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By P. Fredriksson, S. Seetharaman

In the ladle refining process, the ?FeO?-content of the ladle slag is of great importance in the chemistry as well as the energetics of the process. An optimization of the process requires an accurate knowledge of the thermodynamic activities of ?FeO? in the ladle slags. Due to the discrepancies in the existing data, renewed attempts are being made at the Royal Institute of Technology to generate reliable data for binary, ternary and multi component slags containing ?FeO? at steelmaking temperatures. In order to measure the activities of ?FeO? in the slags, a gas equilibration technique was employed in the present work. The slags, kept in Pt-crucibles, were equilibrated with a CO-CO2-Ar gas mixture and quenched after equilibration. The chemical composition of the slag was analyszed. From a knowledge of the thermodynamics of Fe-Pt system, the ?FeO? activities in the slag could be evaluated. The results of the present studies, together with other literature values, were optimized in the slag software, THERMOSLAG® developed in the Royal Institute of Technology, Sweden. The results of the optimization are presented. Model calculations were performed with the KTH slag software, THERMOSLAG®, by using plant data from OVAKO Steel, Hofors, Sweden. It was found that oxygen estimations in the metal from the ?FeO? analyses of slags, obtained by conventional sampling and analysis methods, where less reliable. Estimation of the oxygen levels utilizing the sulphur partition between the slag and the metal were carried out using the THERMOSLAG® software. Reasonable estimations of the oxygen contents in the metal confirmed that this could be a very useful tool for the plant operator. Keywords: ladle, thermodynamics, slags, ?FeO?, experimentation, modelling, sulphur partition

Jan 1, 2004

By Seshadri Seetharuman

The present paper summarises a series of measurements of the interaction parameter of oxygen in liquid copper with respect to a third element, e(M)o, where M is Mn, Zn, As, Se or Te which are common impurities in the liquid metal. The technique employed was the solid electrolyte galvanic cell method. The cell used may be represented as Pt, W or cermet / Cu-O-M // ZrO2 - CaO // AO, A /PT where AO/A represents a suitable oxide/metal reference. The measurements indicate that Mn and Zn interact very strongly with oxygen in liquid copper while, in the case of arsenic the interaction parameter is nearly zero. The behaviour of the elements Se and Te is unique with respect to oxygen interactions in copper bath. At oxygen levels, xo= 10-4 ? 10-5, the apparent interaction parameters are negative, comparable to that for sulphur. On the other hand, at lower oxygen levels, the results indicate that the interaction parameter values are positive. The results are discussed in the light of some of the theoretical models for solute interactions in liquid metals.

Jan 1, 1993

The reported values of the standard reduction potentials of the Au(NH3)2+/Au(0) and Au(S2O3)23-/Au(0) couples are reviewed to emphasise the experimental difficulties associated with the measurement of reliable values for these quantities. The standard reduction potential for Ag(I)/Ag(0) in ammonia and thiosulphate solutions measured at ionic strength 0.1 and 25oCis used to predict the following relevant stability constants () for gold complexes based on the linear free energy correlations: Au(NH3)2+2 = 1013, Au(S2O3)23-2 = 1024 and Au(NH3)43+4 = 1033. The equilibrium constant ( 10-11) for the reaction Au(S2O3)23- + 2NH3 = Au(NH3)2+ + 2S2O32- based on these stability constants is in reasonable agreement with the measured value (10-9) based on potentiometric and spectroscopic data when excess ammonia was added to a solution of Na3Au(S2O3)2. This also indicates that the stability constant of Au(NH3)2+ is 9 to11 orders of magnitude less than that of Au(S2O3)23-. Relevant species distribution and Eh-pH diagrams based on the revised data are presented.

Jan 1, 2003

By Muhammad A. Imam, Ramana G. Reddy

This study provides a reasonable evaluation of the Mg-B binary system. Magnesium and Boron (Mg-B) alloys were investigated to determine their thermodynamic properties employing solid state electrochemical cells based on CaF2 electrolyte represented as –Pt; Ar= MgþCaMgF4 f gCaF2 k kf½Mg B alloy þ CaMgF4 g=Ar; Pt+ Investigations were performed over the temperature range of 773–873 K to measure the electromotive force (EMF), which was used to derive the partial Gibbs Free energies of the alloys in the composition range of XB = 0.07 to 0.95. The activities of Mg were also calculated from partial Gibbs Free energies. The activities of Mg in MgB2, MgB4, and MgB7 were expressed as a function of temperature respectively, ln aMg = 4.27–9.32 × 103/T, ln aMg = −7.54 + 6.67×103/T, and ln aMg = 4.93–19.57 × 103/T, where T is the temperature in K. From this expression, the activity of Mg for these intermediate phases can be extrapolated at a higher temperature to get the accurate phase boundaries for the Mg-B system.

Mar 1, 2017

By Pedro Jorge Walburga Keglevich de Buzin

The steel production in mini mills generates several process residues, among them the electric arc furnace dust (EAFD). This residue has as main elements Fe, O, and Zn, being classified as hazardous by the presence of Pb and Cd. In recent years, a rise in the chlorine content of this residue was observed, motivated by the increased use of scrap with impurities bearing this element. In this work, a qualitative assessment of the presence of chlorine in the electric steelmaking process is made. Complementing it, theoretical considerations based on the computational thermodynamics tool FactSage show the effects of the chlorine on the mineral species in EAFD and on gaseous species in the gas phase (HCl and Cl2). For this study, PVC polymer was used as the chlorine carrier substance which contaminates the EAF charge; presence of other minor elements in the system such as K, Na and Pb were also considered.

Aug 7, 2018

By Kevin Trumble, David Johnson, Kyungjean Min

The electrolytic manganese dioxide (EMD) production through electrodeposition from manganese nodules by reduction leaching in H2SO4 medium using sucrose as reductant followed by purification through 2-stage precipitation methods is described. The purified leach liquor was the starting solution for electrodeposition. Influence of in situ addition of a cationic surfactant Cetyltri-methylammonium bromide (CTAB) (0–500 mg dm −3) on the surface morphology and electrochemical properties of the EMD was examined. The XRD patterns of the deposited material were indexed to the c-MnO2 phase. FESEM results demonstrated that in the presence of CTAB uniform nanofibrous type grains were formed. Higher concentration of CTAB in the electrolytic bath however, drastically decreased the current efficiency (CE) and increased the energy consumption (EC) during electrodeposition. Under the optimum CTAB concentration of 100 mg dm −3 the obtained CE and EC values were 87.64% and 1.70 kWh/Kg respectively.

Mar 1, 2018

By Katsunori Yamaguchi

Secondary materials, that contain relatively high concentrations of platinum group metals, (PGMs) are treated in copper smelting process. The PGMs lost in the slag is increasing with increasing quantities of scrap treated amount. To determine the portion of the PGMs chemically dissolved and that associated with the mechanically trapped matte in the slag will be a key factor to improve the recovery of those metals. An experimental study was carried out to determine the distribution of palladium between the FeOx–SiO2 slag and the liquid Cu2S–FeS matte at 1573 K and a fixed partial pressure of SO2 of 0.1 atm. It was found that the distribution ratios are around 10−3 for platinum and palladium. The distribution ratios show a tendency to increase when the grade of matte is increased above 60 mass% Cu. In addition, the solubility of platinum in FeOx–SiO2 slag equilibrated with a pure palladium and the Pd-Cu alloy was determined at 1573 K and the range of oxygen partial pressure from 10−9 to 10−7 atm. The solubility of palladium in the slag tends to increase with increasing oxygen partial pressure and activity of CuO0.5 in the slag.

By J. Petersen, H. Naderi, M. H. Nikzad, M. Karimi

In this research, the thermodynamic study of sodium persulfate (Na2S2O8) solution in the presence and absence of H2SO4 and Fe3(SO4)3 was done. Eh-pH and equilibrium distribution diagrams were constructed using Outotec HSC Chemistry Software and the main stable ionic species were determined. Also, the mean activity coefficient and Pitzer model coefficients were evaluated. Effects of system composition, sodium persulfate concentration and temperature were investigated. According to the results, HS2O7 -, HS2O8 -, S5O3 2-, S4O3 2-, S3O3 2-, HS- and NaSO4 - are the main stable species in these three systems. Increasing of sodium persulfate concentration resulted in disappearing of SO4 2- and the appearance of NaSO4 -. The main effect of increasing the temperature from 25 to 75oC, is changing the stability regions of HS2O7 -, NaSO4 -, SO4 2- and S2-. From equilibrium studies, it was concluded that at 25 and 50oC, increasing the persulfate concentration results in a 55-60% decrease for HS2O7 - and an 20- 30% increase for HS2O8 -. At 75oC, HS2O8 - becomes the main species and its percentage decreases with increasing the persulfate concentration. Keywords: Thermodynamic, sodium persulfate, activity coefficient

Jan 1, 2020

By R. E. Aune

In the present work, a critical assessment of the thermodynamic information available for the ternary system Ni-W-0 has been carried out; This was complemented by experimental measurements of the standard Gibbs energy of formation of the ternary compound NiWO, by solid state galvanic studies involving Zr02-CaO solid electrolyte. The assessed thermodynamic data, together with the phase diagram information available in literature, were employed to generate the ternary phase diagram for the system Ni-W-0 in the temperature range 1073-1273 K. The calculation of the phase diagram was carried out by computer optimization according to the "CALPHAD" method. The computed phase diagram has been confirmed at isothermal sections by identification of the phases present in samples equilibrated at defined temperatures.

Jan 1, 1994

By Kazuaki Mita

There are various intermetallic compounds in the Zn-Fe system. We synthesized them at about 673K. A specimen was examined chemically and X-ray diffraction was applied to ensure the formation of intermetallic compounds. Material containing two phases was placed in a Knudsen type effusion cell and the mass spectrum studied to evaluate the vapor pressure of zinc. The thermodynamic properties of intermetallics was then evaluated through measured intensity.

Jan 1, 1999

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen temary system, which is of fundamental importance for discussing the recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, Sb015 and Sb203 in the PbO-SbOu and PbO-Sb203 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Satoshi Itoh

Phase equilibria and activities of the components in the liquid lead-antimony-oxygen ternary system, which is of fundamental importance for discussing the' recovery of lead and antimony from a used lead-battery, have been investigated at 1173 and 1223 K. The two liquid phases of metal and oxide were observed at the temperatures studied, and the tie lines indicating isoactivities were determined. The activities of PbO, SbO1.5 and Sb2O3) in the PbO-SbO1.5 and PbO-Sb2O3 pseudo-binary systems were then obtained by applying the Gibbs-Duhem equation to the phase relation of metal-oxide equilibrium. Both in the pseudo-binary systems the activities exhibit negative deviations from Raoult's law. The vapor pressures of lead, antimony and lead oxide, antimony oxide were calculated by using the activities of the components in the lead-antimony-oxygen ternary system. As a result, an oxidation of antimony concentrated in an anode slime followed by evaporation as antimony oxide Sb406 was found to be considerably effective for the recovery of lead and antimony from a used lead-battery.

Jan 1, 2003

By Wei-Tong Du, Yu Wang, Gang Wen

Carbon dioxide (CO2), a major component of the greenhouse gases, could be comprehensive utilized as a valuable resource to oxidize vanadium during the converter vanadium extraction process. The thermodynamic software, FactSage, was utilized to study the oxidation ability and theoretical cooling ability of using weak oxidant CO2 as coolant in vanadium-containing hot metal. Besides, experimental research on vanadium extraction in CO2 and O2 mixed blowing extracting process had been undertaken. The results indicated that the elements C, Si, V, Mn etc. could be oxidized by weak oxidant CO2, and the content of V2O3 in slag was approached to pure O2 blowing. Furthermore, CO2 had a remarkable cooling ability and the molten bath temperature kept on decreasing as CO2 blowing rate increases. This research has proved that CO2 and O2 mixed blowing in vanadium extraction process are effective.

Jan 1, 2015

By H. F. Feldmann

This work was done to provide thermodynamic, electrical, physical, and compositional data on the seeded combustion plasmas of seven coals for the design of MHD generators. The systems were assumed to be at equilibrium, and the design data were generated by solving for the composition of both gas and liquid phases with a digital computer. The coals reported in this study include a western subbituminous, a Pennsylvania anthracite, and five representative bituminous coals. The data include dewpoint temperatures of both slag and seed. A Mollier diagram for each coal is given to allow graphical generator calculations.

Jan 1, 1970

Thermodynamical data of importance in connection with copper smelting have been reviewed and a collection of the most reliable information is presented in Tables XXV-XXVIII and Figs. 67 and 6 8 (folding plate). The data given in these figures and tables consists of (i) graphs and equations showing the variations in the temperature range 0-2000°C. of the standard free energies of formation of most of the oxides and sulphides met with in copper smelting (Table XXV and Fig. 67); (ii) equations showing the temperature variation of the free energy of formation of iron silicates (Table XXVI); (iii) graphs showing the variation with temperature in the range 1000°-1600°C. of the standard free energies of the principal reactions occurring in the smelter (Fig. 6 8 ); (iv) the standard heats of formation at 1200°C. of the main iron and copper compounds and gases reacting in the smelter (Table XXVII); (v) the standard heats of reaction at 1200°C. of a few of the reactions for which the free energy relationships were given in Fig. 6 8 (Table XXVIII). The data presented are discussed in more detail.

Jan 1, 1953

This report presents overview of the authors' results of thermodynamical investigation of some important metallurgical processes and phenomena. Among them: carbo thermal reduction of silica, and boron oxide, silicon carbide obtaining from different precursors, investigations on copper and manganese ores processing, investigations on pollution from different sources. Special attention is paid-to thermodynamical approach to investigation and estimation of multi component multi element compositions stability, developed by the authors. Also are discussed some auxiliary but' important for the thermodynamical investigations issues.

Jan 1, 1997

By Zhang Chuanfu, Tan Pengfu

"A thermodynamic model is developed to simulate nickel flash smelting process. In the nickel flash furnace, oxidation of concentrate occurs at one end, and reduction of slag occurs at the other. The model makes use two zones, namely the reaction shaft/settler zone and the appendage zone and accounts for 6 phases (matte, slag, silica, magnetite, Cu-Ni alloy and gaseous phase), 13 elements (Ni, Co, Cu, Fe, S, 0, N, C, H, Si, Al, Mg and Ca) and 33 chemical components in nickel flash smelting system. The compositions of matte, slag and gaseous phases in equilibrium are calculated by using the data of free energies of formation and activity coefficients of components. Two nickel sulfide species are used to allow for the modeling of sulfur-deficient mattes. The model predictions are compared with the known industrail data from Kalgoorlie Nickel Smelter, and excellent agreement is obtained. The model can be a very useful tool for monitoring and optimizing the actual industrial operations of nickel smelting process. The distribution behaviors of Ni, Co, Cu, Fe, S and 0 in the nickel smelting furnace depend on the process parameters such as smelting temperature, volumes of air, the content of the elements~ charge and oil.1. IntroductionThe nickel flash smelting furnace essentially consists of a reaction shaft where nickel sulfide concentrate is partially oxidized with air, a settle zone where matte and slag are allowed to separate, and a slag cleaning end where coke is added to provide for the reduction of the oxidized nickel from slag, and electrodes are used to provide heat.The theoretical model to consider a mass balance for copper flash furnace is developed by S. Goto and R. Shimpo[1][2J. However, this can not be true for nickel flash furnace as a whole since oxidation of concentrate occurs at one end (in the reaction shaft/settler), and reduction of slag occurs at the other (in the appendage). Despite these limitations, an acceptable pseudo-thermodynamic description of the furnace can be achieved using essentially two zones, namely the reaction shaft/settler zone and the appendage zone. Compositions of gas, slag and matte in two zones are calculated."

Jan 1, 1998

By M. W. Wadsley

"Physical and chemical property models are widely used in process engineering. There exist, in the published literature, completely empirical models of ''thermodynamic properties"", that is, property models that are not consistent with the laws of thermodynamics. There also exist property models that purport to be thermodynamically consistent but are flawed in their implementation. There are also published property models that are consistent with the laws of thermodynamics but that do not reproduce property values with an acceptable accuracy. A practicing engineer might be asked to assess very different property models for which there are a variety of claims. This paper discusses features of thermodynamic and empirical property models that may assist in their practical evaluation and implementation."

Jan 1, 2005

By Jing Zhan, Gui Li, Wei-feng Li, Li-Hua Jiang, Chuan-fu Zhang, Jian-yang Hwang

Thermodynamics analysis for processing the charge with lead concentrate and lead sulfate-containing materials in bottom blowing smelting furnace was conducted. The results show that the technology of large-scale processing PbSO4- containing materials with PbS concentrate in bottom blowing furnace under the condition of using high-iron slag type, batch heat supplement, high temperature and rich oxygen is thermodynamically feasible. The exploration test and industrial experiment confirm the results. When S content in mixed ore is 16~17% with coke foam content of about 5%, the lead paste amount can be increased up to 40%.

Jan 1, 2015

By Zhihe Dou, Guozhi Lyu, Liping Liu, Yi Luo, Ting-an ZHANG, Xijuan Pan, Zhuolin Liu

Due to the high energy consumption, long technical process, low usage rate of vanadium during the traditional smelting vanadium steel process, a new method for decarburization by CO2 to directly smelt vanadium-containing steel in blast furnace was proposed. In this paper, the thermodynamics of CO2 decarburization in molten iron process was calculated out by FactSage. The thermodynamic calculations indicated that in standard state, the transformation temperature of C and V was 1357 °C; the oxidation order of element was Si, C, V, Mn and S when using CO2 as oxidant. The experiment of blowing CO2 temperature showed that decarburization reaction temperature was 1550 °C, carbon content could be decreased to 0.676%, the decarburization rate was 88%. There was no effect on vanadium content in molten iron during the decarburization process, vanadium content was 0.323%, which meets the request of vanadium mould steel.

Mar 1, 2018