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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'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 'CSO or CSC' 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' 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 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 Elliot Schwartz, Julian Szekely

"In this paper we describe an experiment that was recently performed on the IML-2 Space Shuttle mission in which the thermophysical properties of molten metals were measured using electromagnetic levitation. In the planning of these experiments calculations had to be performed to predict the levitation and stirring forces, heating rates, sample deformation, and internal flows within the sample. These predictive calculations were essential for both the planning of the experiments and for the re-planning of experimental runs during the actual Space Shuttle mission.Introduction""Materials Processing in the Computer Age"" involves the use of mathematical modeling to obtain a quantitative understanding of the phenomena that govern materials processing operations. Microgravity, or space shuttle experimentation represents a specific case in point here; the very high cost of the space shuttle flights, the very limited flight opportunities that are available, and the tight resources aboard a shuttle clearly mandate that these experiments be very precisely planned and that all possible opportunities for mathematical modeling be fully exploited.The purpose of this paper is to present the results of calculations performed for the planning of a space shuttle experiment involving electromagnetic levitation and wherever possible present a comparison of the computational predictions with both experimental measurements and asymptotic analyses. Finally we shall seek to discuss the practical implications of both the computational methodologies and the potential experimental findings."

Jan 1, 1994

By Antti Roine

Sulfidic zinc concentrates are usually roasted in a fluidized bed furnace into sulfur-free oxide form. Metallic zinc is produced from this oxidic calcine using hydrometallurgical leaching, solution purification and electrowinning stages. The roasting step is necessary because zinc oxides are easier to dissolve using traditional leaching methods than zinc sulfides. The Kokkola Zinc smelter uses various types of zinc concentrates and secondary materials as feed mixture. This makes it difficult to find optimum process parameters for the roaster when the composition and particle size distribution of the feed mixture varies even on a daily basis. Certain conditions may even cause difficult accretion problems or increase the amount of calcine in the process off-gas line excessively. A thermochemical heat and material balance model was developed for process advisor, in order to estimate the effects of different process parameters (temperature, process air coefficient, concentrate feed, oxygen enrichment, water feed, etc.) on the heat balance, roasting temperature and calcine composition. This model was constructed using the heat balance module of HSC Chemistry 4.0 software. The prevailing chemical compounds in the concentrate and calcine were verified using mineralogical analyses and equilibrium calculations. The roasting process seems to operate near chemical equilibrium conditions, if the behavior of the main components is considered. This paper describes briefly the basic principles of the calculation model and outlines the results with several diagrams and discussion. The calculated results were in reasonable agreement with the recent process air oxygen enrichment and water feed test campaigns carried out at Kokkola in 1999.

Jan 1, 2000

By I. M. S. Moraes

Caraiba Metais has a plant for the purification and the cristallization of the crude nickel sulfate removed from its copper electrolyte purification system. In November 1994, an interdepartmental group was formed to study the Q.F.D. method, through its application on the improvement of the quality of the nickel sulphate hexahydrate. The team, formed with representatives of the following areas : production, technology, marketing, sales, maintenance, laboratory and TQC office, had also the task of checking the applicability of the method to other products of the comp any. This paper describes the main steps such as the survey of customer's demands, the preparation o1 the quality matrix, stablishing the planned quality matrix, the planned and the designed quality, and the consequent identification of the engineering bottlenecks. It is also shown how these bottllenecks were studied and solved. The application of the method allowed the team to identify means of increasing the production capacity by 40%, to improve the intrinsic quality of the product (including packaging), and to increase the reliability of the process.

Jan 1, 1997

By K. G. Wang, M. E. Glicksman, P. Crawford

"We formulate the mathematical solution to late-stage multi particle diffusion in finite systems. The transition from finite system behavior to that for an infinite system is established. Large-scale simulations are reported regarding the dynamics of phase coarsening. Even in the case of a small volume fraction (Vv = 10-4), the particle size distribution is broader than that for the well-known Lifshitz-Slyozov limit at zero volume fraction. We also report the first simulation studies of extremely low volume fraction, for which corresponding experiments, as well as other simulations, do not exist at present for comparison. However, in the case of moderate volume fractions (Vv = 0.1), the fiucutations in the volumetric growth rate of particles are extracted from our simulations. These simulations provide additional insight into the statistical nature of diffusion interactions, including multiparticle stochastics during microstructural evolution.IntroductionPredicting microstructure evolution in alloys remains one of the cornerstones of materials science. Phase coarsening is a common process in microstrucural evolution that leads to a decrease in the excess total interfacial energy of the system. The system typically consists of separate and identifiable units, or domains, such as second-phase particles distributed in a matrix. During phase coarsening, larger particles grow at the expense of small particles. Over time, this ""competition"" results in an increase in the average size of the particle population, and in a concomitant decrease in the number of particles.Particle size and microstructure of many cast alloys depend on similar coarsening processes. Indeed, properties of these materials, such as strength, toughness, ductility, and electrical conductivity, depend on the material's average particle size and particle size distribution (PSD). Understanding and controlling microstructures in two-phase systems are clearly of widespread technological importance."

Jan 1, 2001

By P. M. Swash

The paper describes the use of mineralogical methods in the exploration and evaluation of primary diamond occurrences. The most common methods that are used include the systematic search for kimberlitic indicator minerals, surface textural study of the indicator minerals, (garnet, spinel, ilmenite and chrome diopside) and alluvial macrodiamond studies so as to understand their provenance and guide exploration towards diamondiferous targets. The mineral chemistry of the indicator is used to positively assess the origin of the mineral grains and is also pivotal in the determination of the diamond potential of a deposit. Petrography of the primary deposit is able to identify the body to be kimberlitic and is also a support to the mineral chemistry findings. Unambiguous proof of a prospects potential to contain macrodiamond is proven by the occurrence of microdiamonds in the residues from the rock. The presence of a sufficient number of microdiamonds in the rock is enough to determine a semiquantitative grade estimate and warrant further metallurgical evaluation so as to determine its actual macrodiamond content.

Jan 1, 1991

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 A. Onozaki

The Iijima Refinery was put into operation in 1972 and today has an annual production capacity of 156,000 tons of SHG electrolytic zinc. At the Iijima Refinery, the recoveries of gold and silver are 98.0% and 98.2%, respectively. Gold contained originally in the zinc concentrates reports in the Cu-Pb-Ag residue produced in the residue treatment process. Silver contained in the concentrates is distributed between the Cu-Pb~Ag residue and the copper cake produced in the purification process. The Cu-Pb-Ag residue, which contains gold and silver, is sent to the Oyachi flotatfon plant of the Kosaka Smelter; about 82% of the gold and about 85% of the silver are recovered in the copper flotation concentrate.. In this paper, the distribution of gold and silver in the Iijima. Refinery is discussed and operational results of the Oyachi flotation plant are presented.

Jan 1, 1990

By M. S. Moats

The treatment of oxidized residues of zinc with high iron content continues to present a technical challenge in both the steel and zinc industries. Two main problems are commonly identified and include high treatment costs and environmental concerns about contaminated, iron-bearing residuals. A new approach to this problem is described in which selective separation of the iron and zinc into salable products may be potentially feasible. The waste material is first leached to give a solution having an approximate concentration of 110 g/l Zn, 15 g/1 Fe and 40 g/1 H2SO4 and other impurities such as Pb, Cd, Cu and Sb. A suitable organic, such as D2EHPA, is used to load the majority of the iron. The aqueous phase is then acceptable for zinc electrowinning after standard solution purification. The novel step in the flow sheet is the efficient recovery of the ferric iron from the organic solvent using a solid metal to reduce the iron to the ferrous state. The Fe+2 is easily stripped into an aqueous phase in a relatively pure form, suitable for use in water treatment. Process parameters and possible flow sheet designs are described and discussed.

Jan 1, 1995

By Benoit DeBecker

Laboratory-scale experiments have shown that chromium metal could be recovered from chromate wastes by modifying slightly the chromium electrowinning flow-sheet. After reduction by sulhr dioxide and precipitation of chromic hydroxide, the solid residue is dissolved in the chrome alum solution and the metallic impurities are removed by cementation on manganese. The presence of dissolved manganese in the electrolyte does not affect the cathodic deposition of chromium and it eliminates the anodic production of Cr(V1).

Jan 1, 1994

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 '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

By Toshiaki Tsuru, Takeshi Ohgai, Hisaaki Fukushima, Shigeo Kobayashi, Tetsuya Akiyama

"Electrodeposition behavior of Zn-Cr alloys from the methanol baths was investigated. In the methanol baths of low Cr3+ concentration, Cr (III) compound was incorporated in the deposits and no lusfrous Zn-Cr alloys was deposited. However, Cr was existed as metallic state in the deposits obtained from the baths of higher Cr3+ concentration. With an increase in water content in the baths, the chemical state of Cr in the deposits changed from metallic to trivalent state. Under the condition that metallic Cr can be electrodeposited, Zn deposition was significantly polarized to the potential of Cr deposition.INTRODUCTIONAn attention has been paid to Zn-Cr alloy plated steel sheet because of its excellent properties for body panels of automobile and electrical appliances [1]-[4]. This plating process can be operated using the sulfate solutions containing Cr3+ ion [1] - [6].In decorative single Cr plating, on the other hand, many attempts have been made to electroplate Cr from trivalent electrolytes, which is motived by environmental deficiencies of the presently used hexavalent process [7]. [8]. However, it has been reported that in the aqueous solutions the behavior of the electroreduction of 0 3+ is atypical due to the complicated nature of the chemistry and electrochemistry of cr3+ species [9]-[11]. Even in Zn-Cr alloy plating, it is difficult to codeposit metallic Cr with Zn in simple sulfate electrolytes [l]-[4], [12]. Therefore, it can be expected that the electrodeposition behaviors of Zn-Cr alloys as well as Cr are significantly changed when the electrodeposition is conducted in non-aqueous plating solutions.In this study, the electrodeposition of Zn-Cr alloy was conducted from methanol solutions to clarify the electroreduction mechanism of Cr3·-Cr0 in the alloy deposition process."

Jan 1, 2000

By Toshio Suzuki, Machiko Ode, Won Tae Kim, Seong Gyoon Kim

"The Ostwald ripening and growth and coarsening of the secondary dendrite arm are studied using a phase-field model. The phase-field parameters are obtained at a thin interface limit proposed by Kim et al. In Ostwald ripening analysis, the difference of the concentration due ·to· the curvature effect is shown. The third power of the average particle radius Rav is proportional to time and the ripening constant shows a good agreement with the value by Deppers et al. The particle radii distribution shows the transition behavior to attain a self-similar stationary shape. The growth and coarsening behavior of the secondary dendrite arm is also analyzed using a phase-field model. The estimated arm spacing and its dependence on time are in good agreements with experimental data.IntroductionThe ripening or coarsening process controls the microstructure during the late stage of solidification. The ripening phenomena are recognized firstly by the Ostwald [1]. The first quantitative analysis for the Ostwald ripening in the limit of vanishing solid fraction was provided by Lifshitz, Slyozov and Wagner (LSW) [2,3]. In their study, that the mean radius grows proportional to the cubic root of time and the size distribution of precipitations shows a ""self-similar"" shape are shown. Most of the studies for the Ostwald ripening confirm or predict these two general rules above. In case of finite solid fraction, the general rules are observed but the ripening constant is larger and the self-similar shape is wider than the LSW prediction respectively [4-6]. To analyze· the high solid fraction system, the theories that consider the solute field correlation are proposed [4,7-8]. In the theory, however, since the particle is treated as the point, the effect of the concentration field deviation from the monopole field should be taken into account. Recently the numerical simulation, in which not only diffusive transportation of solute but also convection effect is considered, has been done using a phase-field model [9]."

Jan 1, 2000

By Chris P. Pistorius

Over the past few decades the carbon intensity of ironmaking and steelmaking has been reduced considerably through improved efficiency in blast furnace ironmaking, partial replacement of coke with less carbon-intensive fuels, and increased use of scrap and direct-reduced iron in steelmaking. To evaluate possible further reductions in carbon intensity accurate process information is needed. A preliminary test of the fidelity of publicly reported data as a source of process information is reported here. The sources are industry roundups of electric furnace furnace steelmaking and blast furnace ironmaking (published by the Association for Iron and Steelmaking Technology), and data recorded by the Environmental Protection Agency under the US Greenhouse Gas Reporting Program. From a comparison for an integrated steelmaking plant and an electric furnace furnace plant, it appears that the values from the two data sources are consistent. The comparison does rely on process details such as the quantitative relationship between injected oxygen and carbon emissions in electric furnace steelmaking.

By Chidchai Loyprasert, R. A. Stoehr

"A computer model has been developed to predict grain structures in alloys solidified under unidirectional flow using a combination of three techniques -- solution of the equations for flow of an incompressible fluid bounded by curved surfaces by the SOLA-SURF algorithm, calculation of heat flow by a finite difference method, and simulation of grain formation by a two-dimensional cellular automaton (CA) model. The changing rigid surface has been taken into account. Heterogeneous and homogeneous nucleation are considered, and the growth kinetics of a dendrite tip are evaluated by the Kurz-Giovanola-Trivedi (KGT) model. These calculations were applied to solidification of an Al-4.5% Cu alloy flowing over a chill on the bottom of a channel, a system for which experimental results were available. Using a variety of flow rates and superheats, agreement between the computed and experimental results were very good including transitions between columnar and equiaxed grains, the aspect ratio of the grains, and the inclination of the grains to the flow.IntroductionModeling of casting and solidification processes has developed over the years along two distinct tracks: (1.) modeling of macroscopic heat transfer and fluid flow for design purposes, and (2.) modeling of microscopic processes such as nucleation and growth in order to improve the scientific understanding of the phenomena involved. The present work is an attempt to combine the macroscopic and microscopic approaches for the solidification of an alloy flowing over a chill. The specific case chosen is that of an aluminum-4.5 % copper alloy flowing linearly over a water-cooled copper chill for which experimental results were available over a range of flow rates and superheats. For the macroscopic calculations, the SOLA-SURF algorithm for solution of the twodimensional fluid flow equations was combined with the finite difference method (FDM) for calculating heat transfer. For the microscopic calculations, heterogeneous and homogeneous nucleation were considered, and the growth kinetics at the dendrite tips were evaluated. The cellular automaton (CA) technique was used to apply the microscopic kinetics to the temperature and .flow conditions."

Jan 1, 1999

By C. -S. Jiang

In most copper refineries, addition agents are added at predetermined rates with no further monitoring of their activity or concentration in the electrolyte. Increasingly stringent cathode quality requirements, and a desire for better process control in tankhouse operations, have recently directed a number of refineries to search for a better addition agent control strategy. Extensive development work has been carried out at the Noranda Technology Centre for the monitor in of glue and thiourea in copper refinery electrolyte using cyclic voltammetry (cv~. Data from both synthetrc and commercial electrolytes are presented, showing the ability of CV to produce reliable and easily identifiable fingerprints of addition agent concentrations in copper refinery electrolyte.

Jan 1, 1991

By Run Huang, Xuewei Lv, Lei Lei, Guibao Qiu, Chenguang Bai

"The TiO2-rich slag and pig iron can be produced from ilmenite concentrate by the electric furnace process. In this study, ilmenite concentrate was reduced in a vertical furnace equipped with a weighting data acquisition system. The effects of reducing agent (carbon) amount on the iron reduction were studied. The phase transformation, morphology and chemical compositions of reduced samples were investigated by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS), respectively. It was found that the reductive degree of ilmenite concentrate increased with the increase of reducing time. The phases of reduced samples were mostly iron, rutile, Ti3O5 and Fe2TiO5. The mass loss percentage increased with increasing the carbon amount from 8% to 12%. When the carbon amount exceeded 12%, the mass loss percentage decreased with the increasing of carbon amount.IntroductionIlmenite and rutile are the main raw materials for producing titania pigment and titanium metal. With the development of the titanium industry, huge amounts of titanium resources are needed. As sources of high-grade titania mineral decrease worldwide, more attention should be paid to the processes involving low grade mineral such as ilmenite ore. In ilmenite, MgO and CaO are the gangue parts. Therefore, the ilmenite refining becomes more and more popular. In the previous studies, the methods of ilmenite refining are electric furnace smelting, direct acid leaching, selective chlorination and thermal reduction [1]. Electric furnace smelting method is widely used in the titanium industry, however, which consumes a great deal of energies and has a high CO2 emission. Its essence is to remove iron oxides and obtain a high titania slag. So the thermal reduction of ilmenite concentrate is an important step in titanium industry, which can decrease carbon reagent consumption and save energy.Over the past several decades, many studies have been carried out on the mechanism and kinetics of the reduction of different ilmenite ores, which are as follows: The carbothermal reduction of Panzhihua ilmenite initiated at about 860 oC. In the temperatures ranging from 900 oC to 1400 oC, the reaction rate was changed like a shape of “M”. That was to say that the reaction rate increased with the growth of temperature at first, then decreased, afterward increased again and at last the reaction was arrested [2]. The Mohammad A.R group [3, 4] showed that the carbothermal reduction of primary ilmenite concentrate was faster in hydrogen and initiated at a lower reduced temperature than in argon and helium. The reduction in argon and helium had about the same rate and extent. Titanium oxycarbide started at 1000°C in hydrogen. The conversion of primary ilmenite concentrate to metallic iron and titanium oxycarbide at 1200 °C was completed in 300 minutes. Monoxide as the reductant to reduce ilmenite had been studied intensively by a few research groups [5, 6]. The rate and the degree of reduction depended on the formation of a metallic shell of iron which inhibited the transfer of CO to the reaction zones; titanium had a strong effect on the mechanism and rate of reduction of iron oxides. Wang and Yuan [7] studied the reductive kinetics of the reaction between a natural ilmenite and carbon. At temperature below 1100°C, chemical reaction was the rate controlling step, at 1100 to 1250°C mixed controlling was rate controlling step, above 1250°C diffusion through the product layer controlled the reaction. Zhang [8] investigated the reduction of natural, sintered and preoxidized ilmenite concentrates in hydrogen methane mixtures. Preoxidation and sintering of ilmenite concentrates changed their phase composition and caused a sharp decrease in specific surface area of raw materials and an increase in carburization temperature. Sintering also increased the metallization temperature of iron."

Jan 1, 2011

By Peter R. Sanford

Cyanides are present as a dilute constituent of streams from a variety of metallurgical and mineral-processing operations. In addition, a cyanide concentration in excess of approximately 100ppb is toxic to aquatic life, and consequently these operations require a waste-treatment process to reduce the already dilute cyanide species by several orders of magnitude. Furthermore, the waste streams may have flowrates in excess of a million gallons per day. The paper reports on research conducted with a laboratory?scale electrochemical porous (graphite felt) electrode (anode) flow-reactor, which was conducted in conjunction with a computer-aided simulation of a mathematical model describing the intrinsic rate-phenomena associate with the electrode processes. The laboratory-scale cell, of rectilinear geometry, was found to be capable of reducing a feed-stream anolyte (KCN-KOH and supporting electrolyte of a single salt ? K2SO4) with a cyanide concentration of 10ppm, to less than 100ppb, at current efficiencies in the neighborhood of 50%. The computer simulation of the cell performance based on the mathematical model (and constraints imposed for tractability) was found to provide only for qualitative agreement.

Jan 1, 1998

By James A. Voigt

The efficient separation of metal species from aqueous streams by precipitation techniques requires 'a fundamental understanding of the various processes that occur during precipitation. These processes include particle nucleation, particle growth by solute deposition, agglomerate formation, and agglomerate break-up. The application of the population balance approach has been used to develop a kinetic model that accounts for these competing kinetic processes. The usefulness of the model is illustrated through its application to the precipitation of yttrium hydroxynitrate, YHN. The kinetic parameters calculated from the model equations and system-specific solution chemistry are used to describe several aspects of the effect of pH on the precipitation of the YHN. Implications with respect to the simultaneous precipitation of more than one cation type are also discussed through use of example systems: The effects of solution chemistry, precipitator design, and solvent choice are considered.

Jan 1, 1996