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By Peter V. Barr

Despite the advent of modem firing control systems reheating furnace operations frequently allow significant thermal excursions in the discharged slabs or billets after furnace delays. Although HSM furnaces are not immune to this and other related problems, mini-mill operations are most vulnerable due to their more frequent delays and (often) less sophisticated control systems. In order to reduce these problems control systems will commonly include a thermal model, operating either on-line (interacting directly with the controller logic) or in an advisory, off-line mode. Using a new 'fast' thermal model, the paper examines the thermal response of a typical mini-mill furnace during both delays and the subsequent recovery period. A variety of firing strategies are explored and compared on the basis of maintaining thermal excursions within allowable limits for rolling. Other factors, such as the potential for overheating of billets within the furnace during delays and the overall thermal state of the furnace, are also considered in some detail. Although common practice, the use of conventional thermocouple zone temperatures for furnace control during and after delays is shown to be a dubious proposition. Keywords: Reheat Furnace, Modeling, Process Control

Jan 1, 2003

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

By Takaaki Ishikawa

The distribution equilibria of lead, zinc and copper between CaO-Si02-Ah03 melts and liquid copper were measured at 1623K under a controlled H2-C02 atmosphere. The distribution ratios were plotted against the oxygen partial pressure, and reasonable oxide forms dissolved in the melts were estimated from the slopes of the plots. The activity coefficients of zinc oxide (ZnO), lead oxide (PbO) and cuprous oxide (CuOQs) increased with increasing slag basicity, defined by Xcao /XSiO, The temperature dependence of the activity coefficients was also measured.

Jan 1, 2003

By Masatoshi Ogasawara

Saganoseki smelter & refinery operated two flash smelting furnaces, producing a combined 330,000 metric tons per year (hereinafter mtpy) of copper. In 1996, however, it successfully shifted to a single furnace operation while maintaining production at the same level. Since then, the production capacity has been further increased to the present 470,000 mtpy by technological improvements. Also, in order to reduce the converter load which represents a bottleneck in efforts to increase production, the matte grade was gradually increased and currently runs at 65 to 66% attaining the low copper content in the slag (hereinafter slag loss) of 0.7 to 0.8%. This paper introduces some improvements, recent operation results and thermodynamic analyses.

Jan 1, 2003

By Chikabumi Yamauchi, Mitsuru Tanahashi, Toshiharu Fujisawa

"Thermodynamic properties of impurities in molten silicon are of prime importance in developing economical production methods of solar grade silicon. In the present research work, thermodynamic properties of boron, the most difficult element to remove from molten silicon, were measured by chemical equilibration techniques at 1723 and 1773 K. Activity coefficients and self-interaction parameters of boron in molten silicon were determined by equilibrating the melt with solid BN under controlled nitrogen partial pressures. Interaction parameters between boron and nitrogen in molten silicon were also determined by equilibrating the molten Si-B alloys with solid Si3N4• Based on the data obtained, the stability diagram of the Si-B-N system was established.IntroductionPhotovoltaic power generation using a silicon solar cell is expected to be the most promising energy source, because it is inexhaustible, cleaner and more safety than conventional energy sources, such as thermal or atomic power generation. At present, expensive off-grade silicon for semiconductor (SEG-Si) is used for a solar cell production. However, if a large-scale photovoltaic energy conversion using silicon solar cell comes into wide use in the near future, silicon will be sure to be in short supply for the cell. Therefore, a development of a new large scale process for solar grade silicon (SOG-Si) production is definitely necessary, which can remove contained impurities from silicon.Among the impurities contained in silicon, boron is one of the most difficult ones to remove by a zone melting or an unidirectional solidification, because its segregation coefficient in silicon is close to unity (0.8). In addition, boron behaves as a p-type silicon semiconductor dopant and, therefore, its content in SOG-Si must be severely controlled. Although some attempts to remove boron by various metallurgical methods have been carried out [I -4], quantitative analysis has not been made due to lack in the information on the thermodynamic properties of boron in molten silicon. From this view point, the activity of boron in molten silicon was determined in the present study by chemical equilibration techniques at 1723 and 1773 K."

Jan 1, 1998

By J. W. Tsai

Both diamond crystals and diamond films were grown on silicon and copper substrates using a methane/hydrogen gas mixture as a precursor with thermal CVD techniques at low pressure environment. In addition to diamond particles, other crystalline phases including graphite and aluminum silicon carbide were observed on the substrate surface. ?The grown materials were analyzed with X-ray diffraction, electron microscopy, Auger electron spectroscopy and optical microscopy. Most synthesized diamond crystals were twinned. The flow rate of reactant gases, substrate nature, substrate temperature, decomposition temperature of the precursors, total pressure of reaction chamber, methane/hydrogen ratios and other possible parameters were varied during the growth processes, and the significant effects of these factors on nucleation and growth rate were evaluated.

Jan 1, 1989

By Sevinc Yildirim, Cigdem Oruclus

"Metal-Porous Silicon (PS) based structures dipped in water show the direct hydrogen fuel cell behavior. The effect of the thickness of the cupper (Cu) film on the electrical properties of direct hydrogen fuel cell is studied by fabricating Cu/Porous Silicon/n-Silicon/Indium structures. PS samples were produced electrochemical etching of n-type single crystalline silicon with a resistivity of 1,25 Ocm and (111) orientation. The thin films of Cu with different thickness between 200 and 600 nm were deposited on PS surface by electron-beam technique. Investigation of the effect of Cu layer on the performance of the structure indicates that the performance parameters such as open circuit voltage (Voc) and short circuit current (Isc) strongly depend on the Cu layer thickness. It was observed that the divice with an 350 nm Cu layer exhibits the highest open circuit voltage (0,5 V), short circuit current (0,01 mA) and power density (10 W.m-2).IntroductionHydrogen is the most attractive and ultimate candidate for a future fuel and an energy carrier. Hydrogen is recognized as the environmentally desirable clean fuel of the future since it can be used directly in different types of hydrogen fuel cells [1]. In the past years, the rise in portable electronics requires the development of miniature fuel cells compatible with standard silicon micro fabrication technology. Most silicon micro-fuel cells have used the polyperfluo-rosulfonic acid membranes (Nafion R) as a proton exchange membranes (PEM) that is not really integrated with standard micro fabrication techniques [2-5]. The composite materials such as inorganicorganic hybrid materials (Nafion-silica, Nafion-borosiloxane etc) are next generation of proton conducting membrane [4-8]. But, fuel cells run on pure hydrogen gas, which can be produced with other energy resources. Hydrogen smallest atom and thus the H2 gas can leak easiliy. The application of hydrogen for power sources has been greatly restrained due to the lack of safe and convenient generation and storage methods.A kind of hydrogen fuel cells Metal-PS-Si structures used as an energy water directly. There is no need pure hydrogen. Cu-PS-Si Schottky-type fuel cells with as proton-conducting membrane and the thin-film cupper catalist and water as fuel, which are interesting for fabrication of lowcost miniature fuel cells. Generation of the open-circuit voltage and short-circuit current has been observed by Cu-PS-Si structure dipping in different hydrogen-containing solution."

Jan 1, 2014

By K. Adham

"Fluidized beds are utilized in a wide range of high-temperature applications throughout the metals and materials industry. Their main advantage is the fast and uniform heat and mass transfer between the hot combustion gases and the particulate solid feed. A further benefit can be the lowering of the processing plant's energy consumption, through heat recovery from the fluid bed processes used for solids heating. Here, the enhanced energy efficiency of fluidized systems is investigated and the modeling results are discussed for three configurations: the flash tube, the single bubbling bed and the multi-stage fluid bed. Key thermal design aspects of each system are identified based on results from process simulations, in order to benchmark their main operating features and overall energy efficiency. Suitability and applicability of each configuration is also discussed based on a number of process and material property considerations.IntroductionCombustion based heating of particulate solids is commonly done using three different types of fluidized beds. The flash tube (FT) is similar to a hot pneumatic transport system. The single-stage fluidized bed (FB) typically uses in-bed combustion. The multi-stage fluidized bed (MSFB) can have two or more stages stacked into a tower.Flash tube (FT) suspends the incoming solid charge in a high-velocity stream of hot combustion gases. To maintain the solids suspension in the FT, two parameters are required: high velocity for elutriation of the particles and adequate solid-to-gas ratio for avoiding high pressure drops and solids drop-out [l].The fluid bed (FB) works at much lower velocities than the flash tube. Therefore, most of the solids are not conveyed in the gas stream, but are only suspended in a liquid-like manner. At minimum fluidization velocity (Umr), the gas flow exerts just enough force on the solids to keep them suspended in place [2].Multi-stage fluid bed (MSFB) heats up the solids as they are transferred from an upper bed level to a lower one, counter-current to the rising flow of hot gases generated at the lowest stage. As the temperature and volumetric flow of the gases decrease from bottom to the top stage, smaller bed diameters can be used in the energy recovery stages [3]."

Jan 1, 2014

By Shengli Wu, Wei Huang, Xinliang Liu, Kaifa Zhang

The slagging behavior, the phase of primary blast furnace slag and its transformation law of structure for the single furnace burden were studied in this paper. The results showed that the formation of primary slag was controlled by CaO/SiO2, Al2O3 content, MgO content, reducibility, iron content and porosity of the furnace burden. Fayalite (2FeO•SiO2) was easily formed from acid ferrous furnace burden while kirschsteinite (2(Fe,Ca)O•SiO2) was produced from alkaline ferrous furnace burden

Jan 1, 2015

By Li Kaihua, Li Liang, Miao Qingdong, Wang Cong

The current process of production of titanium sponge involves the use of TiCl4 as a feed material and a huge amount of heat is generated during the magnesiothermic reduction process. For this reason, it is possible to agglomerate into a titanium lump with the partial high temperature. And, it is difficult to obtain soft titanium sponge with low content of impurities. In order to solve the current problems in the titanium sponge production process, process optimization experiments study of TiCl4 feeding speed, vacuum distillation temperature, system pressure and time control had been conducted for obtain high quality titanium sponge. Experimental results show that lower feeding speed can improve the output capacity of titanium sponge and softer products can be obtained. The product grade rate of titanium sponge improved significantly.

Jan 1, 2015

By K. Nona C. Liddell

There is a significant amount of early work that has been largely forgotten that deals with the validity of the pseudo-steady approximation for liquid-solid reactions. Much of this was originally published in the chemical engineering literature but is highly relevant to hydrometallurgical processes. The purpose of this paper is to summarize some criteria that were been developed by various authors for determining the error associated with use of shrinking core models for liquid-solid systems.

Jan 1, 2002

By Krzyszof Borowiec

With the aim of determining the thermodynamic conditions for sulfation of impurity elements, in particular magnesium, in titaniferous slags the equilibrium gas composition for the sulfation reaction: MO + so2 + 1/2 02 = MS04 has been studied by an EMF technique with a solid zro2 + Cao electrolyte. Here M denotes the impurity elements: Mg, Ca and Mn, and the following _oxide systems have been studied: Ti02-MgO-Fe2 o 3 , Ti02-MnO-Mn2 o 3 , and Ti02 -CaO-Si02 , all in the . temperature range 700-1000ºc. Reproducible EMF values were obtained by adding small amounts of -Na2so4 to the oxide-sulfate mixture. From the observed results the Gibbs energy of formation of the phases Mg 2Ti04 , MgTi03 , MgTi 2o 5 , MnTi03 , CaTi03 , and CaTiSio5 , as well as the activity of MgTi05 in the solid solution with Fe2Ti05 have been calculated. The results show that, from a thermodynamic viewpoint, sulfation of these impurities in titaniferous stags i:s favorable- at around and below 800ºC.

Jan 1, 1985

By Byung-Su Kim

The recovery of elemental sulfur from sulfur dioxide has important implications for coal- burning power plants and nonferrous metal smelters. The thermodynamic analyses showed calcium sulfide to be suitable for recovering elemental sulfur from sulfur dioxide. At the temperatures of 1023 to 1153 K under the sulfur dioxide partial pressures of 5.0 - 60.1 kPa, elemental sulfur from sulfur dioxide was recovered by its reaction with calcium sulfide. The kinetics of this reaction were measured at the same conditions using a thermogravimetric analysis technique. This reaction scheme would be attractive if the coproduct calcium sulfate can be reduced to regenerate calcium sulfide. This is the topic of another paper. At 1073 K under the sulfur dioxide partial pressure of 25.8 kPa, 48 % of the original calcium sulfide was converted to calcium sulfate in an hour. Under the same conditions, 55 % of the regenerated calcium sulfide were converted to calcium sulfate in an hour even after third regeneration.

Jan 1, 1999

By Young-Chul Kang

The Onsan Copper Smelter of LG-Nikko Copper Inc. is a unique plant, which has been operating two smelting processes since 1998. The operation of the first one was started in 1979 with a capacity of 80,000tpy of copper in concentrates utilizing Outokumpu flash-smelting technology. The other one was started in 1998 based on Mitsubishi continuous process with a capacity of 160,000 tpy of copper in concentrates. Through several expansion projects, the total smelting capacity of both processes is expected to reach 430,00Otpy of copper in concentrates towards the end of 2002. This article describes operation advantages of having two different processes at one plant and comparative operation results in terms of productivity, impurity distribution, energy consumption and environment issues and etc.

Jan 1, 2003

By Garg. D.

Premixed bronze powders are widely used to produce a wide variety of P/M components including bearings and bushings by the powder metal industry. The physical and mechanical properties of sintered bronze components such as dimensions, strength, microstructural characteristics, and sintered density are well known to change with sinlering furnace design, particle size distribution in powders, green density, preheating and sinlering time" and temperature, and protective atmosphere flow rate. " However, not much is known about the effect of protective atmosphere composition on physical and mechanical properties of sintered bronze components; This paper describes effects of protective atmosphere composition and sintering temperature on physical and mechanical properties of sintered bronze components

Jan 1, 1996

By D. de la Villa

From 1989 to 1992 Rio Tinto Minera has developed and implemented a productivity program in its Huelva Plant, including Smelter, Acid Plant and Electrorefinery. This Plan was designed in order to increase productivity, reduce emissions and produce a better quality of cathodes. This paper describes investments and operating improvements involved in this project, focusing on Smelter and Acid Plants, and comments the results obtained so far.

Jan 1, 1993

By Motohiro Horiguchi, Kazuo Ichii, Toshio Oishi

"As a fundamental study to prepare copper-based alloys with rare earths (RE: La, Gd, Nd, Ce and Y) without any inclusions, the solubility of rare earth in liquid copper was experimentally determined. Liquid copper alloys were equilibrated with carbon and rare earth carbide in a graphite crucible in an argon atmosphere at 1523-1873 K.Solubilities of rare earth in liquid copper were determined by approaching the equilibrium values from both the lower and the ·higher concentrations than those expected· in the preliminary experiments. They were expressed as a function of temperature. Carbon in Cu-RE alloy was also analyzed and thermodynamically discussed.IntroductionOver the past several years, the demand for highly conductive and high strength copper-based alloys, such as Cu-Cr, Cu-Zr and Cu-Cr-Zr for use in electronic materials has increased.1 -7 These alloying elements are very reactive and easily oxidized to form oxide inclusions during melting. To avoid the oxide inclusions, it may be effective to utilize the strong reducing power of carbon in conditions under which no carbides form.In this study, to provide fundamental data for producing Cu-RE( rare earth) alloys without any inclusions, the solubility of rare earth in liquid copper in equilibrium with .carbon .was determined and discussed on the basis of the experimental results and the thermodynamic data.ExperimentalSample preparation for equilibrium experimentsOxygen-free copper (99.99%), lanthanum (99.9%), gadolinium (99.9%), neodymium (99.9%), cerium (99.9%) and yttrium (99.9%), and their oxides were used as starting materials.Each rare earth carbide was prepared by mixing rare earth oxide with carbon, which is a little more than the stoichiometric composition, pressing it into a tablet form and sintering at about 2000.K for 20 ks in a vacuum furnace using a graphite crucible. Powder X-ray analysis showed that only the carbon and rare earth carbide (REC2) was present in each sample.Cu-RE mother alloys (5-20 mass % RE) were prepared beforehand by mixing metallic rare earth with oxygen-free copper, and melting in an electric arc furnace."

Jan 1, 2000

By S. P. Marsh, M. E. Glicksman

"The effect of capillarity-driven diffusion on the recalescence of mushy zones is studied in pure materials. The solid-liquid mixture is formed by rapid partial solidification of an initially undercooled melt, and the ratio of the two phases is subsequently maintained constant by an externally imposed adiabatic constraint. A novel technique has been developed that permits tracking of the kinetics of the diffusion-controlled evolution process in situ using precision temperature measurements averaged on a length scale larger than that of the microstructure.The mean ""temperature of a mushy zone is slightly below the bulk equilibrium melting point, and is related to a characteristic length scale of the microstructure through an appropriate statistical average of the GibbsThomson equation. Theoretical considerations indicate that the diffusion controlled recalescence will progress as t- l / 3, where t is time. This behavior is experimentally verified for both succinonitrile (SCN) and ethylene carbonate (ETC), which have markedly different morphologies. The kinetic rate constant is observed to increase monotonically with increasing volume fraction of solid in the two-phase mixtures, although a firm theoretical foundation for this result has not been developed.INTRODUCTIONA dispersed multiphase system seeking equilibrium will generally contain variations in the local .free energy density. These density variations arise from such factors as variations in the bulk free energies of the phases and the distribution of interfacial energies. In this study, we examine the kinetics of diffusion-controlled recalescence in 1 solid-liquid mixture of a pure substance at its melting point. This type of two-phase system is particularly convenient to analyze because of the well-characterized physical properties of pure phases (crystals and their melts) and their interfacial energies, and the absence of any solutal effects."

Jan 1, 1986

By Takayoshi Fujii, Mitsumasa Hoshi, Chikashi Suenaga, Yoshiaki Suzuki

"In a bid to renovate its Saganoseki Smelter & Refinery and to establish a leading production unit in terms of global competitiveness, Nippon Mining & Metals undertook major - restructuring efforts since 1993.One of its themes was the shift from a two-flash furnaces operation to a single-flash furnace operation. The shift was successfully completed in 1996 while maintaining the production at the same level (330,000 metric tons per year of copper) by adopting such measures as improvements in pneumatic concentrate dryers, the concentrate feeding system, concentrate burners, the furnace cooling system, and a new cryogenic oxygen plant was constructed.With a view to realizing high matte grade operation (at 65%Cu) and increasing the concentrate feeding rate, further steps were taken the capacity of waste heat boiler was expanded and technical improvements were added, including optimization of the smelting reaction in the furnace shaft. As a result, the smelting capacity, as of the year 2000, has increased to 450,000 metric tons per year of copper.IntroductionThe feed rate to the flash furnace was doubled to 140 t/h from 70 t/h in 1996. Teething problems, as a result of the renovation, were almost solved by the end of 1996, and the operation of the single furnace operation has become stable.The main theme was the shift from a two-flash furnaces operation to a single-furnace operation to maintain the production capacity at the same level, namely 330,000 metric tons of copper per year. Then, in a bid to further renovate the Saganoseki Smelter & Refinery and to establish a leading production unit in terms of global competitiveness, further enhancement of the flash furnace's productivity was planned.The purpose of this plan was to raise the copper production capacity to 450,000 mtpy building on the potentialities of existing plants and without installing new equipment."

Jan 1, 2000

By Sergio Bustos

Covellite resulting from an original 0.5 % Cu(tot) chalcocite ore has been leached in columns at different temperatures, in the lower range of 10 - 20 °C, under acid - ferric bacterial leaching conditions. Dissolution of copper from covellite depends on the rate and extent of sulphide oxidation by ferric ion. While it is recognised that the dissolution of sulphide minerals is electrochemical in nature, an apparent chemically controlled dissolution pattern was measured with activation energy of 78.09 kJ/mol (18.66 kcal/mol). Ferric iron is the main oxidant and its production and availability will depend on the bacterial activity developed in the system. This activity is characterised by the population size and by the specific oxidation rate of the bacteria. Bacterial growth was followed directly by the number of bacteria appearing in the column effluent solutions and indirectly by the generation of ferric iron or by the total oxidation observed in the columns. These results have been interpreted by using the heap oxidative capacity parameter, which indicates an equivalent ferric production of about 0.07 - 0.15 kg Fe +3/t/day at 20°C. Although bacterial activity decreases to about 0.03 kg Fe +3/t/day with decreasing temperature, a significant bacterial oxidation is still observed at 10 °C. However, extended lag times are observed, which delay the start of bacterial growth to times concurring with covellite leaching. Under these conditions, bacterial activity is displayed through a population controlled by the rate at which- ferrous iron is released from the reducing covellite surface. These results suggest the potential benefit of including some kind of inoculation when operating at lower temperatures. Also, heat loss control and/or heat addition to the heaps should be considered during process design and operation of ferric bacterial heap leaching of secondary copper sulphide ores at temperatures lower than 20°C.

Jan 1, 1999