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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 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 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 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 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 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 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

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 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 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 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

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 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

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