A thermodynamic model for calculating the phosphorus distribution ratio between top–bottom combined blown converter steelmaking slags and molten steel has been developed by coupling with a developed thermodynamic model for calculating mass action concentrations of structural units in the slags, i.e., CaO-SiO2-MgO-FeO-Fe2O3-MnO-Al2O3-P2O5 slags, based on the ion and molecule coexistence theory (IMCT). Not only the total phosphorus distribution ratio but also the respective phosphorus distribution ratio among four basic oxides as components, i.e., CaO, MgO, FeO, and MnO, in the slags and molten steel can be predicted theoretically by the developed IMCT phosphorus distribution ratio prediction model after knowing the oxygen activity of molten steel at the slag–metal interface or the Fe
 t
 O activity in the slags and the related mass action concentrations of structural units or ion couples in the slags. The calculated mass action concentrations of structural units or ion couples in the slags equilibrated or reacted with molten steel show that the calculated equilibrium mole numbers or mass action concentrations of structural units or ion couples, rather than the mass percentage of components, can present the reaction ability of the components in the slags. The predicted total phosphorus distribution ratio by the developed IMCT model shows a reliable agreement with the measured phosphorus distribution ratio by using the calculated mass action concentrations of iron oxides as presentation of slag oxidation ability. Meanwhile, the developed thermodynamic model for calculating the phosphorus distribution ratio can determine quantitatively the respective dephosphorization contribution ratio of Fe
 t
 O, CaO + Fe
 t
 O, MgO + Fe
 t
 O, and MnO + Fe
 t
 O in the slags. A significant difference of dephosphorization ability among Fe
 t
 O, CaO + Fe
 t
 O, MgO + Fe
 t
 O, and MnO + Fe
 t
 O has been found as approximately 0.0 pct, 99.996 pct, 0.0 pct, and 0.0 pct during a combined blown converter steelmaking process, respectively. There is a great gradient of oxygen activity of molten steel at the slag–metal interface and in a metal bath when carbon content in a metal bath is larger than 0.036 pct. The phosphorus in molten steel beneath the slag–metal interface can be extracted effectively by the comprehensive effect of CaO and Fe
 t
 O in slags to form 3CaO·P2O5 and 4CaO·P2O5 until the carbon content is less than 0.036 pct during a top–bottom combined blown steelmaking process.

A Thermodynamic Model of Phosphorus Distribution Ratio between CaO-SiO2-MgO-FeO-Fe2O3-MnO-Al2O3-P2O5 Slags and Molten Steel during a Top–Bottom Combined Blown Converter Steelmaking Process Based on the Ion and Molecule Coexistence Theory

Slag–metal emulsion plays an important role in the oxidation kinetics of metalloids in oxygen steelmaking. The importance of droplet generation rate, droplet size, and its residence time in the slag–metal emulsion on the overall reaction kinetics has become evident in recent times. Residence times of the droplets are strongly dependent on the decarburization rate, the CO bubbles giving a buoyant force to the droplets. The present work aims at developing a mathematical model for predicting the composition evolutions of the slag and the metal phases as the blow proceeds in an LD converter. The process dynamics are modeled by dividing the LD convertor into three separate continuous stirred tank reactors. Oxidation reactions are assumed to be primarily taking place at the interface between the slag and the metal phases in the emulsion. Among the different mass transfer and reaction steps controlling the kinetics, the mass transfer of FeO in the slag phase and that of the metalloids within the metal droplet are assumed to be rate-controlling. For a Fe-C-X (X = Mn, Si etc.) droplet, simultaneous removal of elements have been modeled by Gibbs’ free energy minimization at the slag–metal interface. Effects of droplet size, mass transfer coefficient, and initial carbon content on the mean residence time of metal droplets in the slag–metal emulsion have also been identified. Mixing in the metal phase is simulated in terms of metal exchange rate and the reactor weight ratio between the upper and the lower parts of the bath.

Dynamic Modeling of LD Converter Steelmaking: Reaction Modeling Using Gibbs’ Free Energy Minimization

The scrap dissolution in an actual process like the BOF is affected both by mass transfer and heat transfer. In this paper, the mass transfer of carbon in liquid melt is considered along with heat transfer. The approaches used in this paper to model the scrap dissolution phenomenon include the application of Green’s function, quasi-static, integral profile, and the finite difference approach for different Biot numbers. Mass transfer coefficients are calculated using the Chilton–Colburn’s analogy for the case of forced convection. Since the quasi-static approach requires the least computational time, it is used for a detailed parametric study, including the effect of other parameters like different scrap ratios and heating rates of liquid melt. The region of control of heat transfer vs mass transfer is also identified. The dissolution of mixed scrap (light and heavy scrap) is investigated for different scrap ratios and the autogenous heating rates of liquid melt, with the help of mathematical models. The heat transfer coefficient is estimated as a function of mixing energy and the mass transfer coefficient by invoking the Chilton–Colburn analogy. The permissible limits of light scrap, which can be charged into the BOF, are also suggested from the results of this model. The Artificial Neural Network (ANN) model is trained on the dataset (patterns) generated by the coupled heat and mass transfer model. The accuracy of the results obtained using different ANN topologies is discussed followed by a recommendation for selecting the best approach.

Scrap Dissolution in Molten Iron Containing Carbon for the Case of Coupled Heat and Mass Transfer Control

New enzymes isolated from the biodiversity of native wine ecosystems could contribute to increase the varietal character of regional wines. This study reports on the production and characterization of Issatchenkia terricola, beta-glucosidase and its potential to release red-wine aromatic compounds. The enzyme, a monomer of 48 kDa with an isoelectric point of 3.5 is tolerant to glucose and ethanol, properties compatible with enological use. Although fed-batch is usually the most suitable system for enzyme production in submerged culture, in this case the yield was practically the same as in batch culture. Enzyme productivity was increased 2-fold in synthetic medium with glucose with respect to the YPG and 3–8-fold with respect to other media assayed. After enzymatic treatment, GC-MS analysis of the released aglycones demonstrated significant increases in the concentration of phenols (83%) and norisoprenoids (65%). According to the judges of the sensory panel, the treatment resulted in a wine with dried fruits and raisins notes, as compared to the control, which was found more sweet and fruity. This, together with the lack of activity on anthocyanin glycosides, highlights the potential of this enzyme in enology, since its high selectivity allowed the development of aroma without compromising wine color.

/pdf/production-and-characterization-of-a-b-glucosidase-from-c3s7b7duvc.pdf

Production and characterization of a β-glucosidase from Issatchenkia terricola and its use for hydrolysis of aromatic precursors in Cabernet Sauvignon wine

Production, characterisation, utilisation, and beneficial soil application of steel slag: A review.

Operational data of BOF and the slag samples for different starting conditions of phosphorus (0.06–0.26%P) and silicon content (0.3–1.2%Si) of hot metal have been analysed. The contribution of parameters which are well known to affect phosphorus distribution at tap, such as basicity, temperature, FeO content of slag, slag mass etc., is investigated through models of the ionic theory of slag, optical basicity, regular solution approach, and molecular theory of slag. The best overall results are obtained by the model based on the molecular theory of slag in which several operational parameters are also incorporated. Investigations of different slag samples, based on optical, SEM, EPMA and X-ray studies, reveal the effect of MgO and Al2 O3 on slag morphology and phosphorus distribution in different phases. It is important to consider the phosphorus distribution ratio in the solid and liquid part of the slag. The solid part of the slag, which is mostly dicalciumsilicate, can contain up to 5% phosphoru...

Effect of MgO and Al2O3 variations in oxygen steelmaking (BOF) slag on slag morphology and phosphorus distribution

A thermodynamic (equilibrium) model is developed for the BOF process. The predictions of this model show the trend of reactions when the process is considered to be at thermodynamic equilibrium. In the case of a real process, however, some tuning and adaptation becomes necessary to make more accurate predictions. A dynamic model is developed in which the kinetics of scrap dissolution is also incorporated. A comparison of the results of the equilibrium and dynamic models (made with some tuning parameters) reveals that mixing is the prime factor whichcanalter thecourseof reactionatanyparticularinstant.Mixingis greatlyaffectedbyoxygenflowrate, lanceheightandthenatureof scrap. The understanding of the secrets of process dynamics becomes clearer with this approach, providing a good insight into the process.

/pdf/an-insight-into-the-mechanism-and-kinetics-of-reactions-in-39kdqgllar.pdf

An Insight into the Mechanism and Kinetics of Reactions In BOF Steelmaking: Theory vs Practice

Decarburization, slag formation, foaming, and slopping in basic oxygen furnace (BOF) can now be partly understood, and to some extent predicted with the help of several on-line measurements and on-line control models. The principal reaction in BOF is decarburization. The bulk of the decarburization takes place in the turbulent region of jet impact irrespective of the fact whether the slag is solid, liquid or foamy. Metal droplets are ejected from the jet impact zone but it is difficult to distinguish the decarburization occurring in the bulk metal from that occurring in the droplets. Slag in BOF is heterogeneous and always contains some entrained gas bubbles and solid material (either un-dissolved or precipitated). At no stage the slag is 100 % liquid. A significant part of the metal droplets fall back and travel through the semi liquid slag. Through this mechanism the droplets can cause slag foaming and slopping in the BOF. Phenomenon of slag foaming and slopping can be monitored and controlled by following, dynamically, the audio signals, gas flow rate and composition, by tracking ‘Chaos’ in chemical reactions, by manipulating the chaotic attractors, and by monitoring the lance water temperature and weight. Relative stability potential (RSP) diagrams are found to be a good indicator of the dynamics of process inside the BOF and help in advance prediction of the impending chaos.

Control of Slag Formation, Foaming, Slopping, and Chaos in BOF

A unique in blow sampling system has been applied to a blowing converter to retrieve simultaneously representative bulk metal bath and slag/metal emulsion samples from seven specified positions and every 2 min from start of blow. Full sample datasets from 20 heats have been grouped according to differences in the bulk bath phosphorus removal profiles and analysed with respect to relative refining ability of the slag/metal emulsion and the bulk metal bath. The complexity of the thermokinetic relationships behind the removal of carbon and the transfer of silicon, phosphorus, manganese and sulphur between the metal and slag is highlighted and the metal circulation rate in the emulsion is derived.

Study of refining performance in BOS converter

In a previous study by the authors (Rout et al. in Metall Mater Trans B 49:537–557, 2018), a dynamic model for the BOF, employing the concept of multizone kinetics was developed. In the current study, the kinetics of decarburization reaction is investigated. The jet impact and slag–metal emulsion zones were identified to be primary zones for carbon oxidation. The dynamic parameters in the rate equation of decarburization such as residence time of metal drops in the emulsion, interfacial area evolution, initial size, and the effects of surface-active oxides have been included in the kinetic rate equation of the metal droplet. A modified mass-transfer coefficient based on the ideal Langmuir adsorption equilibrium has been proposed to take into account the surface blockage effects of SiO2 and P2O5 in slag on the decarburization kinetics of a metal droplet in the emulsion. Further, a size distribution function has been included in the rate equation to evaluate the effect of droplet size on reaction kinetics. The mathematical simulation indicates that decarburization of the droplet in the emulsion is a strong function of the initial size and residence time. A modified droplet generation rate proposed previously by the authors has been used to estimate the total decarburization rate by slag–metal emulsion. The model’s prediction shows that about 76 pct of total carbon is removed by reactions in the emulsion, and the remaining is removed by reactions at the jet impact zone. The predicted bath carbon by the model has been found to be in good agreement with the industrially measured data.

A. Overbosch

Papers

Effect of MgO and Al2O3 variations in oxygen steelmaking (BOF) slag on slag morphology and phosphorus distribution

An Insight into the Mechanism and Kinetics of Reactions In BOF Steelmaking: Theory vs Practice

Control of Slag Formation, Foaming, Slopping, and Chaos in BOF

Study of refining performance in BOS converter

Dynamic Model of Basic Oxygen Steelmaking Process Based on Multizone Reaction Kinetics: Modeling of Decarburization