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By E. Kuzeci, R. Kammel

"Lately various voltametric methods have gained increased attention as an analytic tool in hydrometallurgy. Voltammograms with mercury drop electrodes or glassy carbon electrodes provide information about the electrocrystallization of cathodic deposits and allow calculation of kinetic data by means of characteristic parameters like the peak potential and peak current and their variation with the voltage scanning rate.Cyclic voltammograms are also suitable for identification of reaction sequences. Voltammograms with carbon paste electroactive electrodes containing metal sulphide additions reveal information about the dissolution behavior. The stripping voltammetry can be applied to analyze metal ions and organic additives (e. g., thiourea) in extreme low concentration. Typical application of the various methods studied with microcomputer controlled measurement system are explained by examples selected from copper hydrometallurgy.IntroductionThe use of electroanalytical methods in metallurgical process control can be dated back to the starting period of industrial copper refining, when the deposition of the metal ions was followed electro-gravimetrically by weighing the electrode with deposits (1). The principles of metal deposition and dissolution have not changed but the methods to follow these phenomena were subjected to noticeable developments and especially the introduction of polarographic investigations by Heyrowsky (2) has greatly contributed to the progress in electro-analysis. A review about the fundamental work on the electrochemical kinetics in earlier time is compiled in a monograph of Vetter (2). With the steady improvements in the instrumental techniques, it is nowadays possible to apply several current and potential modulations for measurements with improved selectivity and sensibility. There is however, still a lack in theoretical interpretation of the data obtained. More theoretical information are already available for linear voltametric methods for systems where reduced as well as oxidized species are dissolved in the electrolyte (4, 5). Some recent investigations have also shown the reliability of these techniques to study electro-crystallization (6, 7). Main fields of the application in the hydro - and electro-metallurgy are:"

Jan 1, 1989

A comprehensive numerical capability for the analysis of Thermal Spray (TS) systems consisting of a three-dimensional compressible, turbulent flow Navier-Stokes model and a multi-phase particle flow model in Lagrangian formulation, was developed. This capability is validated for a set of flow conditions typical for TS. The developed methodology is used for analysis of the JP-5000 TS gun gas and coating powder flow conditions. Modeling and analysis of particle/turbulent eddies interaction is performed. Details of gas flow field, particle temperature, and particle velocity histories, and particle temperature, velocity profiles in the system are presented. For the validation of numerical analysis, the computed results are compared with available experimental measurements. The flow phenomena for different flow parameters are analyzed and explained as the results of gas dynamics and heat and momentum transfer between the gas and particle phases. This methodology can be used for process control and reliability improvement, and has the potential to significantly improve TS gun performance through control of its parameters.

Jan 1, 1996

By C. Schwandt

Recent research work has led to the development of a new electrochemical hydrogen sensor, which is based on a proton conducting solid electrolyte in conjunction with a self-contained solid hydrogen reference standard and is operated at elevated temperatures. The incorporation of the internal hydrogen reference renders the sensor versatile and user-friendly and makes it attractive for practical exploitation. The present article focuses on the utilisation of the sensor as the integral part of a probe for the quantitative determination of hydrogen in molten aluminium and aluminium alloys. The main features of the sensor and the probe as well as the measuring technique are discussed. Experimental results obtained with the novel analyser in trials under industrial conditions are presented and highlight the good performance of the device.

Jan 1, 2003

By Ali Akbar Mottahedi

Chromate conversion coating is a process for making a complex layer at the surface of zinc galvanized steel which makes the metal more resistant to corrosion, especially at marine atmosphere, and increases the adhesiveness of color. In this work the influences of various compositions on commercial zinc galvanized steel sheet to the color of chromate conversion coating has been investigated at normal temperature and the factors that affect the control and optimization of the process have been determined. A bath composition of 20 g/liter Cr203 and 10 g/liter NaOH and a dipping time of 50 seconds at room temperature (25-30°C) make a desirable color of chromate coating. A slow agitation at a constant pH of I (with additions of NaOH or H2SO4) assures a constant bath condition and develops the color. This kind of coating has more corrosion resistance and this bath condition and composition are also more economical.

Jan 1, 2003

By M. P. Bohrer

A closed-loop hydrometallurgical process has been developed for treatment of smelter flue dust generated by copper recycling. The process is a semi-continuous operation in which zinc, iron, and copper are first extracted from the dust with a sulfuric acid solution. The lead and precious metals, initially present in the dust, remain as solids and can be recycled to the copper smelting furnace. Cementation with iron and zinc metal purifies the zinc and iron-rich liquid stream prior to spray drying. The spray-dried product, consisting of a mixture of zinc sulfate monohydrate and iron sulfate monohydrate, is a desirable micronutrient additive for use in animal feeds. Treatment of the smelter flue dust in this manner will generate a positive return on investment, as well as mitigate a potential environmental liability.

Jan 1, 1992

By David C. Lynch

FeCl3 particulate of 10 to 100 um in diameter was reacted with radicals produced in an oxygen plasma at pressures between 1 to 20 Torr. The particulate, in a fluidized bed, was positioned above the plasma to avoid over heating the oxide product which is known to lead to crust and clinker formation[ 1 ]. Reaction between the iron chloride and the gas phase occurred at temperatures between 66 and 226 °C. Oxygen radicals react with the surface material to a depth of approximately 2.5 4m. Surface material, analyzed with a x-ray technique, indicates that the maximum amount of FeCl3 reacted on a weight basis was found to be approximately 67%. More typically, 40 to 50 wt% of the chloride was reacted within 30 minutes to 1 hour.

Jan 1, 1996

By R. K. Amankwah

The ability of Streptomyces viridosporus in sorbing heavy metals from wastewater has been investigated. It was found out that the biomass of the soil microorganism could be used in sorbing Pb2+, Cu2+, Zn2+ and Ni2+ ions from acidic solutions of metal ion concentration between 10 and 100 ppm. Over 99% of Pb2+ and 88% of Cu2+ ions were sorbed from wastewater of concentration 10 ppm with Ni2+ and Zn2+ recording values below 50% for a contact period of 4 hours. The quantity of metal ions sorbed per gram of biomass from the wastewater was in the order Pb2+ > Cu2+ > Ni2+ > Zn2+ and this is related to their electronegativities. Biosorption was sensitive to variations in pH and in the range investigated; metal binding was optimum at 5.5. About 63% antimony was also sorbed from dilute cyanide solution.

Jan 1, 2003

Pyrometallurgical reactors constitute a key processing component in the total primary and secondary resource cycle, being involved both in primary smelting, converting and extraction, as well as the reprocessing of scrap, from aluminum cans to end-of-life automobiles. To effectively control the overall resource cycle, one needs to take a systems modeling approach of the whole cycle, seeking to also understand the dynamic process behavior of the individual components of the cycle, and then especially the part that contributes most to the chemical conversion, namely the pyrometallurgical reactor. This paper highlights the role of pyrometallurgical thermodynamics, in the whole resource cycle and specifically places equilibrium thermochemistry in the context of process dynamics where large variable inventories are recycled or maintained within the system. This paper will therefore review the semi-empirical dynamic modeling tools, which are used to model complex systems with the specific goal of developing dynamic predictive models, which also include slag-alloy chemistry, towards controlling the recycling in a feed forward manner. To illustrate the primary processing side, high carbon ferrochrome will be presented as a brief case study. It also will show how the distributed nature of the chemistry of melts in the case of primary extraction, and secondary materials such as recycled end-of-Iife vehicles, have a significant impact on the process outcomes and model predictions. It is therefore argued that the fundamental thermodynamics and kinetics in metallurgical reactors playa final crucial role in modeling the closed material cycle, but only when it is used in conjunction with process systems theory based on reconciled data for parameter estimation and model calibration.

Jan 1, 2003

By W. P. lmrie

The recent years have seen many copper smelting operations become uneconomic due to a combination of low metal prices, high energy and labor costs, environmental requirements and high investment costs for modernization or replacement. Since a copper commodity requirement remains, the industry will recover, but many operations will need to determine which processes can offer the best prospect for economic operation and readiness for reliable investment and implementation. Corporate investment decisions involve the judgment of many factors in addition to topical technical aspects. Consideration of plant management and operational aspects are thus included. Taking account of such proven processes as conventional, flash and continuous smelting, plus modified conventional and new unproven processes, this paper gives a systematic approach to aid optimum choice for a modernization or grassroots investment. Actual achievements in energy form alternates, conservation and cost effectiveness are highlighted, and areas of remaining potential for energy saving are discussed.

Jan 1, 1983

By I. Kim, J. C. Choi, W. D. Cho

"The effect of yttrium addition on the oxidation behavior of Fe3Al intermetallic compound was investigated in the range of temperature 800 to 1100 °C in 0.2 atm 02 in terms of oxidation rate and oxide adhesion. The oxidation rate of alloys, Fe-14.3 wt% Al and Fe-14.1 wt% Al-0.3 wt% Y, was nearly identical and the parabolic rate constant calculated as a function of temperature is Kp=5128 exp[-39506(cal/mol)/RT] mg2/cm4 hr.Rapid cooling and ultrasonic stress tests were carried out to test adhesion of scale formed on the alloys. While the oxide layer formed on the Fe-Al alloy without Y was found to be fragile and detached easily during the tests, the oxide layer formed on the Fe-Al alloy containing Y was protective, dense, and adhesive. The following two mechanisms were proposed to explain the adhesion improvement of Ah03 formed on the Fe3Al containing yttrium : (1) the addition of yttrium decrease generation of growth stress in alumina scale because the preferential diffusion of yttrium through grain boundary in alumina scale prevent internal oxidation of Al, one of main causes of growth stress, and (2) the second phase formed on the oxide scales prevents crack propagation through the scales, leading to better mechanical stability of the oxide scales.IntroductionIron aluminides have attracted the attention of many researchers as a candidate for use at high temperature because of their excellent oxidation resistance due to the formation of protective alumina scale. In order to resist aggressive environments at elevated temperatures, oxide scale formed on iron-uluminum alloy must satisfy the following three requirements : (1) thermodynamic stability (2) slow growth rate (3) adherence on substrate. According to Wallwork and Hed [l], the most suitable alloys for high temperature application are Fe, Ni, and Co alloys with the protection of Si02, Cr203, and Ah03 scales. While chromium oxide can vaporize as Cr03 above 1000 °C and silicon oxide may form low melting silicate [2,3], Alz03 has a high melting point and is the most stable among the three oxides thermodynamically [6]. In this respect, iron aluminides forming alumina seem to be most suitable for use at high temperature. However, alumina scale formed on the iron aluminum alloys tends to be easily spalled during oxidation due to the combination of growth stress and thermal stress."

Jan 1, 1998

By N. J. Tannyan

Laboratory bath smelting tests were conducted to determine the feasibility of smelting nickel- copper concentrate directly to a low iron matte in one step. Concentrate, air/oxygen and a silica flux were fed to a matte-slag bath kept in MgO crucibles at I 300°C. Various oxygen enrichments and smelting rates were used to maintain 0.5 to 2 wt% iron in the product matte. The slag losses are comparable to those obtained under similar industrial conditions. Due to the highly oxidizing conditions required to produce mattes with low iron contents, it is not recommended to target iron contents below about 2% in the matte. The specific bath smelting rates were equal to or higher than those in various industrial bath smelting processes.

Jan 1, 2003

By Lisa E. Helberg

"Titanium tetrachloride is produced through the chlorination of a variety of titanium bearing ores, some occurring in nature, and others enriched in titanium content by a variety of ""beneficiation"" processes. The chlorination step can produce a variety of metal chloride impurities, such as iron chlorides and vanadium chlorides, which must be removed from the TiC14 before it can be used to produce pigmentary TiO2, titanium metal or for any other commercial use. The requisite manipulations involve both physical and chemical separations in a multi-step process. The history of various purification strategies will be discussed.TextThere are a wide range of titanium-based products available, all of which start with titanoferrous ore of some type. Two main routes are used to convert ores into products, known as the sulfate and chloride processes. The sulfate process uses sulfuric acid to digest the ore, separate the impurities, and then precipitate titanium dioxide from the resulting titanyl sulfate (TiOSO4) via metatitanic acid. This process can also supply TiOS04 for other applications."

Jan 1, 2011

By Mahmood Alemrajabi

When LKAB processes their iron ores in northern Sweden, they generate apatite as a by-product. The apatite has been recovered by flotation and the concentrate contains about 0.4 wt% rare earth elements (REE). Both phosphate rock and REE are listed as critical raw materials for the European union. In the present study, the recovery of REE within the nitrophosphate process of fertilizer production has been studied. In the first stage, the REE are precipitated and isolated as a phosphate concentrate. For further purification and individual separation of REE by solvent extraction, removal of phosphorous from the concentrate to enhance the dissolution of REE in mild acidic solutions is essential. In this study, thermal treatment of the concentrate with sodium hydroxide at elevated temperatures followed by water leaching has been studied in order to separate the phosphorous and thereby facilitate dissolution of the REE. The results show that 95% of total phosphorous initially present in the REE phosphate concentrate is removed after thermal treatment with NaOH 1:1 mass ratio, at 400 °C.

By Andrey Tarasov, Erki Unn, Valery Paretsky

"The stability of the markets of energy resources and labor in countries of the Baltic Sea Region including Estonia is determined to a significant degree by the use of combustible shales as fuel and their distillation resulting in generation of up to 70% of non-recyclable waste. The objective of this business plan is to substantiate the investments for establishment of a new facility in Estonia for waste-less and environmentally safe processing of fossil minerals and man-made products generated in the shale industry, as well as other hazardous wastes. The proposed facility will use a basically new waste processing technology developed in Russia - i.e., processing in sparged molten slag This technology eliminates any release of harmful pollutants to the environment and a facility using this technology does not require, therefore, any sanitary protection zone.IntroductionIn the Baltic region, and first of all in Estonia and some other European territories, there are large natural deposits of combustible shale, which due to the lack of other own resources of energy and hydrocarbons for the chemical industry is burned and distilled with low technical and economic efficiency generating large amounts of toxic and highly toxic wastes and intermediate products. Currently, the penalties for disposal of such wastes have grown to such an extent that shale burning and distillation might become unprofitable. This might result in suspension of the given operations, which in turn will affect in an adverse way the markets of energy resources and labor market in those countries. Furthermore, in addition to the “shale problem”, Estonia, similarly to most member countries of the European Union, faces the challange of environmentally safe processing of highly toxic wastes, such as municipal solid wastes, oilpolluted materials, medical wastes and infected materials, spent rubber tires, etc. These wastes are at present stored or processed with release of a significant quantities of extremely toxic cancerogenic substances (dioxins, furans) or collected and exported for treatment at an extremely high cost and with a loss of valuable components contained in these types of waste and often with return of supper toxic processing products."

Jan 1, 2008

By J. M. Floyd

"Top submerged lance furnace developments started in CSIRO in the early 1970s and was given the name Sirosmelt. In the early work the technology was developed for tin smelting and processing tin slags but once a small pilot plant was established other slag processing applications were soon recognised and evaluated for various copper, nickel, zinc and cobalt-containing slags. The process was tried for copper smelting and converting, which was proven in the small pilot plant in 1978. In the same year the first commercial application of the technology was established for the recovery of tin from slags at Associated Tin Smelters, Sydney. Work on lead smelting was initiated by the CSIRO team in the late 1970s and laboratory work led to pilot plant trials by Mount Isa Mines.In the second decade of the technology the focus of development became commercial acceptance of the technology through marketing, development and application by Ausmelt and Mount Isa Mines; the former commercialising and developing the technology for a wide range of applications, while the latter concentrated on its own commercial needs of copper and lead smelting. This decade saw a number of commercial plants built in Australia, with considerable interest becoming evident from other parts of the world. Towards the end of this decade Mount Isa also entered into the business of marketing of the technology through rights dating to the joint work with CSIRO in the late 1970s.So far, after five years, the third decade of the technology has been characterised by diversification of applications of the technology to areas outside the non-ferrous and precious metals production industry. The waste processing and recycle industry and the iron and steel industry have recognised that the top submerged lancing system is a new type of reactor with many significant features which provide new opportunities for processing a range of materials under good environmental controls in a cost effective manner.I hope this audience will excuse my boldness in talking about the third decade of the technology when we are only half way through! I am aiming in this paper to not only talk about the past, but to try illustrate the future directions which I envision."

Jan 1, 1996

By John J. Jonas, Sang-Hyun Cho, Ki-Bong Kang

"The recrystallization behavior of Nb micro alloyed steels containing Cr, Mo, Ni and Ti. was studied using hot torsion testing with the aim of modeling the recrystallization processes and the mean flow stress taking into account the microstructural behavior during hot rolling. The kinetics of static and metadynamic recrystallization were characterized and appropriate expressions were formulated for the recrystallization kinetics. These are shown that the recrystallization kinetics depend on steel composition and the processing conditions. The stress-strain curves were determined in order to derive new equations for the peak stress, peak strain, mean flow stress and softening kinetics. The peak strain is influenced by the presence of alloying elements; their addition, which has a solute drag effect, retards the rate of grain boundary motion, shifting the peak to the right. The addition of Nb to the steel results in a significant increment in the activation energy for hot deformation, and Mo has smaller effect than Nb, but Cr has the opposite effect. It was also found that the deformation activation energy in these steels was not altered by the addition of Ni. The rate of metadynamic recrystallization increases with strain rate and temperature and is observed to be independent of strain, in contrast to the observations for static recrystallization.The mean flow stress (MFS) calculations, based on the Sims analysis, are then compared with the predictions of a model based on an improved Misaka mean flow stress equation in which solute effects, strain accumulation, as well as the kinetics of static and metadynamic recrystallization are accounted for. Good agreement between the measured mean flow stresses, which is obtained from the mill logs of POSCO Kwangyang #3 HSM (hot strip mill), and 'predicted ones is obtained over the whole range of rolling temperatures. The results demonstrate that dynamic recrystallization followed by metadynamic recrystallization, supported by the unexpected load drops, sometimes occurs for the rolling schedules studied in the present analysis."

Jan 1, 2001

By Zhongliang Tian, Yun Cheng, Yexiang Liu, Ming Jia, Yanqing Lai

"A fundamental electrochemical study of Si ions in Na3AlF6-LiF melts and electrolysis using liquid cathodes was conducted. Cyclic voltammograms (CVs) clearly showed the depolarization of silicon deposition on liquid cathode by forming chemical complexes with the liquid solvent metals. Besides, co-deposition of Al and Si is possible when Si ions are insufficient in the molten salt. Based on the electrochemical results, silicon diffusion into liquid cathode is modelled and evolution of Si activity with concentration is deduced by a mathematic approach. Electrochemical study using liquid metals as working electrodes, can be used as an alternative approach for the acquisition of basic data on alloy behavior. Galvanostatic electrolysis showed that liquid cathodes are appropriate to collect the deposited solid silicon and the highest collection efficiency is almost 85%.IntroductionRecent years have witnessed an increasing demand for solar-grade silicon (Si) by the photovoltaic industry [1-4]. The preparation of high-purity metals through electrolysis and electrorefining offer many advantages such as low cost, low-energy consumption, and environment-friendly process, and thus has been widely used worldwide. From the perspective of electrochemistry [5-7], by utilizing the electronegativity difference between the impurities and Si and controlling the relevant process parameters, it is possible in principle to electrodeposit monatomic Si from a Si4+-containing compound melt. Moreover, because the carbon content of the high-purity Si obtained through electrolysis can be effectively controlled and used as a very ideal raw material in the preparation of electronic-grade and solar-grade Si, the preparation of high-purity Si through electrolysis has received widespread attention [8,9]. Monnier et al. [9] used a graphite electrode to obtain high-purity Si (99.9 %-99.99 %) from Si02/Na3AlF6 system through electrolysis; however, because the Si was precipitated in a solid form and showed poor conductivity, the deposition rate was too slow. Olsen et al. [10] obtained high-purity Si films via electrodeposition in K2SiF6/KF-LiF system by selecting electrode materials with high surface quality (such as Ag and graphite). However, in order to ensure the film quality, the deposition current density must be relatively low (10-50 mA/cm2), resulting in a low current efficiency and low deposition rate, which are not conducive to reducing energy consumption and applying to practical use"

Jan 1, 2014

By Rodney L. Williamson

Vacuum arc remelting (V AR) is an industrial metallurgical process widely used throughout the specialty metals industry to cast large alloy ingots. Part of the V AR control problem consists of adjusting arc current to control electrode melt rate which also depends on the electrode temperature distribution. Because the temperature distribution responds very slowly (1-4 hours depending on size and material) to changes in melt power, the melt rate response is history dependent and highly nonlinear. The situation is complicated further because measurement of the electrode temperature distribution is not practical. To solve the problem of accurate, responsive melt rate control. a low order electrode melting model has been developed and incorporated into a V AR process controller. Data from laboratory and industrial tests show that the goal of responsive, accurate melt rate control has been achieved, even when melting under highly dynamic process conditions. Keywords: Vacuum Arc Remelting. Model-Based Control

Jan 1, 2003

By R. H. Rubisov

Sulphuric acid pressure leaching of nickeliferous laterites has attracted considerable attention from the nickel industry during the past five years. The process is especially advantageous for limonitic laterites that mostly contain goethite, because iron precipitates releasing acid and thus rendering low acid consumption. It is also applicable to mixtures of limonites and saprolites, although at higher acid consumption due to magnesium. Effective process design requires the solubility of metals that precipitate during the process to be known. In the present work, determination of metal solubilities is based on a simple speciation program that assumes the presence of only one dominant complex for each metal. The thermodynamic data for the precipitation reactions are extracted from high-temperature experiments with monometallic systems published previously. The validity of the approach is then tested against mixed bimetallic systems, and finally applied to calculate the solubility of aluminium, iron and magnesium in laterite leaching effluents "at temperature". In both cases of limonitic feed and limoniticfsaprolitic blends, the prediction closely follows metal solubilities measured experimentally at temperatures from 230 to 270°C and at terminal he acidities ranging from 10 to 75 g/L.

Jan 1, 1999

By F. Chabchoub

A mathematical model has been developed to study the influence of process variables on the horizontal Ohno continuous casting process. The model simulates the heat transfer and fluid flow in a wide plate ingot of pure tin. A two dimensional numerical analysis based on a control-volume finite difference approach, the Semi-Implicit Method for Pressure-Linked Equations algorithm (SIMPLER), and an Enthalpy Transforming Model was used. The shape and position of the solid-liquid interface were calculated at different casting speeds, ingot thicknesses, and cooling device characteristics, as well as various mould temperatures. Results of the mathematical model were compared with

Jan 1, 1992