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By R. Tunold, Y. J. Zhang

"The cathodic kinetics of aluminum deposition from aluminum chloridealkali chloride melts was studied by use of electro-cnemical transient techniques at 700 °C. Aluminum deposited as an insoluble product on a glassy carbon electrode and as a partly soluble product on a tungsten electrode. The deposition was found to be a simple diffusion controlled process involving the exchange of three electrons. The diffusion coefficient of aluminum chloride was calculated - 4.sx10-s cm2 ·S-I in AlCl3 -NaCl-LiCl melts and 2.6x10-s cm2 ·S-' in AlCl3 -NaCl-KCl melts. For AlCl3 -NaCl-CsCl system the diffusion coefficient exhibited some uncertainty due to nucleation. The determined rate constant of aluminum deposition reaction was on the order of 10-' -10-2 cm'S:' Constant potential electrolysis was carried out. TiB2 was well wetted by aluminum. The species of melts penetrated into graphite and glassy carbon but not into tungsten. The diffusion coefficient of species in glassy carbon was evaluated.IntroductionAluminum chloride electrolysis is attractive for its power saving of 30%. Different process to circumvent the conventional chlorization to obtain aluminum chloride economically, such as directly chlorizating mixture of Al~03 and C in a cell with A-shaped laminated bipolar electrodes by rising chlorine (1), or by use of a composite anode (2), will promote the electrolysis technology to be realized industrially. With the appearance of the Alcoa process periodically there are studies on the kinetics of aluminum deposition. Some discrepancies seem to exist on the mechanism of aluminum deposition. Borne studies (3,4,5) showed that the deposition of aluminum was hindered by diffusion process in the melts. M.Gabco et a1. (6) claimed a preceding dissociation of a complex being the rate controlled step. This paper presents our results on the mechanism of aluminum deposition from the study by use of transient techniques and some results from constant potential electrolysis."

Jan 1, 1988

By Francis Vanbellen

Umicore Precious Metals Refining operates an integrated precious metals smelting and refining plant in Hoboken, Belgium. Once a smelter and refiner of complex concentrates, the plant today?s feed consists exclusively of industrial and consumer recycled products, making it the world?s largest recycling facility for precious metals. Unlike the fairy tale of the Frog Prince, it took much more than a princess? kiss to successfully realize this makeover. A completely renewed plant has been built over the past decade. The most visible technological innovation was the commissioning of the Pb-Cu smelter. Its flexibility towards very different types of feed makes it perfectly suited as main entry to the Hoboken flow sheet. A new Cu-leaching & electro winning plant and precious metals refinery make up the Precious Metals Operations (PMO) whose targets are fast throughput and maximized yields for gold, silver and the platinum group metals. The Base Metals Operations (BMO), flexibly process the by-products from the PMO, valorizing ?impurities? like indium, tellurium, selenium and others. Off gas and waste water treatments ensure compliance with strict environmental standards. Precious metals recycling is an art that goes beyond mastering a unique flow sheet. Umicore Precious Metals Refining offers a complete recycling service, taking care of sampling and assaying, metals management and logistics. The quality of this integral service is recognized through the attribution of ISO certifications for our operational activities, sampling and the environmental care. And it?s an art that follows Michelangelo?s experience: ?Art is 5% of inspiration and 95% of transpiration.?

Jan 1, 2006

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014

By Torn H. Okabe

A fundamental study was conducted with the purpose of establishing an environmentally sound recovery process for recycling of valuable metals, by combining scraps containing such metals. As an example, direct extraction and recovery of neodymium (Nd) in magnet scraps was investigated by utilizing liquid metal as an extraction medium. It was found that liquid magnesium (Mg) is a suitable extraction medium and can extract Nd from iron alloys with high efficiency at around 1100 K. The newly developed extraction apparatus for Nd is a mechanically simple and static device without moving parts, where the Mg extraction medium circulates due to differences in the temperature inside the reaction vessel. This developed device can simultaneously accomplish continuous extraction of metal Nd from scraps, re-extraction of Mg from Mg-Nd alloy and the eventual recovery of pure Mg. As a result, metal Nd with 98 % purity was directly recovered from magnet scraps under certain conditions. It was also shown that the extraction agent Mg could be reused. The results of this investigation show the possibility of establishing a new process for the direct extraction of Nd in pure metal form without oxidization.

Jan 1, 2003

By Torn H. Okabe

A fundamental study was conducted with the purpose of establishing an environmentally sound recovery process for recycling of valuable metals, by combining scraps containing such metals. As an example, direct extraction and recovery of neodymium (Nd) in magnet scraps was investigated by utilizing liquid metal as an extraction medium. It was found that liquid magnesium (Mg) is a suitable extraction medium and can extract Nd from iron alloys with high efficiency at around I 100 K. The newly developed extraction apparatus for Nd is a mechanically simple and static device without moving parts, where the Mg extraction medium circulates due to differences in the temperature inside the reaction vessel. This developed device can simultaneously accomplish continuous extraction of metal Nd from scraps, re-extraction of Mg from Mg-Nd alloy and the eventual recovery of pure Mg. As a result, metal Nd with 98 % purity was directly recovered from magnet scraps under certain conditions. It was also shown that the extraction agent Mg could be reused. The results of this investigation show the possibility of establishing a new process for the direct extraction of Nd in pure metal form without oxidization.

Jan 1, 2003

By Liang Li

Thermodynamic analysis and experiments were conducted in order to verify the feasibility of preparing crude titanium tetrachloride (TiCl4) via the carbochlorination of low-grade titanium slag in molten salt. Titanium slag, assaying 74.6 wt% TiO2 with high calcium and magnesium oxide impurities, was treated by an optimized carbochlorination process in NaCl molten salt. These impurities in the titanium slag were chloridized simultaneously, and chlorination products FeCl2, MnCl2, MgCl2, CaCl2 and CrCl3 were collected in the furnace slag. XRD and SEM/ EDS analysis of residue shown that SiO2 and Al2O3 in titanium slag were difficult to chlorinate completely. Theoretical calculations and industrial-scale experimental studies reveal the content of TiCl4 in the products was more than 98.8 wt% and thus proved the feasibility of utilizing low-grade titanium slag for TiCl4 preparation by molten salt chlorination technology.

By V. I. Lakshmanan

Crown ethers are gaining importance in separation technology specifically for rare earth elements (REE, La to Lu plus Y) and precious metals (Au, Ag, Pt, Pd, Rh and Ir) due to their specific binding ability, metal complex stability and high extraction efficiency. The selectivity of crown ethers in extraction of these metals depends on different factors, including the cavity diameter and nature of a donor atom of the crown ether, size and charge of the metal ion, diluents and counter ion. Demand for strategic REE and precious metals are consistently increasing in the world while the separation of these metals is most challenging tasks. In this paper, the use of crown ethers in separation of REE and precious metals, reaction mechanisms and simplified process flowsheets will be elucidated. New reagents with high selectivity for the separation of these metals are further expected to produce high purity metals.

By Wagner Aldeia, Duclerc Fernandes Parra, Danae Lopes Francisco, Ademar B. Lugão, Lucilene Betega de Paiva

The inorganic nanotube halloysite (HNT) is a promising type of natural occurring filler for polymers. Its characteristics, such as high aspect ratio (10–50), small size, and high strength (elasticmodulus—140GPa) suggest that HNT shave a potential use in high-performance polymer nanocomposites. Compared to other nanoclays and nanosilica the relatively low content of hydroxyl groups on their surfaces makes HNTs relatively hydrophobic, although, sometimes, this is not sufficient for guaranty a good interfacial adhesion in composite systems. Further hydrophobic treatment is required to improve HNTs compatibility with polymer matrixes, maximizing interfacial interactions. In the present study, different percentages of EPB (2,2-(1,2-ethene diyldi-4,1-phenylene) bisbenzoxazole) was used to perform anon-covalent functionalization of halloysite, based on electron transfer interactions. The functionalization is characterized by specific surface area (BET), thermogravimetric analysis (TG) and water/toluene extraction experiment.

Mar 1, 2018

By Yoichi Takeda

The CaO-FeOx-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Yoichi Takeda

The CaO-FeO,-Cu20 slag has been practically applied to continuous converting of copper, and also has potential for refining of copper. Liquidus lines of the slag system and phase stability diagram for the liquid slag and the existing solid compounds under copper saturation are presented. Liquidus composition was determined by chemical analysis of slag sample saturated primary solid. The temperatures of invariant equilibria were investigated by thermal analyses. Oxygen potentials on the liquidus lines, the univariant and invariant equilibria were estimated from the relation slag composition and oxygen potential that relation was confirmed in separate experiments.

Jan 1, 2003

By Jian Li, Tiejun Chun, Jian Pan, Deqing Zhu, Vinicius Mendes

"A study of the coal-based direct reduction behaviors of composite binder magnetite pellets was carried out in a simulating coal-based grate-rotary kiln process. It is shown that preheated pellets possess much better reducibility than fired oxide pellets: 40 min are required for preheated pellets to reach over 90% metallization degree compared to 100 min for fired oxide pellets. The compressive strength of preheated pellets decreases dramatically at the earlier stage of reduction, climbs quickly after reducing for 30min and achieves a high value at the end of reduction. However, the compressive strength of metallized pellets from reducing of fired pellets is much lower, more cracks and fractures being formed. In the preheated pellets, crystallite of metal iron is coarse. In the oxide pellet, a large number of interconnected crystals of metal iron are formed inside pellets, and pellet structure is very compact.IntroductionDirectly reduced iron is an excellent feed in electric arc furnace (EAF) steelmaking, and possesses low tramp element content and steady component. It is generally preferred in the production of high quality steel [1-3]. Nearly 64.44 million tons of DRI were produced in 2009 over the world, over 80% of which were produced by gas-based processes, the left by coal-based processes. However, the DRI capacity was only 600 thousand tons in China in 2009. The EAF steel production has exceeded 40 million tons annually, and most of EAF operate on hot metal as feed [4]."

Jan 1, 2011

The oxidation of zinc vapour plays a very important part in the operation of the Imperial Smelting Process. The kinetics of the reoxidation of zinc vapour by carbon dioxide and water vapour onto quartz and zinc oxide substrates is qualitatively understood and this pertains to the conditions found as the gases are being transferred from the furnace to the splash condenser. However, re-oxidation also occurs in the shaft of the furnace where the solid substrates are sinter and metallurgical coke. It was found that there was a threefold increase in the rate of oxidation on sinter, compared to quartz and a 30 to 300 increase in rate on the coke. This was attributed to the high surface area offered by these materials.

Jan 1, 2003

By Adam Powell

A Cahn-Hilliard phase field model is formulated to describe transport-limited electrochemical reactions coupled with fluid flow in a metal reduction cell. When the reaction is limited by mass transfer of metal ions from the electrolyte to the cathode, the metal-electrolyte interface at the cathode exhibits a Mullins-Sekerka instability, leading to the growth of dendrite-like "streamers" of liquid metal into the electrolyte, which in turn significantly enhance the apparent mass transfer coefficient there. Model results for iron reduction from ferrous oxide in slag show formation of these streamers. Although the double-layer is not included in this model, the related phenomenon of electrocapillarity can be represented by a gradient penalty term which includes the electric potential gradient, such that interfacial energy is a function of the electric field normal to the interface.

Jan 1, 2003

By Marcelo Mourao, Adolfo Pillihuaman, Alberto Nogueira, Cyro Takano

"The self-reduction is an alternative and promising process for production of pig iron because offers decisive benefits such as enhancing the reaction kinetic with decrease in fuel consumption and C02 emissions. The self-reduction mixture of iron ore fines, carbonaceous reducer and additives for slag forming components, without agglomeration, was tested in a laboratory rotary kiln. The additives for slag were defined for presenting two different estimated liquidus temperatures (1623 Kand 1773 K) to verify the effect of these temperatures on the iron-carbon nuggets coalescence process. These mixtures were tested at 1673 and 1773 Kin an experimental rotary kiln. After reduction-melting and coalescence processes the samples were disaggregated and the iron nuggets were classified by size. It was considered that nuggets larger than 7,93mm would be a good reference for coalescence index. Low liquidus temperature slag presented 37% of this larger fraction against only 13.5% for high liquidus temperature one. The low liquidus temperature slag would facilitate contact between the particles of iron-carbon in a rotary kiln, enhancing the coalescence.IntroductionThe slag composition usually depends on the reducer ash composition, the ore gangue, the binder composition and any fluxing material [l], and the mechanism of carbon transportation in slag that contains iron oxide reducible by carbon can be explained by the oxide reduction and the metal carburization. During carbon transportation, the carburized particle is transported to slag-metal interphases by the gravity effect, being assimilated by the metallic phase [2]. When the slag's iron oxide comes in contact with the solid carbon, it is immediately reduced, forming Fe particles and CO bubbles as it is shown in the figure l(a). The Fe particles are carburized by carbon particles; they are liquefied simultaneously in the carbon-slag interphase. The Fe-C liquid particles are transported from the slag-carbon interphase to iron-slag interphase as a result of slag flow, based on the surface tension difference (Marangoni effect), figure l(b). The Fe-C liquid particles coalesce on the iron surface and the carbon is immediately diffused in the iron as it is shown in figure l(c). The reduced iron is carburized continuously by repeated sequences [3]."

Jan 1, 2013

By T. T. Chen

Hydrometallurgical products are difficult to characterize because of their fine grain sizes, heterogeneity, often amorphous structures and water soluble or hydrated constituents. Such products are advantageously studied using complementary mineralogical techniques including >50, ore microscopy, SEM-EDX, electron microprobe analysis, selective leaching and wet chemical analysis to determine the phases and their morphologies, to identify specific element carriers, and to elucidate the chemical reactions occurring during the metallurgical process. Sample preparation is an important consideration for these materials. For extremely fine-grained particles, or soft and brittle products such as elemental sulphur, the study of loose powder mounts provides information not available from the examination of polished sections. To demonstrate the application of the various mineralogical techniques, commercial zinc roaster calcines and leach residues, copper refinery anodes and anode slimes, and laboratory bornite leach residues were examined in detail. The various sample preparation and mineralogical methods are presented, and the use of these complementary and practical mineralogical techniques to improve the understanding of a particular hydrometallurgical system is discussed.

Jan 1, 1989

By George Kazonich

The high costs and environmental problems associated with making iron and steel in the United States is driving the development of new technologies to replace the blast furnace. A prototype reactor incorporating rocket technology was designed and built. This rapid rate reactor was operated successfully and consistently made iron metal. Minus 325-mesh magnetite particles could be reduced to iron metal in less than 50 ms in a high temperature flow through reactor. Iron product was recovered inside the reactor and in a downstream cyclonic separator. The results of typical operation and how parametric changes affected the reduction of iron ore concentrates are discussed.

Jan 1, 1993

By J. van Driel

NOx is a growing concern for acid plant operators due to recent legislation reducing the allowable stack limits, as well as continually more stringent requirements for product acid quality. NOx also causes a major problem during maintenance as NOx rich acid residues fume following exposure to moisture in the air. Until recently, the solution for NOx related issues was to treat the symptom, rather than the cause. NOx in product acid was treated using chemicals and the NOx in the plant stack was generally left untreated. As part of an environmentally driven change in concentrates, Budel Zink installed the first gas phase NOx destruction process to be incorporated into a commercial scale acid plant. Nitrogen oxides contained in the process gas are reduced selectively with ammonia over a catalyst to form nitrogen and water. As a result, the NOx reduction is in agreement with the permit requirements.

Jan 1, 2002

By J. Leon-Torres, D. M. Stefanescu, P. A. Curreri, S. Sen

"Experiments were performed under terrestrial gravity (lg) and during parabolic flights (10·2 g) to study the solidification and macrosegregation patterns of Al-Cu alloys. Alloys having 2% and 5% Cu were solidified against a chill at two different cooling rates. Microscopic and Electron Microprobe characterization was used to produce rnicrostructural and macrosegregation maps.In all cases positive segregation occurred next to the chill because of the shrinkage flow, as expected. This positive segregation was higher in the low-g samples, apparently because of the higher heat transfer coefficient.A 2-D computational model was used to explain the experimental results. The continuum formulation was employed to describe the macroscopic transports of mass, energy, and momentum, associated with the solidification phenomena, for a two-phase system. The model considers that liquid flow is driven by thermal and solutal buoyancy, and by solidification shrinkage. The solidification event was divided into two stages. In the first one, the liquid containing freely moving equiaxed grains was described through the relative viscosity concept. In the second stage, when a fixed dendritic network was formed after dendritic coherency, the mushy zone was treated as a porous medium.The macrosegregation maps and the cooling curves obtained during experiments were used for validation of the solidification and segregation model. The model can explain the solidification and macrosegregation patterns and the differences between low- and high-gravity results."

Jan 1, 1999

By Srinath Viswanathan, Adrian Sabau

"In general, the occurrence of microporosity during metal casting is due to the combined effects of solidification shrinkage and gas precipitation. The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies on microporosity, it is considered that the porosity formation does not influence the fluid flow in the mushy zone. In this study, a computational methodology is presented for the numerical simulation of interdendritic fluid flow and microporosity evolution. The solution algorithm presented includes a fully coupled, implicit treatment of microporosity and local pressure in the mushy zone. The effects of microporosity evolution due to the local pressure drop in the mushy zone, and pore expansion in casting regions where liquid feeding alone cannot compensate for the solidification shrinkage are also considered. It is shown that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops. By its growth, microporosity partially compensates for the solidification shrinkage, reducing the feeding demand. A reduced feeding demand requires less fluid flow to compensate for solidification shrinkage, and results in smaller pressure drops in the mushy zone. Therefore, in order to accurately describe casting defects, comprehensive models of fluid flow, heat transfer, and solidification must include the effect of microporosity as well.IntroductionIn the terminology commonly used by foundrymen, porosity is usually considered to be either ""hydrogen"" or ""shrinkage"" porosity. Hydrogen porosity is the term given to porosity that is generally rounded, isolated, and well distributed. Porosity that is interconnected or clustered, and of an irregular shape corresponding to the shape of the interdendritic region, is usually termed shrinkage. In general, the occurrence of microporosity in aluminum alloys is due to the combined effects of solidification shrinkage and gas precipitation [1]. Continuum models [1, 2- 7] have been used to predict the level of porosity in castings. A number of other studies have also attempted to understand the phenomena of porosity formation and pore growth [8-10] and pore morphology [11].The governing equations for fluid flow and hydrogen evolution indicate that porosity formation and fluid flow are strongly coupled. However, in most studies [4, 9, 10], it is considered that the porosity formation does not influence the fluid flow in the mushy zone. Kubo and Pehlke [3] presented a methodology for the prediction of microporosity distribution in shaped castings by considering the effects of both the hydrogen precipitation during solidification and the pressure drop in the mushy zone. In their approach, the local pressure and porosity were computed in an uncoupled manner based on a ""flux of interdendritic liquid"" criterion, i.e., either pressure or porosity was first computed using the other variable at the previous time step. Their approach has been used with little change in numerous studies [6, 12, 13]. Recently, Kuznetsov and Vafai [14] presented a fully coupled, one-dimensional model for the computation of pressure and porosity. They showed that neglecting the effect of porosity formation on the pressure in the mushy zone yields higher pressure drops and an over-prediction of final porosity. They also showed that the influence of porosity formation on the pressure is larger at lower pressures in the mushy zone."

Jan 1, 2001

By Carlos M. Fontes Vieira, Ruben J. Sanchez Rodriguez, Carlos E. Gomes Ribeiro

"The worldwide demand for ornamental stones in building construction is motivating the use of their wastes, generated during fabrication, to produce compound stones. This work has as its objective to investigate the production of an ornamental compound marble (OCM) under vacuum and compression processing of a polyester matrix composite with addition of marble waste as load and as filler. Square OCM composite plates were subjected to compression and flexural mechanical tests. Samples were analyzed to obtain the density and water absorption. The OCM composites presented properties within the expected range of an artificial stone.IntroductionMarble is a limestone, composed mainly of calcite, more or less crystallized by metamorphism that ranges from granular to compact in texture. It has a density 2.7 g/cm3 and its porosity is approximately 0.4%. The UNI 8458 standard defined marble as: ""every crystalline rock constituted mainly by minerals with a Mohs hardness equal to 3-4"". In marble production around70 - 75% of whole extract material is lost in byproducts generation [1,2].In function of large volume of residues generated, the ornamental stones industry has attracted ever more the attention of environmentalists [3].Actually the marble can be pulverized to obtain calcium carbonate for industrial applications. It is also possible to obtain a thinner powder to produce concretes [l]. Some authors study the use of stone residues in concrete mortars and ceramic bricks, getting better properties to these materials [3,4].The marble residues can be also used in engineered stones, or ''agglomerated"" stones, production. The most common engineered stones in the market consist, like a polymer concretes, in polymer matrix composites incorporating petreous components. In the formulation of the engineered stones, the particulate or granular petreous components are the result of fragmentation or trituration processes to which natural stones were submitted to [ 5]."

Jan 1, 2014