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By S. R. Steinacker, H. Schnideritsch, J. Antrekowitsch

Primary copper industry flue dust plays an increasingly important role in the creation of matte and slag. From a thermodynamic point of view, the chemically formed section of fine particles play a techno-logically interesting role in comparison to the mechanical carry-over. Here, the volatilization and the sub-sequent condensation in the off gas system lead to a characteristic distribution of the contained elements which are represented by various compounds of desired metals like zinc and lead. On the contrary, certain undesired components such as arsenic, bismuth and cadmium accumulate within the product as well. This paper describes existing models and theories concerning the formation of flue dust in the copper smelting process and presents a thorough investigation of the physico-chemical fundamentals by verifying assump-tions with thermodynamic calculations. By fully understanding the formation patterns at different stages and temperatures within the process, better knowledge for flue dust in the first step of the pyrometallurgi-cal copper smelting can be obtained - hence leading to new ideas and incentives for the following stages in the copper production cycle.

Jan 1, 2015

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 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 A. D. Davis

Limestone-based material is effective for reducing arsenic concentrations below the current limit of 10 parts per billion for drinking water, typically resulting in final concentrations of about 4 to 6 ppb. However, in laboratory and field testing, further reductions to the 1 ppb range are difficult to achieve with limestone unless other material such as iron is added. The removal mechanism with untreated limestone appears to be the formation of a low-solubility precipitate of hydrated calcium arsenate, in the form of arsenate-apatite. Likely reactions and thermodynamic data indicate a theoretical removal limit of about 2 to 4 ppb for arsenic using raw limestone. Limestone also can reduce concentrations of cadmium and lead below 1 ppb in water, resulting in >99% removal efficiency. Thermodynamic constraints appear to be favorable for reactions involving the formation of otavite during cadmium removal and the formation of hydrocerussite during lead removal.

Feb 27, 2013

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 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 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