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By Broggi Andrea

Condensates produced by SiO(g) and CO(g) have a crucial importance in silicon production. Condensation will follow the reactions 3 SiOðgÞ+COðgÞ→ 2 SiO2 + SiC and 2 SiO ðgÞ→Si+SiO2. Solid compounds generated during silicon production contain Si, SiO2 and SiC in different microstructures and amounts. In industrial systems, condensates limit the SiO(g) escape to the off-gas system. On the other hand, they can block the gas flowing from the high temperature zone, hence the necessity of studying an optimized condensation process. This review discusses SiO(g) condensation and its interaction with CO(g). The report gives an overview of the condensates found both at laboratory and at industrial scale. The two main compounds are the Si–SiO2 and the SiOx–SiC mixtures. The hypothesis on the mechanism of formation of SiC–SiOx condensates is presented through a wide selection of performed works. The advantages and disadvantages of the former experimental procedures are discussed.

By G. R. Palmer

The success of future electric vehicles will depend greatly upon the power supply choices made today. Research is presently being conducted by automotive engineers and electrochemists to determine what battery type may be the most promising. Not only are product production and application efficiencies being evaluated but also environmental concerns of reclamation and recycling. Rechargeable batteries using nickel-metal hydride electrodes are strong candidates for these electric vehicle applications. The U.S. Bureau of Mines is investigating hydrometallurgical technology that separates and recovers purified metallic components present in nickel-metal hydride battery scrap. Sulfuric, hydrochloric, and nitric acids are all capable of dissolving the battery electrode alloys given the proper operating conditions. Solvent extraction of the leach solutions using D2EHPA removes iron, and selective precipitation shows promise of recovering the other metals in the H2SO4 and HNO, systems.

Jan 1, 1994

By George P. Demopoulos

n this study we have sought to highlight the critical linkage between individual reaction kinetic parameters (usually determined in small bench scale experiments) and large continuous reactor performance by focusing on the industrially significant zinc pressure leach process. To this end a comprehensive mathematical model previously developed for the description of this process was employed. In this paper we have examined in particular how small variations in key kinetic parameters impact on the autoclave&apos;s performance, i.e. attainment of autogenous steady-state temperature, zinc conversion and solution chemistry. The reaction parameters studied were: (i) stoichiometry of the marmatite leaching reaction; (ii) the activation energy of the same reaction, E,; (iii) the rate constant of the ferrous to ferric oxidation reaction, k,; and (iv) the apparent equilibrium constant for ferric precipitation, K,. This parameter sensitivity analysis was done under no oxygen mass transfer control limitations. Model predictions were found to be more sensitive to the kinetic parameters under certain conditions than others. The most dramatic finding was the one related to the small amount of sulfate produced during marmatite leaching. In connection to this it was found that the small percentage (< 5 %) of sulfate produced enhances the autothermal operational stability of the autoclave. The need for accurate kinetic parameter determination under conditions similar to those encountered in industrial zinc pressure leaching was demonstrated.

Jan 1, 1999

By Keith E. Forrester

This paper presents results of bench scale laboratory evaluation of a processes developed by FESI and Brookhaven National Laboratories for the extraction and recovery of Pb and other heavy metals from incinerator ash which was subsequently modified by FESI for the extraction and recovery of Pb from soils excavated from a FESI client scrap yard and battery breaking operation facility. The specific waste matrix presented within the paper is a battery acid contaminated surficial soil at 0" to 12" depth. The extraction method was found to be highly successful on the bench scale in generating a final post-extracted soil matrix which passed TCLP Pb regulatory limits and retained minimal Pb after aggressive extraction application. The paper findings at this time are brief, as a majority of the research results are currently being compiled and additional efforts are underway based upon initial screening findings.

Jan 1, 1995

By S. E. Khalafalla

A method for preparing ferrochromium alloys containing less than 2 pct carbon has been devised in a single vacuum furnace reactor. This method can conserve chromium and should reduce the capital and energy requirements relative to chromite electrothermal reduction. Reduced products containing less than 2 and as low as 0.01 wt pct carbon were obtained by reacting pellets of chromite and carbonaceous reductant mixtures at pressures of 0.1 to 1 ton and temperatures of 1,230° to 1,320° C. The extent of reduction increased with increased temperature and decreased pressure; however, operating conditions were limited due to the onset of significant chromium vaporization at higher temperatures and lower pressures. Foundry coke, anthracite, and carbon black were found to be superior to graphite as reductants. The reduction of chromite to metallics was found to proceed via the carbide intermediates Fe3C or Cr3C2. Lime accelerates the. rate of solid state reduction of chromite and can shorten the furnacin1r time at 1,3000 C under vacuum from 13 hours to less than three hours. Additional lime and silica are added to the hot reduced chromite after releasing the vacuum and raising the furnace. temperature to 1, 700° C. Soaking the charge for about 20 minutes gave a button of low carbon ferrochromium alloy beneath a well-defined slag layer.

Jan 1, 1985

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 M. Misra

The volume of low-level contaminated soil at the. Department of Energy&apos;s Nuclear Weapon Sites are in the order of several million tons. Most of the contaminants are uranium, plutonium, other heavy metals and organic compounds. Selected Physical separation processes have shown demonstrated potential in COD Centratingthe radio nuclides in a small fraction of the soil. Depending upon the size, nature of bonding and distributions of radio nuclides, more than 90 percent of the radio nuclide activity can be concentrated in a small volume of fraction of the soil. The physico-chemical separation processes such as flotation in a mechanical and microbubble tall column cell have shown, promising applications in cleaning up the high volume contaminated soil.

Jan 1, 1995

By H. -P. Behrendt

Muldenhiütten Recycling und Umwelttechnik GmbH is a lead smelter with a very long tradition. The first reference to the existence of smelters on this site is given by a document of inheritance dated 1318. Originally run as a primary lead smelter, which was supplied with ores from the Freiberg mining district and from overseas, it was required to change it over to secondary raw materials due the abandonment of mining in the Freiberg area in 1968. Today, Muldenhüitten Recycling und Umwelttechnik GmbH has two production lines; lead production from secondary lead and waste incineration, which are closely connected and gain advantage from each other. Installations, improved technologies, and the highly skilled personnel have contributed to satisfy all demands for a production concerning quality and environment.

Jan 1, 2000

By Z. M. Zheng

Cyclic voltammetry, potential step, and ac impedance techniques were applied to study the electrochemical reaction of arsenopyrite in chloride solutions. The relationship between anodic current density and time in potential step measurements indicates that the oxidation of arsenopyrite is irreversible. The results of the constant potential coulometry show that the stoichiometric factor of the total electron involved in the overall reaction is 14. It is proposed that the dissolution of arsenopyrite is retarded by coverage of sulfur produced in the reaction as an intermediate product. The measured results of ac impedance strongly support the proposition. The proposed reaction mechanism also explains satisfactorily the charging current density and Tafel slopes measured in potential step measurements.

Jan 1, 1995

By A. Kar, J. Mazumder

"Laser ablation is a process that can be used to synthesize novel nanoscale particles as well as to deposit thin films of various materials. Usually, nanoscale particles and thin films are formed at relatively high and low pressures, respectively, inside the ablation chamber. This paper presents a mathematical model to predict the particle size distribution in the plasma generated during laser ablation. The model is developed by considering the effects of the laser-matter and laser-plasma interactions, the Stefan condition, and the discontinuity across the Knudsen layer. The nanoscale particles are found to be located at the central region of the plasma near the target. The particles have very high velocity and temperature. A good qualitative agreement is observed between the results of this model and experimental data. IntroductionRapid solidification produces novel microstructures whose atomic arrangements and/or chemical compositions are different from those of conventional materials. The conventional materials are either crystalline or amorphous. The crystalline materials have both short- and long-range orders, whereas the amorphous materials have only the shortrange order. The nanocrystalline materials have neither short- nor long-range orders, and for this reason, they exhibit novel properties which are important for synthesizing new materials. The atoms of a nanocrystal can be classified as ""crystal atoms"" and ""boundary atoms"", where the ""crystal atoms"" have the nearest-neighbor configurations similar to the lattice configuration, whereas the nearest-neighbor configurations of the ""boundary atoms"" differ from the lattice configurations 1. Various aspects of the nanoscale materials have been discussed in Refs. [1-7]."

Jan 1, 1994

By Robert Mensah-Biney

The loading characteristics of gold-tetrabromide species onto a weak-base resin, PAZ-4, were evaluated using a completely mixed batch reaction system. The time. to attain equilibrium loading was substantial, on the order of several days. However, abnormally high loading capacity values of 15 to 20 meq Au/g dry resin (1000 to 1300 kgAu/tonne) were attainable in 24 hours. The loading of gold-bromo species by P AZ-4 was visualized as consisting of two processes: (i) the rapid adsorption of [AuBr4r species by simple ion exchange mechanisms and (ii) reduction of [AuBr4r to metallic gold by an electron exchange mechanism. Elution of gold from loaded resin was feasible provided the resin had not been loaded to high capacity values. If loading is carried to high levels, complete elution becomes impractical and the gold may be recovered by ashing the loaded resin. For the high loading capacities observed this option would appear to be cost effective.

Jan 1, 1991

By H. Y. Sohn

"The nonferrous production industry has gone through a remarkable transformation in recent years in terms of developing and adopting new technologies. Technology innovations have largely been driven by the need for greatly improved environmental protection in addition to increased productivity. One of the most notable aspects of the new technologies is their ability to reduce the emission of sulfur and other pollutants to extremely low levels.The current industry trends towards more environmentally friendly technologies are bringing about additional benefits of developing more efficient, technically advanced, and continuous processes in closed reactor vessels. Key aspects of these modem trends include the use of increased oxygen enrichment in the process gas, better process control, reduced manpower requirements, and plant operations with more skilled personnel.Computer simulation and modeling of complex processes have become more reliable, realistic, and thus increasingly useful in metal production. Some of the notable examples are reviewed.Finally, the need and advantages for value-added production in the nonferrous industry are discussed.I. IntroductionMost recently commissioned technologies for nonferrous metals production have been developed largely in response to environmental concerns. One of the most remarkable improvements made by the nonferrous industry in the last decade has been the rapid increase in sulfur capture. Before the start of the last decade, 90% capture of sulfur was considered good. Since then, strict emission regulations have become the norm in advanced societies, although smelters in many parts of the world still operate with limited pollution control. Other emissions and discharges have also been substantially reduced, resulting in much improved working conditions and worker hygiene in addition to the overall environmental protection. The development of the more environmentally friendly technologies has accompanied other advantageous advances made in the nonferrous industry, i.e., the trend towards more gas-tight, continuous processes and larger plants. This has increased the competitive edge enjoyed by the industry in the industrial countries, offsetting the higher costs of labor and pollution abatement that they have to overcome in those countries. Experience has shown that clean technology often leads to a profitable business, because its adoption forces the concomitant advancement of related technologies in addition to the avoidance of penalties imposed by the public on pollution-prone industries. Needless to say, there are other driving forces for new technologies such as reduction of operating and capital costs, improved product quality, and energy considerations in terms of reduced consumption and utilization of readily available sources."

Jan 1, 2000

By D. M. Hausen

Applications of process mineralogy to the exploitation of molybdenum ores begins with early exploration and continues through the evaluation of mineralized prospects, to amenability testwork and pilot plant studies, to the development of a mineable orebody and to the development of a viable process for recovery. After plant construction, a broad range of products from a wide selection of sampling locations, i.e. grinding circuit, flotation cells, smelters and roasting kilns. etc., are evaluated analytically and microscopically, followed by periodic troubleshooting of problem points. The various crystalline phases of molybdenum that occur naturally and throughout various hydrometallurgical and pyrometal1urgica1 processes are identified and characterized by a variety of instrumental methods, including XRD-XRF, optical and electron microscopy, infrared spectrographic and differential thermal analysis.

Jan 1, 1989

By Liming Wang

One of the steps in the extractive metallurgy of lead is a refining process called drossing. Hot dross is mixture of impurity compounds that form on the surface during the cooling of lead blast furnace bullion, and in Missouri, the main impurities are copper and sulfur. The slow cooling of bullion throws out of solution all other minor impurity elements (or their compounds) which are much less soluble at lower temperatures (mainly nickel, arsenic, iron, and zinc). The transfer of bullion from the blast furnace to the refinery and the subsequent hot drossing step cause fugitive emission of lead-containing fume and dust, which creates a plant hygiene problem. One cause of the emissions is the high vapor pressure of lead and its compounds during transmission of = 1000 °C bullion to the drossing kettle. Another cause is the lifting of dross dust during manual skimming of dross. The environmental problems associated with the traditional hot drossing process provided an incentive to investigate a new drossing process that avoids contact between plant air and hot bullion or dross. A key aspect of the process development was a detailed mineralogical examination of dross from two different bullions. The bullion samples were cooled at different rates, and the dross filtered out and examined. The morphology, phase identification, and composition of the dross was examined by optical and SEM microscopy. The principal dross phases were copper and cuprous sulfide, galena, a complex sulfide containing copper, nickel and lead, and speiss (containing nickel, cobalt, iron, copper, lead, and arsenic compounds). The copper was acicular, with nickel and arsenic in solid solution. The cuprous sulfide was largely digenite in a granular or dendritic form. A substantial part of the dross was solidified matte with a eutectic microstructure, consisting mainly of CU2S and PbS. Small particles (some of which had a eutectic microstructure) never floated to the surface of the lead during the slowest cooling rate, thus indicating that flotation of tiny matte droplets and dross crystals is exceedingly slow. The success in separating dross and lead by centrifugal filtration suggests its application in industry as a replacement for traditional hot drossing.

Jan 1, 1995

By Lauri Holappa

Copper converting is mostly performed in Peirce-Smith converters. The process is still very similar to the original one developed in the early 20th century. It is a batch process in a horizontal cylindrical reactor with air blowing via tuyeres along the length of the reactor side. The Peirce-Smith converter has its roots in Bessemer&apos;s inventions in the 1850&apos;s as he tested both horizontal and vertical vessels for steel converting. However, for steel making a vertical pear-shaped converter with air bottom-blowing was established. In the course of time, there was a distinct necessity for oxygen usage instead of air due to harmful effects of nitrogen to steel properties and its cooling effect. In-bath blowing of oxygen did not succeed, however, and top-blown oxygen converter with oxygen lance (LD or BOF) was first developed in he 1950&apos;s and emerged rapidly to a dominating position. Somewhat later oxygen bottom-blowing via special shrouded tuyeres was developed (OBM or Q-BOP) but has attained only fractional share. Bottom-blowing technique had, however, impact on the current combined blown converters which adopted the benefits of both top and bottom blowing. In copper converting Peirce-Smith type converters have kept their position until today although new processes have been introduced and at least few of them seem to be emerging. In one respect copper converting has a clear leading position i.e. in the progress of continuous converting processes (Mitsubishi, Ausmelt). These processes utilise top-blowing lances instead of in-bath blowing tuyeres. A different principle for continuous converting is flash converting by Kennecott Outokumpu, which makes smelting and converting independent of each others. Solid ground matte is used as a feed for flash converting in a reactor shaft similar to Outokumpu matte flash smelting. A comparable process has been presented by Inco too. The paper discusses principal physico-chemical and process technical similarities and differences in copper and steel converting. Although these processes are metallurgically quite different it seems that during the modem history of ferrous and non-ferrous metallurgy, starting from the 1850&apos;s, the exchange of knowledge between these disciplines has been quite intensive. In long-term perspective, many similarities in the development can be found but also divergences due to different ambient circumstances.

Jan 1, 2003

By Veena Sahajwalla

The cupola furnace is a coke-fueled shaft furnace used as a primary melting unit in iron foundries. Control of chemical composition of the iron tapped from the cupola is a key factor in productivity and quality control. In an effort to develop a control model for the cupola, a fundamental approach based on physical and chemical principles has been taken to describe the melting process. The behavior of oxidation of the solid charge in the stack of the cupola has been studied. Sulfidation of the charge materials by sulfur-bearing components released to the furnace gases from the coke has been described. Carburization of metal droplets of iron and of steel in separate molten streams has been characterized. Finally, reactions with alloying elements in the hearth (well) of the furnace have been defined. These reactions have been described in a computer-implemented model developed to predict the composition of the iron tapped from the cupola. The model has utilized the thermodynamics and kinetics of the oxidation, sulfidation, and carburization reactions, including temperature and physical aspects, in the various zones of the melting unit. The model predictions have been compared favorably with operating results.

Jan 1, 1992

By I. Gaballah

About forty percent of the SOx emissions are generated during the processing of metal sulfides of Cu, Pb, Zn, Ni, etc. Although new technologies for metal sulfide&apos;s smelting allow the production of H2S04 with a reasonable cost and decrease the emissions of sulfur oxides, the generated quantity of SOx is considered as a serious threat to environment. This paper suggests alternatives for low temperature processing of complex sulfide ores or concentrates &apos;CSO or CSC&apos; under neutral, reducing and chlorinating atmospheres or their combination. At T > 400 "C, The neutral and reducing treatments allow the decomposition of pyrite and the partial recovery of sulfur as So and H2S. At 300 "C, the chlorinating treatment of CSC is fast, exothermic and allows the separation of FeC13 from the valuable elements&apos; chlorides. It also generates SyCIx that can be either reduced by H2 or hydrolyzed in presence of sodium sulfide. The recovery rate of elemental sulfur with respect to the sulfur input exceeds 90 %.

Jan 1, 1999

By I. Gaballah

Spent hydrorefining catalysts may contain 4 to 6 % of COO and/or NiO, 8 to 16 % of Moo3 and up to 10 % V205 generally supported by alumina. Raw samples are roasted in order to eliminate carbon, sulfur and hydrocarbons contained in the spent catalysts. The roasting optimum temperature and time are 500 "C and 7 hours. Selective chlorination of roasted samples with Cl2 + air, Cl2 + N2 and Cl2 + CO is investigated in order to recover the valuable metals. Depending on the chlorination it is possible to recover more than 80 % of the Ni and Co about 95 % of the Mo and up to 80 % of vanadium compounds. Cobalt and nickel chlorides are obtained by leaching the chlorination residues&apos; by acidified water. Molybdenum and vanadium chlorides and/or oxychlorides are obtained by selective condensation from the vapor phase. The chlorination of the catalyst support, Al2O3, can be limited to less than about 5 %. Besides the reaction temperature and time, the oxygen partial pressure of the chlorinating gas mixture appears to be the key factor for the reactions&apos; selectivity.

Jan 1, 1993

By Glenn C. Miller

Cyanide is the most common lixiviant for extraction of precious metals, and its efficient use in open pit mines has contributed to the increase in world production of gold during the previous two decades. With this expansion of precious metals mining using cyanide, public concerns have developed in response to the inherent public perception of cyanide as a tox-in as well as a series of environmental problems that are directly or indirectly related to cyanide use in open pit mining. Some of these have technical or regulatory solutions, while others will require additional investigation before they can be resolved. The following discussion will summarize some of the public concerns regarding the use of cyanide in precious metals mining. The issue of cyanide use in large scale precious mining is controversial, and recent banning of cyanide use in open pit mines in Montana, or complete banning of cyanide in Hungary has reflected those international concerns. The underlying basis for some of the bans (e.g. Montana) reflect a general concern of the environmental impacts of mining, rather than specific issues related to risk of cyanide use. The human safety record for cyanide use, particularly in the developed countries is good, and cyanide is clearly the most efficient lixiviant for precious metals. Indeed, the relatively short lifetime for cyanide in the environment renders it one of the less problematic chemicals used for extraction of gold from ore. Mercury amalgamation or use of bromide as a lixiviant are certainly much more problematic. What, then, is the basis f~r the international concern about precious metals mines that use cyanide. Ifuse of cyanide for gold recovery is to continue, what additional infom1ation needs to be developed that will allow a better management of the risks of cyanide? Which of the concerns are directly related to cyanide, and which are indirect concerns that more related to effects of open pit mining. Under what conditions should use of cyanide be discouraged? DUl::ing June of 2000 the United Nations Environmental Program conducted a two-day workshop on cyanide use in mining that was attended by persons from the mining industry, regulators and environmental community. Support and attendance at this workshop reflected concerns by all three groups on further restrictions for cyanide use and the emerging potential for guidelines for better management of the catastrophic release of cyanide-containing mining waste. The following discussion is meant to focus-on those risks and explore the basis for an often negative reaction to precious metals mining using cyanide. It is presented in the format of a statement, followed by a discussion. While admittedly provocative, the statements are meant to express the concerns? of the public regarding cyanide and the mining industry.

Jan 1, 1998

By Robert D. Rogers

The demand for phosphate will continue into the future, because phosphate is currently irreplaceable as a plant nutrient and in many chemical applications. Phosphate is not recycled, so the supply must be replenished through a process of mining and purification. Numerous microbial isolates. obtained from the environment were screened find those which demonstrated the greatest promise of solubilizing PO4 from the ore of interest. Screening was accomplished in a step wise manner an agar plate bioassay, shake flask studies, and semi continuous growth conditions. It was found that with the proper conditions of nutrient supply and solution pH; the bacteria and. fungus used in the semicontinuous process were able to solubilize in excess of 80% of an Idaho rock phosphate ore (RP) within nine days. A significant amount of solubilization occurred within the first six days. There was a &apos;reasonable correlation between the occurrence of soluble Ca and PO.4 during the processing of the RP thus providing evidence that the RP was being disintegrated by the organisms. In all cases, HPLC analysis of the solutions in which PO4 had been. extracted from RP showed that organic acids, which have been implicated as the mechanism of solubilization, were present.

Jan 1, 1991