Search Documents

By S. N. Ojha, Gouthama, R. K. Mandal

"Spray deposition processing of liquid immiscible alloys, based on AI-Pb and Cu-Pb systems have been investigated. Process variables have been optimized to generate uniform dispersion of ultrafine second phase particles in· the matrix of the primary phase. Mechanisms governing the microstructural evolution in this synthesis methodology are discussed. Results of the present investigation are used to demonstrate that rapid solidification of atomized droplets initially provides a high nucleation rate of the second phase during the liquid phase separation. The solid matrix phase nucleates at a later stage and grows with a high velocity enabling trapping of the dispersed phase. Subsequent alteration in the size and size distribution of the second phase is suggested to arise further during deposition of high velocity droplets. Possible reasons for this effect are brought out. Microstructural features of atomized powders and spray-deposits of these alloys are presented to support the present approach of synthesizing composites. IntroductionIn recent years, synthesis of advanced materials with metastable microstructures and ultra fine dispersion of second phase particles has led to the development of novel techniques of materials processing. The other requirement of such a processing methodology is to achieve near-net shape geometries in less number of processing steps. The solidification processing method via spray deposition route qualifies these criteria. This process primarily involves atomization of a melt by high energy gas jets into spray of droplets which are subsequently propelled by the kinetic energy of the gas towards a deposition substrate to build-up a thick high density preform. Although the concept of spray deposition was pioneered by Singer [1] in the early seventies, the fundamentals of the deposition process has been understood only recently [2-4]. Several benefits of spray deposition processing are by now well established [5,6]. Rapid solidification effects are inherent in spray deposition processing due to high heat exchange rate at the droplet-gas interface and also on the deposition surface by force convection. Since considerable heat extraction occurs from the atomized spray prior to droplet consolidation, a relatively low processing temperature is ensured in this process. As a result deleterious coarsening phenomenon can be minimized. In addition, controlled maneuvering of the substrate provides the capability of the process in producing disc, sheet or tube shape preforms of difficult to work materials in a single operation. A significant improvement in properties, resulting from microstructural homogeneity and refinement in grain size induced by spray deposition has been reported for several alloy systems [7,8]."

Jan 1, 1994

By B. Erik Ydstie, Tor Lindstad, Vianey Garcia-Osorio

"As a result of the high temperatures present in a Carbothermic Aluminum Process the content of aluminum and aluminum sub-oxide in the gases leaving this process is high. These gases as well as energy must be recovered. In a Vapor Recovery Unit were the aluminum compounds react in a series of Heterogeneous Non-catalytic Reactions forming solid, liquid and gas products. The different product phases depend on the temperature present in the system. In this work we present dynamic model of the Vapor Recovery Unit of a conceptual Carbothermic Aluminum Process. Because of the complexity of the system several models are developed and coupled to capture the essential physics of the multiphase reaction problem. A Shrinking Core Model describes the reaction mechanisms. Then material and energy balances are coupled with the thermodynamics properties from the FACT database of thermodynamic properties, resulting in a system of nonlinear Partial Differential Equations. In the paper we describe the model development and governing equations for the reaction mechanisms and fluid flow. Finally we review the numerical schemes created for the solution of the model system. The model can be used for control and design purposes.IntroductionThe Carbothennic Processes for producing Aluminum can be divided into two groups (Motzfeldt et al. (1989)) In the first approach pure alumina is produced and reduced to pure aluminum. In the second approach an alloy (e.g. aluminum and silicon) is made and then aluminum is produced from the alloy. The history of both processes has been described by Ginsberg et al. (1965). At least three aluminum producers began largescale testing of this process in the 60's Alcan, Pechey-Ugine and Reynolds. Alcoa did some smaller scale experiments.Alcoa was one of the first companies to produce aluminum by Carbothennic Reduction (Foster et al. (1956)) and US Patent 2,829,961 April 8, 1958. In this process a carbon containing molten aluminum phase was a floated on top of an oxy-carbide melt. During the cooling the dissolved carbon deposited as aluminum carbide. The carbide was then separated from the molten aluminum by a fluxing agent. This process was successful but economic unfeasible."

Jan 1, 2001

By M. Huang

A conductivity-based sensor for on-line measurement of free acid was recently built. This sensor is suitable for high ionic strength solutions and its corrosion-free operation is based on induction currents. It has been tested against literature data and measurements made using a previous developed contact-type conductivity cell, with an average difference within 1%. The electrical conductivities of H2SO4?H2O, H2SO4?MgSO4?H2O and NaCl?Laterite-H2Osolutions at temperatures up to 250 °C were discussed. It was found that the solution conductivity depends on various factors, such as the electrolyte concentrations, the type of electrolytes, temperature and the amount of dispersions. A semi-empirical model was developed to account for all the factors discussed. This model was further tested on actual process solutions from the hydrometallurgy of nickel where sulphuric acid solutions containing a variety of metal sulphates and solids. The average difference between the estimated acid concentration from this model and the one from titration was generally less than 5%, which is excellent for industrial applications.

Jan 1, 2006

By Jun Sugiyama, Hiroyuki Sano, Toshiharu Fujisawa, Hideki Takeuchi, Chikabiuni Yamauchi

"The solid .state electrotransport (SSE) is one of the most promising methods for the elimination of gaseous impurities from chemically active metals, such as rare earth metals. . In the present work, the SSE process was applied for the oxygen removal from praseodymium. The SSE factors, such as effective valence, were measured under the various temperatures, electric field intensities and initial oxygen contents, and the effects of those conditions on the SSE process were discussed. Furthermore, the solubility of oxygen in .solid praseodyillium was also measured·, by using the SSE method and metal-oxide equilibrium method.IntroductionWhen a direct current is passed through a solid alloy, not only electrons but also solute atoms are transported as charge carriers toward the anode or cathode. This phenomenon is referred to as an electrotransport or electromigration. The solid state electrotransport (SSE) is the application technique, based on this principle, to the pUrification of the solid metallic materials.Rare earth metals are used for various functional materials, such as magnetic, optical or electronic materials, therefore their high purity metals are required [l ,2]. However, rare earth metals are chemically active and have a strong affinity with gaseous elements (e.g. oxygen, nitrogen, hydrogen and carbon). In many cases, eliminating operations of gaseous elements have not been always made commercially, because these impurity elements could not be eliminated by usual treatments applied to the purification of ·common metals. As an alternative method, authors have proposed the· application of the SSE process to the elimination of gaseous impurities from rare earth metals. Investigations have been carried out on the yttrium-oxygen and neodymium-oxygen systems and the results were already reported[3,4]."

Jan 1, 2000

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By R. M. Reynolds

Engitec Impianti, S?.p.A. of Milan, Italy has successfully designed, constructed and has in operation state-of-the-art battery breaker systems at two European locations. A third facility i:s partially completed in Toronto, Ontario, Canada. The CX system crushes whole batteries, separates the various components and desulfurizes the battery paste. The system also produces sodium sulfate from the sulfuric acid and lead sulfate contained in the batteries. Actual plant operating data indicates that the desulfurized paste contains less than 0. 6 percent sulfur and less than 0. 5 percent antimony. The CX system utilizes mechanical screening and an up-flow hydrodynamic separator to accomplish the component separation. Sodiwn hydroxide or sodium carbonate is used for desulfurization. The sodium sulfate brine is evaporated and crystallized to produce clean anhydrous sodium sulfate suitable for use by detergent or glass manufacturers. Plant data also indicates that an increase in furnace productivity of about 25 to 30 percent is achieved using feed from the CX system. The desulfurized paste is very suitable for electrolytic processing as an alternative to pyrometallurqical processing.

Jan 1, 1990

By Niloy K. Nath

Two layer sintering by charging green sinter mix with normal coke rate in the upper layer and reduced coke rate in the lower layer, can substantially reduce the coke rate and also improve the sinter quality by producing more uniform thermal profile through out the bed height. The two-layer sintering process have been analyzed by numerical simulation of the process by a detailed CFD based model, considering all the important phenomena like gas-solid reaction, melting and solidification, flow through porous bed, heat and mass transfer etc. Optimization techniques like genetic algorithm, differential evolution is then applied to evaluate the optimum coke rate in the two layers of the bed to produce the ideal thermal profile and melting fraction in the sinter bed for optimum sinter quality. Through this optimization method both high quality sinter with minimum return fines can be achieved along with reduced coke rate. Application of a genetic algorithm for this type of process optimization has several advantages over the traditional optimization techniques since it can identify global optimum condition and perform multi-objective optimization much easily for complex industrial process like iron ore sintering. Keywords: Two-layer Sintering, Iron Ore Sinter Quality, Ergun's Equation, Gas-solid reaction, Melting Fraction, Multi Objective Optimization, Pareto Set, Genetic Algorithm

Jan 1, 2003

By Peter K. Everett

One of the major driving forces behind the development of the Intec Copper Process has been the increasingly stringent regulations governing SO2 emissions and, in some parts of the world, a declining H2SO4 market. Other incentives include operating cost (9.2 US c/lb Cu), capital cost (US $1400/annual tonne Cu compared with smelter cost of US$3-4000/annual tonne Cu) and the ability to treat low grade and contaminated concentrates. With such advantageous features, widespread use of the process is expected over time, leading to the production of large amounts of residues containing around 25% elemental sulfur, together with approximately 50-60 % akaganeite (FeOOH) and the ganggue minerals originally present in the concentrate feed. This paper briefly describes the Intec process chemistry involved in the formation of elemental sulfur, thereby avoiding atmospheric sulfur dioxide pollution, and the investigations to be carried out either to extract it or to turn the residue into a valuable by-product while minimising any adverse environmental effects, The process is being developed jointly by a group of fifteen major international mining companies.

Jan 1, 1996

By C. M. Wai

"Metal species in solid and liquid materials can be extracted by supercritical carbon dioxide containing a suitable ligand. This in situ che1ation-supercritical fluid extraction technique offers several advantages over conventional solvent extraction including minimization of organic liquid waste generation and exposure of personnel to organic vapors. One unique feature of this technique is that metal species can be removed from solid materials directly using supercritical carbon dioxide as a solvent. Several ligand systems including dithiocarbamates, B-diketones, organophosphorus reagents, and macrocyclic compounds have been tested for metal extraction in supercritical carbon dioxide. This novel extraction technique may have important applications for metal recovery and mineral processing.IntroductionSupercritical fluid extraction (SFE) offers several advantages over conventional solvent extraction including the minimization of organic liquid waste generation and exposure of personnel to organic vapors.[1] The high diffusivity, low viscosity, and T-P dependence of solvent strength are some attractive properties which make supercritical fluids excellent candidates for extraction and recovery of organic compounds from solid materials [2] Carbon dioxide is a gas of choice for SFE because of its moderate critical constants (Tc = 31 °·C and Pc = 73 atm), inertness, and availability in purified form. After extraction, the fluid phase is depressurized to separate organic solutes from CO2 gas and the gas can be recycled for repeated use. The SFE technology has been applied to industrial scale operations such as the preparation of decaffeinated coffee and hop extracts."

Jan 1, 1996

By Hiroshi Hashimoto

For the application of sodium carbonate slag treatment to product high purity copper on an industrial scale, the counter-flow batch process that reduces the amount of utilized slag is proposed from the viewpoint of the post-treatment of slag. Based on the distribution ratios of several impurities between the slag and molten copper determined previously, the effectiveness of this process is discussed using a mathematical model and confirmed experimentally. According to the model, the slag consumption to remove Sb to a required level in case of the counter-flow batch process with 3 reactors is calculated to be around 30 % of that in the case of an ordinary batch process, where pure sodium carbonate is used as a slag at every stage.

Jan 1, 2003

By Keith M. Axler

This report addresses issues specific to the generation of hydrogen fluoride via reaction of calcium fluoride with sulfuric acid. This process has been established on a commercial scale and is under consideration for treatment of calcium fluoride residues from uranium processing. Magnesium fluoride slags are also available as a product of uranium processing. The technique of using sulfuric acid for the production of hydrogen fluoride from magnesium fluoride is also under consideration as a residue processing scheme. In the current study, thermodynamic modeling was used to investigate these chemical processing systems. The results presented herein reveal information relevant to the selection of processing temperatures and conditions. Details include predicted effects in system composition based on operating temperatures for both the calcium fluoride and the magnesium fluoride systems.

Jan 1, 1996

By Robert S. Gärtner

The selective aluminum extraction by 3 different calixarenes (p-tert-butyl-calix[4]arene-tetra¬2-acetic-acid-ethyl-ester, p-tert-butyl-calix[4]arene-tetra-2-acetic-acid and p-tert-butyl-calix-[4]arene-di-2-acetic-acid-ethyl-ester) from an industrial pickling bath solution was studied. The pickling bath solution contained hydrofluoric and phosphoric acid as its main components. The aluminum removal was not successful and also no significant extraction of trace metals present was observed.

Jan 1, 1999

By Guo Chang Jiang

In order to improve the IIAZ toughness of X-60 pipe steel, the intragranular ferrite plate (IFP) technology was used. The characteristics of IFP is claimed to be much fine ferrite plates appear inside the original austenite grains. By means of suitable Re, Zr, Ti additions in a bath with a higher initial oxygen potential, a good control of the peak temperature and the cooling rate during welding simulation, one can get a %IFP in volume over 50%, and the toughness gets up from 55 J to 160 J. It was found that the inclusions most effective in nucleating IFP are some deformable complex silicates which either entrap Re, Zr, Ti oxides or contain these elements. The greater the number of the evenly distributed and effectively nucleating inclusions, the more the %IFP in volume, and the finer the microstructure of the HAZ, so the better the relevant toughness. Generally, these silicates bahave as fine spheres along a line. The present authors revealed that these fine spheres result from the remelting of the shuttle- like silicates due to heating in the process of welding simulation. These silicates used to get a higher sulphur capacity, so MnS deposits might be observed on the periphery of the silicates. IFP was proved to be directly rooted in the [Mn] depleting zone which locates beside MnS deposits.

Jan 1, 1997

By Oleg Ostrovski

Industrial pyrometallurgical processes in ferrous metallurgy are based on carbothermal reduction of metal oxides. Carbothermal reduction of stable oxides requires high temperatures. Lowtemperature reduction can be implemented by using methane-containing gas with high carbon activity, or by carbothermal reduction under reduced CO partial pressure. Under standard conditions, methane is thermodynamically unstable above 550 °C and decomposes to solid carbon and hydrogen. At appropriate CH4/H2 ratio and temperature, carbon activity in the methane-containing gas phase can be well above unity relative to graphite, which provides favorable thermodynamic conditions for reduction. To maintain these conditions, the rate of reduction/carburisation should be higher than the rate of solid carbon deposition. The paper discusses reduction of pure manganese and chromium oxides at relatively low temperatures, and constraints in reduction of manganese and chromium ores. Reduction of metal oxides by carbon in hydrogen as an alternative use of natural gas is also discussed.

Jan 1, 2014

By Yoshifumi Abe, Akinori Toraiwa

"Nippon Mining & Metals started a new copper anode slime treatment plant that processes slimes in a chloride media. The basic plan of the process was proposed by Mr. James E. Hoffmann and Nippon Mining & Metals modified and advanced to produce precious metals in acceptable qualities for the company. The process has a wet chlorination stage of decopperized slimes, a solvent extraction and a reduction stages of gold, a silver chloride reduction stage and separative reduction stage of its gold extraction raffinate. The new plant of this process started in 1997 and has been operated in good condition.IntroductionThe old anode slime treatment plant of Nippon Mining & Metals, located in it's Hitachi Refinery, processed anode slimes through a combination of pyrometarllurgical processing and electrorefining. There was a need to plan a future of the plant because the maintenance cost increased year by year and a new selenium registration was going to be applied to the plant. Some plans were discussed and the result was that the process proposed by Mr. Hoffmann was superior among them.Nippon Mining & Metals started 'to examine the process and the experimental result showed that the process had an ability to be its new process but further research should be necessary to produce precious metals in acceptable qualities. The final process flow has some modified and additional stages to be suitable for its requirement. Silver processing stage is quite changed. Gold extraction stage has a new step to polish gold loading DBC. Gold extraction raffinate treatment stage is advanced to be able to recover precious metals, selenium and tellurium, separately. Aeration under atmospheric pressure is employed in decopperizing stage.The basic design of the new plant started in 1995 and finished in 1997. The construction of the new plant began in April 1997 and finished in October. The plant has been operating well after the four months test operation."

Jan 1, 2000

By W. W. Albrecht

I. Introduction Refractory metals like tungsten, molybdenum, rhenium, tantalum and niobium and their compounds are essential ingredients of our modern technology. Especially in purified form, they are used in special alloys, electronics, optics and ceramics. The processing route from raw material to high purity refractory metals and their compounds includes, as a prime option, the following steps: - dissolution of raw materials. - liquid liquid extraction. - precipitation of high purity intermediate compounds. - calcination/reduction to high purity oxides/metals. Especially in the first three steps, major amounts of chemicals like acids or sodium hydroxide are used and, as by-products, substantial quantities of residues and effluents are generated. The impact of environmental regulations on these by-products and the attempt to reduce or minimize the amount of residues and effluents produced will be discussed in this presentation using Ta/Nb chemistry as the example. The basis of our considerations will be the way these by-products are handled at HCST, a major, and in some cases, the biggest producer of refractory metals (tungsten, molybdenum, rhenium, tantalum, and niobium).

Jan 1, 1992

By H. Itou, J. M. Toguri, T. Takasu

"Marangoni convection has a large effect on materials processing since it remarkably enhances heat and mass transport near a free interface. To have a better understanding of the behavior of Marangoni convection in molten salts, observation and calculation of the thermal convection in a column held between a pair of Pt disks (2mm in diameter) fixed to hot thermocouples, were carried out.Calculated flow patterns and absolute values of fluid velocity agreed well with the observed results. When the temperatures of both disks were set equal and the height of liquid column was 2.4mm, four vortexes were generated on the longitudinal plane with a typical velocity of 15mm/s . From the calculated isothermal lines, the behavior of the enhanced heat transport was obvious; fluid heated at the disks was conveyed to the free surface and the cooled fluid at the surface was conveyed to the inner region. Increase in the height of column and/or increase in the absolute value of applied temperature difference lead to increase in fluid velocity lineally in this calculation range.IntroductionIn the processing of many materials, fluid flow of melts has a large effect on refining capabilities and on the characteristics of the produced material. Marangoni convection is generated when a spatial gradient of interfacial tension exists on the free interface due to differences in temperature and/or concentration. This promotes heat and mass transfer locally near the interface.For example, Marangoni convection which are created following the dissolution of interfacially active materials, increases the local corrosion rate of refractories (1-3). In absorption and discharge of oxygen and/or nitrogen in a molten metal, the effective reaction rate of the gas components through the gas-liquid interface increases (4-7). Also in crystal growth, the distribution of defects and impurities in the crystal is affected and this can alter its quality (8-11 ). The temperature distribution is also affected and can greatly change the productivity. For these reasons, the effectiveness of Marangoni convection in refining should be quantitatively clarified and its control should be better understood."

Jan 1, 1997

By Takeshi Yoshikawa, Kazuki Morita, Kunitoshi Matsunaga

"In metallurgical grade silicon (MG-Si), most impurities mainly exist at the grain boundaries and distribute in silicon grains at extremely small contents. Grain boundary phases in MG-Si transform into liquid above the eutectic temperature, and migrate towards high temperature regions when heated under a temperature gradient. With the migration of all liquid phases in MG-Si to the surface, the impurity contents will be decreased less than their solubilities in principle.In the present work, the fundamental research was conducted to discuss the possibility for purification using the liquid phase migration technique. The purification limit was estimated by thermodynamic calculations, and metallic impurities were estimated to be effectively removed except for Fe and Al. The migration behavior of the liquid phase in the synthesized silicon substrate was investigated by unidirectional heating under infrared radiation at 1523-1548 K, and the proceeding of migration was confirmed. The migration velocity was 1.4--2.0xl0-7 mis, and found to be controlled by the liquid phase diffusion.IntroductionPhotovoltaic energy is one of promising energy resources in a sustainable society because of its inexhaustibility and cleanliness. Although the production and installation of solar cells have increased significantly during the last decade, the cost of solar cell installation is still high. To enable the widespread use of photovoltaics and for the photovoltaic electricity price to reach grid parity, a low-cost and abundant feedstock of solar grade silicon (SOG-Si) is essential. Recently, a modified Siemens process and a fluidized bed reactor process were developed to address the cost and energy issues associated with the conventional Siemens process. However, their cost reduction potential is limited because of the large energy consumption needed to convert silicon into gaseous compounds. Purification of silicon through metallurgical routes offers a promising way for producing SOG-Si from metallurgical grade silicon (MG-Si), because it enhances productivity and can also lower the process costs. Although several metallurgical processes such as directional solidification [l ], vacuum refining [2-4] and plasma oxidation [5-7], have been developed, processing times and refining efficiencies still have to be optimized."

Jan 1, 2013

By Y. K. Rao

Relatively pure crystalline lead sulfate (PbSO4) can be produced by chemical vapor transport from an impure source such as the lead-acid battery paste or the roast-ore-leach-residue from a hy¬drometallurgical process-route. In a closed-reactor, transport of matter is induced by a tempera¬ture-gradient and the steady-state transfer rate can be calculated using the data on the standard free energies of formation for the species present and the pertinent binary diffusion coefficients. The present work focusses on chemical vapor transport in a tubular reactor (1.4-cm inner diameter x 10-cm long) with the source- and deposition-ends held at 850°C (T,) and 750°C (Td), respectively; PbC12(g) is the 'solvent' or 'transport agent' and NiSO4(s) placed in the source-zone -serves to maintain a sufficiently high S0,-potential such that the stability of the lead sulfate species is ensured. For the purposes of analysis, the gas-phase in the reactor is assumed to consist of eight species: H2O, PbC12, SO3, SO2. O2 HO, C12, and PbC14. The reaction between C12(g) and PbSO4(s) in the high-temperature source-zone produces PbCl2, SO2, and 02; four more reaction-equilibria in the same zone yield other species. In the low-temperature deposition-zone, reaction equilibrium involving PbC12, H2O, and SO, leads to the nucleation and growth of PbSO4 crystals; three other reaction-equilibria occur in this zone. By employing the virtual equilibrium state for the end-zones and coupling it to the Stefan-Maxwell diffusion equations for each of the gas species, the respective partial pressures for these, in the source- and deposition-zones, are computed at steady-state. From these data, the molar fluxes of PbCl2. PbCl4, and so forth, are determined. Allowing for the transport-enhancing effects of thermal convection, the net transport rate of lead (or PbSO4) is duly calculated for specified initial conditions. The predicted rates show very good agreement with measured rate data reported in the literature [ V. Plies, T. Kohlmann and R. Gruehn: Z. anorg. allg. Chem, 568, 62 (1989)

Jan 1, 1995

By Petrus Christiaan Pistorius, Ming Tang

Magnetite concentrate is pelletized and then hardened by elevated-temperature oxidation to hematite, to produce pellets for ironmaking. Previous work showed that the rate of oxidation is under mixed control of gaseous mass transfer of molecular oxygen through the pellet pores, and solid-state diffusion into the oxidizing grains. Because of the partially limiting role of solid-state diffusion, concentrate size distribution strongly affects pellet oxidation. Previously, a simple mixed-control model was formulated to describe isothermal oxidation. In that model, the main effect of concentrate size distribution was on the plateau level of oxidation which is reached at a given temperature. However, the extent of plateau oxidation increases with increased temperature, requiring a more complex model for non-isothermal oxidation. In this paper, predictions of the non-isothermal model confirm the strong effects of concentrate size distribution and oxygen enrichment. In particular, a greater fraction of coarse magnetite particles would be beneficial, decreasing the size of the macroscopic unoxidized pellet core.

Jan 1, 2015