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By J. M. Boxall

The electrolytic zinc plant at the Bartlesville division of Z.C.A. originally used lead anodes containing only 0.25% silver because only H.G. zinc and alloy was to be produced. In 1984, a small addition of strontium carbonate was made to control the surf ace morphology of the cathodes which reduced short circuits and increased current efficiency. Later a drastic reduction in colloid addition further reduced short circuits. Increased strontium additions allowed the production of some S.H.G. zinc. Increasing the silver content of the anodes reduced the lead in cathodes only slightly. More important, the anode scale that was not removed during anode cleaning, entered the electrolyte and contaminated the cathodes with lead. A piping system has been installed to purge the contaminated electrolyte directly back to the leaching section. This has allowed the plant to produce S.H.G. zinc consistently.

Jan 1, 1990

By Devon A. Hannan

Thermodynamic modeling calculations were undertaken for the recovery of mercury from HgTe using a vacuum retort reactor. However, discrepancies were noted in the available thermodynamic data which introduced uncertainty in the model results. Consequently, a series of transpiration experiments were first undertaken on the thermal decomposition of HgTe into an inert carrier gas stream according to the following reaction: HgTe(s) Hg(g) + Te(s) From the measured weight loss of the HgTe samples, the Gibhs free energy change for the above volatilization reaction was determined as a function of temperature. The experimentally determined Gibbs free energy values were found to be approximately 30% larger (more posi-tive) than the values available in databases such as HSC Chemistry. By conducting a second-law analysis on the experimental data, the heat of formation of HgTe at 298.15 K and the en-tropyat 298.15 K were determined, which then formed the basis for a new database for the modeling calculations. The results of this study showed that HgTe was more stable at elevated temperatures than was generally indicated in the literature. The new database is given in a for-mat for direct insertion in HSC Chemistry. Using the new database, modeling calculations were conducted to examine the effects of the re-tort pressure and the molar ratio of purge gas to HgTe on the volatilization of mercury from HgTe. A diagram is presented that shows the minimum temperature for 100% volatilization of mercury from HgTe as a function of retort pressure for different molar ratios of purge gas (N2) to HgTe. For example, it was found that the minimum temperature for 100% volatilization could be decreased by 175 K, at a retort pressure of 0.05 bar, if the molar ratio ofN2 to HgTe is increased from 1.0: 1 to 100.0: I.

Jan 1, 2003

By Kuniaki Murase

Cadmium telluride (CdTe) semiconductor has been well investigated as a CdS/CdTe heterojunction solar cell material since its band gap is suitable for energy conversion from sunlight into electricity. In this paper a new electrochemical processing of thin-layered CdTe using basic aqueous electrolytes is reviewed from the standpoint of thermodynamics using a potential-pH diagram. The cathodic electrodeposition of the stoichiometric CdTe with a flat surface morphology took place at more positive potentials than that of the Nernst potential for the bulk-Cd deposition and at more negative potentials than that for the hulk-To. In this potential region deviation from the stoichiometric composition of eleetrodeposited CdTe was controllable by the Cd(II)/Te(IV) concentration ratio, pH, or concentration of complexing agent for Cd2+ ions of the electrolytes, The deposition behaviors for ammoniacal media were well accounted for by the potential-pH diagram of the Cd-Te-NH3-H2O system devised by a combination of those of the Cd-NH3-H20 and the Te-H2O systems, Diagrams for other complexing agents, ethylenediamine and diethylenetriamine, were also constructed to investigate and discuss the electrodeposition conditions regarding the corresponding media.

Jan 1, 2003

By Wolfgang Van Hooff

Encouraged by a strongly growing and evolving market for granulated products, Paul Wurth continuously improves its granulation and dewatering technologies to provide customers with state of the art installations. Continuously developed know-how about the granulation process of iron blast furnace slag enabled application to non-ferrous materials such as Ni-Slag, Pb-Slag, Blister Copper, Cu-Matte and even TiO2-Slag, which rank among the most difficult materials to granulate. This paper identifies how critical objectives in granulation and dewatering technologies applied to different molten materials with respect to various product quality objectives can be addressed. The differences between hot and cold water granulation systems are explained, including the step from cold runner to granulation water tank. Development of a flow and pressure controlled blowing box is the latest step to optimize the granulation process in order to meet the latest standards in terms of quality, power consumption and environmental protection.

Jan 1, 2006

By Rick Honaker

Rare earth elements (REEs) contained in coal and associated mineral matter exist in several forms including micro-dispersed minerals, ion adsorption onto clay surfaces, and chemically bound. Tests found that REEs can be effectively recovered from certain components of three coal sources by leaching under mild conditions followed by solvent extraction. A range of pH values were evaluated at solution temperatures of 25 and 75 °C. When using 1.2 M of sulfuric acid, nearly 85% recovery of the REEs was extracted from the middlings material collected from an operating plant. Acid leaching of a second middling source from another plant resulted in 60% of the total REEs being recovered under the same leaching conditions. Solvent extraction treatment of the leachate produced from six different coal sources resulted in products containing up to 50% total REEs from feedstocks starting with around 300 ppm.

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 G. Van Weert

The pellet reactor was developed approximately 20 years ago in the Netherlands for softening drinking water. Since then, some 35 plants have been built, ranging in capacity up to 8500 m3/h. Applications now also include removal of phosphates and fluorides and the production of metal carbonates and sulphides from waste streams. The pellet reactor consists of a fluidized bed, wherein the process solution is thoroughly mixed with the precipitation reagent at special inlet nozzles to give over-saturation of the compound to be precipitated. In water softening applications, the compound is CaCO,. In the case of nickel or other metal waste streams, Na2CO3 solution is added in sufficient amounts to precipitate metal (hydroxy) carbonate on the fluid bed particles. These grow typically to dense spheroids, which are removed when they reach 0.8 to 1.0 mm diameter. These spheroids are easily dewatered, free flowing and low dusting. The latter property is becoming an attractive advantage in connection with new plant hygiene regulations. The operation of a 60 cm diameter pellet reactor on nickel containing plating waste is described and the properties of the produced nickel carbonate spheroids are discussed.

Jan 1, 1993

By John J. Dunkley

Recent years have seen the increased use of hydrometallurgy in the smelting and refining of metals. However this is often used as a final refining step, following an initial pyrometallurgical smelting process. Huge amounts of material are produced as melts which have to be cast, comminuted, and taken up into solution or leached. A common method is to granulate the melt and then grind it. In the case of metallic melts this can be difficult or unfeasible due to the ductility of the granulated particles. Water atomisation is capable of replacing the granulation and grinding stages with a single process step that can process in excess of 30tlhour of melt into particles as fine as 50 microns. Applications in operation in Co, Cu, Ni, Ag, Au, Pt and Rh refining are discussed together with potential applications in copper smelting.

Jan 1, 2003

By Kenneth N. Ham

Hydrometallurgy covers a wide spectrum of areas and its knowledge base is enlarged and enhanced by contributions from many other fields. Dissolution of metals and alloys in aqueous media will be used to illustrate how rich the field of metal extraction can be. Comprehensive understanding of the fundamentals of metal and alloy dissolution in aqueous systems requires creative application of thermodynamic principles, solutions chemistry, ligand complexation theory, electrochemistry, transport phenomena and heterogeneous kinetics. In addition, recent developments in instrumentation in the fields of interfacial phenomena and corrosion have tremendously advanced the field of metal extraction in aqueous system. The close relationship between metal extraction in aqueous systems and various physicochemical phenomena occurring in corrosion and interfacial systems will be discussed and illustrated with examples.

Jan 1, 2002

Two pilot-plant investigations were conducted in which strong-base resins were compared with activated carbon for the extraction of gold cyanide from leached pulp from the Golden Jubilee Mine. The results show that gold can be recovered with carbon, but that the extraction efficiency is poor, probably because high concentrations of humic and fulvic acids are. present m the pulp. .However the extraction of gold cyamde from this material with strong-base resins JS very effo:1ent, and the overall efficiency of extraction is better with resin than with carbon, even when the concentration of resin is one-third that of carbon, and the flowrate of resin is one-third that of carbon. The results of the pilot-plant campaign reported in this paper led to the conversion of the Golden Jubilee plant from carbon-in-pulp to resin-in-pulp in February 1988.

Jan 1, 1989

Lime-enhanced carbothermic reduction may provide an alternative process for treating low grade chalcopyrite concentrates. To date, most research on lime-enhanced reduction has been on pure, synthetic sulfides. In this study, preliminary experiments were carried out on natural chalcopyrite using a thermal analysis system to assess the rate and extent of reaction at several temperatures and identify the major solid and gaseous reaction products. Calculations were performed to establish the thermodynamic limits of the reactions in the temperature range of interest in order to identify the potential conditions for processing chalcopyrite concentrate. The study found that finely ground chalcopyrite can be reduced carbothermically in the presence of lime at moderate temperatures and in a reasonable time to form metallic copper, with the sulphur reporting virtually entirely to calcium sulfide. At temperatures below about 750?770ºC calcium ferrite is the stable form of iron whereas at higher temperatures metallic iron is stable. Further work is required to demonstrate the reaction on a scale to obtain sufficient sample for evaluation of subsequent processing steps to remove the gangue material and iron products from the copper.

Jan 1, 2009

"Mixing phenomena in a bottom blown air-stirred one-seventh water model of CLU (Creusot-Loire Uddeholm) reactor was studie9-using three different configurations of straight circular nozzles fitted axially at the bottom of the vessel. The mixing time has been determined by pH measurements at various gas flow rates, bath heights and nozzle orientations in the presence and in the absence of a second phase.Experimental results reveal that the mixing time decreases with increasing gas flow rate. For a given gas flow rate the mixing time increases non-linearly with increasing bath height. Off-center configuration gives slightly lower mixing times as compared to center configuration. It is found that the contribution of buoyancy to the total stirring energy density is very small, but its contribution increases with increasing bath height. In the presence of an upper oil layer, the mixing time increases significantly for all configurations.IntroductionIn high temperature metallurgical melts mixing is carried out by injection of a gas either from top or bottom of the vessel in order to accelerate the rates of chemical reactions and to promote bath homogenization. When a gas is injected into a liquid through a submerged lance, porous plug or nozzle, the gas, rising as a two phase plume to the surface, imparts momentum to the surrounding liquid and causes gross circulation in the bath which promotes mixing."

Jan 1, 1997

By W. J. Mitchell

During the months of April and May 1992, the Phelps Dodge Hidalgo smelter underwent a major turnaround. This was the third such turnaround in the life of the facility which was commissioned in 1976. During the third furnace campaign, the smelter processed 5.2 million tons of concentrate producing 2.6 billion pounds of anode copper over a 7.5 year period. The critical path on the fifty-nine (59) day turnaround schedule was the reconstruction of the Outokumpo flash furnace which integrated some modifications with standard rebuild practices. Modifications included incorporation of horizontal cooling jackets throughout the furnace settler as well as the installation of castable refractory in the reaction and uptake shafts.

Jan 1, 1993

By M. J. Collins

A hydrometallurgical process has been tested at the Sherritt Research Centre for separation of zinc, lead, copper and precious metal values from the zinc oxide fume leach residue stockpiled at the HBM&S operations in Flin Flon, Manitoba. Zinc is found primarily as zinc femte and sphalerite in the residue, lead as lead sulphate and jarosite, and copper as sulphide and jarositic compounds. Gypsum and siliceous gangue are significant diluents. The separation process includes hot acid, atmospheric and reducing (sulphur dioxide) leaching; zinc, copper and lead flotation; and atmospheric iron removal steps. Zinc is recovered to a high strength zinc sulphate solution and to a zinc sulphide concentrate suitable for feed to a roaster or to a zinc pressure leach plant; lead to a high grade lead sulphate concentrate suitable for feed to a lead smelter, and copper to a high grade copper sulphide concentrate suitable for feed to a copper smelter. Precious metals are divided between the zinc, lead and copper concentrates.

Jan 1, 1993

By Gordon Lewis

A complex mixture of hydrated reaction products is obtained from hydrothermally treated refractory cements and castable concretes. TGA can be used both to identify the product phases in the mixture and to determine a quantitative relationship among the phases. When reacted mixtures contain compounds that decompose simultaneously, or nearly so, additional assumptions must be introduced in order to develop a quantitative phase analysis. It is the purpose of this paper to examine some of these assumptions and to demonstrate their application, particularly to refractory cement systems.

Jan 1, 1982

By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

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 A. Dutta, B. Devulapalli, A. Mukhopadhyay, E. W. Grald

"Computational Fluid Dynamics (CFO) has matured over the past two decades as an analysis tool for conducting virtual experiments with significant time and cost savings. It complements and reduces physical testing. CFO has penetrated the diverse materials industry in much the same way as Computer Aided Design (CAD) did more than a decade ago. As the basic numerical algorithms used in CFO have steadily improved, so have the reliability, consistency and user-friendliness improved significantly, too. Other recent trends have also contributed to the rapid growth and widespread adoption of CFO. In this presentation, CFO applications from several materials processing industries will be presented using case studies. Emphasis will be on metals, glass and semiconductor applications.IntroductionThe term materials processing covers a diverse array of industrial applications and products today. From the continuous casting of steel, to the deposition of semiconductor materials atom by atom, to the extrusion of molten polymers, materials processing applications span an incredible range of length scale, process times, pressures, temperatures and velocities. The properties of the materials themselves, in terms of density, viscosity, thermal conductivity, etc., can be complex functions of temperature, shear rate, chemical composition and time. And the processing equipment may be very complicated in geometric shape.Computational fluid dynamics (CFD), the technique of solving the governing equations of fluid motion and other related phenomena using a computer, has enjoyed widespread and rapid growth, which started in the aerospace and automotive industries. More recently, CFD has also been successfully applied to a great many materials processing problems, in spite of the challenges described in the previous paragraph. The reasons for the growing usage of CFD in materials processing are many. Using CFD to test design options and reduce the number of physical prototypes can decrease the time and cost associated with new product and process development. CFD gives insight and provides detailed predictions of operating conditions in lieu of difficult, intrusive and often expensive experimental methods. CFD can be used as an aid to scale-up processes from lab or pilot scale to full production. Troubleshooting the performance of existing equipment is often carried out with the help of CFD. Determining how an existing piece of process equipment will operate under new conditions, or with new input ,materials, is also a common task for CFD."

Jan 1, 2004

By Yiling Zhang, Paul A. Salvador, Gregory S. Rohrer

"Photocatalysis utilizes solar energy to produce hydrogen by splitting H2O. When a thin film of photocatalyst TiO2 is supported on a ferroelectric BiFeO3 substrate (band gap ~2.5 eV), the TiO2/BiFeO3 heterostructure is capable of photochemically reducing Ag+ to Ag0 in aqueous solutions under blue light with enhanced efficiency. The observation of spatially selective silver patterns on surface of the heterostructure after reaction suggests that photogenerated electrons and holes in ferroelectric BiFeO3 are driven in opposite directions to reduce their chance of recombination. Comparisons of the amounts of reduced silver on TiO2 film grains with distinct phases/orientations show that the reactivity is mildly preferential on anatase TiO2 phase and does not strongly depend on crystallographic orientation of BiFeO3.IntroductionTitania (TiO2) is capable of photocatalytically converting H2O to hydrogen and oxygen under the irradiation of ultraviolet light. [1, 2] One of the limiting factors for titania to be used as an effective photocatalyst is its band gap. Because the absorption edges of rutile and anatase titania are at 3.0 eV and 3.2 eV, respectively, they can only absorb light in the UV portion of the spectrum, which is about 3% of the available solar energy. [3-5] This limitation has motivated attempts to modify the absorption edge of titania so that it can absorb visible light.One strategy is to substitute a portion of the titanium and/or the oxygen with other atoms. There are numerous reports on visible light absorption of titania by doping and co-doping of Cr, V, Mo, Sb, Fe, N, S, C, and F. [6-34] Another strategy is to add an adsorbed molecular species that absorb visible light and donate an electron or hole to the titania, such as organic dyes [33, 35, 36] and Ce3+/Ce4+. [37, 38]The strategy in the present work takes the approach of depositing a pure titania thin film on a visible light absorbing substrate BiFeO3 to induce visible light activity of the heterostructure. BiFeO3 is a semiconductor with a band gap of about 2.5 eV [39-41] and is photocatalytically active in visible light. [42, 43] It is also ferroelectric with spontaneous polarization along pseudo-cubic <111> directions of 6.1 µC cm-2. [44] The spontaneous polarization gives rise to internal electric fields that drive photogenerated charge carriers, namely electrons and holes, in opposite directions to reduce their chance of recombination. [45-47] Additionally, the separation of electrons and holes leads to the spatial separation of reduction and oxidation half reactions so that the back reaction of intermediates is also suppressed. Such charge carrier separation has been reported in TiO2/BaTiO3 heterostructures with UV light illumination. [48-51] The TiO2/BiFeO3 heterostructures in this work combine both advantages of the relatively narrow band gap and the internal fields in BiFeO3 to enhance the overall photocatalytic activity."

Jan 1, 2014

By Takeshi Nagano

Copper pyrometallurgy in Japan has experienced quite fundamental changes in last fifteen years. The severe environmental restriction coupled with increase of energy costs accelerated the development work of the new continuous process in Mitsubishi Metal Corporation. After several years of pilot plant test work the commercial plant was put into operation at Naoshima Smelter in 1974, the design capacity of which was 4,000 tonnes of copper per month. Many modifications and improvements have been incorporated into the process and 7,200 tonnes per month of copper production was achieved in 1983, proving that continuous process was much more economical than conventional process. It is now possible to design and operate the continuous process in wide range of capacity. This paper will review the process and describe the progress of the process in these 10 years. 311

Jan 1, 1985