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By M. Bugdayci, Onuralp Yucel, K. C. Tasyurek

This paper is a contribution to the theory and quantitative understanding of the processes for the production of magnesium, calcium and strontium metals by metallothermic process. In the present study, effect of reductant type was investigated. Thermodynamic simulation of system was made by Fact Sage 6.4 program. In order to produce magnesium metal, effects of reductants “FeSi, Al, Si and CaC2” were investigated. To understand Calcium-oxide reduction system, effects of Al and CaF2 addition were investigated for different temperatures. In the last simulations, SrO reduction parameters were simulated. Al used as main reductant and BaO, CaO, CaC2 were added to green mixture as a functional additive. Finally probable phases and minimum reduction temperatures are determined.

Mar 1, 2018

By Wadsley MW

This paper gives an overall view of the CSIRO-SGTE computer system for thermodynamic calculations. The basis of the system is the coupling of a large self-consistent numeric data bank of thermodynamic information to a modular set of application programs. These seven programs cover management of data files, calculation of thermodynamic properties for species and reactions, plotting of predomin- ance area diagrams, equilibrium and enthalpy balances for complex processes, analysis of thermodynamic efficiency and the estimation of unknown properties. The data bank contains a wide coverage of species and data types so that the system may be applied to many areas of chemistry and metallurgy.

Jan 1, 1984

By Chunlin Chen

Published data on thermodynamics of a number of minor elements (As, Sb, Bi, Pb, Zn, Se, Te, Cr, Sn) in liquid copper, matte and slag have been reviewed, assessed and used in development of thermodynamic solution models of melts. The behavior of antimony in alloys, mattes and slags is used as an example to illustrate the approach taken in assessment of published data and validation of the developed models with respect to the activity of Sb in condensed phases as well as the effects of matte grade, slag chemistry, temperature etc on the equilibrium distribution of Sb between melts and the gas phase. Results obtained from a comparison of different smelting processes with the modeled multi-phase equilibrium are presented and discussed. The predicted effects of slag chemistry and matte grade on the deportment of other minor elements during smelting of copper mattes will be presented and discussed.

Jan 1, 2006

By H. Y. Sohn, Hang Goo Kim

Computer simulations were carried out using calcium ferrite slags containing 25 wt% CaO, and the results compared with those obtained using fayalite slags. There was little difference in overall elimination of Pb and Bi, but elimination of Sb and As was much lower with calcium ferrite slag. When calcium ferrite slag is used only in the converting stage and fayalite slag in the smelting stage, as in the Mitsubishi process, the contents of Sb and As in the blister copper can be kept to reasonable levels. This allows advantage to be taken of the considerably higher iron oxide-holding capacity of calcium ferrite slag than of fayalite slag at the high oxygen potential under converting conditions, thus preventing precipitation of magnetite. Satisfactory agreement was obtained between predicted values and observed data from a Mitsubishi converter

Jun 18, 1905

By M K. Nahian, R G. Reddy

The thermodynamic model for species distribution in aluminium chloride (AlCl3) and 1-butyl-3- methylimidazolium chloride (BMIC) system was developed. The experimental thermodynamic data, considering a range of aluminium chloride species, such as AlCl4-, Al2Cl7-, Al3Cl10-, Al4Cl13-, and Al2Cl6 were used in developing the model. When the XAlCl3 was in the range of 0 to 0.50, only anion species Cl- and AlCl4- were existing in the solution. As the XAlCl3 value increased more than 0.50, the available anions were Al2Cl7-, Al3Cl10-, Al4Cl13-, and Al2Cl6. Specifically, the concentration of Al2Cl7- increased in the composition range from 0.50 to 0.67 XAlCl3, after which it decreased. This change in the concentration of Al2Cl7- was due to its reaction with excess AlCl3, leading to the formation of Al3Cl10-. The average cathode current density was determined by the electrochemical experiments varying XAlCl3 from 0.50 to 0.71 in the AlCl3:BMIC solutions. The average cathode current density increased as the XAlCl3 increased from 0.50 to 0.67. However, it decreased when the XAlCl3 > 0.67. This trend can be attributed to the electroactive species Al2Cl7-. The Al2Cl7- promotes the reduction rate at the cathode, resulting in an increase in the average cathode current density.

Aug 21, 2024

By A. D. Pelton, Y. -B. Kang, S. A. Decterov

Computerized thermodynamic databases for solid and liquid metal, slag and solid oxide phases in the Al2O3-CaO-CoO-CrO-Cr2O3-FeO-Fe2O3-MgO-MnO-NiO-SiO2-S system have been developed by critical evaluation/optimization of all available phase equilibrium and thermodynamic data. The databases contain parameters of models specifically developed for molten slags, liquid steel and solid oxide solutions such as spinels, pyroxenes, olivine, monoxide (wustite, periclase, lime), corundum, etc. By means of the optimization process, model parameters are found which reproduce all thermodynamic and phase equilibrium data within experimental error limits. Furthermore, the models permit extrapolation into regions of temperature and composition where data are not available. The databases are automatically accessed by user-friendly software that calculates complex equilibria involving simultaneously slag, metal, refractories and gases, for systems with many components, over wide ranges of temperature, oxygen potential and pressure. A short review of the available databases is presented. The critical evaluation/optimization procedure is outlined using the Al2O3-CaO-FeO-Fe2O3-SiO2and Al2O3-CaO-MnO-SiO2systemsas examples. Several applications of the databases to deoxidation of iron and to inclusion control in steel are discussed. Keywords: thermodynamics, phase equilibrium, phase diagrams, databases, ferrous metallurgy, steelmaking, inclusion control, slags, oxide systems.

Jan 1, 2004

By Y B. Kang, Y J. Park

Ti-added ultra-low carbon (ULC) steel is produced by adding Al and Ti during the secondary refining process to deoxidise molten steel and to bind C and N which are detrimental to the deep drawing quality of the steel product. However, the production of Ti-added ULC steel faces challenges, including submerged entry nozzle clogging and surface defects on cold rolled coils. The troubles were often attributed to ‘Al-Ti complex inclusions’ in the molten steel. However, the evolution of oxide inclusions including their stability has been still unclear. In the present study, the evolution of these inclusions in Ti-added ULC steel was investigated by phase diagram measurement, CALPHAD thermodynamic modelling, high-temperature stability test for the oxides, and observation of transient behaviour of oxide inclusions in the steel. The phase diagram of the Al-Ti-O system was elucidated with an emphasis on oxygen potential, which significantly controls the stability of the oxides. CALPHAD thermodynamic models and a self-consistent database were developed. The transient behaviour of Al-Ti complex inclusions in Ti-added ULC steel was observed in situ using a confocal scanning laser microscope. This was additionally validated by the new thermodynamic model. The equilibrium phases of the oxide inclusions were investigated using a high-temperature resistance furnace, and were analysed using a secondary electron microscope, energy dispersive spectrometer, and electron back-scattered diffraction. By considering the morphology and crystal structure of these inclusions, the evolution of Al-Ti oxide inclusions was elucidated. Various behaviour of Al-Ti inclusions and their influence on steel cleanliness are discussed.

Aug 21, 2024

By A. D. Pelton

The evolution of thermodynamic models of molten salts and slags, starting with Temkin in 1948, has culminated in today?s sublattice models. These modern models have permitted the development of large thermodynamic databases of model parameters, which can be used to calculate and predict accurately the properties of multicomponent solutions. The model parameters are mainly obtained by the critical evaluation and optimization of available thermodynamic and phase equilibrium data for binary and ternary subsystems. The models are then used to estimate the properties of multi component slags and salts from these assessed binary and ternary parameters. When used in conjunction with thermodynamic databases for solids and solid solutions (salts, oxides, sulphides, metals, etc.), other liquid solutions (such as liquid metals),and gases, these databases permit the calculation of complex multiphase equilibria in multicomponent systems, with applications in a wide variety of industries. These calculations can be performed with general commercial software for Gibbs energy minimization, which can also be incorporated into process simulation software packages. Keywords: slags, salts, solution models, thermodynamics, phase diagrams, oxide systems, molten salts

Jan 1, 2004

A simulation program has been developed tc predict the airflow distribution and thermal environment in multi-level narrow lode Cornish =n mines. Because of the approximate equality between fan power and natural ventilation _rergy a true thermodynamic mesh balance using mass flow rather than volume flow rate was required. Compressibility is allowed for by calculating mesh corrections on a mass flow of dry air basis. In this context, and within the confines of any steady state model, both the steady flow energy and pressure equations are satisfied with equal validity. The mesh balance includes natural ventilation energy, frictional losses, moisture lift work, water droplet energy and fan energy.

Jan 1, 1988

By Michael L. Sorokin

The metallic nickel production by converting of nickel matte is analysed from the thermodynamic point of view using earlier developed thermodynamic models for sulphide, metal and slag phase. Three-suffix Margules equations are used to calculate thermodynamic properties of melts. Potential diagrams of Ni-FeS-OSiO2 system are calculated for various temperatures and Fe to Ni ratios. The diagrams used for consideration about possibilities of the direct one-stage metallic nickel production.

Jan 1, 1995

By Merritt RR

The equilibrium phase relations in the Fe- Mn-Ti-0-S system were established at 1380 and 1485 K. The elemental distributions between the equilibrium phases were obtained by chemical- ly analysing selected samples from the phase study. The results are considered in relation to the coal reduction process for upgrading ilmenite. The beneficial effect of adding sulfur to a kiln that uses a manganese-rich feed is ex- plained by the formation of a metal-sulfide solid-solution phase that removes part of the manganese from the oxide system. The optimum conditions for operating the reduction kiln are determined, and the practical need to operate the kiln at other than optimum conditions is explained. It is shown how the experimental data can be used to predict the best compromise conditions for reduction and the resultant purity of the product.

Jan 1, 1980

By Tuncel M. Yegulalp, Anuta Belova

This paper expands on the ZECA (Zero Emission Coal Alliance) technology, which is aimed at making coal a sustainable source of clean energy in the near future. The technology proposed immediate capture of carbon dioxide and other pollutants upon generation, thus alleviating their negative effects in the Earth’s atmosphere. ZECA proposes using chemical energy of coal to produce hydrogen; the latter is then used to produce electricity via fuel cells or Hyrogen-Oxygen turbines. In this study, a chemical engineering package, AspenPlus 12.1, is used to simulate the reactor (reformer) in which hydrogen is produced from methane water and lime as part of the zero emission power plant. Thermodynamic conditions, pressure and temperature, are optimized with respect to molar hydrogen production. Under the proposed conditions, molar conversion efficiency, carbon to hydrogen, of 95% is achieved. Further studies are required to model the complete power plant and to optimize it for efficiency.

Jan 1, 2005

By Youn-Bae Kang, Jong-Jin Pak, Min-Kyu Paek

The critical evaluation and thermodynamic optimization of Mn-Si-C and its sub-binary systems have been carried out over the whole composition range from room temperature to above the liquidus temperature. The solution properties of the liquid systems have not been clearly described because the liquid solution exhibits a high degree of short-range-ordering. In order to predict the thermodynamics of the liquid solution, the liquid phases were optimized by the modified quasichemical model. The model parameters of the solid phases were also optimized by the compound energy formalism to best reproduce the phase diagram and important thermodynamic properties in Mn-Si-C system. Using the model parameters, various thermodynamic calculations were carried out. The present database will be a part of larger thermodynamic database for the ferromanganese alloy database.

Jan 1, 2014

By Kwan Soo Han

A thermodynamic model for predicting the distribution coefficients has been developed by taking into account the extraction mech-.ism and the chloride complexation when Sm, Eu, Gd, Tb, Dy and Ho for single component systems are extracted from acidic chloride solutions by di-2-ethylhexyl phosphoric acid and 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester in kerosene, respectively. The model equation includes two constants, of which one corresponds to the apparent extraction equilibrium constant and the other is due to the variation of the activity coefficients of organic species. These values are determined from a few experimental data by the curve fitting method Then, the distribution coefficients under untried conditions have been predicted from only the initial data by iterative calculations. Bromley's formulation is used to estimate the activity coefficients of aqueous species and the interaction parameters for some rare earth chlorides are reported in terms of molality and molarity using data from Spedding et al. The validity of this method has been confirmed by excellent agreement between the experimental and the predicted distribution coefficients.

Jan 1, 1989

By Q. Liu, P. Katsabanis, J. A. Meech

A thermohydrodynamic computer code has been used to simulate dust explosions. For sulphide dusts, the thermodynamic predictions are used to investigate the effect of dust concentration, mineral content and inert materials as well as the quantity of sulphur dioxide produced. It was found that the amount of oxygen available for the explosion is very important and that the dust concentration which gives maximum explosion pressures is obtained at zero or slightly negative oxygen balance values. The sulphide minerals were found to have the following explosibility sequence: pyrrhotite, pyrite, chalcopyrite, sphalerite, covellite, chalcocite and galena, which is in agreement with mine experience. The results show that theoretical calculations can be used to predict explosion pressures and toxic gases produced by a dust explosion and therefore they can assist in the design of protective measures .

May 11, 1988

Activity-composition-temperature relations for both gold and nickel have been determined for the solid and liquid states of the gold-nickel system by the application of the Margules equations. These relations are in satisfactory agreement with activity measurements of nickel in the solid state, the observed phase boundaries of the system between 700 and 1725°K, as well as being consistent with data on the enthalpy of mixing.

Jan 1, 1971

By L. B. Pankratz

Thermodynamic data on carbides, nitrides, and other selected substances were reviewed, evaluated, and compiled at the U.S. Bureau of Mines Albany Research Center. Values for Cp°, S°, H° - H°298, -(G° - H298)/T, ?Hf, ?Gf, and log Kf are given in tabular form. Cp°, H° - H°248, ?Hf°, and ?Gf° are also expressed algebraically.

Jan 1, 1994

By P. T. Velu

Solubility of metal oxides in the molten salt electrblytes is an important parameter in the electrochemical processing of metals and alloys. The efficiency of an electrochemical process primarily depends on the quantity of metal oxide present in the electrolyte in the dissolved form and its thermodynamic properties. The activity of CeO2 was calculated using the free energy of fusion of CeO2,{ AG°m, CeO2. The AGOm,CeO2 }was deduced from the values of enthalpy, heat of fusion and melting point of Ce02. The activity coefficients of CeO2 as a function of temperature and melt composition were calculated. The thermodynamic data such as integral molar enthalpy, entropy and Gibbs energy of formation were calculated as a function of composition and temperature.

Jan 1, 1994

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-1301 mass-spectrometer designed for studies-of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase, In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003

By A. V. Tarasov

Investigations of thermodynamic properties of Cu-Ni and Cu-Ni-S systems and mattes have been conducted with the aid of a MC-130 I mass-spectrometer designed for studies of processes of vapor formation of hardly volatile substances. The instrument comprised a combination of an evaporator of Knudsen chamber type with a mass-spectrometer for analysis of the vapor phase. In the process of studies of molten Cu-Ni-S systems and commercial-grade mattes within a temperature interval of 1400-1800 K the partial pressure of sulfur was measured by means of complete isothermal evaporation and the partial pressure of copper and nickel by comparison of ionic currents. The partial pressure values of the components above the molten Cu-Ni-S were used for calculation of activities of the respective components in the melt. The copper and nickel activity data obtained was used for assessing the amount of dissolved losses of these metals in autogenous smelting slags.

Jan 1, 2003