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By Matthew Tunnicliffe, Akram Alfantazi, Paul Nesbitt, Farzad Mohammadi

"Lead and its alloys are proper candidates for anodes in electrowinning processes mainly because they are insoluble in the leach solutions and relatively cheap. However, the annual cost of corrosion problems associated with these anodes is millions of dollars. In this study lead-silver and lead-calcium anodes were tested under typical nickel electrowinning conditions and the effect of chloride on the corrosion performance of the anode materials was investigated. Corrosion rates of the anodes were calculated using the discharge plateau (reduction of lead dioxide to lead sulfate) after galvanostatic experiments. It was found that lead calcium anodes have the highest corrosion rate both in the presence and absence of chloride. Surface morphology of the electrodes was studied using SEM and the corrosion products were characterized using XRD.IntroductionLead (Pb) is usually the preferred material for commercial anodes since it is insoluble in the leach solution and the costs are manageable. One advantage of using an insoluble material as an anode is the higher purity of the cathodic deposits and better quality of the end product. During nickel electrowinning, metallic nickel is deposited on the cathode while oxygen evolution reaction (OER) takes place on the anode. In practice, relatively high potentials are necessary for the reaction to proceed at the desired rate because of the high overpotential of OER on lead. Lead anodes get oxidized in typical electrowinning conditions and usually have two to three years of lifetime. Although the price of each anode is insignificant, the overall cost of corrosion of these anodes is considerable, which is due to the large number of anodes used in a plant, typically two to three thousand. Therefore, corrosion is a significant problem associated with lead anodes in commercial nickel electrowinning plants and industries show interest in addressing this problem. Corrosion of lead electrodes in acidic environments has been previously the subject of many research studies [I-7]. It has been reported that, during the anodic polarization of lead, several phases may be present on the surface, depending on the potential range that is being studied [8]. Lander showed that lead is oxidized at potentials higher than 0.252 YsHE with tetragonal lead monoxide being the main reaction product [9]. At 0.666 YsHE lead can transform to lead dioxide; however, it is not stable and transforms to lead sulfate and lead oxide. At potentials higher than 1.684 YsHE, lead dioxide is eventually a stable phase and forms a protective layer on the surface [I 0, 11]. Under conditions of a typical nickel electrowinning plant, usually a 200 A/m2 current density is passed through the electrodes."

Jan 1, 2012

By Sergio Demetrio

Based on the current reality of the copper smelters industry, besides the advances that have been and are expected for the next few years, the authors present a futurist vision of the processing of copper concentrates and copper smelters in the years 2000. Outlined new development strategies and ways of improvement in this business, including research, development and management of the works that today posses characteristics of a profitable operation, as well as the changes expected with respect to the entry of new actors and the creation of new products The authors finally bet for small or tailor-made smelters with ad hoc technology for their raw materials and few units to coordinate -devoted to specific concentrates using high technology and low manpower. Considering the in-situ hydrometallurgical route, as well as the pyrometallurgical route in works or conversion facilities that buy or process white metal and produce copper and other metals associated with this such as gold and silver, besides sulfuric acid, plants which should be strategically located in zones with high sulfuric acid price to make this a product which contributes to the profitability of the business.

Jan 1, 1999

By Ruiling DU, Xiao YUAN, Keng Wu, Daan XU, Changyao CHAO

To utilize low grade coals to produce high quality semi-coke which can be used in blast furnaces, the pyrolysis of low grade coals was studied in this paper. According to the characteristics of coal pyrolysis process, the temperature range was divided into three parts. The interfacial chemical reaction model, random pore model and the internal diffusion model with the shrinking volume of resultant were established to describe the different ranges of pyrolysis process respectively. The results showed that the experimental data was fitted well, and all the correlation coefficients (r2) exceeded 0.97. Finally, the kinetic parameters for each temperature range have been calculated, which laid a necessary foundation for the simulation and expanded production.

Jan 1, 2016

By Liang Li

Thermodynamic analysis and experiments were conducted in order to verify the feasibility of preparing crude titanium tetrachloride (TiCl4) via the carbochlorination of low-grade titanium slag in molten salt. Titanium slag, assaying 74.6 wt% TiO2 with high calcium and magnesium oxide impurities, was treated by an optimized carbochlorination process in NaCl molten salt. These impurities in the titanium slag were chloridized simultaneously, and chlorination products FeCl2, MnCl2, MgCl2, CaCl2 and CrCl3 were collected in the furnace slag. XRD and SEM/ EDS analysis of residue shown that SiO2 and Al2O3 in titanium slag were difficult to chlorinate completely. Theoretical calculations and industrial-scale experimental studies reveal the content of TiCl4 in the products was more than 98.8 wt% and thus proved the feasibility of utilizing low-grade titanium slag for TiCl4 preparation by molten salt chlorination technology.

By L. M. Bianchi

"Oxide, nitride and other compound coatings often do not have adequate properties for newer applications when produced using very high deposition rates and simple evaporation techniques. Solar control, abrasion resistance, low reflectance and barrier effective engineered coatings require exacting properties. Such properties can be obtained by adapting the activated reactive evaporation (ARE) technology to Web production processes. Adaptions of the HAD and MAD processes will be described along with data on the high deposition rates obtained. These fast production capabilities were developed in order to make the processes economically competitive.IntroductionThe Physical Vapor Deposition technique (PVD) has been used to coat steel strip for over 20 years. (1) However, its use as a production process has been very limited because of the high cost of the PVD coating process and because, in some instances, the properties of the coating were not good enough to meet the customers requirements. Nevertheless, the PVD process has found wide application in the airplane engine and electronic component markets. These production processes have stimulated further development and advances in the technology.In 1971, Profession R. F. Bunshah developed the Activated Reactive Evaporation (ARE) process which was then used to produce hard coatings such as carbides, nitrides, oxides and other refractory compounds. (2) The process from a fundamental viewpoint -produces a coating on the substrate via the evaporation of metal in the presence of a low pressure (typically around 1 millitorr) of reactive gas, with a plasma created in the space between the metal source and the substrate.The plasma may be created by many means but its function is two-fold. First, it activates the reaction between the metal vapors and the reactive gas atoms/molecules resulting in the formation of a compound that deposits on the substrate. Second, because the plasma is in contact with the substrate, it results in a negative bias on the substrate and produces bombardment of the growing film with ions and energetic neutrals from the plasma. This bombardment causes many significant changes in the microstructure, properties and appearance of the coating.Recently another new technology Pulsed Magnetron Systems (PMS) has been introduced into PVD. This new technology has been pioneered in production scale equipment by Dr. S. Schiller (3) and associates. The use of a pulsed power supply on the magnetron prevents the problem of the anode being coated with a insulating layer which will then lead to micro and macro arcing producing defects in the coating."

Jan 1, 1998

By M. E. Myers

An experimental program is being carried out to determine the thermodynamic characteristics of zinc solubilization in high-temperature iron and iron-carbon alloys. Two versions of an isopiestic technique are being used, with zinc at a lower temperature being equilibrated with pure iron foils or molten iron-carbon alloys at a higher one. The lower temperature sets the partial pressure of zinc vapor, and thus the activity relative to a given reference state. Initial results show Henrian behavior for dilute zinc solutions in austenite and a molten 4.6% C alloy, with unit-pressure solubilities in pure Fe that closely match the predictions of Wriedt.

Jan 1, 1992

Aluminum has experienced significant growth in automotive applications over the last decade as a result of its properties and performance attributes. Looking to the future, the opportunities for continued growth in powertrain and suspension applications plus light weighting of body structures offer the potential for considerable further growth. This represents a growing "energy bank" of aluminum that will become available for recycling at the end of these vehicles' lives. Today, around 90% of the aluminum is recovered and recycled from scrapped vehicles because of its high value relative to other materials. The future growth offers opportunity for new technology and practices, to maximize scrap quality and recycling application. This paper will review the demand for these new technologies and practices and will discuss industry activities being pursued in this area.

Jan 1, 2000

By Jincheng Hu, Honggang Zhong, Qijie Zhai, Congsen Wu, Cheng Zhang, Jingzheng Ye

"The influence of cooling intensity on the solidification structure and ferrite phase content of a new duplex stainless steel (DSS) was investigated by using a thermal simulation setup for continuous casting. The results showed that the characteristics of the solidification structure were similar to their industrial scale manufactured slabs, including chill zone, colunmar zone and equiaxed zone. And austenite morphologies were mainly primary and secondary Widmanstatten sideplates as well as intragranular Widmanstatten plates. In addition, it revealed that the ferrite content increased with an increasing distance from the chill surface and decreased at colunmar to equiaxed transition (CET) position, then the value remained relatively stable at equiaxed zone. Furthermore, the ferrite content presented the same trend with the cooling intensity ranging from 100 mL/min to 2000 mL/min with the values just varying in a slight range.IntroductionThe duplex stainless steel (DSS) is the kind of steel that ferrite phase and austenite phase occupy about 50% respectively, or the content of the fewer phase has to be more than 30% [l]. The success of modem duplex stainless steels is to a large degree due to their higher strength than austenitic stainless steels, higher toughness than ferritic stainless steels, good weldability and high resistance to stress corrosion cracking as well [2,3]. The cost of stainless steel production continues to soar in recent years due to the increasingly higher price of Cr. In order to decrease the production cost, a new type of duplex stainless steel was developed by Bao steel [4]. This newly developed duplex stainless steel had low Cr content compared with 2205 DSS, and was expected to be applied into automobile industry. However, this type of steel was still in the initial stage of development, and the influence of continuous casting process on its solidification process and structure was still unclear, which needed to be studied further. Several works published in literature presented the effect of continuous casting conditions on duplex stainless steel (DSS) 2205, 2304 [5,6]. It was discussed that the cooling intensity in the chill-side had little efficient influence on the phase transformation. In this paper, the effect of cooling intensity on the solidification structure and ferrite volume fraction of this DSS at a given cooling rate was investigated."

Jan 1, 2014

By Tejs Vegge

The lack of suitable means of storing hydrogen for use in the transport sector is generally viewed as a primary showstopper for a hydrogen economy. Recent developments within solid state hydrogen storage in complex hydrides and metal ammines have sparked new hope of a long term solution, but as of now, no materials fulfill all the DoE targets for onboard storage [1]. A detailed physical understanding of the ab-/desorption processes and the role of the essential catalytic additives is an essential prerequisite for the development of new optimized hydrogen storage systems. Here, we illustrate the potential of utilizing the synergy of combining state-of-the-art in theoretical methods and experimental techniques in the analysis and design of materials for hydrogen storage. Recent advances in computer hard- and software has made it possible to treat many of the essential problems in such materials, i.e. structural stability, hydrogen dissociation and diffusion, with high accuracy methods like density functional theory. We rely on such results to guide our synthesis of new materials, and to interpret our experimental results from, e.g. time dependant in situ x-ray diffraction, synchrotron/neutron experiments, and advanced materials testing. Through a continuous feed-back optimization loop between theory and experiments, the obtained nano-scale insight is used to expedite the design and development of novel materials for hydrogen storage.

Jan 1, 2006

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

By Zuomei Jin

The Mineralogical form of Silver in a Ag-rich complex ore was determined. In the complex sulfide ore, acidic thiourea leaching resulted in 35% extraction of silver directly. In the same complex sulfide ore, under the effect of ultrasonic treatment, 65% of silver can be ex¬tracted. After the above ore had been roasted and acidically leached of Zn and Cu, the silver extracted from this Pb-Ag residue was 96.8%. The effets of temperature, thiourea and ferric ion concentrations and partical size were examined. The leaching rate of silver from the Pb-Ag residue was diffusion controlled. The activation energy was calculated to be 10. 49%KJ/mole. The kinetic model for the thiourea leaching of silver from Pb-Ag residue was obtained and is given by, The kinetics of silver cementation by aluminium in thiourea solutions was also investigated. The activation energy was calculated to be 65. 13KJ/mole, which is reasonable fora rate-limiting surface reaction.

Jan 1, 1995

By Zdzistaw MiGzkowski

At KGHM Polska Miedi S.A. a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass ex-change inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed. The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ? The second zone moves slower into the grain and the rate of the movement is deter-mined by the presence of oxygen. In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined. The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Zdzislaw Miczkowski

At KGHM Polska Miedz S.A, a direct flash smelting process is used for smelting of chalcocite concentrate for the production of blister copper. The paper presents a model of complex oxidation process of single concentrate grains smelted at KGHM. The description covers main chemical reactions, phenomena of heat and mass exchange inside the grains and between a grain and the surrounding space. In the model, two zones describing the course of process inside the grain were distinguished: ? The first one, which moves faster towards the centre of a grain, both organic and carbonate carbon are freed, The process takes place without the presence of oxygen and results in an increase of the temperature in the core of the particle. ?The second zone moves slower into the grain and the rate of the movement is determined by the presence of oxygen, In that zone the sulphur is eliminated and the oxidation of the organic compounds vapours moving from deeper layers of a grain takes place. Based on the results of laboratory tests, the coefficients that describe the oxygen transportation into the grain and decide the progress in the chemical reaction were determined, The paper contains the results of model calculations for single grains reacting in environment of various content of oxygen as well as the results of model calculations for the laboratory reactor system.

Jan 1, 2003

By Zongliang Zhang

Electrowinning is a significant step in metal extraction processes. Because the nature of electrowinning is to reduce metal from its oxidized state, substantial energy consumption accompanies it. Electrowinning processes of different metals have much in common—the deposition of the metal on the cathode and the counter-reaction on the anode. An advanced model was developed that can be applied to a variety of metal electrowinning processes. A model for specific metals can be readily obtained by modifying parameters such as potential, kinetics, and side reactions in the model. The model incorporates mass transfer, gas-liquid flow, electrochemistry, and deposition, making it a comprehensive electrowinning model. The model is applied to copper, nickel, and zinc and verified with the experimental results. In addition, the parameter settings and results of different metals were compared, showing that this model has great versatility and accuracy, thereby making it an efficient and effective research tool.

By Jorge A. S. Tenorio, Girley F. Rodrigues, Joner O. Alves, Denise C. R. Espinosa

"Rock wools are mineral fibers composed of amorphous silicates, due to their thermo-acoustic characteristics this material has a broad consumer market in the construction, automotive, and electric-electronics industries. This work studied the recovery of wastes from ornamental rocks (granite and marble) as partial raw materials in the production of rock wools. Residues from granite and marble cuttings are industrial wastes with considerable production and limited applications. These wastes should be appropriately managed because when discharged in rivers or lakes can cause siltation, and also they can cause serious human health problems, such as silicosis. Samples of produced materials with thickness smaller than 500µm were characterized by chemical analyses, XRD, and DTA. Results showed that the rock wools produced using granite or marble wastes have important properties, especially the melting point. This process decreases the extraction of mineral resources and provides a profitable destination for the ornamental rock wastes.IntroductionThe ornamental rocks industry is a sector with large production of wastes. During the granite and marble extraction processes and specifically during the rocks cutting (see Figure 1), approximately 35 tons of powdered rock per month can be produced. These residues should be appropriately managed, because when discharged in rivers, lakes or watersheds, they can cause siltation. Also, these wastes can cause serious human health problems, such as silicosis [1].Currently, the granite and marble wastes are mainly used in civil construction to produce materials in the form of mortar, bricks and tiles. However, due the current produced volumes and the average growth of world production estimated at 6% per year, new applications for these wastes are necessary [2]."

Jan 1, 2011

By David G. C. Robertson

A new approach is described for the calculation of the kinetics of metal/slag, metal/slag/gas, and metal/matte/slag/gas reactions. The algorithm assumes that equilibrium is achieved at the interface between phases, and uses an equilibrium solver (such as SOLGASMIX) to compute the equilibrium state at the interface at each time step during the reaction. For multiple phase systems a number of unit operations, representing the different phases and interfaces, must be connected together in a reasonalbly complex manner, and the METSIM software package has been utilized for this purpose. The new approach is superior to the SMAK software developed by the author and his co-workers over the past decade, for the reasons discussed in this paper.

Jan 1, 1995

By E. O. Stensholt

The Hybinette electrorefining process for production of cathode nickel was in use at Falconbridge Nikkelverk A/S, Norway, until 1975 when conversion to the new chlorine leach process was started. In 1978 the conversion to electrowinning had been completed, but further major improvements to the process have been made up to 1987. After a major expansion program in 1985 - 87 the refinery has a nickel capacity of 54 000 mt Ni/year. The main feed materials to the process are converter matte from the Falconbridge smelter in Sudbury, Ontario, Canada, and from the BCL smelter in Selebi-Phikwe, Botswana. A typical composition of the mixed feed to the refinery is: 40 - 45% Ni, 25 - 30% Cu, 20 - 22% S, 2 - 3% Fe and 1.0 - 1.5% Co. The matte is chlorine-leached in the first process step, nickel being dissolved selectively in a train of leach-cementation tanks. Essentially all copper and sulphur that was present in matte appears in the leach residue as CuS. In 1986 an autoclave treatment stage was added to the process to improve nickel extraction from the leach residue. The resulting strong nickel chloride solution is purified by the process steps (1) precipitation of iron and arsenic, (2) solvent extraction of cobalt and other minor elements and (3) precipitation of lead and the remaining impurities. The nickel solution is then fed to the tankhouse, where various nickel products are produced by electrowinning. The chlorine gas that is produced during the electrolysis is returned directly to the chlorine leaching tanks to dissolve more matte. After stripping from the loaded organic phase and solution purification cobalt is also produced by electrowinning. The copper sulphide leach residue, which contains some nickel, is dead- roasted in fluidized-bed roasters. The sulphur is recovered and sold as sulphuric acid. The calcine is leached in spent copper electrolyte, from which cathode copper is produced by electrowinning. Precious metals and the remaining base metals are recovered from the copper leach residue. The Falconbridge chlorine process is very versatile. It can accept a wide range of impurities in the feed and still produce metals of exceptional purity.

Jan 1, 1988

By S. Yokoya

With increasing requirement of steel productivity and quality in continuous casting in the conventional casting system using an immersion nozzle, it is very difficult to establish a reasonable molten flow pattern. In order to overcome this difficulty, we propose a new method of imparting swirling motion onto the flow in the immersion nozzle and to control the flow pattern in the mold. Following results have been obtained during the studies. For the case of slab continuous casting mold: High amplitudes of oscillation with a period of 10 to 15 seconds are observed in the outlet flow of the immersion nozzle and meniscus flow in the conventional casting system, while these phenomena are remarkably suppressed using swirling motion in the immersion nozzle, which leads to very calm and uniform flow pattern at the outlets of the immersion nozzle, in the mold and on the meniscus in the mold; For the case of billet continuous casting mold: (1) heat and mass transfer near the meniscus can be remarkably activated compared with a conventional straight type immersion nozzle without swirl, and (2) Quite different mold flow patterns are observed between the divergent and straight immersion nozzles. Heat and mass transport in the mold using the divergent nozzle is much more reasonable compared to that of straight nozzle. The findings, mentioned above, are very useful to control the flow pattern in the slab, and billet continuous casters. Such effectiveness of swirling flow in the SEN on the mold flow has been put into practical use. As a result, remarkable progress on the quality and production of continuous casting products has been observed in practical application.

Jan 1, 2006

By K. B. McTaggart, G. Owusu, P. J. Merrin

"This study was conducted at Hudson Bay Mining and Smelting's zinc electrowinning tankhouse to determine the effects of varying levels of antimony and continuous gelatin addition on current efficiency. The levels of antimony and gelatin were varied from 0.012 to 0.030 mg/l and 0 to 10 mg/ll2 • 31 respectively, based on neutral ZnS04 electrolyte. A non-linear mathematical model relating current efficiency with antimony and gelatin was produced. The optimum operating point for gelatin was 6.5 mg/l. On the other hand the current efficiency increased with decreasing antimony levels. An interaction term between gelatin and antimony is present but is not significant enough to improve the ability of the tankhouse to handle purification upsets in antimony. Individually, the current efficiency was linear (decreasing) with antimony, and parabolic with gelatin concentration. However, at low antimony concentrations stripping of the cathode sheet was difficult. IntroductionThe zinc electrowinning tankhouse at Hudson Bay Mining and Smelting was designed in the 1930's and consists of 120 rows with each row containing ten cells. This system cascades acid from cell to cell In a row, with neutral zinc sulphate solution added to each cell through manually controlled spigots. Animal glue additions are made manually three times per day by operations personnel. The problem with this type of cell design and operation is that feed solution flows and composition can vary from cell to cell and from row to row due to the large number of manual control points. A new system which reduces the number of manual control points was designed and tested to determine if improvement in control of cell conditions would affect current efficiency. This system mixes spent acid, neutral ZnS04 electrolyte and reagents (gelatin, antimony and strontium carbonate) in a separate mix tank, ensuring that all cells receive a uniform feed solution. Gelatin was used in the test system instead of animal glue (which is presently used) because of the poor solubility and supply of industrial animal glue. The study reported here is the first in a series of experiments designed to justify the need to modify the present cascading cell feed system (Figure 1) to the proposed feed system (figure 2)."

Jan 1, 1997

By F. Sanchez, A. Mejias, C. Frias, G. Diaz

"Crude zinc oxides are the major source of secondary zinc and are produced from fuming processes like Waelz kilns. The impurities of crude zinc oxides make difficult their processing in primary zinc refineries due to mainly high chloride tenor. Washing with sodium carbonate is a costly operation and chloride removal efficiency is not good enough, so further purification steps are required. The crude zinc oxides are easily treated using ZINCEX™ technology based on leaching, solvent extraction, and electrowinning. The ZINCEX™ process is commercially available and is designed to be a perfect barrier for metallic impurities and halogens, allowing selective zinc extraction in mixed chloride and sulfate leaching solutions. Other valuable components as lead and silver can be efficiently recovered from the leaching residue using PLINT technology in chloride media. Silver is recovered as silver cement and lead is precipitated as pure lead oxide or carbonate, which can be smelted at low temperature.IntroductionZinc is a fully recyclable metal and at present approximately 70% of the zinc produced worldwide comes from primary zinc while 30% originates from secondary materials. Nowadays, the zinc recycling rate is continuously increasing mainly through galvanized steel scrap processing, and crude zinc oxides are the major source of secondary zinc [1]. Secondary zinc oxides are obtained from fuming processes like W aelz Kiln, Rotary Hearth Furnace or Primus Furnace. Waelz is the dominant technology accounting for 80% of total crude zinc oxides production worldwide. In the Waelz process, steel dust is mixed with solid fuel reductant (coke breeze) and pelletized. It is then fed to the kiln and heated to a reaction temperature of l ,200°C. In such conditions, zinc, lead, and other non-ferrous metals are vaporized into the flue gas together with chlorides and alkaline metals. Mixed oxides are drawn from the kiln with the process gases and separated to produce typical crude zinc oxides [2]."

Jan 1, 2011