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By A. W. Bryson, K. C. Lenthall

"With the growth in the use of cobalt in industry, interest in its extraction and recovery has increased. With this increased interest comes the need for a fundamental knowledge of the processes involved in the recovery of cobalt metal. This paper examines the effects of cobalt concentration, catholyte pH, operating temperature and current density on cobalt electrowinning with respect to the current efficiency, cell potential and nature of the cobalt deposit. It is found that the cobalt concentration and catholyte pH affect the current efficiency, while current density and temperature affect the cell potential and thus the specific power consumption. Pitting on the deposit is affected by the catholyte pH and the operating temperature. Furthermore, the effect of feed flow-rate on catholyte pH, and thus current efficiency, is investigated. A model to predict the cell performance, which includes the flux of hydrogen ions through the diaphragm, is proposed.IntroductionCobalt metal is a silvery transitional metal found between nickel and iron on the periodic table. Due to its resistance to corrosion and other properties under high temperatures and its good work-hardening characteristics, it is favoured in alloys used in high temperature applications. These include aerospace, aircraft and high speed tools. Other applications include its use as a colourant in glass and ceramics, a drying agent in paints, a nutrient for livestock, a catalyst in the petroleum industry and, in the medical field, in prosthetics and radiology.The main deposits of cobalt are found in Central Africa, specifically Zaire and Zambia, although deposits also occur in Morocco, Canada and Australia. The cobalt is generally associated with other transitional metals including nickel, iron and copper. It is generally extracted by hydrometallurgical means and recovered from solution by electrowinning or hydrogen reduction. Little data [1-2] exists in literature on the electrowinning of cobalt from aqueous solutions. This paper investigates the effects of various operating conditions on the current efficiency, cell potential and deposit nature under continuous operation."

Jan 1, 1997

By B. Bichel

For the last 70 years, molten blister copper has been transferred by rail in hot metal cars from the Copper Cliff Smelter to the Copper Cliff Copper Refinery (ex Ontario Refining Company) where it was processed in two (2) reverberatory anode furnaces by poling with logs, cast on four (4) wheels, and then electrorefined. This practice was modernized in 2001 with the installation of two (2) rotary anode furnaces at the. Copper Cliff Smelter which employ steam and. natural gas for reducing and which provide a significant reduction in emissions. A new casting shop with a single anode casting wheel is used to cast regular and stripper constant weight anodes which are transported by truck to the Copper Cliff Copper Refinery for anode preparation and electrorefining. This paper provides an overview of the copper circuit at the Copper Cliff Smelter and a description of the CDN$31 million capital project.

Jan 1, 2002

By Xiaobing Yang, Abhishek Lahiri, Animesh Jha

"In the FFC-Cambridge process, the cathodic dissociation of oxide and CO/CO2 production on carbon anode is the basis for metal production in a CaCl2 bath. By using an inert intermetallic anode, the CO2 evolution can be eliminated altogether with acceleration in the electro-reduction kinetics. At present the process suffers from slow reduction kinetics of TiO2 to Ti metal, which can be enhanced significantly by the incorporation of alkali species in the TiO2 pellet at the cathode and in the CaCl2 bath in the presence of an intermetallic inert anode. Nearly full metallization with greater than 99% of Ti metal containing 1500 ppm of oxygen is possible to achieve in less than 16 hours of electro-reduction. Analyses of phase composition and the microstructures morphology in fully metallized pellets revealed the presence of localized solidified Ti layer, indicating that fast reduction process also involved formation of liquid phase as middle stage reaction. In addition, in situ creation of porosity and maintain higher current level during electrolysis process were two key factors to fully reduction of TiO2.IntroductionDuring cathodic dissociation of TiO2 in a CaCl2 bath and anodic evolution of CO2 on a carbon anode, which is the basis for the FFC Cambridge process [1], the rate of metallization slows down due to the formation of CaTiO3 at the reaction interface. Calcium and alkaline earth perovskites are known for their poor electrical conductivity which adversely affects the overall electro-reduction. One of the ways to increase the porosity is via the addition of polyethylene precursors in the pellet or by directly starting from perovskite [2, 3]. The experimental evidences shown in the literature confirm although the speed of reaction increases, but a complete or near complete metallization is not possible by enhancing the in-situ porosity alone, as the insulating perovskite is very slow to decompose under the equilibrium that prevails in the cell. Plethoric evidences on carbon anode show with the current decrease gradually, and finally stabilize at a very low value between 0.2 and 0.4 A, which is a testimony of the presence of perovskite insulating barrier in the current path. Our aim in this paper is to demonstrate the mechanism of enhanced electro-reduction when alkali ions are present in the oxide pellet at cathode and in the bath. We also show for the first time the use of an intermetallic anode for Ti-metal production using the FFC Cambridge process."

Jan 1, 2009

By Mansoor Barati

The present paper is based on a term project for final year undergraduate students, requiring them to evaluate a process for producing silicon from rice husk. The traditional method for production of silicon involves carbothermal reduction of quartz in electric arc furnaces at temperatures exceeding 2000 °C. The technology consumes a considerable amount of electrical energy as well as fossil fuels, resulting in significant CO2 emissions. A flowsheet for production of silicon metal from rice husk is laid out in this paper. The technology will consist of combustors, which will generate steam using the rice husk biomass, power generator, and electric furnace for reduction of the rice husk. Materials and energy balance calculations presented here indicate that such process can be operated independent of external electricity.

Jan 1, 2014

By Nieves Iglesias

The removal of the refractoriness of a gold bearing pyrite- arsenopyrite ore is studied. Flotation concentrates were prepared and leached with a dilute acidic ferric sulfate solution. The elemental sulfur film which forms on arsenopyrite in the oxidation process is not responsible for the low rate of the arsenic dissolution observed. A positive effect on the leaching rate is observed when Ag' is added. This pretreatment eliminates the refractory nature of concentrates.

Jan 1, 1993

By Kenneth S. Coley, Michael Pomeroy, Elaine Chen

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Jan 1, 2014

By S. M. I Kytö, J .. K. Mäkinen, K. Saarhelo

"At the Outokumpu Oy Harjavalta Copper Smelter the control philosophy of the flash smelting process has been changed from the slow feed-back control to feed-forward control. This is important as the fluctuations in the flash smelting furnace matte grade and slag temperature are desired to be minimized.The system is based on a specially designed automatic sampling device and the Outokumpu Courier 20 on-stream X-ray fluorescence analyzer. A microcomputer-based Analyzer Operator Station (AOP) controls the system and calculates the process parameters for the furnace from the analyzed chemical composition and other existing data.A considerable reduction in the deviation of the matte grade and slag temperature has been gained. This has resulted in conservation of energy and refractories, lower copper losses and higher through-put in the flash smelting furnace and converters.1.0 IntroductionThe flash smelting technology for copper concentrates was developed at the Outokumpu Oy Harjavalta Smelter soon after the World War II. The incentive for this development was shortness and high price of any form of energy. The fact that smelting can be carried out autogenously, without external energy by utilizing the latent heat of sulfide combustion was known decades before, but Outokumpu Oy was the first company to take the advantage of this knowledge in practical operation. A further advantage of this technology was that the SO2 containing gases suited well for sulfuric acid production, thus minimizing the detrimental effects on the environment (1).The very heart of the flash smelting process is the reaction shaft of the flash smelting furnace (see Appendix I). Heating up of the dried feed mixture, dissociation of several compounds, ignition and oxidation of the feed take place very intensively in the reaction shaft during 2 - 3 seconds, which the fine grained particles reside in the reaction shaft. A very accurate control of the amounts of the feed materials as well as of oxidizing gases, fuel, etc. is of primary importance."

Jan 1, 1989

By F. Elgersma

A high purity electrolysis solution is essential for hydrometallurgical zinc winning processes. For this reason ferric iron containing compounds such as jarosite are precipitated as iron and impurity collector during the calcine leaching. Jarosite thus forms a chemical waste and creates environmental problems. This research contributes to the development of a wet jarosite treatment process, where less contaminated jarosite is produced which can act as an iron source. The present work studies jarosite precipitation kinetics and the uptake of zinc cations in batch and continuous experiments. The distribution coefficient for zinc in continuous experiments is constant for a wide ratio of zinc over ferric ions in the solution. Addition of NH, + ions in batch experiments accelerates the conversion rate equivalent to the driving force increment. Addition of 50,2-ions above the stoichiometric ratio increases the conversion rate less then could be expected from the increase in the estimated driving force. Zinc ions tend to retard the conversion rate. An increasing reaction temperature increases the conversion rate. Below 75 ?C the conversion rate approximates zero.

Jan 1, 1990

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as 'burning' of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By Vitalij K. Pecharsky

Recent interest in complex aluminohydrides as potential near ambient, ultra-high capacity, solid-state sources of hydrogen (e.g., for fuel cells) calls for an improved understanding of the processes occumng in these hydrogen-containing materials during both the release and the uptake of hydrogen. Lithium aluminohydride (LiAlH4) rapidly releases 5.2 wt. % of hydrogen (i.e., nearly four times more than LaNis-based alloys) during mechanochemical processing at ambient conditions in the presence of transition metal catalysts. Using a variety of solid-state characterization techniques, the mechanochemical transformations in a series of LiAlH4 - metal catalyst systems have been examined and preliminary insights on the mechanism have been obtained. Surprisingly, the well-known hydrogenating-dehydrogenating catalysts, such as Ni and Pt, are practically inactive in the mechanochemical dehydrogenation of LiAlH4.

Jan 1, 2002

By Y. K. Rao

In the carbonyl process for the refining of crude nickel CO(g) reacts with nickel in the 310-370K range producing nickel tetracarbonyl, Ni(C0)4(g). Iron and cobalt impurities also form gaseous carbonyls but their partial pressures are low. The carbonyl is led to a decomposer plant wherein the gas disproportionates in the 500-600K range depositing pure metal on nickel pellets that move countercurrent to the gas-flow. This system serves to illustrate the fundamental principles involved in the vapor phase mass transport of elements, against temperature-gradient, under the influence of chemical potential gradient. Unlike in the crystal growth, the source is at a lower temperature (say 350K) whereas the seed is in the hot-zone (say 550K) of the closed ampoule-type reactor. By assuming virtual gas-solid equilibria in the end zones, with diffusion of gaseous species between them acting as a slight perturbation, the quasi-steady- state mass-transport rates are computed for a range of CO-pressures and temperatures.

Jan 1, 1993

By Robert Vidal

The performance of a laboratory-scale cell for the electrolysis of an aqueous chrome alum solution was studied. Electrode potentials, pH, and Eh were recorded. An optimum catholyte pH of about 2.5, consistent with information from the literature was observed. Values exceeding this range resulted in a precipitate formation and are detected by wavering cathode potentials. The role of anodically produced dichromate ions was investigated by chemical analysis. It was found that the steady state concentration of dichromate ions varies inversely with fluid flow from catholyte to anolyte. This concentration was also reduced with the use of precious metal coated titanium anodes.

Jan 1, 1994

By C. P. Broadbent

Due to growing .public awareness of environmental issues and greater sensitivity towards waste management, many countries around the world are implementing more stringent legislation governing the storage and disposal of hazardous wastes containing heavy metals such as As, Sb, Pb, Cd or Hg. These wastes can no longer be dumped without providing clear guarantees that the material concerned is environmentally safe and will not leach toxic elements to the surroundings. In the Netherlands the current dumping charge for chemical waste (i.e. worst category) is $280/t, and for industrial waste this cost reduces to $75/t. If the material can be reused there may be a small positive credit for selling it, for example discard slag as an aggregate to the construction industry. A number of (pyre)-metallurgical operations, mostly associated with the extraction of metals from sulphidic ores, produce arsenic residues in the form of As2O3 containing flue dusts and speises. If the flue dust is of high purity it can be sold, though many traditional uses are being substituted by other materials. In many cases upgrading the quality of the arsenical dusts is not possible for either technical or economic reasons. Traditional practice is to dissolve these dusts in acid prior to precipitation as ferric arsenate, which is at present classified by many countries as industrial waste and can be dumped. Recent work, however, has cast doubt on the stability of arsenates for disposal and alternative disposal routes have been investigated. Tests have shown that up to 10% (dm) As can be incorporated into "glassy" silicate slags with very low levels of arsenic leaching in the cooled product. Calcium arsenate was added to a range of synthetic and industrial slags from the system SiO2-FexOy-CaO-A12O3-AsmOn, under mildly oxidising conditions and quenched subsequently in water. It would appear that this represents an environmentally acceptable method for the disposal of many arsenical residues and there is some optimism that this method will be equally applicable to the disposal of other toxic metal residues.

Jan 1, 1994

By G. J. Abbaschian, A. B. Gokhale, M. M. Kunjapur

"A laboratory scale model furnace was constructed for obtaining radially inward oriented columnar grains in disc shaped castings. The furnace consisted of eleven circular, concentric, equispaced resistance heaters on each half of a split graphite mold. Water or air flowing through a copper pipe along the periphery of the disc constituted the heat sink. After filling the mold, the heaters were turned off consecutively in top and bottom pairs from the rim towards the center, causing the temperature gradients to move inward. Equiaxed structure was obtained at the center by turning off the inner coils together when desired. Sn:15%Pb alloy was used to cast integral blade disc castings using the above technique to obtain dual-property discs with a central equiaxed structure and an outer columnar grain structure projecting inwards from the blades to the rim. A numerical technique was used to predict the temperature profile in the disc during solidification, and good correlation was obtained with the experimentally measured temperature profiles. The corresponding heat transfer coefficient values obtained were h = 544 Wm- 2k-1 (0.013 cal/cm2- ° C-sec) for cooling between metal and chill and h' = 71 Wm- 2k-1 (0.0017 cal/cm2- ° C-sec) for the heat input from the hot mold to the liquid metal. BackgroundHigh temperature alloys used in the current generation of gas turbine engines have evolved through two main stages of development: in 1950's, the increase in the efficiency of gas turbines was paced by improvements in alloy design, which led to the development of Ni and Co-based superalloys (1). By mid-1960's, it was realized that improved alloy chemistry alone was inadequate in meeting the increasingly stringent service requirements. The focus of research then shifted from alloy development to process development, and resulted in the introduction of directional solidification (DS) techniques for the production of turbine blades and vanes (1,2).Under typical operating conditions, the blades and vanes are subjected to aerodynamic loading, while the blades are additionally subjected to high centrifugal loading and vibratory stresses. The primary material requirements for blades may be summarized as follows (1,3):•,High creep resistance•,Good high temperature tensile strength (typically in the range of•,275 to 550 MPa at temperatures in excess of 750°C)•,Resistance to both low cycle and high cycle fatigue (LCF and HCF)•,Resistance to erosion, corrosion, and oxidation•,Resistance to thermal fatigue"

Jan 1, 1986

By M. Sakamoto, S. Karaswa, Y. Yoneoka, Y. Ohmizo

"The Annaka Refinery has been processing leach residue by Waelz process for 17 years. Recently, the quantity of the leach residue has increased due to a decline in the quality ~f zinc concentrate. Meanwhile, negative factors (e.g. deterioration of water balance due to improved electrolytic power consumption rate) have increased· in the processing of the leach residue.We have implemented various measures in responses to this situation, while striving to increase ·processing capacity and achieve stable operation. AS we have largely completed our assessment of the efficacy of these measures, we report on our recent process improvements.IntroductionWe have been treating leach residue by the Waelz kiln process since 1981. At that time, treatment of only 50,000 tons of leach residue per year was anticipated. However, subsequent process improvements have revised this figure up to 75,000 to 80,000 tons per year.However, today's increased Fe zinc concentrate grade has resulted in increased amounts of leach residue. In addition, improvements have reduced electrolytic power consumption rate of zinc electrolysis, limiting the amount of water that can be used in ·the zinc refining processes and for deaning leach residue. Consequently, we encounter an increasing number of problems and factors adversely affecting leach residue treatment, including increases in water-soluble Zn (WsZn) and. S (S04) in leach residue.To solve these problems, we have taken several measures to ensure long-term continuous operation and treatment of this increased · amount of leach residue. This paper discusses these measures."

Jan 1, 2000

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Richard D. Hagni

Microscopic examination of selected, representative, unweathered samples of Birmingham, Alabama, Silurian, sedimentary iron ores has fully revealed the nature of the phosphorous-bearing mineral grains. The grains are composed of carbonate-fluorapatite (collophane), range in size from 1 um to 2.25 mm, and exhibit varied types of intergrowth with hematite. Modal analyses conducted under cathodolumi-nescence have provided quantitative data on the a3undance of each of 15 types of phosphorous-bearing mineral grains and made it possible to assess the potential phosphorous liberation from four types of iron ore. The results indicate that 27% of the total phosphorous contained in the iron ores in the western part of the Birmingham district can be expected to be liberated by fine grinding; 60% for ores in the eastern part of the district.

Jan 1, 1982

By Donald R. Sadoway

Molten salt electrolysis is a proven technology for the extraction of metals -- all the world's primary aluminum is produced in this manner. The unique properties of molten salts, also make them excellent media in which to treat a variety of forms of waste. Of special .note in this regard is electrolysis in molten oxides, a .concept put forward by. the author, initially as a ."clean technology" for producing primary metal. However, in the context of waste treatment, electroly-sis in molten oxides is a process offering the prospect of changing the. valence of dissolved heavy metals while making pure oxygen gas as the main by-product .Laboratory tests conducted at a temperature of 1550°C on chromate sludge dissolved in an melt composed of Al2O3 and MgO have confirmed electrochemical production of oxygen on a carbon-free anode.

Jan 1, 1996

By W. Dresler

Design details of a 100 kVA DC electric-arc reduction furnace are described. The furnace is equipped with a 610 mm (24 inch) diameter graphite crucible hearth. A 76 mm (3 inch) diameter top graphite electrode is used as a cathode. The current passes through the bottom of the crucible and is carried to a bottom plate (the anode) by conductive magnesia carbon bricks. The furnace can be operated up to a maximum of 120 V, 1800 A, and presently 100 kW. The start-up operating experiences and metallurgical results of one reduction test with a Montana chromite containing 38% Cr2O3 are discussed.

Jan 1, 1994