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By Y. -B. Kang

New databases are being developed to provide the capability to evaluate the suitability of present and potential new Mg alloys for automotive applications through cost-effective calculations. An extensive and complete thermodynamic database is being prepared for Mg alloys formed from among 25 present and potential alloying elements. The database is being developed by critical evaluation, modeling and optimization of available phase equilibrium and thermodynamic data. It contains model parameters giving the thermodynamic properties as functions of temperature and composition. Using the FactSage thermodynamic software, users can access the database to calculate the amounts and compositions of all phases at equilibrium at any temperature and composition or to calculate any phase diagram section in multicomponent alloys, to follow the course of equilibrium or non-equilibrium cooling, to calculate corresponding heat effects, etc. A database of densities and lattice parameters of Mg alloys and intermetallics (as functions of temperature and composition) is also being developed in order to permit the calculation of volume changes during cooling and phase transformations, c/a ratios of the hcp phase, etc.

Jan 1, 2006

By Yunyan Wang

Diagrams of pc-pH for the complex ions concentration and pH value and -g- for activity coefficient and ionic strength ln±MnSOI4had been drew based on the thermodynamic principle of coordination chemistry and combined with Pitzer theory at 298.15K. The diagram of -g- indicated that -gincreased sharply from 0.0000 up to 1.2147 when I changed from 0.00 ln±MnSOIln4±MnSO4to 0.09; The increase of -gbecame slowly when I was more than 1.00 and less than 1.69; kept still when I ln±MnSOln4-g±MnSO4was more than 2.25 and less than 4.00. Diagrams of pc-pH illustrated that the minimum solubility of Mn(OH)2(s) increased with the increase of I, the pc increased from 6.5 to 5.5 when I increased from 0.00 to 4.00; The pH of the minimum solubility of Mn(OH)2(s) increased with the increase of I, the pH increased from 11.80 to 12.76 when I increased from 0.00 to 2.89, the pH kept still when I (I was less than 4.0) increased. There is single function relationship between the minimum solubility of Mn(OH)2(s) and relevant pH in different I.

Jan 1, 2010

By Jonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the Ni3S2-FeS matte with either FeOx-CaO or FeOX-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By lonkion M. Font

Due to the known disadvantages of the use of iron silicate slag in the nickel converting stage, i.e., high metal losses, high magnetite content, and low fixation of impurities in the slag, the development of the new proposed "ferrous calcium silicate slag" for smelting and converting processes of nickel is very promising. Hence, considering the successful experimental results of using CaO base slag for the nickel smelting process, a study based on a detailed comparison for the phase equilibrium, and the minor elements distribution between the NilS2-FeS matte with either FeOx-CaO or FeOx-Si02 base slag was investigated. The main results are summarized as: no difference in the nickel losses between both slags was found at high nickel content in the matte, and the fractional distribution analysis for arsenic and antimony pointed out their preferential fixation in the calcium ferrite slag rather than in the iron silicate slag. Considering the energy and pollution issues, the technical feasibility of using calcium ferrite slag in a converting process of the Bessemer matte will have a prominent future for the nickel industry.

Jan 1, 2003

By Yoichi Takeda

Copper solubility in Si02-CaO-FeOx slag equilibrated with copper matte in 10% S02 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag. A classical thermodynamic model postulating CUOO.5 and CuSo.; molecules assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated Si02-FeOx binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeOx-SiOrCaO ternary slag saturated with 2CaOSi02 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Yoichi Takeda

Copper solubility in SiO2-CaO-FeOx slag equilibrated with copper matte in 10% SO2 atmosphere at 1573K was estimated. Essential parameters are activity coefficients of copper oxide and sulfide, oxygen and sulfur potentials and activity of copper in the slag-matte system. A large number of experiments provide proper parameters to calculate copper solubility in slag, A classical thcrmodynamic model postulating CuO0.5 and CuS0.5 moleculcs assists in estimating copper solubility in slag. Additions of Si02 and CaO reduce copper solubility almost in any condition. Copper loss, that is function copper solubility and slag volume, in the silica saturated SiO2-FeO. binary slag is minimally equilibrated with less than 66% copper matte while copper loss in the 50% FeO.-SiO2-CaO ternary slag saturated with 2CaOSiO2 is minimally equilibrated with over 66% copper matte. This slag composition has potential for continuous copper converting, direct copper production or high-grade matte production.

Jan 1, 2003

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By Scott A. Shuey

Keywords: E-Waste, Pyrometallurgy Many might think addressing the issue of e-waste is a new area of study. Electronics disposal has been discussed in some circles for at least the past 25 years. The recycling of electronic waste (e-waste) tends to be a rather complex undertaking when considering the intimate bonding of materials in the average printed circuit board. The development of a recycling process is further complicated when considering the wide variety of products being generated under the heading of ?electronics.? Focusing only on the primary constituents (polymers, Cu, Al, Fe, etc.) tends to lead one to fairly simple flowsheets. Ignoring trace elements, and the various halide species generated, will lead process engineers down a development path that is sure to cause material handling issues. Researchers at Colorado School of Mines are modeling the complex chemistry that exists within the body of e-waste?comprising 39 of the known elements. An understanding of the systems thermodynamic behavior will result in the development of a more robust, long-term process for the recovery of valuable materials from the e-waste stream.

Jan 1, 2005

By C. A. Young, J. D. Miller

Thermodynamic data has been obtained for oleate chemisorption at fluorite (CaF2) and calcite (CaCO3) surfaces using adsorption isotherms determined previously at room and elevated temperatures by in-situ Fourier transform infrared/internal reflection spectroscopy (FT-IR/IRS). Linear regression analysis was used to statistically derive free energy data as a function of temperature assuming oleate chemisorption followed Langmuir-type adsorption. Enthalpy and entropy changes were subsequently ascertained from the Clausius-Clapeyron equation and fundamental thermodynamic relationships. Essentially, no difference in the free energy of chemisorption at the two mineral surfaces was found; however, the differences in enthalpy and entropy values were significant. By comparison, the results showed that oleate chemisorption at fluorite surfaces was more extensive and more entropically driven due to more water being displaced. Results correlate well with values determined in the literature for other mineral collector systems. These findings help explain the greater hydrophobic character of fluorite than calcite in both the absence and presence of oleate.

Jan 1, 2002

By Nestor Cezar Heck

Aim of the present work is to continue the theoretical evaluation of the slags of the fundamental system CaO-SiO2-CrOx-MgO (Ca-O-Cr-Si-Mg quinary system) at the temperature of 1,873 [K], with the help of a computational thermodynamic tool. Driving force for this and the previous research works is the understanding of chromium losses from the molten bath into the slag. Especially motivating is the presence of solid phases in the slag, since they may prevent refractory degradation and help in the production of foaming slags. Nevertheless, Cr-bearing solid phases can lead to Cr losses, being therefore detrimental. Determination of the states of thermodynamic equilibrium for this system using a slag with fixed composition as a start material were made using MgO amount as variable. Results show the impact of the MgO content on the equilibrium phases (molten metal, liquid slag, solids) and their composition for this system.

Jul 30, 2018

By H. Arima, T. Fujita, W. Yen

The copper catalyzed gold oxidation and reduction mechanisms in ammonium thiosulfate solution were investigated by Eh-pH diagram based on the optimum reagent combination for 60 mass% -75 µm silicate ore at 16g/t Au with the maximum gold extraction of 92% and the minimum ammonium thiosulfate consumption of 23 kg/t-ore for 24 hour’s leaching at ambient temperature. The gold recovery by cementation was nearly 100% by Zn and Al powders at Metal/Au mass ratio of 30, and around 95% by Cu powder at Cu/Au+ mass ratio of 50. In order to oxidize the gold efficiently with the less thiosulfate consumption, the stable region of [Cu(NH3)4]2+ should be as wide as possible in the region, where [Cu(S2O3)2]3- was more stable than [Cu(NH3)2]+. In order to reduce gold from the pregnant solution with the less metal powder’s (Zn, Cu, Al) consumption, the stable region of [Cu(S2O3)2]3- should be wider than [Cu(NH3)2]+ on copper precipitation. Zinc powder may recover gold more efficiently than copper powder with the similar trend on the effect of ammonia, copper and thiosulfate. However, the large amount of copper will be co-precipitated along with gold since the stability of zinc ammine and thiosulfate complexes are higher than that of copper’s. Aluminium may reduce gold efficiently at higher thiosulfate concentration and pH. These results were confirmed and compared with the optimum reagent combination for finer grind sample at 100 mass% -75 µm, which is the optimum ore size for the standard cyanidation at 1.0 g/ l NaCN to obtain about 95% gold extraction. The optimum reagent combination was concluded as 0.5 mol/l NH4OH, 0.0001 mol/l CuSO4*5H2O and 0.05 mol/l (NH4)2S2O3 with the result of 94% gold extraction and 3kg/t-ore of ammonium thiosulfate consumption. Gold and copper stabilities were well agreed with the result of coarser grind ore thermodynamically. The lower reagent combination will reduce gold oxidation power, but significantly minimize the reagent consumption. From this pregnant solution, nearly 100% of gold was successfully recovered by zinc precipitation at Zn/Au+ mass ratio of 30. Aluminium and copper precipitations resulted in less than 40% of gold recovery at Metal/Gold mass ratio of 30. The reagent consumption cost on this lower reagent combination followed by zinc precipitation was $1.6/t-ore, while the cyanidation was $3.1/t-ore. Thiosulfate oxidation mechanism indicated the similarity to Belousov-Zhabotinsky reaction.

Jan 1, 2002

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 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 T. Markus, K. Hilpert

Discharge vessels of advanced light sources are made of translucent polycrystalline Al2O3(PCA).These tubes contain salt mixtures, which essentially consist of metal halides. The salt mixture is present as a melt at the coldest spot of the vessel under operating conditions and vaporizes partly. The temperatures of the coldest spot range between 1200 K and 1300 K, depending on the lamp performance. The maximum wall temperatures range up to 1500 K and for special purposes up to1700 K. Important constituents of the melt are alkali halides AX (A = Na, Cs, X= Br, I) and rare earth metal halides LnX3(Ln = Dy, Ho, Tm). Severe corrosion attack on the wall material is observed in the PCA discharge vessels. The aim of this work is to elucidate the corrosion mechanism. Annealing experiments under well defined temperatures were carried out in order to understand the complex chemical corrosion processes. Two different annealing vessels were used, one for experiments under isothermal conditions with a temperature of 1473 K and one for experiments with a linear temperature gradient from 1450 K to 1600 K. The vessels were filled with salt mixtures of different compositions and annealed for 1000 h. The corrosion attack was characterised by XRD, analytical electron microscopy, high temperature mass spectrometry, and chemical analysis of the salt melts. The results of our investigations show that the corrosion attack is caused by vapour species and by the salt melt. The most severe corrosion is observed in vessels filled with mixtures of alkali halides and rare earth metal halides. No corrosion of the alumina is practically observed if pure alkali halides or pure rare earth metal halides are present in the annealing vessel. Keywords: thermodynamic, corrosion, lamps, metal halide salt

Jan 1, 2004

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 P. Taskinen, D. Lindberg, H. Viitala

The formation of copper chlorides in flue dust or deposits in heat recovery boiler of copper smelters or waste-fired boilers may lead to formation of corrosive partially molten deposits on walls and heat exchangers of the boilers. These deposits can contain various other metals, such as alkalis, Fe, Zn, Pb together with oxides and sulfates. In the present study, a thermodynamic model for copper-containing binary and ternary metal chloride systems within multicomponent CuCl-CuCl2-FeCl2-FeCl3- PbCl2-ZnCl2 system has been assessed and optimized based on own experimental phase equilibrium data, as well as literature data. The thermodynamic properties of the liquid phase was modelled using the quasichemical quadruplet model and a thermodynamic database was optimized to predict all available experimental data within the experimental error limits. The thermodynamic database allows for more accurate predictions of potential corrosion-related issues in various heat recovery boilers and waste-fired boilers due to formation of copper chlorides. INTRODUCTION In the copper flash smelting, flue dust can cause severe problems in the gas train, used for separating dust from the SO2-rich off gas, by forming corroding accretions on the walls of the heat recovery boiler. Formation of dust build-ups in the boiler need to be cleaned regularly and potential corrosion damage checked, requiring costly and unscheduled shutdowns of the flash smelting process. Compounds of copper and zinc among other elements having high vapour pressures may volatilize during the smelting of the copper concentrate, forming dust when the process gas cools down. Also, particles of solid or liquid iron oxides originating from the ore get transported with process gas to the heat recovery boiler as a result of entrainment in the flue gas (Miettinen, 2008) The dust deposit build-ups on the boiler walls are formed partly by direct impact of particles and partly by vapour condensation on the boiler walls. The initial deposition takes place by the condensation of vapours that contain zinc, lead, arsenic and other metals having high vapour pressures. Also, low melting point eutectic components of alkali salts such as chlorides and sulphates can act as sticky cohesive particles attaching to the boiler walls. The fine particles landing on the surface of the porous dust deposit layer react in the SO2-rich atmosphere of the boiler to sulphates. The process gas within the boiler contains SO2, O2, SO3, H2O and N2 that diffuse into the porous accretions to form a stagnant gas layer within the dust deposit structure. The composition of this gas layer may differ greatly from the composition of the process gas that is flowing on the surface of the accretion layer. Locally HCl and H2SO4 are formed and even a reducing atmosphere may exist within the dust deposit layer, allowing new reactions to take place. The local micro-atmosphere may enable metal sulphates to be reduced to secondary sulphides and even metallic components. Within the accretion layer, components may be formed that would not be stable in the gas atmosphere inside the boiler (Miettinen, 2008). This may be the mechanism by which for instance chlorides of Cu, Fe and Zn are formed within the deposit layer.

Jan 1, 2019

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