determined. Modelling and predictions of the process of injecting and blowing the lime based powder flux under assumed operating modes with the different initial contents of sulphur and amounts of powder injected and blown in a RH degasser of 300 t capacity have been carried out using the model. The relevant circulation rate of the liquid steel and the powder injection and blowing rate were taken to be 100 t min^-1 and 150 kg min^-1, respectively. The initial contents of sulphur in the liquid steel to be treated and the amounts of powder injection and blowing were respectively assumed to be 0·007, 0·006, 0·005, 0·004, 0·003, 0·002 wt-%and 10, 8, 6, 5, 4, 3 kg/t steel. The total treatment time for desulphurisation under each mode was set at 24 min, equivalent to eight circulation cycles of the liquid steel to be treated. The results indicated that the predictions made by this model are in good agreement with data from industrial experiments and practice. By injecting and blowing the lime based powder flux with the composition of 85 wt-% lime (CaO) + 15 wt-%fluorspar (CaF₂ ) of 3–5 kg/t steel, it is possible to decrease the sulphur content in the molten steel to an ultralow level below (5–10) × 10^-4 wt-%from (60–80) × 10^-4 wt-%. The total treatment time needed will be 12–20 min. Intensifying the powder injection and blowing operation and increasing the circulation rate of the liquid steel may effectively increase the rate of the process in RH refining. The model may be expected to offer some useful information and a reliable basis for determining the reasonable process parameters and help in optimising the technology of desulphurisation by powder injection and blowing in the RH refining of molten steel.     

Deep steel desulphurisation technology in ladle furnace at KSC

Abstract

At the Mizushima Works of Kawasaki Steel Corporation, a new deep desulphurisation technology to produce ultralow sulphur steels has been developed to replace the conventional process that comprised ladle furnace treatment followed by flux injection. In the new process, the use of a double plug gas injection system in the ladle furnace to promote desulphurisation, and optimisation of the ladle slag composition by thermodynamic calculations to maximise sulphide capacity, have enabled the flux injection stage to be omitted and shortened the desulphurisation time. As a result of these modifications, 35min after treatment start the sulphur content can be reduced to 5·3 ppm. On average, the time from tapping at converter until teeming start at caster has been reduced by 20·8min enabling production schedules to be synchronised and the maximum number of sequential casting heats to be increased from 3 to 10. There have also been economic benefits: the total steelmaking cost of ultralow sulphur steel has been reduced by 25·5%.     

Preliminary Investigation of Fluid Mixing Characteristics during Side and Top Combined Blowing AOD Refining Process of Stainless Steel

The fluid mixing characteristics in the bath during the side and top combined blowing AOD (argon‐oxygen decarburization) refining process of stainless steel were preliminarily investigated on a water model unit of a 120 t AOD converter. The geometric similarity ratio between the model and its prototype (including the side tuyeres and the top lances) was 1:4. On the basis of the theoretical calculations for the parameters of the gas streams in the side tuyeres and the top lances, the gas blowing rates used for the model were more reasonably determined. The influence of the tuyere number and position arrangement, and the gas flow rates for side and top blowing on the characteristics was examined. The results demonstrated that the liquid in the bath underwent vigorous circulatory motion during gas blowing, without obvious dead zone in the bath, resulting in a high mixing effectiveness. The gas flow rate of the main tuyere had a governing role on the characteristics, a suitable increase in the gas flow rate of the subtuyere could improve mixing efficiency, and the gas jet from the top lance made the mixing time prolong. Corresponding to the oxygen top blowing rate specified by the technology, a roughly equivalent and good mixing effectiveness could be reached by using six side tuyeres with an angle of 27 degrees between each tuyere, and five side tuyeres with an angular separation of 22.5 or 27 degrees between each tuyere. The relationships of the mixing time with the gas blowing rates of main‐tuyeres and sub‐tuyeres and top lance, the angle between each tuyere, and the tuyere number were evaluated.