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By T. Nagano

Mitsubishi Metal Corporation started the development work of a new process for continuous production of copper in 1961. After a series of experimental and semi-commercial operations, the first commercial plant of the Mitsubishi Continuous Copper Smelting and Converting Process was put into operation in March, 1974. The new plant, which has a design capacity of 4,000 metric ton copper per month, was built within the premises of Naoshima Smelter, replacing the old No.1 reverberatory smelter there. The SO2-rich exhaust gas from this new plant is blended with the off-gas of the No.2 reverberatory furnace for production of sulfuric acid and the overall emission of sulfur at Naoshima has been greatly reduced. The operation of the continuous plant has been satisfactory and several advantageous features of the Mitsubishi Process have been proven on a commercial scale. This paper first gives a brief description of the history of the development work and the characteristic features of the process. The paper then describes the new commercial plant and operating data obtained so far.

Jan 1, 1976

By L. J. Cabri

The level of mineral exploration activity for platinum in recent years, especially in North America, has ranged widely. Exploration programs have been based on a variety of ore deposit models and deposit types. These range from the classic magmatic model for sulfide/oxide deposits and their associated placers, through hydrothennal models for bonanza-type deposits, to low-grade mineralization potentially amenable to lower cost bulk mining methods. The platinum-group element (PGE) distribution in these different deposit types is not well-known however, and PGE determination is fraught with analytical difficulties. To properly assess a prospect or to achieve effective recovery by mineral processing, it is important to determine the mineralogical distribution of the PGE.

Jan 1, 1988

By Kandipati Sreenivasarao

Ion and precipitate flotation involve adding an appropriate collector to aqueous solutions containing metal ions, to form hydrophobic metal-collector complexes or precipitates that can be removed by flotation. With a better fundamental understanding of the effects of physical, engineering and chemical parameters on the performance, ion and precipitate flotation techniques could usefully complement techniques now available for removing metal ions from dilute solutions. The removal of Cu(II), Pb(II), Cd(II), Cr(III) and Cr(V1) has been studied, using different types of collector, according to the nature of the metal-bearing species. The effects of collector/metal ion ratio, and solution and froth height on the flotation kinetics, bubble coverage by the metal-collector complex, recovery of metal and effluent quality are reported. The observed behavior is related to the solubility products of the metal-collector complexes, which were also determined.

Jan 1, 1994

By R. Singh, C. Gong, J. Chaudhry

"Metalorganic chemical vapor deposition (MOCVD) is an ideal technique for the deposition of conducting and non-conducting oxide based thin film materials. In this paper we have presented a study of photo assisted MOCVD for the low temperature deposition of a number of oxide based advanced materials. We have used incoherent light sources as the source of optical and thermal energy in our MOCVD system. The vacuum ultraviolet (VUV) and ultraviolet (UV) photons can enhance the surface reaction of the absorbed molecules through the perturbation of the electronic state of binding between the absorbed molecules and the solid surface. Unlike plasma process, no surface damage is expected and high quality materials have been deposited. At a given substrate temperature, the performance of deposited film depends on the lamp configuration.INTRODUCTIONMetalorganic chemical vapor deposition (MOCVD) has become the standard manufacturing technique for the deposition of large area thin films of compound semiconductors. l.(.w-cost, high crystalline quality, atomically clean and sharp interfaces, atomic layer epitaxy, high throughput rates and potential for direct writing are some attractive features of MOCVD. Due to a number of potential advantages mentioned above, MOCVD is considered as an ideal technique for the deposition of various electronic and optical materials for a wide variety of applications. Rapid isothermal processing based on incoherent radiation as the source of optical and thermal energy is emerging as the key low thermal budget (integral of processing time and temperature) processing technique for the fabrication of current and next generation of microelectronic and optoelectronic devices and circuits [1]. In this paper we have demonstrated that the design of the lamp assembly plays an important role in determining the properties of the materials deposited by RIP assisted MOCVD. We have studied the growth rates, structural properties and electrical properties of Y2O3/Si structure. At a given substrate temperature, best results are obtained for the lamp assembly that provides maximum number of VUV and UV photons."

Jan 1, 1994

By R. Boom, Y. V. Meteleva-Fischer, B. Kraaijveld, H. Kuntzel

"Segregation of impurities during refining of metallurgical grade silicon (MG-Si) is an option to produce solar grade silicon (SG-Si). Directional solidification is a last step in production of SG-Si effective for removal of metallic impurities. The possibility is investigated to use metallic impurities originally present in MG-Si for removing boron and phosphorus. MG-Si has been treated using two methods: 1) alloying with calcium and 2) refining with Na2O-CaO-SiO2 slag, both by controlled cooling. The microstructure of silicon and the impurities distribution have been studied before and after the treatments. Using EPMA phosphorus and boron have been detected in 1-2 wt% concentration range in several intermetallic compounds in grain boundaries after both treatments. This observation points to a different possible mechanism of silicon refining from boron and phosphorus. Controlled cooling improves migration of phosphorus and boron to the silicide phases in grain boundaries, which can be removed by acid leaching treatment.2. IntroductionStandards for silicon solar cells and growing demand on “green” energy require economical and efficient route to the production of solar grade silicon. Refining of cheap metallurgical grade silicon is one of the promising options, where application of existing metallurgical approaches can result in cost-efficient production on industrial scale. Focus in refining is on impurities, which are most difficult to remove: B, P, Al, Ti, due to their large segregation coefficient in silicon and low vapour pressure [1]. Moreover, more environmentally friendly technology in comparison to the traditional Siemens process [2] will be in accordance with societal needs. Based on properties of common impurities in metallurgical grade silicon, alloying refining and slag refining are suggested as competitive techniques having potential effect on removal of impurities harmful for conversion of solar energy [3, 4]. Alloying with Ca followed by acid leaching was found to be effective for removal of Fe and Ti from silicon [5] and to enhance also removal of boron [6] and phosphorus [7, 8]. In the work of Inoue et al. [8] drastically increasing removal of phosphorus from silicon has been observed with an increase of Ca content and a thermodynamics-based explanation was provided. Since phosphorus has been found to condense in the secondary precipitate mainly composed of CaSi2, it can be removed together with iron and titanium by consecutive acid leaching treatment. Slag refining is one of the metallurgical methods proposed to be effective for refining of metallurgical grade silicon from boron [9, 10]. Slags with additions of the following oxides to silica have shown positive effect on removal of boron: CaO [11-13], Na2O [11,14]. Mechanism of slag refining from boron is based on oxidation of boron followed by its incorporation in the slag network [9,11]; the same mechanism is suggested for refining from phosphorus taking into account that oxides of boron and phosphorus are known as network-formers [15]."

Jan 1, 2012

Physical and chemical methods were investigated to tower thorium levels in Eneabba Ilmenite from the natural levels of 180-500 ppm to give Becher Process synthetic rutile with less than 100 ppm thorium. Chemlcal treatments, but not physical separations were successful. A pilot plant trial of a sodium hydroxide leach (25M NaOH at 75°C and 40 wt% solids for Ih) followed by a sulphuric acid leach (3M H2S04 at 90°C and 60 wt% solids for 211) confirmed that thorium could be removed to below 100 ppm. However, the activity of the ilmenite was not lowered to the same extent

Jan 1, 1996

By Marion Dattilo

The search for an improved anode for the electrowinning of lead from fluosi1icic acid medium has led the U.S. Bureau of Mines to investigate composites. Polymer bonded metal oxide powders which may contain catalyst additions were prepared by pressing. These composites display an improved activity toward the oxygen evolution reaction over electrodeposited lead dioxide on titanium, carbon, and nickel substrates. These composite electrodes contain 5 to 10 wt. " binding polymer, with the balance being metal oxides. Lowered anodic potentials achieved using the compnsite anodes resulted in lower levels of lead dioxide deposition during electrowinning.

Jan 1, 1995

By Takeshi Ohgai, Hisaaki Fukushima, Tetsuya Akiyama, Joon-Seo Ki

"Recently, an intensive attention has been paid to the electrodeposition of Zn-Cr alloy in the field of the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation. In this study the electrodeposition of Zn-Cr alloys from the sulfate baths was conducted to investigate the codeposition mechanism of Cr with Zn. As a result, Cr was codeposited with Zn at higher current densities in both polyethyleneglycol(PEG)-free and PEG- containing baths. However, PEG made it possible to reduce Cr+ to the metallic state and Cr existed in the form of Cr(III) hydroxide in the deposits obtained from PEG-free bath. The measurements of the partial polarization curve of Zn and the pH in the cathode layer revealed that PEG acted as a polarizer to shift the cathode potential to the reduction potential of the composited hydroxides of Zn and Cr formed due to the pH rise in the cathode layer.1. IntroductionRecently, much attention has been paid to the electrodeposition of Zn-Cr alloys because of its application to the production of super-highly corrosion-resistant alloy plated steel sheets for the next generation1Hl_ Some researches have already tried to commercialize this type of steel sheet. High corrosion-resistance of this steel sheet is brought about by codeposited Cr in the alloys. According to Piontelli's classification5l concerned with metal deposition from aqueous solution, Cr belong; to an inert metal and its deposition is associated with a large amount of hydrogen evolution. Therefore the current efficiency for Cr deposition is extremely poor. It has been also reported that Cr is unable to codeposit in the electrodeposited Zn film in the absence of a certain additive in the solution. 0-compounds group colloids7l, ether group organic compounds8), 9>, peptide based compounds10l, etc., have been found to be effective additives to induce the codeposition of Cr with Zn. However, few studies have been made on the codeposition mechanism of Cr with Zn. In this research, the fundamental electrodeposition behavior of Zn-Cr alloys from sulfate baths was investigated to clarify the codeposition mechanism."

Jan 1, 1998

By D. J. Senor

Closed chamber incineration (CCI) is a novel technique by which irradiated nuclear graphite may be destroyed without the risk of radioactive cation release into the environment. The process utilizes an enclosed combustion chamber coupled with molten carbonate fuel cells (MCFCs). The transport of cations is intrinsically suppressed by the MCFCs, such that only the combustion gases are conducted through for release to the environment. An example CCI design was developed which had as its goal the destruction of graphite fuel elements from the Fort St. Vrain reactor (FSVR). By employing CCI, the volume of high level waste from the FSVR will be reduced by approximately 87 percent. Additionally, the incineration process will convert the Sic coating on the FSVR fuel particles to SiO2, thus creating a form potentially suitable for direct incorporation in a vitrification process stream. The design is compact, efficient, and makes use of currently available technology.

Jan 1, 1994

By Willem P. C. Duyvesteyn

A novel hydrometallurgical process for Escondida copper concentrates has been developed by The Minerals Laboratory of BHP. The Escondida Process consists of concentrate leaching, solution purification, electrowinning and residue flotation. Part of the copper will be sold as high grade concentrate and part as high purity SX-EW copper. Contrary to previous efforts for the development of a hydrometallurgical process for copper concentrates, this patented process does not advocate the total dissolution of copper. It only aims for the copper that is readily soluble in a mildly oxidizing environment with an ammoniacal or acidic lixiviant. Both lixiviants were studied, but ammonia was preferred because of fast kinetics at ambient temperatures and pressures. By controlling the oxidation potential, the formation of sulfate ions and, consequently, of an ammonium sulfate byproduct, is precluded. These mild leaching conditions also prevent the dissolution of unwanted impurities and result in the production of ultra-high purity electrowon copper. Solution purification is carried out by solvent extraction with LIX-54. The very high loading capacity of this organic results in a compact SX circuit, consisting of two loading, one scrubbing, and one stripping stage. As the organic is selective for simple copper ions, the copper amine complex is broken down and free ammonia is regenerated and recycled for leaching. High purity copper cathodes are produced in a conventional sulfuric acid based electrowinning system. One scrubbing step is needed to separate the ammoniacal circuit from the acid circuit. Limiting copper dissolution to less than 50% also provides an opportunity to produce high grade concentrates by residue flotation. Copper recoveries in excess of 98% with precious metal values reporting to the final concentrate can readily be obtained. Complete breakdown of the copper mineral- pyrite middlings results in a final concentrate grade that can be even higher than the original feed material. The Escondida Process also provides an opportunity to accept lower grade copper concentrates producing improved copper recoveries in the mill and yet high quality concentrates for marketing. The Paul E. Queoeau International

Jan 1, 1993

By R. Cavanagh

Studies relating to the fixation of sulfur by reaction of 4 to 8 mm diameter cylinders of calcined limestone or dolomite with high strength sulfur dioxide in the temperature range 880°C to 1020°C were undertaken. Dolomites are far superior in sulfate capacity and reactivity than dense limestones even at high strength SO2. The sulfation reaction was first order with respect to SO2 concentration below 100 percent. Zero reaction rate at 100 percent SO2 concentration indicates that sulfate was the exclusive reaction product and that sulfite had no role in the reaction. At relatively low SO2 concentrations gaseous diffusion through the reaction product layer has a marked effect on the rate. As SO2 concentrations were increased up to 100 percent more complex rate controlling mechanisms unfold. By sectioning partially reacted dolomitic limestone pellets a moving interface was observed. Reaction ceased because of pore plugging for dense non-porous limestones at 30% conversion. With dolomitic material virtually complete sulfation of the calcium was observed. S.E.M. analysis showed that the average atom ratio Ca:S was 1.01, thus supporting the argument that little if any of the magnesium was sulfated.

Jan 1, 1996

By Yuanbing Ling

Keywords: Calcium sulfate, Sulfuric acid, Phase transformations, Thermodynamic analysis As part of a boarder research project, seeking the development of a cost-effective process for direct production of the high value material, -calcium sulfate hemihydrate, from sulfuric acid at atmospheric as opposed to elevated pressure conditions, the fundamental work presented here has been undertaken. This includes experimental monitoring of phase transformation reactions and thermodynamic analysis of the relationships among the various phases, namely, calcium sulfate dihydrate, hemihydrate and anhydrite in aqueous sulfuric acid solution at temperatures ranging from 20oC to boiling point.

Jan 1, 2004

By M. W. Kennedy

Prediction of the thermal duties of copper coolers in freeze lined furnaces is challenging. Where copper coolers are immersed in liquid slag the heat transfer is often defined by a natural convection cell immediately adjacent to the wall, in the absence of other factors producing forced convection. Slag coolers are typically not fully immersed, slag temperature, liquidus and superheat can vary, and bath levels may change significantly with batch tapping, leading to substantial variations in radiation heat fluxes. Radiation heat transfer is discussed with reference to the non-obvious impact of slag liquidus on radiation losses in the exposed cooler sections. Reference is made to literature and the results of analytical and FEM models.

By A. Bilodeau

A new hydrometallurgical process for the production of refined gold and the recovery of palladium and platinum from silver anode slimes has recently been developed and installed at the, CCR Division of Noranda Inc. The process, which facilitates the production of gold of >99.99% purity in the face of increasing palladium receipts comprises; leaching silver anode slimes with hydrochloric acid and hydrogen peroxide at 95°C to solubilize gold, palladium, platinum and base metals while simultaneously rejecting silver as insoluble silver chloride; precipitating gold from the leach solu¬tion with sulphur dioxide gas in two stages to produce a first-stage high purity gold product and a second stage impure gold which is recycled to the leach; washing, melting and casting of the pure gold; precipitation of a palladium-platinum concentrate from the gold-free solution by reduction with sodium formate at pH 4 and 95°C; and neutralization of the palladium precipitation effluent to pH 10 with lime. The results of laboratory and pilot plant studies leading to the adop¬tion of this process are discussed, and data are presented for each of the unit operations. Details of the engineering of the commercial plant are given, and plant start-up experience is described.

Jan 1, 1987

By M. Jortikka

The smelting process of the old reverberatory furnace including its capacity has been improved over the years in different ways eg. with oxy-fuel burners, parallel reactors with the reverb or with various modifications of the reverb furnace itself. The future reverb modifications with old concepts are difficult or impossible as the increased copper losses in slag call for separate slag treatment and particularly the process modifications do not solve the environmental issues but instead mean unavoidable high capital and operating costs in gas cleaning and sulphur recovery. During the last decades improvement in process performance and increase in capacity of copper flash smelters has been achieved easily by substituting the pre-heated process air by highly oxygen enriched air. The flash furnaces of today, however, are inherently designed to operate with high oxygen enrichment. Further process improvement with a view to production costs and capacity increase as well as to the more stringent environmental requirements is possible with even higher oxygen enrichment. This, apart from the advantages it generates, requires improvements in and careful design of the feed system, concentrate burner, furnace cooling and the off-gas line as well as adaption of the flash converting instead of the conventional Peirce-Smith converters. A logical answer even for the revamping of the reverb smelters in the future is the total replacement of the reverb furnaces with flash smelting together with flash converting. This paper discusses the possibilities for future process improvements of the existing flash smelters taking into account the process concepts, equipment modifications and capital aspects not forgetting the environmental issues. The revamping of the PASAR smelter in Philippines is introduced as an example of a recent success story.

Jan 1, 1994

By Osamu Takai, Yoshiki Sato, Nobuhiro Tajima, Hiroyuki Sugimura

"Amorphous carbon thin films doped with nitrogen ( a-C:N) have been synthesized by means of shielded arc ion plating (SAIP). Their electron field emission properties, that is, threshold field strengths for electron emission and maximum emission current densities, were evaluated and compared with those of pure amorphous carbon (a-C) films prepared by the same SAIP apparatus. Among all of the fabricated a-C:N films, the a-C:N films with a N concentration of 23 %, which prepared using Nz arc plasm at a pressure of 1 Pa with applying a sample bias voltage of -100 V, showed the lowest threshold filed of 13.4 V/µm and the highest emission current density of 1.87 µAfcm2 at a field of20 V/µm. These field emission properties of the a-C:N film were much better than those of the a-C films. The best results obtained on the a-C film in this study were the lowest threshold filed of 15.5 V/µm and the highest emission current density of 0.052 µA/cm2 at a field of 20 V /µm. Nitrogen doping to aC was found to be effective for lowering threshold voltage for field emission and for increasing emission current density. The electron field emission characteristics of the a-C:N films depended not only on N concentration but also on chemical bonding state of nitrogen in the a-C:N films. The presence of the ~-C3N4-like phase, which contributes to improve wear resistance of a-C:N as well, distinguished by the NlsXPS peak at 400.5 eV is proved to be crucial in order to enhance field emission properties of a-C:N.IntroductionThere has been much interest in electron field emission from a cold cathode due to its potential applications in vacuum microelectronic devices including field emission displays which are expected as flat panel displays in next generation [l]. It is well known that efficient emission can be rather readily realized using tip-like shape cathodes, e.g., microfabricated three-dimensional electrodes [2], carbon nanotubes [3-5], etc. However, electron emission from planar surfaces is of particular importance since such a type of cathode is· simply fabricated and assembled into microelectronic circuits. Currently, amorphous carbon thin films doped with nitrogen (a-C:N) prepared by plasma processes have attracted attention because their threshold voltages of field emission are relatively low [6]. Among various methods for preparing a-C:N films, the process using arc plasma is of special interest since, in arc plasma, nitrogen is highly activated and new types of carbon nitride phase are expected to be synthesized. However, field emission properties of a-C:N prepared by arc plasma have been studied in less detail compared with that prepared by the other methods such as sputtering."

Jan 1, 2000

By Bora Derin

The partial pressure ratios of sulfur and oxygen for several copper flash smelting plants were derived using the Reddy-Blander (RB) model and predicted dissolved sulfur contents available in the literature. The sulfide capacities (Cs) of six different flash smelting plants (FeO-CuOo.5- CaO-MgO-FeOu-AlO15-SiO2) slags were calculated. The log (PO2/PS2) versus matte grades of various industrial processes was determined. The PO2/PS2 ratio increased with an increase of copper grade. The calculated partial pressure ratios for the copper flash smelting are in good agreement with those of the experimental data.

Jan 1, 2003

By Xiyun Yang, Hui Xu, Xichang Shi, Xiang Xiao

"Rod-like magnetite particles were prepared by precipitation of iron salts with urea under the induction of magnetic field. Temperature and initial Fe3+/Fe2+ ratio have a significant effect on the composition of the product. Magnetite particles change from spherical into rod shape in the presence of a 0.35 T magnetic field, The addition of a small amount of spherical seeds increases the rod-like magnetite particles yield. The seeds are prepared by aging ferrous and ferric solution with sodium hydroxide as precipitator. The aspect ratio of the rod is controlled by varying the volume ratio of seed to iron salt.IntroductionMagnetite, an important member of magnetic materials, has attracted a lot of attentions for its super magnetic properties. The rod-like magnetite particles have high anisotropy and coercive force as well as super magnetic properties compared to other shapes, and are widely used as high magnetic density media, magnetic devices and microwave materials [1-4]. Recent studies have found that magnetic field can direct magnetite growing along easy magnetization axis to get one-dimension particles [5-6]. Chen et al. [7] synthesized single crystalline nanorod magnetite under magnetic field. Wang et al. [8] discovered that magnetite grew along easy-magnetization directions under 0.35T magnetic field. Vereda et al. [9-1 O] found that magnetic field had a dramatic effect on the morphology, inducing the aggregates to line along one direction to form rodlike particles.At present, most of the synthesis methods reported in the literature result in a low yield of rod particles and the aspect ratio are difficult to control. Recently, we developed a seed-mediated growth approach to making rod-like particles in an aqueous solution. The spherical magnetite generated by oxidation serves as a seed. These seeds are then added to a solution containing iron salt and urea, and provide nucleation sites for magnetite rod growth."

Jan 1, 2011

By Florian Kongoli

Converters have been playing an important role in the extraction and processing of metals ever since the first type of converter was invented about 100 years ago. Historically their operation has been mainly based on the experience of talented operators rather than on strict control and optimization technologies. However, in the new realities of unavoidable necessity to increase productivity and in the conditions of diversification of primary materials from various geographical areas, improving control and optimization techniques have become indispensable. In this paper a review of the authors? previous work in terms of improving control and optimization of converter operational practices related to magnetite content and precipitation, slag and metal blows, problematic and dangerous elements such as As, Sb etc. has been described by highlighting the advantages that the new control and optimization methods and tools bring to everyday converter practices. Several examples are given and future work is underlined

Jan 1, 2005

By Ole Rud Bendixen

Topsoe has developed a Wet gas Sulphuric Acid (WSA) process which effectively recovers SO2 in off-gases from non-ferrous smelters and roosters. The product is concentrated sulphuric acid of typically more than 96 wt% irrespective of SO, concentration in off-gas. The process does not generate any waste products or waste water and does not use any absorbents or other chemicals. In the process, up to 99.3% of the SO2 is converted catalytically into SO3, which reacts with water in the gas, hereby forming gaseous sulphuric acid. The acid is condensed in a WSA condenser of proprietary design. Excellent heat economy and practically no sensitivity to the water balance mean that no extra sulphur burning is required at any S02 concentration, The process is especially well suited for treating off-gases where the SO2 content is lower than approx. 5-6%, and it is a good alternative to a complete renovation of a smelter. However, also off-gas from flash smelter may be treated. The process has found good use in both molybdenum and lead roosters. An example from a molybdenum roaster in Chile shows that 97-98wt% acid is produced from a 2.3 % S02 gas. This plant is situated in the outskirts of Santiago and represented a major local source of SO2. The plan was started in May 1993.

Jan 1, 1996