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By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By Tim Robinson, Michael S. Moats, Masatsugu Moritmitsu, Kathryn C. Sole, Lauri Palmu, Frank K. Crundwell

"Process technology and design trends for copper, zinc, and nickel electrowinning cellhouses include focusing on energy reduction, productivity, and acid mist abatement. Larger electrodes, longer cells, automation, and higher current densities are leading to more capital-effective designs. The latest cellhouse designs include installation of automated electrode-handling systems, thereby removing more operators from the cellhouse. These technology and design trends result in lower electrowinning operating costs and improved purity of electro won cathode.INTRODUCTIONTechnology transfer between similar industries is an important process in improving product quality and productivity, and reducing operating costs. The electrowinning (EW) recovery of base metals, such as zinc, copper and nickel, is no different. The zinc industry with its larger EW product-handling requirements as compared to nickel and copper, has been driven to automation technology and the use of larger equipment. This technology has been transferred to copper. Nickel has led development and application in large-scale anode and divided-cell technologies but, due to nickel being produced in multiple forms (not just cathode) and being a small part of the whole complex nickel process route, the quantities of electrowon nickel are small compared to copper and zinc. Copper process technology in acid mist abatement was recently transferred to nickel. The focus in copper EW has been on energy reduction and productivity."

Jan 1, 2012

By E. G. Noble

The potential for using heterotrophic microorganisms to solubilize manganese from low-grade domestic ores is being assessed at the Reno Research. center, U.S. Bureau of Mines. More than 90 pct of the manganese has been extracted from a variety of oxide ores in shake-flask tests using molasses as a source of .. nutrients for the microorganisms. It has also been demonstrated that high recoveries of manganese can be obtained from a domestic wad ore using column bioleaching. 'l'he isolation and identification of organisms responsible for manganese extraction is discussed, as are the mechanisms responsible for manganese solubilization.

Jan 1, 1991

By W. K. Connor, O&apos

The Bureau of Mines has conducted beneficiation, carbothermic reduction, and leaching tests of Mn oxide ores as part of its evaluation of the Mn and Co resources of the West- Central Arkansas District. The major Mn oxides in the ore include cryptomelane, psilomelane, pyrolusite, and lithiophorite. Cobalt is contained within the Mn oxides. Nonbeneficiated ore was reduced at 800' C with coal and leached in ammonium sulfate and ammonium carbonate leach liquors. Ore concentrates were calcined at 600" C prior to reduction under the same conditions as the raw ore. Head analyses reported up to 21 ptt Mn and 0.11 pct Co. Extractions of 70 to 90 pct Mn and 40 to 60 pct Co were achieved.

Jan 1, 1992

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 30t/hour 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 B. Wasmund, K. Adham, K. O'Keefe, C. Lee

"Metal chlorides (e.g. iron and nickel) can be pyrohydrolysed at elevated temperatures to yield an HCl rich off-gas and a metal oxide product. Typically, the high energy requirement for pyrohydrolysis is provided by the combustion of a hydrocarbon fuel with air. Here, it is demonstrated that the use of oxygen-enriched combustion can result in lower fuel requirements and higher HCl concentrations. In addition, the oxygen enrichment can result in a smaller volume of off-gas and thus, smaller and less expensive process equipment. This new concept can be applied to both the spray roaster (SR) and the fluidized bed reactor (FBR). Similar to the aircombustion case, the oxygen-enriched process can use a direct contact venturi scrubber, to recover energy from the roaster off gas, but at a higher efficiency. The new process also uses an absorption tower for capturing HCl from the roaster off-gas, but generates a stronger HCl solution than is possible with pyrohydrolysis in air.BackgroundIn recent years, the metallurgical industry has become increasingly involved with developing methods for extracting metals, upgrading products or cleaning metallic products by using hydrochloric acid. These applications of chloride metallurgy often result in metal chloride solutions, which should be processed to regenerate HCl for reuse, and to recover the metal value as a product or by-product oxide [2, 3, 4].The pyrohydrolysis of metal chloride solutions has been done in two types of air roasters: spray and fluidized bed. The existing roasters burn a hydrocarbon fuel in air, to provide the required energy for evaporating the feed solution and to provide an elevated temperature for the chloride pyrohydrolysis to occur, according to the following reactions:"

Jan 1, 2011

By R. J. Kuczynski

The U.S. Bureau of Mines operated a 2,000-9 (4.4-lb) batch process development unit for recovering platinum-group metals (PGM) from automobile catalysts. Virgin monolith, used pellet and used monolith catalyst samples were tested. Leaching twice with 1-pct sodium cyanide (NaCN) solution at 160' C for 1 h in a pressure vessel dissolved over 95 pct of the PGM from virgin catalysts and over 90 pct from used pellet catalysts. Over 85 pct of the PGM was dissolved from used monolith catalysts when a third leaching step was added. PGM concentrates as metallic powder containing over 99.8 pct of the dissolved PGM and analyzing greater than 70 pct PGM were recovered by heating the pregnant leach solutions from virgin catalysts to 250' C and used catalyst to 275" C for 1 h. The solution after heating contained primarily sodium carbonate from cyanide decomposition and less than 0.2 ppm total cyanide.

Jan 1, 1993

By Richard A. Leiby

The recycling of lead-acid batteries in the United States has become a challenge as to how to balance ever increasing environmental regulation and cost with efficient operations. East Penn's captive secondary lead smelter has developed into a recycling facility producing lead, polypropylene, sulfuric acid, ammonium bisulfite, and non-hazardous discard slag. The emphasis has been to design a facility to comply with environmental regulations, to eliminate wastes, and to produce products, while at the same time, continuing to supply the company's battery manufacturing raw material needs.

Jan 1, 1993

By John J. J. Chen, Barry J. Welch

"As in many industrial processes, the detailed mechanisms involved must first be understood before being able to redesign, or to carry out improvements or optimisation of the process and equipment performance. In a great majority of metallurgical processes, visual observation and actual measurement of process variables are either very difficult or near impossible. Often, the cost and effort involved are prohibitive. Consequently, physical modelling is often used to provide some understanding of the process and for the validation of computer numerical models. In this paper, we summarise some of the work carried out at The University of Auckland on the modelling of the Hall-Héroult electrolytic cell, the in-line melt treatment process, and the steel casting tundish. IntroductionIn any industrial process, it is essential to understand the underlying mechanisms before any optimization or process improvement can be carried out. In many metallurgical operations, the processes are conducted at elevated temperature and under rather hostile environments. Consequently, it is often difficult, and sometimes impossible, to observe the actual processes occurring, or conduct measurements which are pertinent. In some situations, it is possible to formulate mathematical equations purported to describe the process, and obtain the solutions numerically. However, in this latter case, the validity of the simplifying assumptions made are often uncertain. Physical modelling may provide the necessary information for the validation of such numerical models. Furthermore, through an application of the principle of similitude, it is possible to apply data obtained from physical modelling to actual metallurgical processes. This paper will summarise some the work carried out at The University of Auckland on the physical modelling of gas-induced flow in the Hall-Héroult electrolytic cell, an in-line melt treatment unit, and the flow in a steel casting tundish.Gas-Induced Flows in a Hall-Héroult CellIn an aluminium cell, the effects due to electro-magnetic forces have been addressed and various design modifications such as magnetic shielding and the positioning of risers have been carried out to control or lninimise the effects of magnetic fields'. Consequently, the effects of gas-induced flows are now becoming significant providing the impetus for the study of the gas behaviour in the bath. Furthermore, the shape and size, and the rate of evacuation of the anodically generated gases affect the cell voltage affecting the energy efficiency; at the same time, the back-reaction between the anode gas and the metal produced is the predominant cause of the loss of current efficiency. Figure 1 shows a cross-section of a conventional cell in which the gas evolution occurs directly under the anodes, and the gas induced flow is confined mainly to the region occupied by the bath"

Jan 1, 1994

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 D. Papazoglou

This work was undertaken to investigate the thermodynamic and kinetic feasibility of using hot sulfur dioxide bearing gases from smelting processes to selectively sulfate the nickel in nickel laterite ores for subsequent extraction in water. The environmental benefits ofthis approach, as opposed to releasing the gas to the atmosphere, and the economic benefit of directly utilizing the S02 rather than converting it to sulfuric acid are strong drivers for such a process. A thermodynamic analysis indicated that selective sulfation of the nickel could be feasible under appropriate conditions and these were explored through a series of laboratory scale experiments. Laterite samples were reacted at temperatures between 500 and 800°C with an equilibrated mixture of sulfur dioxide, oxygen and nitrogen in a fixed bed reactor. Tests were conducted on saprolitic ore from Bulong, Western Australia, limonitic ore from New Caledonia and garnieritic ore from Indonesia. Nickel extractions were highest from the limonite and relatively low from the other ores. The maximum selective extraction of nickel from the limonite in a single stage sulfation was 73%. Sulfation of other elements present in the laterites was also examined. A two-stage process was also identified which involved sulfation using a strong sulfation potential followed by weaker sulfation potential to attempt to convert ferric sulfate formed in the first stage to ferric oxide. This increased the extraction for the limonite ore to around 84% Ni, 95% Co and 2% Fe. Direct sulfation of laterite could be feasible in locations where sulfide smelting or roasting operations are relatively close to laterite deposits.

Jan 1, 2003

By Young-Geun Park

A new decarburization model for the RH system was constructed for calculating the decarburization reaction using a three-dimensional fluid dynamics program. The entire fluid flow in the RH process was calculated by evaluating the shape and volume of the plume zone, formed by Ar gas blown through multiple nozzles on the wall of the snorkel. On the basis of this fluid flow, the decarburizaiton reaction was calculated through establishing the decarburization reaction model, which considers the thermodynamics, reaction kinetics, and the decarburization sites (Ar bubble surface, bath surface, and the CO bubble fomtation at inner sites). The results from this model were compared with a real RH operation results with good agreement. Because it is possible to predict the carbon concentration at various conditions using this model, it may be useful in increasing the decarburizaiton rate. Key words : RH process, plume zone, decarburization, Ar bubble surface, bath surface, inner site, circulation flow rate.

Jan 1, 2001

By J. N. Kondo, M. Hara, T. Smida, N. Ooto, K. Domen

"A porous material composed of two-dimensional anionic sheets of a layered perovskite, KSrNb30 10, was studied as photocatalyst for the production of Hz in the presence of alcohol sacrificial donors. Colloidal single and multi-layered HSr2Nb30 10 sheets were formed by intercalating ietra(n-buthylammonium) cations into the interlayeres of H+-exchanged KSr2Nb30 10 (HSr2Nb30 10), and addition of HN03 solution to the colloidal suspension precipitated the porous materials in which HSrNb30 10 sh~ets rand~mly stuck together. Original HSr2Nb30 10 before exfoliation had a BET surface area of 1 m2 g-1, whereas the surface area of a porous material prepared under optimal conditions exceeded 100 m2 g-1. The porous HSr2Nb30 10 had considerably higher photocatalytic'activitie8 for oxidation of 1-propanol and 1-buthanol than HSr2Nb39io, indicating that in the porous materials many niobate sheets are available for decomposition of these large alcohols.IntroductionQuite a research effort has gone into the design and study of porous materials. Such materials with large surface areas would have applications in highly efficient adsorbents or catalytic reactions.We have been studying photocatalytic reaction by cation-exchangeable layered metal oxides, where alkali metal cations are intercalated into the interlayers of inorganic sheets.[1,2] There are several advantages to using layered compounds rather than bulk powders for photocatalysis. Layered compound is rich in variety, in addition, modifications of them are easily performed by exchanging alkali metal cations in the inter layers for H + or other metal cations. The most important advantage is that some layered compounds have considerably high photocatalytic activities than bulk catalysts because the electrons and holes generated in each thin inorganic sheet readily reach interlayer spaces as reaction sites at the illterlayer spaces. It should be very important for further improvements· of layered photocatalysts to utilize two-dimensional inorganic sheets effectively."

Jan 1, 2000

By Zhong g. Shui-ping

A new type Pb-Ag (0.8wt%)-Bi (0~5.0wt %) alloy used as anode in electrowinning of zinc from sulphuric acid electrolytes was prepared. The electrochemical properties of this ternary lead alloys have been tested and compared with those of Pb-Ag (0.8wt %) anodes used in industry. Results show the anodic overpotential decreases with the increasing of Bi content in the alloys. When the content of Bi was 1.0 wt% and 5.0 wt%, the anodic overpotential is about 40?50 mV and 60?80 mV lower than that of Pb-Ag (0.8wt %) alloy, respectively. The formation of oxide layers on the surface of these alloys was traced by LSV methods and the composition of the anodic oxide layers was characterized by XRD and SEM analysis. The surface layer on the two type anodes examined is mainly composed of a?PbO2 and ß?PbO2. But different structure of the surface layer was observed, Pb-Ag (0.8wt%)-Bi (1.0wt %) has a more fine-grained structure as compared to Pb-Ag (0.8wt %). But the film on Pb-Ag (0.8wt%)-Bi (3.0wt %) alloy is rather friable, cracked and not tightly attached to the anode.

Jan 1, 2008

By G. S. Rao

Levitated drops of Fe-18%Cr-2%C were reacted with oxygen-argon mixtures to study the reactions that occur in the AOD process, where the gases are injected into the melt and form bubbles. In the laboratory an argon-oxygen pulse, followed by pure argon, was flowed past the levitated drop to simulate the transient conditions in the gas phase as the bubbles rise in the melt. Oxide layers formed on the drops immediately when they came into contact with gas pulses containing 75% or more oxygen. Once the oxygen flow had ceased, the oxides reacted with the carbon in the drops to form CO gas and eventually disappeared. The de-carburization reaction occurred without oxide formation when the gas contained 50% oxygen or less. Melts that were sampled after EAF tapping, ready to be charged into the AOD, showed a higher tendency to oxide formation and consequent carbon boil than pure ternary Fe-18%Cr-2%C alloys made in the laboratory. The actual steel samples contained significant impurities, such as 0.25% Si and 0.56% Mn. A similar effect of oxide-forming impurities had been observed previously with binary Fe-C alloys. Movies were taken of the oxide formation and decomposition, and the results will be presented, along with data on the experimental conditions, including temperature and oxide compositions. The results are important because they give an insight into the reaction mechanisms in the AOD, which must be understood in order to improve and model the process.

Jan 1, 2006

By C. Pereira

Spent nuclear fuel (SNF) can be treated in a molten salt electro refiner for conversion into metal and mineral waste fonns for geologic disposal. The fuel is dissolved in molten chloride salt. Non-transuranic fission products in the molten salt are ion-exchanged into zeolite A, which is subsequently mixed with glass and consolidated. Zeolite was found to be effective in removing fission product cations from the molten salt. Breakthrough of cesium and the alkaline earths occurred more rapidly than was observed for the rare earths. The effluent composition as a function of time is presented, as well as results for the distribution of fission products along the length of the column. Effects of temperature and salt flow rate are also discussed.

Jan 1, 1996

By J. D. Budai, D. H. Lowndes, D. P. Norton, D. K. Christen, B. C. Chakoumakos, J. R. Thompson, B. C. Sales

"Artificially-layered structures, consisting of (Sr,Ba,Ca)CuO2 layers in the tetragonal, ""infinite layer"" crystal structure, have been grown by pulsed-laser deposition. Superlattice chemical modulation is observed for structures with SrCuO2 and (Sr,Ca)CuO2 layers as thin as a single unit cell (~3.4 Å). In addition, novel thin film superconductors were formed by using the constraint of epitaxy to stabilize SrCuO2/BaCuO2 superlattices in the infinite layer structure. Using this approach, two new structural families, Ba2Srn-1CUn+l O2n+2+ d) and Ba4Srn-1CUn+3O2n+6+ d, have been synthesized which superconduct at temperatures as high as 70 K. These results represent not only the synthesis of new structural families of superconductors, but also demonstrate that pulsed-laser deposition and epitaxial stabilization can be effectively used to engineer artificially-layered thin-film materials.Advances in the understanding of epitaxial thin-film growth of the cuprates have heightened interest in creating artificially layered superconductors.(1-3) The layered structure of the copper oxide superconductors opens the possibility of forming novel materials by carefully controlling the epitaxial growth of sub-units of the crystal structures. Thin-film growth methods offer unique opportunities for the atomic engineering of new high-temperature superconducting (HTSc) materials through the ability to form artificially layered crystal structures.(4,S) Moreover, the surfaces of single-crystal substrates provide an ""atomic template"" that can be used to stabilize epitaxial films in metastable crystal structures.An important development in forming new HTSc compounds by artificially-layered epitaxy has been the epitaxial growth of (Sr,Ca)CuO2 films in the so-called infinite layer structure.(6-17) This material, which can be considered the parent compound of all of the copper oxide superconductors, has a relatively simple, layered structure consisting of CUO2 planes separated by planes of alkaline earth elements.(18) Bulk synthesis of (Sr,Ca)CuO2 with the tetragonal, infinite layer structure generally requires the use of high pressure and high temperature bulk processing techniques.(19-24) However, recent experiments show that this metastable compound can be epitaxially stabilized at less than atmospheric pressure, resulting in the growth of tetragonal (Sr,Ca)CuO2 single crystal thin films of the infinite layer defect perovskite structure by pulsed-laser deposition (PLD) over a wide range of growth conditions.(6-17)"

Jan 1, 1994

By Agnes Y. Lee

he U.S. Bureau of Mines developed a method to treat lead-contaminated soil and ebonite battery casing wastes to produce a nonhazardous material. The cleanup procedure involves wet screening to separate a minus 18-mesh soil fraction; removal of metal1ic lead, rocks, wood, etc. ; carbonation to change lead sulfate to acid-soluble lead carbonate; size reduction; acid leaching; and rinsing. The casing wastes undergo size reduction and washing to remove the lead sulfate sludge before carbonation. Similarly, the minus 18-mesh soil is carbonated, then acid leached and rinsed. In leaching, fluosilicic acid (H SiF,) and hydrogen peroxide (H20,) are used to dissolve lead compounds. An electrowinning method is employed to strip lead from the lead-rich leachate. The acid content in the leachate is replenished with fresh H,SiF, acid prior to recycling. Treated casing wastes and soils pass the Toxicity Characteristic Leaching Procedure (TCLP) test and can be reclassified as nonhazardous materia1s. Based on this process, a conceptual pilot plant has been designed which will be demonstrated on wastes from two Superfund sites.

Jan 1, 1993

By Fujio Ishii

The deoxidation of liquid nickel and nickel binary alloys with silicon has been determined at temperatures between 1500°C and 1650°C using quartz crucibles in order to investigate the deoxidation of nickel based alloys. The equilibrium constant of the deoxidation reaction in liquid nickel and the effects of the different alloying elements such as chromium, molybdenum, tungsten, iron, cobalt and coppcr on the activity coefficient of oxygen in liquid nickel have been established.

Jan 1, 1993

By J. J. Talja

An investigation of oxidation of various nickel concentrates was carried out using differential scanning calorimetry (DSC). The aim of this study was to determine the ignition temperature and investigate other oxidation behavior of various sulfide-based nickel concentrates. Variables in the experiments were mineralogy, particle size and partial pressure of oxygen with temperature increasing linearly at 25 K/min from 323 to 1023 K (50-750 °C). The igni¬tion temperature was determined to represent the starting point of rapid oxidation. The reac¬tion enthalpies of the concentrates were determined and the amount of heat generated up to various time were used to calculate the extent of reaction. Mineralogical changes at various stages of oxidation were also investigated. For this purpose a second set of DSC-experiments were carried out in which each experiment was interrupted at a desired temperature between 673-873 K. From these tests the weight loss of samples were determined and changes in the individual constituent of sulfide minerals were analyzed. For pentlandite-based Ni-concentrates the ignition temperature was 705-710 K (approximately 435 °C). Pyrite was the first sulfide to oxidize. Reactivity of the violarite-based concentrate was greater than those of the pentlandite-based concentrates. The stoi-chiometry of pentlandite changed before ignition because of preferential oxidation of iron. Rapid oxidation of the pentlandite mineral occurred at about 823 K (550 °C). By 900 K about 90 % of the iron in pentlandite was converted to hematite, and NiS containing some iron was formed.

Jan 1, 1994