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By C. Caballero, A. Warczok, K. Itagaki, A. Moyano, J. Font

The Codelco Norte Smelter process 2,500 tpd of arsenic-bearing concentrates with an arsenic content of up to 1.5% in one of its two main smelting units, the Teniente Converter. The product, 1,100 tpd high-grade matte or white metal, is traditionally fed to the PS converters, while the 1,700 tpd of slag is fed to the slag cleaning electric furnace for copper recovery. This is achieved in a very reductive environment which reduces the viscosity of the slag and enhances the sedimentation of the high-grade matte droplets. The behavior of arsenic in this non-oxidative environment was studied at lab-scale and fundamental thermodynamic data were obtained. Based on these data a thermodynamicbase model to assess the arsenic behavior in reductive environment was developed. It is based on a mass balance for the reduction and sedimentation stages performed in an electric furnace which allows the recovery of high-grade matte droplets after decreasing the viscosity of the slag. This model can be a very suitable tool for predicting fractional distribution of arsenic in the slag cleaning electric furnace, when the distribution ratio, vapor saturation degree, temperature, y As and pO2 are given.

Jan 1, 2007

By William E. Frazier

The presence of minute amounts of sulfur (10ppm) in nickel-base superalloys has been associated with reduced oxidation resistance and the premature spallation of protective coatings. Removal of sulfur by annealing these alloys in a hydrogen atmosphere has been successfully attempted by several researchers. This paper examines the fundamental thermodynamics and kinetics governing hydrogen desulfurization of elemental nickel. Limiting conditions for successful desulfurization are delineated. Assuming that the diffusion of sulfur is the rate limiting process of desulfurization, the effectiveness as well as time associated with hydrogen desulfurization is explored.

Jan 1, 1994

By R. C. Reed, L. T. Wu, H. C. Harada, K. Kawagish, R. T. Wu

Oxidation of pure metals is a chemical reaction in which the metal loses one or more electrons, such that the atom of the metal changes from the neutral state to a positively charge ion and reacts with oxygen to form an oxide of the metal. The oxide can form as a protective and adherent scale that slows down further oxidation, or may spall off repeatedly, exposing fresh metal surface to react with oxygen. In multi-component alloy systems such as typical high temperature NiCrAlY bond coats, more than one oxidation mechanism may take place at once and thus, complicates the study of oxidation. To better understand the competition between formations of oxides of different compositions, a thermodynamic assessment is carried out to study the oxidation mechanism of a Ni-27Cr-9Al (at %) ternary alloy. Based on the assessment, it is demonstrated that the layering of different oxides can be determined, with the most stable oxide (alumina) existing directly above the metal-oxide interface and the least stable oxide (nickel oxide) locating on the outer most layer. A comparison between the calculated results and previously published experimental observations shows excellent agreement.

Jan 1, 2010

By Shilai Yuan, Huimin Lu, Zhijiang Gao, Panpan Wang

"Solvent refining of silicon through using Si-Al melts is a valid method to remove the impurities from metallurgical grade silicon (MG-Si) melt. The thermodynamic behavior of impurities Fe, Al, Ca, Ti, Cu, C, B and P in MG-Si during the solidification of MG-Si was studied based on the available thermodynamic parameters and experimental data. The morphology of inclusions was investigated by Scanning Electron Microscope (SEM). The chemical composition of inclusions in MG-Si and Al-Si melt was analyzed by EPMA. It is found that the amount of white inclusion reduces and most impurities are solved into the Al-Si melts. After solidification of Si–Al alloy using induction heating and acid leaching, impurities can be effectively removed. The solidification of silicon from the Si–Al melt is found to be more effective for purification than general silicon solidification.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. Multicrystalline silicon has now become the main material in the photovoltaic market because of its low production cost and because of the relative high conversion efficiency of solar cells made from this material, which has been studied for a long time [1-3].Electronic grade (EG) silicon (99.9999999% Si) is commonly used as the raw material to produce SOG-Si (99.9999% Si). Silicon produced from the chemical routes restricts the development of solar cells due to environment threaten, high energy consumption and low productivity. Purification of metallurgical grade silicon (MG-Si) is a low cost, environment friendly method. Although several metallurgical processes such as directional solidification, vacuum refining and electron beam melting [4], have been developed, the cost reduction and refining efficiencies for manufacturing silicon is still have to be further optimized.In the purification process, it is difficult to remove boron and phosphorus by the conventional metal refining method. The refining efficiency depends on the segregation behavior of different elements in solid silicon and the liquid phase. The segregation ratios of all investigated impurities were found to be much smaller than the segregation coefficients between solid and liquid Al-Si melts [5]. For instance, the segregation coefficient of B in Si is 0.8 at the silicon melting point (1687K), whereas it is around 0.2 when silicon is solidified from Si-Al melt at 1273K. For phosphorus the segregation coefficient is 0.06 when silicon is solidified from Si-Al melt at 973K°C, which is much less than 0.35 for recrystallization from liquid silicon. Since the segregation coefficient of boron in silicon is 0.8, it cannot be removed by directional solidification."

Jan 1, 2014

By Xueqin Li, Xuewei Lv, Yu Zhang, Wenchao He

In order to make full use of the chromium-bearing vanadium titanium magnetite with chromium, a new process of “direct reduction-electric furnace smelting separation” has been developed for recovering the iron, vanadium, titanium and chromium in recent years. In this paper, FactSage, one of the most frequently-used thermodynamic calculation software, was used to calculate the reduction degree of Fe, V and Cr with different n C/nO (mole ratio of carbon and oxygen). It was found that the suitable operating conditions of direct reduction process were n C/nO > 1.07 and T > 1473 K. In addition, the direct reduction experiment of Hongge vanadium titanium magnetite was carried out and the obtained samples after direct reduction were analyzed by XRD and chemical composition. The result shows that the metallization rate of carbon-containing pellet is nearly 90%.

Mar 1, 2018

By P. Piga, O. Sammarco

There is a markedly increasing tendency to design deeper and deeper mines, to use larger amounts of explosive per round, to increase the advance rate of the excavations and so the natural ventilation tends to be more intense in the new mines. For this reason, the mines that make use of powerful mechanical ventilation should also take into account such factors as natural ventilation pressures, especially in the case of mines excavated in high-temperature rocks for which natural ventilation is particularly intense. The results of the studies reported here refer to a very hot mine excavated in an area with a high geothermal flow (the Boccheggiano - Campiano mine, southern Tuscany). At various external temperatures, experimental measurements and analyses have been made of the trend of the thermodynamic characteristics of the ventilation air and of the trends of the air/rock heat exchange along the downcast shaft and along the upcast shaft. These data were then used to work out approximate values of the corresponding natural ventilation pressures. After having identified the most conspicuous variations of the thermodynamic parameters of the ventilation air and the factors causing them, an assessment was made of the repercussions they have on the air flow rates and, above all, on the climatic conditions of the underground excavation sites. The natural ventilation pressures were found not to be constant in time; indeed they change continously and it is difficult to predict the changes. Moreover, it was found that their influence on the ventilation of a section of the mine network is greater if the effect of mechanical ventilation on that section is weaker. In the mine section where the measurements were carried out, some portions were found where the ventilation could become insufficient as a result of the effects of natural ventilation pressures. Finally, some guidelines to be followed in designing hot mines have been put forward which ensure efficient ventilation throughout the network at times with the aid of the natural ventilation pressures, which in certain circumstances may reach very high values in mines of this type.

Jan 1, 1987

By Nourreddine Menad

Plastic materials have been associated with electric and electronic applications since the early days of the electrical industry. Plastics can amount to 30 percents of the scrap mass. Generally, they are treated with flame retardants such as halogenated ones and they can result in different toxic chemical compounds. These plastics can be used as combustibles in the recovery of copper and precious metals. However, during their combustion, halogenated flame retardants can produce dibenzo-p-dioxins and dibenzo-furans. The estimated thermodynamic data of several organic compounds resulting from combustion of electric and electronic scrap, have been used in conjunction with the program HSC to calculate the conditions for dioxin and furan formation. The results show that the formation of the dioxins is dependent on the quantities of carbon, hydrogen, chlorine and oxygen reacting in a given system, as well as on parameters such as temperature and pressure.

Jan 1, 1998

By Eric Klaffenbach

Valorization of slag from metallurgical industrial processes becomes ever more important as this may help optimizing and reducing the use of natural resources such as rock and sand. In view of this objective, metallurgical processes have to be analyzed in order to modify the slag composition so that it will meet the expected requirements of potential users of these resources. This paper gives the results of a thermodynamic analysis of the flash smelting process to understand the impact of operational parameters on slag chemistry and elemental partitioning in the process. It is shown that an increase of the matte grade and temperature leads to higher deportment of Pb, Zn and As to the slag. With increasing matte grade the volatilization of these elements decreases. Furthermore, the results indicate an increasing solubility of Cu and S in slag at higher temperatures.

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000

By Animesh Jha

Univariant diagrams are constructed for the reduction of nickel and cobalt oxide and sulphide minerals. The results from the carbothermic and hydrogen reduction of sulphide minerals are compared. The importance role of lime and calcium sulphate in controlling the emission of sulphurous- gases during reduction reaction is also explained. The mechanism of carbothermic reduction of nickel sulphide is explained by examining the sulphur exchange and reduction reactions. The phase equilibrium relationships that determine the formation of multicomponent liquid are characterised. Also the governing equilibria for inert atmosphere calcination- roasting of nickel and cobalt sulphide minerals are also described for the metallization of nickel and cobalt.

Jan 1, 1993

By Miao Tian

Large quantities of copper complex resources are produced globally and urgent to be cleanly processed. This article presents a thermodynamic analysis of mixed smelting process including low-grade polymetallic copper sulfide concentrates, high copper content sulfide concentrates, metallurgical by-products (copper removal slag from lead metallurgy), and copper powder from electronic waste. A top blown smelting reactor to simulate mixed smelting process is developed using a metallurgical process simulator, METSIM. Reactor parameters, heat loss and phase distributions are estimated from actual plant data. The proper proportion between complicated primary and secondary copper resources is determined by analyzing the influence of the feed rates of various resources, oxygen, silica flux and revert on the smelting performance. Autogenous smelting process is built by optimized matching materials of copper complex resources, in terms of the reactor temperature, copper content in matte and slag, and the percentage of magnetite in slag.

By L. B. Pankratz

Thermodynamic data on the elements, oxides, sulfides, halides, and selected hydrides, carbides, nitrides, carbonates, sulfates, silicates, and miscellaneous compounds were reviewed, evaluated, and compiled at the Bureau of Mines. Values for CP°, S°, H° -H°298, ?Hf°, and ?Gf° are given in tabular form. A brief thermodynamic background and a number of examples and applications are presented.

Jan 1, 1984

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 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