Coupled experimental and thermodynamic modeling studies for metallurgical smelting and coal combustion slag systems

An extensive research program focused on the characterization of various metallurgical complex smelting and coal combustion slags is being undertaken. The research combines both experimental and thermodynamic modeling studies. The approach is illustrated by work on the PbO-ZnO-Al2O3-FeO-Fe2O3-CaO-SiO2 system. Experimental measurements of the liquidus and solidus have been undertaken under oxidizing and reducing conditions using equilibration, quenching, and electron probe X-ray microanalysis. The experimental program has been planned so as to obtain data for thermodynamic model development as well as for pseudo-ternary Liquidus diagrams that can be used directly by process operators. Thermodynamic modeling has been carried out using the computer system FACT, which contains thermodynamic databases with over 5000 compounds and evaluated solution models. The FACT package is used for the calculation of multiphase equilibria in multicomponent systems of industrial interest. A modified quasi-chemical solution model is used for the liquid slag phase. New optimizations have been carried out, which significantly improve the accuracy of the thermodynamic models for lead/zinc smelting and coal combustion processes. Examples of experimentally determined and calculated liquidus diagrams are presented. These examples provide information of direct relevance to various metallurgical smelting and coal combustion processes.

Predicting coal ash slag flow characteristics (viscosity model for the Al2O3-CaO-'FeO'-SiO2 system)

A model has been developed which enables the viscosities of coal ash slags to be predicted as a function of composition and temperature under reducing conditions. The model describes both completely liquid and heterogeneous, i.e. partly crystallised, slags in the Al2O3-CaO-'FeO'-SiO2 system in equilibrium with metallic iron. The Urbain formalism has been modified to describe the viscosities of the liquid slag phase over the complete range of compositions and a wide range of temperatures. The computer package F * A * C * T was used to predict the proportions of solids and the compositions of the remaining liquid phases. The Roscoe equation has been used to describe the effect of presence of solid suspension (slurry effect) on the viscosity of partly crystallised slag systems. The model provides a good description of the experimental data of fully liquid, and liquid + solids mixtures, over the complete range of compositions and a wide range of temperatures. This model can now be used for viscosity predictions in industrial slag systems. Examples of the application of the new model to coal ash fluxing and blending are given in the paper. (C) 2001 Elsevier Science Ltd. All rights reserved.

The prediction and representation of phase equilibria and physicochemical properties in complex slag systems

The development of new experimental techniques for the determination of phase equilibria in complex slag systems, chemical thermodynamic, and viscosity models is reported. The new experimental data, and new thermodynamic and viscosity models, have been combined in a custom-designed computer software package to produce limiting operability diagrams for slag systems. These diagrams are used to describe phase equilibria and physicochemical properties in complex slag systems. The approach is illustrated with calculations on the system FeO-Fe2O3-CaO-SiO-Al2O3 at metallic iron saturation, slags produced in coal slagging gasifiers, and in the reprocessing of nonferrous smelting slags. This article was presented at the Mills Symposium Molten Metals, Slags and Glasses-Characterisation of Properties and Phenomena held in London in August 2000.

Kinetics of reduction of FeO from slag by graphite and coal chars

The rates of reduction of FeO from iron-saturated FeO-CaO-Al2O3-SiO2 slags by graphite, coke, bituminous coal and anthracitic coal chars at temperatures in the range 1 673-1873 K have been measured using a sessile drop technique. The extents of reaction were determined using EPMA analysis of quenched samples, and on line gas analysis using a quadrupole mass spectrometer. The reaction rates have been shown to be dependent critically on carbon type. For the reaction geometry used in this investigation the reduction rates of graphite and coke are observed to be faster than with coal chars. This unexpected finding is shown to be associated with differences in the dominant chemical and mass transfer mechanisms occurring at the reaction interface. High reaction rates are observed to occur with the formation of liquid Fe-C alloy product and the associated gasification of carbon from the alloy. The rates of reduction by coal chars are determined principally by the chemical reaction at the carbon/gas interface and slag phase mass transfer.

Observations of the reduction of FeO from slag by graphite, coke and coal char

The reduction of FeO from iron-saturated FeO-CaO-Al2O3-SiO2 slags by graphite, coke and coal char at 1 673 K has been investigated using a sessile drop technique. Metallographic analysis of samples quenched from the reaction temperature, and in situ observations of the reaction interface, reveal significant differences in the slag/carbon contact, and in the morphologies of the product iron and its composition; these differences were found to depend on the carbon type used in the reduction. In particular it has been shown that, in the case of graphite and coke, liquid Fe-C droplets were rapidly formed at the slag/C interface. Reactions of the slag with coal chars, in contrast, result predominantly in the formation of solid iron. These observations indicate that the reaction pathways, and hence reaction kinetics, are dependent on carbon type.

The effect of Al2O3 on liquidus temperatures of fayalite slags

The effect of alumina on the liquidus temperatures of fayalite slags at iron saturation has been investigated experimentally. Equilibrated synthetic slags were quenched, and the samples were subsequently examined using optical microscopy and electron probe microanalysis (EPMA). The isotherms in the fayalite primary field and boundary lines were determined, and the results were presented in the form of pseudo-ternary phase diagrams of FeO-CaO-SiO2 with 0, 2, 4, and 6 wt pet Al2O3 in the slag. The experimental results show that the alumina addition expands the fayalite primary phase field and decreases the liquidus temperatures in the fayalite primary phase field.

Phase equilibria and thermodynamics of zinc fuming slags

A range of materials is treated in zinc fuming processes to recover metal values and produce benign slag waste products. The selection of the optimum process conditions in these various technologies can be greatly assisted by the use of a chemical thermodynamic model of the system. In this paper the effects of slag chemistry on the liquidus temperatures, subliquidus phase equilibria and thermodynamic properties are described by the F*A*C*T computer package with the new thermodynamic database of the ZnO-PbO-FeO-Fe2O3-CaO-SiO2 system. The implications of these findings for plant practice are discussed.

Prediction of coal ash fusion temperatures with the F*A*C*T thermodynamic computer package

This paper outlines research on the processes taking place within the coal mineral matter at high temperatures and development of the relationship between ash fusion temperatures (AFT) and phase equilibria of the coal ash slags. A new thermodynamic database for the Al-Ca-Fe-O-Si system developed by the author was used in conjunction with the thermodynamic computer package F*A*C*T for these purposes. In addition, high temperature experimental studies were undertaken that involved heat treatment and quenching of the ash cones followed by the analyses using different techniques. The study provided new information on the processes taking place during AFT test and demonstrated the validity of the AFTs predictions with F*A*C*T. Examples of practical applications of the AFT prediction method are given in the paper. The results of this study are important not only for the AFT predictions, but also in general for the application of phase equilibrium science to the characterisation of the coal mineral matter interactions at high temperature. (C) 2002 Elsevier Science Ltd. All rights reserved.

Experimental study of phase equilibria in the PbO-ZnO-"Fe2O3"-(CaO+SiO2) system in air for the lead and zinc blast furnace sinters (CaO/SiO2 weight ratio of 0.933 and PbO/(CaO+SiO2) ratios of 2.0 and 3.2)

Experimental studies on phase equilibria and liquidus in the multicomponent system PbO-ZnO-CaO-SiO2-FeO-Fe2O3 in air have been conducted over the temperature range between 1323 K (1050 degreesC) and 1623 K (1350 degreesC) to characterize the phase relations of the complex slag systems encountered in lead and zinc blast furnace sinters. The liquidus in two pseudoternary sections ZnO-Fe2O3-(PbO + CaO + SiO2) with the CaO/SiO2 weight ratio of 0.933 and PbO/(CaO + SiO2) weight ratios of 2.0 and 3.2 have been constructed.