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By Takahiro Miki

In order to use metallurgical grade silicon (MG-Si) as a starting material for solar cell, phosphorus has to be removed from silicon because phosphorus is a n-type dopant. On the other hand, silicon, ferrosilicon, and silicomanganese are widely used as deoxidizers in steel refining processes. Since most of the phosphorus introduced during the deoxidation process is brought into final products, it is important -to lower the phosphorus content of these alloys. Hence, thermodynamics of phosphorus in such metals is important for the evaluation of dephosphorization processes. In the present study, thermodynamic properties of phosphorus in molten Si-P alloys at 1723- 1848K and those of Si-Fe-P and Si-Mn-P alloys at 1723K have been determined by equilibrating respective metals in a controlled phosphorus partial pressure. The results are expressed as follows.

Jan 1, 1998

By Isrun Bohlinger

Resources recovery of brasses for semifinished products often results in the formation of hard spots impairing the quality of following abrasive and/or surface finishing processes. A short survey is given on the recycling processes, followed by the actual knowlegde of genesis, composition, and possibilities of avoidance of hard spots. Informations on genesis and composition of hard spots are completed by data from recent experiments.

Jan 1, 1998

By K. S. Kumar

FLS miljø, Inc. markets, designs and supplies particulate collection devices for dusts, fumes, and mists; In this paper, the application of both wet and dry electrostatic precipitators (ESPs) in smelting, and roasting plants is discussed.

Jan 1, 1998

By Oleg B. Girin, Yuliya O. Proshenko

"Several approaches to electrolytic synthesis of new types of composite coatings with improved properties were devised using the authors' findings on development of texture, substructure and structural state in metal electrocrystallization. Addressed are texturally composite coatings having improved resistance to wear and corrosion; substructurally composite coatings having improved hardness and corrosion resistance; phase-change constitutionally composite coatings having improved corrosion resistance, reflectance, hardness and resistance to wear; structure-change constitutionally composite coatings having improved electric and magnetic properties; restricted-substructure composite coatings having improved resistance to abrasive-impact wear; and modified-substructure composite coatings having improved strength and plasticity.IntroductionIn recent years, some trends in the formation behavior of crystal texture, crystal substructure and structural state of electroplates were revealed and effects of texture, substructure and structural type on electroplate properties were discovered (1-3). Our interest was in using these findings and effects to develop some ways of synthesizing new types of composite electrolyte coatings having enhanced properties."

Jan 1, 1998

By A. Rawat

The removal of oxyanions of arsenic present in mine process water and drinking water to a regulatory level is a challenging problem. Recently a patented adsorbent lanthanum oxide has been developed which has shown strong specificity for the anions of arsenic. In this paper the kinetic and thermodynamic aspects of arsenic adsorption on to lanthanum oxide are discussed. Adsorption tests were performed at different temperatures using synthetic solutions of arsenic of varying concentrations. From the kinetic data and adsorption isotherms thermodynamic properties such as Gibb's free energy, standard enthalpy of adsorption, standard entropy, isosteric heat of adsorption and activation energy were determined. The results showed that temperature had a positive effect on the rate and degree of adsorption:The activation energy decreased with increase in the initial concentration thus indicating solute-solute interactions in the system. Also, the isosteric heat was found to decrease with increase in the adsorption density implying a heterogeneous adsorbent surface.

Jan 1, 1998

By P. M. Tait, N. A. Warner

"The refining of thermally produced zinc is currently performed using a highly energy intensive and arguably outmoded process, distilling zinc under atmospheric pressure at temperatures of 900°C to 1000°C. In order to produce refined zinc more profitably and with less environmental impact a new process has been proposed. This process is generic to all thermal zinc smelters and aims to match the purity of zinc from current technology (99.99%-99.999%). The objective is to perform all separation processes using only the heat contained in the smelter product stream. Vacuum conditions are extensively used lowering operating temperatures and enhancing separations. As part of this process zinc is distilled under vacuum from high concentration obtaining a refined product with respect to lead content. A mathematical model has been developed from fundamental principles to describe this stage, the distillation of zinc across a temperature difference between two circulating zinc streams in open channels under vacuum. Heat for the distillation is supplied by the liquid phase, necessitating a large recycle to maintain high operating temperatures, and keep zinc concentrations high. In determining this model and the operating conditions required, relationships between temperature, pressure and composition are considered.IntroductionCurrent technology (the Refluxer) used to refine thermally produced zinc is both expensive and highly inefficient. At present 80% of the worlds zinc is produced via the electrolytic process reflecting the poorer performance of the thermal route, the zinc-lead blast furnace and Refluxer. A new process is proposed to overcome the drawbacks of current processes. These drawbacks are both economic and environmental. The Refluxer requires 6.6 GJ of energy to refine one tonne of SHG zinc 1, other disadvantages of the Refluxer stem from high operating temperature, around 900°C, and liquid zinc being highly corrosive towards ferrous metals. The Refluxer is constructed from silicon carbide sections which join together by means of flat machined faces making liquid metal leaks inevitable. The Refluxer columns are very sensitive to thermal cycling, thermal shock and mechanical vibration, which easily lead to structural failure. To avoid thermal stress on the columns the feed rate and feed temperature need to be kept constant which means the feed baths to the columns must be able to accept solid and liquid feed as the Refluxer has to operate when the smelter is shut down."

Jan 1, 1998

Several processes are now available for the recovery of free and WAD cyanide from gold plant solutions and pulps. In the past, the incentive for evaluating cyanide recovery in gold plant flowsheets has been economic. In many cases, it has been possible to demonstrate (at least in the laboratory and on paper), an improvement in process economics by; (i) reducing the costs of tailings detoxification, (ii) recycling cyanide at lower cost than the purchase/delivery price of new cyanide, and (iii) generating additional revenue via by¬product sales. Despite these convincing arguments, few cyanide recovery plants have been built at operating gold mines. Also, there is arguably an even more compelling reason for mining companies to consider cyanide recycling. With the growing storm of negative public opinion that the use of cyanide in the mining industry is attracting - following several highly publicized spills over the last couple of years - the time has come for the gold industry to demonstrate environmental diligence and stewardship in the use of this commodity that is so vital for their industry. There is no doubt that the widespread implementation of cyanide recycling will reduce the impact of the cyanidation process on the environment, both by reducing the risk of spills (with less cyanide being transported from manufacturing plants to gold mines), and by reducing the loading of toxic and non-toxic metals and ions in the tailings. In this paper, the various processes that are available for cyanide recovery are discussed, along with the process chemistry. Results of several laboratory and pilot plant trials that have been conducted over the last few years are also presented.

Jan 1, 1998

By D. Doungdeethaveeratana

The extraction kinetics in a novel solvent extraction process have been investigated. In this process, the liquid-liquid emulsion is generated by bottom gas injection into countercurrently flowing aqueous and organic phases. This process has a number of advantages over the mixer-settler unit or the spray column in terms of simple equipment configuration, without any mechanical moving parts, and the ease of cleaning and process control, while providing a sufficiently large interfacial area for rapid mass transfer. The overall rate increased with increasing gas injection rate and height of the aqueous phase but decreased with increasing injector diameter at the same gas injection rate. The variation of the overall rate constant was correlated against a set of dimensionless numbers, representing the operating conditions. Extraction rates and efficiencies comparable to those in a mechanically generated emulsion were attained in this new process.

Jan 1, 1998

By S. S. Ryu, J. C. Kim, H. Lee, Y. D. Kim, I. H. Moon

"Recently, W-Cu alloy becomes one of the very important candidate materials for heat sink and packaging in the field of microelectronics due to its good thermal properties. The metal injection molding of W-Cu powder can satisfy the requirement for mass production of complex shaped parts in microelectronic devices. In the present study, the application of MIM process to the nanostructured W-Cu powder prepared by mechanical alloying was investigated. The multi-component binder system of 45PW+ l 5BW+ 30PE+ I OSA was proven to be suitable one for the MIM of the W-Cu composite powders by adopting the debinding cycles of multi-stage in N2 and H2 atmospheres. Other process conditions for the MIM of the nanostructured W-Cu composite powder were also studied. The MIM debinding part of W-30wt.%Cu was sintered to the relative density of more than 96% by sintering at 1200 °C for !hour in H2 atmosphere. Such an improvement of sinterability was attributed to the intrinsic homogenous and fine mixing state of W-Cu phases in nanostructured W-Cu composite powders, and also partly to the effect of the activated sintering by the presence of impurity introduced during the extensive milling.IntroductionW-Cu alloys have been widely used for heavy duty electrical contacts and arcing resistance electrode(1-2). Recently there has been a growing interest in this W-Cu alloy because of its superior thermal managing properties and its high micro wave absorption capacity(3). Such W-Cu alloy parts are conventionally fabricated either by the Cu infiltration sintering technique or by hot pressing of W-Cu powder mixtures. However, these conventional PM techniques are hardly applicable for mass production of small size parts with a complicated shape such as the parts required for microelectronic devices. The metal injection molding(MIM) technique is potentially applicable for the mass production of small and complicatedly shaped parts compared with other PIM forming techniques."

Jan 1, 1998

By Steven M. Puricelli

Sulfuric acid plants associated with smelters, have historically been an overworked and often neglected pollution control device. They could do little more than manage the wide fluctuations in gas flow and SO2 strength from the smelter. With the introduction of flash smelting, the picture began to change, but the fluctuating batch converters continued to dictate acid plant design. More recently, the commercial use of continuous converting processes utilizing high levels of oxygen enrichment has dramatically upgraded the SO2 strength and stabilized the gas flow to the acid plant. The SO2 gas now issues continuously and at concentrations that allow for compact and, cost effective acid plants. Relieved of the burden of excessive dilution air, the heats of reaction can also be recovered as medium pressure steam and used to drive a generator, making the acid plant a net producer of power and a valuable asset to balance sheets. This concept was put into practice at the Kennecott Utah Copper Corporation smelter modernization project, located in Salt Lake City, Utah. The new acid plant, which was commissioned in June of 1995, is a sophisticated, low environmental impact, energy producing plant, worthy of review. This paper examines the key features of this acid plant, such as controlling its tail gas, by catalysis alone, to an environmentally friendly, 100 ppm of SO2, while feeding the acid plant converter with an efficient 14% SO2. The acid plant is also a prudent steward of energy resources, recovering 220,000 lb/hr of 140 psig steam from process heat which is used to generate a substantial 20 MW of gross power. Also discussed will be some of the ongoing issues, such as handling of selenium and fluorine in the gas cleaning sections, as well as a review of some. of the problems that were identified and resolved. Today's modem acid plants, by necessity, are becoming a producer of quality, valuable products, making the acid plant an asset and not a liability. Plants like Kennecott are already gaining wider acceptance and are expected to be the vision of the future.

Jan 1, 1998

By C. J. Newman

Prior to 1995, the smelting process at the Kennecott Utah Copper Corporation (KUCC) smelter consisted of Noranda reactors and Pierce-Smith converters. In the consideration of expansion opportunities, the existing process did not lend itself to a program geared towards processing the total output of KUCC mining and milling operations. During 1989 and 1990, a number of smelting options were evaluated. The final selection was the Outokumpu flash smelting process, coupled with the new Kennecott-Outokumpu flash converting technology. Facilities were designed and installed to process 1:0 million tonnes per year of copper concentrate, with the ability to expand to 1.2 million tonnes per year. Following the shutdown of the smelter facility utilizing the Noranda technology in May 1995, the flash smelting, furnace commenced operation in June with the flash converting furnace startup following a few weeks later. The smelter has achieved design production targets and environmental goals. Current operating rates are at or above design rates for concentrate and matte processing. Emissions are lower than the permit levels and equate to less than 3.5 kg of SO2 per tonne of copper. This paper outlines the design, construction, startup and the first two years of operation of the modernized KUCC smelter.

Jan 1, 1998

By LuisW. Pommier

The industrial wastes generated by the plating industry, the circuit board manufacturing industries and other related industries normally contain high concentrations of metals, which make them hazardous. The extraction of the contained metals and their separation may be achieved by both pyro and hydro metallurgical processes. Some of the industrial wastes, those rich in some metals like nickel for instance, are being treated like mine ore concentrates and are being fed to smelting furnaces. The slags from these smelter operations are hazardous. They have, however, special environmental dispensations issued by the regulatory authorities. Hydro-metallurflcal processes have been reported. They also generate a residue which is hazardous because not all the valuable metals are leached out and also, because "non valuable" components, like chromium, are less readily leached. Residues from the plating industry, containing nickel, copper. zinc, iron and chromium as the major constituents and also sodium and calcium, together with cadmium, cobalt, lead. manganese, magnesium, molybdenum, and potassium, have been processed for the extraction of the valuable components. The generation of electrolytic nickel, copper and zinc and also of ferric chloride and chromium oxide is reported. The operation is achieved by a caustic leach for the extraction of zinc, followed by a sulfuric acid leach for the extraction of nickel and copper. This acid leach also extracts the iron and some chromium. The nickel copper and zinc are rendered pure by electrolysis, the iron is oxidized for the production of ferric chloride and the chromium is recovered as an oxide. The leaching operation is performed in two stages, first at a pH of 2.5 to generate an electrolyte for the partial recovery of the metals and then at a pH of 0.5 for the complete extraction of the metals. This leaching operation generates a residue, which although small in volume compared to the initial feed, still contains traces of the valuable metals and a portion of the chromium which makes it hazardous. Additional leaching with hydrochloric acid or nitric acid is required for its complete dissolution. The other minor constituents mentioned are present in concentrations each of less than 0.1% and are handled as impurities in the process. The metals which are soluble at a pH 0.5 and precipitate between 0.5 and 2.0 are bled off. Other impurities will concentrate on the raffinate from the solvent extraction operations from whence they are bled off. These bleeding streams are hazardous and the "impurity metals" are now present in concentrations which would make them valuable, however, the size of these streams is so small that they do not warrant their processing, however they could be marketed to specialized smelters. The extraction of the valuable metals, of the hazardous constituents, the generation of a marketable mixture of minor constituents and the production of a non-hazardous residue for declassification is profitably achieved.

Jan 1, 1998

By Jr. Loper, M. H. Kim, H. H. Jo, C. S. Kang, T. S. Song

"An investigation has been conducted to describe the effect of grain refiner (e.g.,Ti) or modifier (e.g., Sr) on the microstructure of an Al-11.3wt%Si alloy produced by the Ohno horizontal continuous casting process using a heated mold so as to obtain directional solidification at high cooling rate of 300 to 2000°C/s. Experimental results demonstrated that the directionality of the primary a grain was promoted by the addition of0.2 to 0.4%Ti or by the addition of0.02%Sr, whereas the addition of0.6%Ti suppressed this directionality. Feathery a grains were promoted by the addition of 0.2%Ti, while these feathery a grains were suppressed when over 0.4%Ti (grain refinement) or when 0.02%Sr was added. The addition of Ti also resulted in increased coarsening of the eutectic Si in these Al-1 l.3wt%Si alloys.IntroductionThe mechanical properties of conventionally cast Al-Si alloys can be enhanced through judicious control of the casting parameters, by the addition of grain refiners (e.g., Ti) and by the addition of eutectic modifiers (e.g., Sr).[1-3] The Ohno continuous casting process[4-5] uses a heated mold (maintained at a temperature above the alloy liquidus temperature) to produce a casting with a mirror surface free of shrinkage defects. The process is especially suitable for the production of high quality and non-deformable rods of small diameter. This study was conducted at investigate the effects of Ti and Sr on the microstructure of Al-1 l .3wt%Si rods cast by the 01).no process."

Jan 1, 1998

By N. Kanari

Kinetics of the carbochlorination of Cr2O3 has been studied with C12+CO gas mixtures between 500 °C to 900 °C using thermogravimetric analysis. The apparent activation energy is about 100 kJ/mol. Mathematical fitting of the experimental data suggests that the shrinking sphere model is the most adequate to describe the carbochlorination mechanism of chromium oxide and that is controlled by the chemical reaction. In the temperature range of 550 "C to 800 OC, the reaction order is about 1.34 and is independent of temperature. Changing the C12+CO content from 15 pct to 100 pct increases the reaction rate and does not affect the reaction mechanism. Similarly, changing the ratio of C12/(Cl2+CO) from 0.125 to 0.857 do not modify the carbochlorination mechanism of Cr203. In these conditions, the reaction rate passes through a maximum when using a chlorinating gas mixture having a Cl2/(C12+CO) ratio of about 0.5.

Jan 1, 1998

Lead removal has been problematic in nickel production by electrowinning from chloride solutions, as developed by Falconbridge. The C12 leach liquor needs to be diluted by electrolyte to allow precipitation of the lead prior to electrowinning. This results in higher solution purification costs and an aversion to consider lead contaminated (secondary) feeds. In this paper, the electrowinning of nickel chloride is carried out in a membrane equipped electrolytic cell. When lead containing nickel solutions are fed into the anode compartment and the anolyte is separated from the catholyte with a cation exchange membrane, lead remains in the anolyte due to the presence of a negatively charged chloride complex. The positive nickel ions migrate preferentially through the membrane to the catholyte, allowing a lower lead nickel cathode to be produced. Lead concentration in the catholyte and the cathode product has been tested as a function of lead concentration in the anolyte. Results are presented and discussed.

Jan 1, 1998

By Yong J. Kim, J. M. Park

"Solid/melt interface shape during continuous casting process has a strong influence on the resulting microstructure of the ingot. The interface shape is primarily governed by the heat flow condition between the molten metal and mold (or container). The roll of the microstructural transition resulting from various solid/melt interface shapes is discussed using the Sn-22.6wt%Pb alloy. Three different types of mold such as cold mold, resistantly heated mold, and electromagnetically heated mold were used to generate those interfaces having different curvatures. Experimental measurements of complete temperature profile along the axis and surface of the ingot during downward continuous casting are presented to determine the solid/melt interface geometry. The results provide an explanation of the ingot property with emphasis on microstructure.IntroductionA large scale of continuous casting process of alloys often has a rather deep V channel type of solid/melt interface resulting from a limited heat flow condition. As a result, the deep V type solid/melt interface shape entraps defects such as pores and inclusions and also creates canter segregation. In order to reduce the defects concentration, electromagnetic stirring(EMS) mechanism has been applied to the melt in the channel[l]. Speith and Bungeroth introduced first experimental EMS device to the continuous caster in 1952.[2] Today, with wide ranges of benefit, a large variety of such technique is available. Electromagnetic field on the melt can be divided into three aspects. First, eddy current is induced on the metal surface by alternating magnetic field with high frequency, which results in heating the metal. Second, electromagnetic body force which is generated by the magnetic field and the eddy current reduces the melt pressure on mold or support the melt not to contact with the mold[3,4,5]. This force is used for electromagnetic casting process(EMC). Finally, it causes stirring in the melt. Many research efforts have been done on the EMC process to improve surface quality of slab[6] and control meniscus shape where three phases such as melt, solidified metal, and mold powder coexist[7,8]. However, the eddy current heating effect on the surface of the ingot was less considered. It is worth noting that induced eddy current on the surface of slab melts the solidified shell and thus changes the heat flow condition between the mold and melt. Mold heating effect was first proposed by A. Ohno[9] and its processing conditions were identified in details[ 10, 11]. The so-called Ohno process is based on the fact that by keeping the mold temperature slightly above the melting temperature of the liquid, no grain can be nucleated on the mold wall[12]."

Jan 1, 1998

By Courtney A. Young

All cyanide species are considered toxic and can be found predominantly in industrial effluents generated by metallurgical operations. For example, cyanide's strong affinity for metals makes it favorable as an agent for metal finishing and treatment and as a lixivant for metal leaching, particularly gold. These technologies are environmentally sound but require safeguards to prevent water contamination. Various methods of cyanide remediation by separation and destruction are available, but certain methods are more effective than others depending on the cyanide species being remediated. Photolytic destruction is regarded as the one technique that is independent of the cyanide species involved. The destruction of various cyanide species by several photolytic techniques has been investigated for the past few years. A literature survey suggests heterogeneous photocatalysis with anatase (TiO,) should behave similarly to homogeneous photolysis with hydrogen peroxide (H,O,) since proposed reaction mechanisms for both processes involve hydroxyl radicals. However, experimental evidence on a suite of cyanide species suggests otherwise. A new mechanism for the photocatalytic destruction of cyanides, especially SAD species, is therefore proposed.

Jan 1, 1998

By Wenxian Zhu, Patrick R. Taylor

"The small dimensions of nano-sized materials leads to novel and enhanced mechanical and physical properties. A thermal plasma reactor has been developed to study the formation of nanometer sized metal powders. A supersonic nozzle and a powder filter were designed and built. By vaporizing coarse metal powders in the plasma flame, and quenching the metal vapors through the nozzle at the rate of 107 K/sec, nanometric sized powders have been produced. The powders were collected in an airtight secondary quench-filter system. The particle size of the product power is 5 -20 nanometers, obtained through TEM analysis. The XRD analysis showed that the powder did not oxidize after the filter was handled in an inert atmosphere glove box.IntroductionNanostructured materials have been shown to exhibit improved physical and mechanical properties compared to conventional materials with larger grain sizes (1,2). There have been several methods proposed for preparing nanometer size materials. Thermally induced vapor-phase reactions have been used to produce a variety of powders. A common feature of these processes is the rapid production and cooling of condensable reaction intermediates and products, by gas-phase reactions, leading to the formation of a large number of very small particles. Thermal plasma synthesis of ultra-fine size particles has been attracting increasing interest (3,4,9-11), because it offers many advantages, especially in refractory materials processing, compared to conventional processes: (a) thermal plasma temperatures are very high(> 5000 K); (b) the rates of chemical reaction are much faster than those encountered in conventional processes; (c) high-purity materials may be obtained using fewer processing steps by collecting the product at temperatures where the by-products are in the vapor phase; ( d) the mean particle diameter can be controlled; (e) unifom sized particles may be produced with clean surfaces (these particles are particularly suitable for pressureless sintering); and, (f) high throughput per reactor volume can be achieved. In addition, the process used for generating particles determines the degree of sintering ability of the powders, since the process dictates the morphologies, the purity and its size distribution. In the future, thermal plasma synthesis nanometer size particles may play an important role in vapor phase reaction techniques and might be expected to be one of the first full scale commercial installations in the future."

Jan 1, 1998

By Satu Jyrkönen

A single-particle laminar-flow technique was used to study reactions of sulfidic nickel particles. The studied materials were three natural nickel concentrates and four synthesised nickel mattes. The variables of the experiments were the gas preheating temperature (500 - 1300°C), the composition of the reaction gas (N2 + 0 - 75 vol-% 02) and the ,particle size of the feed. Chemical analysis of the particles was used to determine the oxidation degree of the materials, and optical and scanning electron microscopy were used to detect alteration in their morphology, internal composition and structure. General reactivity of the materials was monitored by the extent of sulfur removal. The reaction mechanism of the studied materials was found to depend primarily on the materials composition as well as oxygen content of the reaction gas.

Jan 1, 1998

By Caisa Samuelsson

Experimental studies in laboratory-scale equipment have been carried out to study the vaporisation from dust generated during the copper converting process. In the present work the vaporisation of Zn, Pb, As, Sb, and Bi from a dust collected in the electrostatic precipitator after the copper converter were studied. The results show that Pb, Bi and As were vaporised to a high degree from the dust at a temperature above 900°C in a gas containing N2, SO2 and a small amount of H2. The vaporisation was high for these elements also in a gas containing N2, SO2 and 02 at temperatures above 1120°C. In an earlier study, thermodynamic calculations showed that it is possible to selectively condense metals at high temperature' in a gas atmosphere generated during a copper converting process. The present study was carried out to verify the thermodynamic model. The results indicate that it should be possible for a selective condensation of Zn at high temperature. The temperature required for a selective condensation of Zn is dependent upon the gas atmosphere, e.g., the oxygen potential.

Jan 1, 1998