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By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By F. Sekula

Tetrahedrite and siderite are two main valuable minerals present in the silver Mária Bana deposit. The tetrahedrite concentrate prepared from it by flotation has certain specific properties from the metallurgical point of view. Siderite is concentrated in the flotation tailings. The paper presents results of the laboratory and pilot-plant testing of the combined hydrometallurgical and pyrometallurgical methods proposed for treatment of the tetrahedrite concentrate and siderite waste. The testing conditions were based on thermodynamic analysis of the reactions that proceed in the process. The proposed technology makes it possible to separate copper from sulphur, mercury and iron in a straightforward way. Copper, after its refining, can be subsequently treated in the finishing operations. At the same time it is a valuable source of precious and noble metals. The siderite-containing flotation tailings can be converted to iron of the technical purity and slag. The proposed method is a good starting point for the development of the closed-cycle technology.

Jan 1, 2006

By H. Masuda

The lijima Zinc Refinery started operation in 1972, and has today an annual capacity of 200, 000+-Zn. The hematite process was employed for the first time and the ideal of waste-free refinery has been pursued for 30 years. In recent years, however, only half of the hematite produced would be sold to the cement industry and hence a reduction of arsenic level has been necessary in order to sell the entire amount produced, The arsenic cementation process with zinc powder, developed through a long time laboratory research was found among some options as the best for the hematite process. The construction work started in 2000 and the facility was put into operation in 200 I. As a result in the same year all hematite were sold to the cement industry. The outline of this project, present operations and technical issue are reported in this paper.

Jan 1, 2003

By Vladyslav M. Sokolov

The cost effective and environmentally friendly recycling technology was developed and tested. It enables utilization of the fine nickel-base superalloy scrap in a form of heavily oxidized scarfing granulates. The process of granulates generation was discussed in details. Their properties were investigated. The results of literature search showed anticipated sufficient improvement of the properties of cast iron by its alloying with the elements from the scarfing granulates. The novel alloying approach is based on the two stage reduction operation. Firstly thegranulates were partially reduced in a solid state by their exposure with powdery carbon at the range of 1550 ? 1700°C. Then the gotten product was efficiently introduced into liquid iron since it has a form of fine natural agglomerates for arranging the optimal conditions for reduction of the granulates. The thermodynamic evaluation demonstrates higher reduction efficiency of carbon and silicon dissolved in iron than of the same elements in a form of the separate phases. The considered process partially provides itself by energy since the reaction of reduction of the chromium oxide by silicon dissolved in liquid iron has exothermal character. The mostly complete extraction of Ni was received. The sufficient reclamation of Cr was gotten at the same time.

Jan 1, 2006

By Z. Smieszek, W. D?browicz, J. Pawlowski, G. Krawiec, J. Czernecki, J. Por?mbski, S. Gizicki

Rapid development of the automotive industry and motorization has been observed in Poland over the last decade. This phenomenon has increased the amount of used car batteries requiring recycling and has thus posed new challenges for their processing. Orzel Bialy" S.A, is the major secondary lead smelter in Poland. Ibis paper describes the program for smelting technology modernisation and productivity increase through the application of oxy-fuel burners, which has been implemented at "Orzel Bialy'' S.A. The main objective of smelter modernisation, which was to increase the furnace productivity by 20%, has been achieved. This paper outlines the previous and present state of the lead acid battery scrap smelting technology at the "Orzel Bialy" S.A. Specifications of the burners and of oxygen installation are given. Industrial tests with the modernised smelting technology and optimisation of the process parameters are described, and the results obtained are discussed.

Jan 1, 2000

By Y. A. Chang, L. M. Pike, C. R. Kao

"Knowledge of the site preference of ternary solute additions is essential to developing an understanding of how these solutes affect the properties of B2 intermetallic compounds. A quasichemical model will be presented which is able to predict the site preferences of dilute solute additions to tliple defect B2 compounds. The only parameters required are enthalpies of formation at the stoichiometric composition. General equations are developed which can be used to determine site occupations and defect concentrations for dilute as well as non-dilute solute additions. These equations use atom pair bond enthalpies as the parameters. It is found that the site preferences of dilute additions are not always in agreement with predictions based on the solubility lobes in ternary Gibbs isothelms. Predictions for dilute additions to NiAl and FeAl are compared to expel1mental results found in the literature. Satisfactory correlation is found between the model and the experimental results. In addition, the predictions from the model on vacancy concentrations in Fe doped NiAl are compared to recent experimental results by the authors.1.0 IntroductionIntennetallic compounds with the B2 crystal structure such as NiAl and FeAl have been investigated recently for possible use as structural materials in high temperature, oxidizing, and/or corrosive environments. The major limiting property of these materials has been a lack of sufficient room temperature ductility. Attempts to improve the ductility have often been made through ternary or higher order alloying. For B2 compounds, substitutional alloying additions can occupy either of the two sublattices and this site occupancy can be crucial in determining how the alloying addition affects the properties of the alloy. In this manuscript we will discuss the use of thelmodynamic modeling to predict the site occupancies of ternary alloying additions in B2 compounds with the triple defect structure."

Jan 1, 1996

By I. J. Moon

The reduction behavior of hematite by H2 and H2-CO gas mixtures was investigated to elucidate the reduction mechanism at 800-950 °C. The hematite compacts were made by Cold Isostatic Pressing to produce compacts of uniform shape and size. The compacts were sintered at 1000° C for 30min, and showed a contraction of 29%. Mercury pressure porosimeter was used for measuring the total porosity, pore size distribution and pore surface area of the compacts. Reduction was measured by means of weight-loss technique using Cahn Balance (Model : TG-171, capacity log, accuracy f 10pg). Microscopic examination and X-ray analysis were used to correlate the structure of reduced compacts with the mechanisms of reduction. Neither chemical reaction control nor diffusion control is adequate in describing the complete course of reduction of the hematite compact. The reduction of hematite compacts was initially controlled by the chemical reaction at oxidelmetal interface. The reaction goes through a transition phase .where it is undergoing a mixed control, followed by the diffusion control towards the end of the reduction. The values of apparent activation energies for chemical reaction control were 3.48-8.43 kcal/mol depending on the gas compositions.

Jan 1, 1997

By Ana Bohé

Nowadays, Gas-solid processes are widely used in the industry. The chloration and carbochlorination of metallic compounds are some of this kind of non catalitic heterogeneous reactions. In particular those related with extractive metallurgy of refractory elements (Zr, Ti, Nb, Ta, RE, etc). The development of materials to be used in reactors at elevated temperatures and with high corrosion performance, enhance the application of this kind of processes. Although they are currently carried out in the production of many comodities, the mechanism of most of them are yet not well understood. The present work is a deep discussion on the most important aspects to take into account for determining the mechanism of gas- solid reaction, and those criteria fulfil in this analysis were applied to chlorination and carbochlorination examples. The microstructural characteristic of solids, the mass and heat transfer phenomenon, the adsorption and desorption of gaseous species on active surface, surface diffusion processes and chemical elementary steps, which are the mainly contributions to the mechanism of these reactions were analysed. Furthermore, the effect of them on the reactivity of solids and the control step of the reactions were determined. The application of catalitic mathematical models to this kind of reaction and the modification for the better interpretation of experimental results is also undertaken. The most appropriate experimental procedures for following these reactions and the microstructural characterization techniques needed to be use in each case, there limits and applicability are also indicated.

Jan 1, 2006

By Jörg Wallner

In order to limit SO2 emissions, the Montanwerke Brixlegg AG has installed a desulphurisation plant with the primary aim of reducing the peak emissions from the copper converter that are of particular ecological concern. The author discusses the process requirements, the desulphurisation process selected and the results achieved.

Jan 1, 1996

By Glenn C. Miller

Cyanide is the most common lixiviant for extraction of precious metals, and its efficient use in open pit mines has contributed to the increase in world production of gold during the previous two decades. With this expansion of precious metals mining using cyanide, public concerns have developed in response to the inherent public perception of cyanide as a tox-in as well as a series of environmental problems that are directly or indirectly related to cyanide use in open pit mining. Some of these have technical or regulatory solutions, while others will require additional investigation before they can be resolved. The following discussion will summarize some of the public concerns regarding the use of cyanide in precious metals mining. The issue of cyanide use in large scale precious mining is controversial, and recent banning of cyanide use in open pit mines in Montana, or complete banning of cyanide in Hungary has reflected those international concerns. The underlying basis for some of the bans (e.g. Montana) reflect a general concern of the environmental impacts of mining, rather than specific issues related to risk of cyanide use. The human safety record for cyanide use, particularly in the developed countries is good, and cyanide is clearly the most efficient lixiviant for precious metals. Indeed, the relatively short lifetime for cyanide in the environment renders it one of the less problematic chemicals used for extraction of gold from ore. Mercury amalgamation or use of bromide as a lixiviant are certainly much more problematic. What, then, is the basis f~r the international concern about precious metals mines that use cyanide. Ifuse of cyanide for gold recovery is to continue, what additional infom1ation needs to be developed that will allow a better management of the risks of cyanide? Which of the concerns are directly related to cyanide, and which are indirect concerns that more related to effects of open pit mining. Under what conditions should use of cyanide be discouraged? DUl::ing June of 2000 the United Nations Environmental Program conducted a two-day workshop on cyanide use in mining that was attended by persons from the mining industry, regulators and environmental community. Support and attendance at this workshop reflected concerns by all three groups on further restrictions for cyanide use and the emerging potential for guidelines for better management of the catastrophic release of cyanide-containing mining waste. The following discussion is meant to focus-on those risks and explore the basis for an often negative reaction to precious metals mining using cyanide. It is presented in the format of a statement, followed by a discussion. While admittedly provocative, the statements are meant to express the concerns? of the public regarding cyanide and the mining industry.

Jan 1, 1998

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By E. T. White, Dean Ilievski

"Mathematical modelling of the precipitation process requires that the kinetics of crystal growth, nucleation and agglomeration be known. This paper reviews the current state of knowledge on these precipitation sub-processes (ie. growth, nucleation and agglomeration) and describes a number of experimental techniques for estimating their kinetics. The experimental methods used to generate the precipitation data and the data analysis techniques used to extract the kinetics information from the data are discussed separately. There is no universal ""best"" technique for determining the kinetics. However, studies on multi-crystal systems are more reliable for modelling purposes than are single crystal studies. The selection of a technique will depend on which sub-processes are present. A problem with all kinetics studies is that there is generally a large uncertainty in the estimated kinetic parameters. This stems from the scatter in the experimental data being further propagated by the mathematical techniques used to extract the kinetic parameters.IntroductionCrystallisation operations, including precipitation, are widely used in a number of hydrometallurgical processes to recover a desired component or to remove an undesired impurity. The goals of industrial precipitation processes are to maximise the recovery while maintaining product quality (generally product crystal size distribution, purity and morphology and product handling properties). Knowledge of the precipitation mechanisms and kinetics is invaluable for designing new precipitators or for improving existing units. The mechanistic and kinetic information is generally incorporated into mathematical precipitator models, which are then used for process design and optimisation."

Jan 1, 1996

By Tamas Kekesi

Anion exchange in HCl media is considered an efficient alternative to the combination of the conventional purification methods. Anion-exchange distribution functions have been determined for cobalt and the main impurity elements by the technique of batch equilibration. Results were confirmed by spectrophotometric investigations and elution tests. Based on the new and the available distribution functions, combined with the assessment of thermodynamic stability, a procedure of anion exchange separation has been devised to eliminate virtually all the impurities from the cobalt-chloride solution. Separation of copper has been enhanced by the introduction of a preliminary step under reduced conditions. The rest of the impurities are eliminated in a second anion-exchange step applying rinsing and elution stages under oxidized conditions. The optimum parameters of the procedure have been determined according to performance characteristics (purification ratios, yields and volume efficiencies) derived from the analysis of elution curves obtained with laboratory scale ion-exchange columns. Special computer programs have been developed to facilitate thermodynamic simulation, analytical correction and data processing.

Jan 1, 2003

By H. Kurokawa

Sumitomo Metal Mining decided to expand copper production capacity of Toyo Smelter and Refinery to cope with the recent copper demand growth in Asia, and to survive by reducing cost. The expansion plan is promoted to increase electrorefined copper production capacity from 270,000 metric tons in 2001 to 450,000 metric tons in 2007. The major changes in smelting section are introduction of the rotary steam dryer, renewal of the feeding system for flash furnace, improvement of the concentrate burner, modification of the flash furnace cooling materials, renewal of the slag cleaning furnace, modification of the flash furnace waste heat boiler, installment of a new converter furnace, enlargement of two anode furnaces. In addition, the gas cleaning system was upgraded and the second acid plant was installed. In the refinery section, the existing tank houses have been operated at high current density of 300A/m2 using the conventional starting sheet cathode technology and moreover a new tank house utilizing the permanent cathode technology was constructed. Although the copper production capacity has been increased, SO2 emission has been kept the lowest in the world through consideration of influence on the environment by expansion project.

Jan 1, 2006

By Pengfu Tan

A thermo-chemical model of the copper P-S converter and a viscosity model for the converter slag have been developed to predict the behavior of magnetite in the converter slag, amounts of slag and matte, compositions of slag and matte, volume of the bath, bath temperature, slag blow endpoint determination, SEMTECH OPC signals, and the viscosity of converter slags. The predictions of bath temperature, slag and matte compositions, and magnetite content in the slag have been validated by the industrial data. The effects of fluxing strategy, returns and skim charges, oxygen enrichment, and temperature on the magnetite formation in the slag have been predicted and discussed. The effect of oxygen potential, SiO2/Fe in slag, detection of slag blow endpoint, and temperature on Fe3O4 content in converter slag, slag viscosity, liquidus temperature of converter slag and skimming operation has been modeled and discussed as well. Some applications of the industrial operations have been presented.

Jan 1, 2009

By Ryosuke O. Suzuki

A new cell concept for calciothermic reduction is proposed in which the titanium dioxide instead of TiCl4 is used as the raw material for reduction, Metallic calcium is needed as the reductant of a thermochemicaily stable oxide, such as TiO2. CaCl2, is selected as the solvent of Ca and simultaneously as the solvent of CaO. The reduction system consists of a single cell where both the reduction reaction and the electrolytic reaction for recovery of reducing agent coexist in the same molten CaCl2 bath. A few mol%Ca dissolves in the melt and gives the media a strong reducing power. Sufficiently deoxidized metallic titanium deposits and forms a slightly sintered granular sponge. Both mechanisms of the halide flux deoxidation and the electrochemical deoxidation work efficiently for these fine precipitates, The reducing agent is in situ recovered by electrolysis of CaO because the molten CaCl2 he a relatively large solubility for CaO Some cell designs and modifications are proposed for industrial applications.

Jan 1, 2003

During electrowinning of nickel chloride, hydrochloric acid was regenerated instead of chlorine in a two membrane cell, by segregating the chloride catholyte with an anion exchange membrane, and the sulphate anolyte with a cation exchange membrane from the middle electrolyte (ampholyte) compartment. Successful operation of such a cell depends on controlling chloride leakage through the cation exchange membrane to the anolyte. Small amounts of chlorine gas could be detected in the oxygen evolved at the anode. In this paper, the chloride. leakage as a function of various types of cation exchange membrane and different composition of the anolyte is reported and discussed. Ag+ was added to the anolyte to eliminate chloride leakage to the anode. The cell voltage, electrode potential and voltage drop over the membrane as a function of current density has also been investigated.

Jan 1, 1996

By M. L. Cunha

The lack of control of As and Sb compounds from copper smelters and converters has rendered some chalcopyrite containing arsenopyrite, stibnite and tetrahedrite minerals unusable for metal extraction. In the present investigation, we have studied the carbothennic reduction of Portuguese chalcopyrite mineral concentrate in the presence of lime/CaS04 and CaS04/Si02. Thermodynamic equilibrium calculations were performed to study the distribution of As and Sb between metal and the CaO-Si02-FeO slag phase. The phase equilibrium calculations also show the effect of oxygen partial pressure on the increase in the volume of the slag phase, which helps in lowering the copper metal formation temperature and facilitates a better separation between metal, matte and slag. The reduction reaction kinetics was studied between 850°C and 1100 °C, and the phases formed were identified by X-ray powder diffraction and scanning electron microscopy techniques. The importance of this research for using recycled matte, lean and rich minerals with As and Sb is also explained.

Jan 1, 2001

By Robert Vidal

A model of the homogeneous chemistry and transport processes within the separator of a chrome-alum electrowinning cell is introduced, discussed, and compared to experiment. The influence of diffusion, electromigration, and convection are included; it is found that convection was the dominant mode of transport for the experimental conditions. Simulation results explain experimental observations concerning an apparent disappearance of dichromate ions produced at the cell anode. The relation between potential drop across the diaphragm and the current and fluid flow is also illustrated. The model is used to recommend future experimental and theoretical work.

Jan 1, 1994

By Richard P. Roberts

This paper will discuss the methods for the cooling of aluminum melting furnace? dross .and their impact on the environment. Also discussed will be a case history of an AROS Dross Processor installation, which is designed to maximize the recovery of metal content of the dross in a manner which is not only environmentally cleaner, but which also prepares the output in such a way as to facilitate downstream processes. Handling of the discharged material will be discussed in regards to the recycling of the preserved metal content and deposition of the unusable-materials.

Jan 1, 1992