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By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from Copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu10), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, Cu2O bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties of the CaO-FeOX-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation. -

Jan 1, 2003

By Fumito Tanaka

The Mitsubishi process is the sole pyrometallurgical process for the continuous production of blister copper from copper concentrates and has been successfully operated around the world. The development of calcium ferrite slag (CaO-FeOx-Cu20), the so-called "C-slag", has enabled continuous converting from matte to blister copper in the commercial scale operations. Commercial interests in the slag led to many papers over the CaO-FeOx slag. However, CU2O- bearing slag has not been studied well due to experimental difficulties. The authors have quantified the thermodynamic properties ofthe CaO-FeOx-Cu2O system. The results have been utilized to analyze various issues related to the converting furnace, such as the magnetite precipitation from the slag or from blister copper and to develop better controlling criteria for the continuous converting operation.

Jan 1, 2003

By Akira Yazawa

Oxidic dissolution loss of metal in slag is discussed thermodynamically in terms of oxygen potential, activity coefficient and equilibrium constant. To understand basic principle, regular solution model is applied for model calculation of the activity behaviour of metal oxide in FeO-SiO2-CaO slag, and effects of slag composition, temperature, and basicity of oxide on dissolution loss are demonstrated. As: a simplified but practical conclusion, the dissolved metal loss in slag is inversely proportional to activity coefficient of metal oxide, and also to FeO content in slag when amount of slag is taken account.

Jan 1, 1994

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By Vladimir Mindin

This paper presents results of thermodynamic investigations and experimental' studies of some essential for pyrometallurgy of sulfide concentrates topics. Among them: 1. Thermodynamic simulation and experimental investigations of roasting process, 2. Thermodynamic investigations of sulfur dioxide off-gases treatment technologies. 3. Investigations on "Mind in -Kiknadze" effect of suppression of sulfur dioxide formation during sulfide concentrates roasting in the vapor containing atmosphere. 4. Thermodynamic simulation and experimental investigations of sulfide concentrates and manganese containing materials co-roasting processes. Some essential aspects of thermodynamic simulation techniques are also discussed.

Jan 1, 1998

By Tan Pengfu

By using computer-aided techniques of equilibrium calculations for multicomponent and multiphase systems, a computer model has been developed to simulate QSL, KIVCET and Outokumpu flash lead smelting processes. A mathematical description is studied using two zones or three zones, namely smelting zone and slag reduction zone for QSL furnace, or offtake shaft zone, smelting shaft zone and electric furnace zone for KIVCET furnace. The amount of each component in lead, slag and gaseous phases under equilibrium is calculated by using the data of free energies of formation and activity coefficients. The predictions by the present computer model are compared with the known data from QSL-Plant at Korea Zinc Co. in Korea, KIVCET-Plant at Nuova Samim Co. in Italy and Outokumpu Co. in Finland. The agreements between the computer predictions and the known data are excellent, so that the present computer model can be used to monitor and optimize the actual industrial operations of direct lead smelting.

Jan 1, 1998

By Florian Kongoli

The behavior of cobalt as a by-product in the NilCu smelting and converting processes effects directly the quality of the final products as well as the revenues gained from the overall process. An effective way to evaluate and predict this important behavior is thermodynamic modeling which reduces the time and the cost of experimental investigation. In this work a thermodynamic model of cobalt-containing matte phase in NilCu smelting and converting processes is presented. The model predicts a priori the thermodynamic properties and phase relations of the ternary and multicomponent matte based solely upon the optimized parameters of the binary systems. This model can be used with other models such as those of slag, metal, gas etc. to predict various aspects of cobalt behavior such as matte- slag, metal-slag distribution, etc.

Jan 1, 1999

By Pengfu Tan

Lead blast-furnace bullion cools to near its freezing point in an operation known as copper drossing or hot drossing usually contains 0.02-0.06% copper. The removal of this copper is usually carried out in a batch operation known as sulfur drossing. Sulfur is stirred into the bullion at temperatures near its freezing point, and the dross of copper and lead sulfides that floats to the surface is skimmed off manually. A thermodynamic model has been developed to simulate the copper drossing. The phase diagram of Pb-Cu-S system has been calculated, and the effects of the process parameters, such as temperature, copper content, and sulfur content, on the drossing process have been simulated and discussed.

Jan 1, 2006

By Pengfu Tan

A thermodynamic model has been developed to model the desilverising process of lead by the addition of zinc during lead refining, whereby silver-zinc solid solutions are formed, and floats out of the dissolved zinc/silver in the lead bath. The solubility of silver-zinc solid solutions in lead decreases with falling temperature. A number of variations and modifications of the desilverising process are modeled, and applied to a wide range of silver contents in lead bullions in the industry.

Jan 1, 2005

By Pengfu Tan

A thermodynamic model of KIVCET lead smelting process has been developed. The model has the capability to predict the distribution behaviors of Pb, Zn, Fe, S, O, As, and heat balance in KIVCET direct lead smelting furnace. The compositions of lead bullion, matte, slag and gaseous phases, and heat balance are calculated. The effect of the ratio between oxygen and feed on the chemistry of the smelt and heat balance of the coke checker has been simulated and discussed. The thermodynamic model also helps to understand the tapping issue of the lead bullion. In this paper, some applications of this model in the industry have been presented.

Jan 1, 2006

By S. R. Reddy, R. G. Reddy

"The Margules equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.1 IntroductionIn most of the pyrometallurgical high temperatures processes, interactions of solutes such as oxygen, nitrogen and sulfur, with the solvent atoms are most important during refining processes. There are numerous theories are developed [1-25] to interpret the thermodynamics of solutes in multicomponent alloy systems. Which are mainly developed using statistical or Quasichemical equations.Wagner [4] developed one energy parameter ideal solvent model based on activity coefficient of solutes compositional dependency. He used one energy interaction term which is not able to account for interaction energy parameters for the same solute concentration at different solvent compositions and also it is ineffective model to predict for strong interacting systems."

Jan 1, 1996

By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of 'a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By Songsong Wang

Recently, replacing Pierce-Smith converting process with the oxygen bottom-blowing continuous converting technology has become a new research focus. Based on the principle of Gibbs free energy minimization, the thermodynamic model of oxygen bottom-blowing continuous converting multiphase equilibrium system has been established. The elements distribution behavior is calculated at the same burden composition and operation parameters as the industrial production. The results show that the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in crude copper are 0.06, 0.0030, 0.070, 0.38, 0.39, 0.020, 0.017, 0.034, 0.010, respectively, and the absolute errors of the mass fraction (wt%) of Cu, Fe, S, Pb, Zn, As, Sb, Bi in slag are 0.53, 0.81, 0.020, 0.23, 2.5, 0.0048, 0.0010, 0.0030, 1.49, respectively. The calculated results agree well with the actual industrial production data, indicating that the model can be well applied in the oxygen bottom-blowing continuous converting practice.

By Dmitri Nassyrov, In-ho Jung

"All relevant thermodynamic and phase diagram data in the CaO-Fe10-CaF2 system were critically reviewed. One set of model parameters describing the Gibbs energy of all phases has been obtained as a result of critical evaluation of the available data and optimization of the model parameters. The Modified Quasichemical Model was used to describe the interactions in the liquid phase. All calculations were performed using the FactSage thermochemical software.IntroductionSlags contaimng CaF2 are of significant interest to the steelmaking community. Notable examples of slags containing significant amounts of CaF2 include Electro-slag Remelting (ESR) slags [1] and mould flux for continuous casting [2]. The role of these slags is, among other things, to refine steel by absorbing inclusions and dissolved impurities. During slag-steel interaction, some iron from the steel will inevitably get oxidized and form iron oxides which will dissolve into the slag. With this in mind, it is important to understand the interaction between CaF2 and Fe,0 for accurate prediction of slag composition and process optimization. A thermodynamic optimization of the CaO-FetO-CaF2 was thus undertaken."

Jan 1, 2013

By Omid Marzoughi

Chromium has a wide range of applications, including as an alloy addition in various steels and also as a corrosion resistance coating. Carbothermal reduction of chromite ore (FeCr2O4) in a submerged arc furnace is an important industrial process for extracting chromium, but the energy consumption is excessive. It is suggested that one area for future research is the low temperature carbothermic solid state reduction of chromite to produce an intermediate product, which can subsequently be upgraded to ferrochromium. In this regard, a thermodynamic model has been developed to investigate this process and the effects of temperature, carbon additions and ore composition on the recovery of chromium and the grade of the ferrochromium, have been studied. Further development of the model may allow it to be applied to the simulation of other processes for the recovery of chromium from chromite ores.

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 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 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 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