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By Du Sichen, S. Seetharaman, J. A. Bustnes

"The present study deals with the kinetic studies of reduction of some selected transition metal tungstates with hydrogen. The measurements were carried out by the isothermal thermogravimetric method. Shallow powder beds were employed in order to avoid the effects due to transport phenomena affecting the reaction rate. In this way, the chemical reaction rates could be selectively studied. The experiments were carried out in the temperature range 873 - 1173 K. From the experimental data, the activation energies were evaluated and were found to be around 88 kJ / mol in the case of both iron as well as cobalt tungstates indicating the similarities in W-O bonds in both cases. The activation energies obtained are discussed in the light of the position of the transition metal in the periodic table as well as the thermodynamic stabilities of the various tungstates.IntroductionThe tungsten containing hard metals, characterized by high density, belong to a class of two-phase metal matrix composites. While these types of materials have traditionally found their applications within the defence industry as armour-piercing projectiles, counterbalance in helicopters and military aircrafts, outer casings of hand-grenades, etc., commercial applications for this class of alloys also exist, including radiation shields, penetrators for the oil industry, turbines for turbo-jet engines and a wide range of sports related parts. A possible route to the production of these alloys is to reduce the tungstates such as FeW04, Co W04 and NiW04 using a reductant like hydrogen or carbon monoxide. In order to have a better understanding of the processes involved in the production, it is important to have a knowledge of the reduction kinetics for these tungstates. According to the knowledge of the present authors, while the reduction ofNiW04 by hydrogen gas has been investigated earlier in the present laboratorypl no systematic reduction study has been carried out previously for the tungstates of iron, cobalt."

Jan 1, 1996

02, NaCI03, H202, Na0CI and Ce+4 have been examined as oxidants in an alkaline carbonate system for uranium in in situ leaching. The South Texas and New Mexico ores contained up to 2.6 meqJg of reducing compounds which consume oxidants in the leading operation. Leaching rates did not increase linearly with the oxidation potential of the oxidants. A mild oxidant can be used to maximize uranium oxidation selectively and oxidant efficiency. 02 can oxidize most of the uranium mineral with an adequate rate and high oxidant efficiency.

Jan 1, 1990

By Gabriel Riveros

Fire refining of copper consists of two stages copper oxidation and copper reduction. Very frequently the capacity of the anode furnace is determined by the rate of copper reduction, The analysis of factors affecting the rate of the oxygen reduction from a liquid copper with solid carbon or injected hydrocarbons pointed out the role of the mass transfer in a liquid copper in final stage of the reduction. Experimental results of copper reduction with graphite and injected natural gas in laboratory-scale crucibles showed two stages of the reduction process with a sharp change of the controlling mechanism. The estimated dynamic surface area of gas bubbles based on the measured bubble frequency and the gas flowrate allowed for the determination of the reaction constant as a degree of the partial pre-combustion of the air/natural gas mix. The variation of the used reductant as a function of the oxygen concentration and temperature has been evaluated based on the determined kinetic model. The intensification of copper reduction in fire refining has been discusses on the basis of obtained kinetic data and analysis of various factors determining the time of reduction.

Jan 1, 2003

By Lenny Winkel

With the aim to develop a solar-driven process for the extraction of copper from sulfide concentrates research on the decomposition of copper sulfides under inert atmospheres has been initiated. Thermogravimetric measurements on chalcocite (CuzS) revealed that copper is formed already at 1823 K. Chalcopyrite (CuFeS2) also disintegrates at this temperature, although at a lower rate. Copper and iron have been identified in the solid residue. The results confirm the feasibility of copper extraction by direct decomposition of sulfides under atmospheric pressure. The decomposition under inert atmosphere prevents generation of SO2, it also alters the behavior of volatile impurities during decomposition of copper sulfide concentrates. Chemical eqUilibrium calculations for chalcopyrite contaminated with enargite (Cu3AsS4) have shown that the absence of an oxidic slag allows for a complete evaporation of arsenic and subsequent separation from intermediate sulfides. The need to better assess the potential of direct sulfide decomposition has prompted the development of an experimental setup for studying the decomposition reactions. The experiment has been devised such that data on the decomposition kinetics and on impurity removal can be obtained at temperatures up to 2500 K.

Jan 1, 2003

By Michael Zinigrad

The quality of metallic materials depends on their composition and structure and these are determined by various physico-chemical and technological factors. To effectively prepare materials with required composition, structure and properties it is necessary to carry out a research in two parallel directions: Comprehensive analysis of thermodynamics, kinetics and mechanisms of the processes taking place at the solid-liquid-gaseous phase interface during welding processes and development of mathematical models of the specific welding technologies. We have developed unique method of mathematical modeling of phase interaction at high temperatures. This method allows us to build models taking into account the thermodynamic characteristics of the processes, the influence of the initial composition and temperature on the equilibrium state of the reactions, the kinetics of heterogeneous processes, the influence of the temperature, composition, hydrodynamic and thermal factors on the velocity of the chemical and diffusion processes. The model can be implemented in the optimization of various technological processes in welding, surfacing, casting as well as in manufacturing of steels and non-ferrous alloys, materials refining, alloying with special additives, removing of non-metallic inclusions.

Jan 1, 2003

By Tetsuro Ohashi, Tooru Matsumiya, Yoshio Abe

"The three-dimensional deformation of a continuously cast slab was modeled into two-dimensional deformation by developing the solidified shell of the slab. The developed solidified shell was divided into rectangular elements. The thermal strain produced as the slab is wi thdrawn over one roll spacing in the casting direction was calculated from the temperature change during that time and the increment of the geometrical unbending strain during the time was calculated from the change in the radius of curvature of the slab by assuming that the neutral axis of bending is located at the mid-thickness of the slab and that the transverse section of the slab is kept in a plane during unbending. These strains were imparted to each element as initial strains. The interaction between the elements and the overall deformation of the solidified shell were analyzed by the finite element method.The analysis was performed on a slab being cast on a machine of the circular arc type with progressive unbending. The following findings were obtained as a result. The effect of unbending is spread in the upstream and downstream directions of the slab by the shear deformation of the narrow and wide faces. As the shear deformation increases, the strain in the unbending zone decreases and the strain outside of the unbending zone increases. The effects of secondary cooling conditions, slab size, radius of caster circular arc section, compression casting, etc., were also analyzed. IntroductionTo develop a method for preventing the internal cracking of continuously cast slabs, it is important to acurately analyze the deformation of the slab and this subject has been extensively investigated. Many researchers, including the present authors, have analyzed slab bulging. (1)- (11) Analysis has also been made of thermal deformation that assumes importance in continuous casting of small-section blooms.(12)-(18) However, unbending deformation, an extremely important subject for continuous casters of the circular arc type, has not been fully analyzed."

Jan 1, 1986

By R. L. Nyirenda

An investigation of the reducibility of a cassiterite concentrate with charcoal was made in the temperature range of 1123-1373 K. The course of the reaction was monitored by a combination of sample weight loss measurements, product gas analysis, and chemical analysis of the reaction product. It was found that the cassiterite could be best reduced by a combination? of high temperature, reasonably high charcoal proportions, high charge poroslty, and the addition of a small percentage of lime. Analysis of kinetic data obtained from isothermal experiments using theory from the oxidation of carbon by carbon dioxide gave an activation energy value of 255 lci/mole for the consumption of carbon by reaction with cassiterite.

Jan 1, 1990

By J. T. I. Poijärvi

The smelter off-gas cleaning and the weak acid treatment at Outokumpu Harjavalta Metals Oy are presented and described in this paper. The smelter consists of the copper and nickel smelters and the acid plant of three separate acid plants two of which are double contact and one single plant and of one liquid sulphur dioxide plant. The preliminary cooling and flue dust separation of the smelter off....,gases from the copper ?and nickel flash smelting furnaces and converters? in the waste heat boilers and in the hot electrostatic precipitators are described. The final cooling and cleaning of the gases in the scrubbers at the sulphuric acid plant and the treatment of the weak acid in the vacuum and in the submerged combustion evaporators for the removal of impurities are presented as well as the treatment of the condensates from the evaporators. The attention is paid to the generation of sulphur trioxide in the smelter off-gas.and to the treatment of that in the weak acid bleed-off and to the utilization of the treated acid.

Jan 1, 1992

By S. E. James

EAF dust has been listed as a "hazardous waste" due to the presence of lead and cadmium, and at times chromium. The 550,00 tpy production of . .EA]' dust, estimated for the United States alone, contains more than 10,000 tpy of lead and about 250 tpy of cadmium in addition to nearly 1'00,000 tpy zinc. Even though the listing of .EAF dust as a hazardous material stimulated extractive metallurgical work worldwide, process development efforts have focused only on the recycle of the potentially-valuable zinc units. However, the recycle of the lead and cadmium, while not lucrative, is the more critical effort. Horsehead Resource Development Company, Inc. (HRD), in conjunction with its sister company, Zinc Corporation of America (ZCA), has taken a unique approach to total recycle of the toxic heavy metals found in the EAF dust. Impure oxide, produced by either a Waelz kiln or FLAME REACTOR Process and containing the lead and cadmium, is calcined in a rotary kiln at Palmerton, Pennsylvania, to produce a refined zinc-rich intermediate for ZCA's electrothermic zinc plant at Monaca, Pennsylvania. During the calcining operation, lead and cadmium are concentrated in a fume product and shipped to ZCA's electrolytic plant at Bartlesville, Oklahoma. At Bartlesville, a new hydrometallurgical circuit has been constructed and the existing cadmium plant expanded. The combined facilities permit the total recovery of cadmium to refined metal and the lead to .a silver-rich intermediate, which is sold to lead smelters. In this paper the Waelzing, calcining and new leaching facilities will be described.

Jan 1, 1990

"Mixing phenomena in a bottom blown air-stirred one-seventh water model of CLU (Creusot-Loire Uddeholm) reactor was studie9-using three different configurations of straight circular nozzles fitted axially at the bottom of the vessel. The mixing time has been determined by pH measurements at various gas flow rates, bath heights and nozzle orientations in the presence and in the absence of a second phase.Experimental results reveal that the mixing time decreases with increasing gas flow rate. For a given gas flow rate the mixing time increases non-linearly with increasing bath height. Off-center configuration gives slightly lower mixing times as compared to center configuration. It is found that the contribution of buoyancy to the total stirring energy density is very small, but its contribution increases with increasing bath height. In the presence of an upper oil layer, the mixing time increases significantly for all configurations.IntroductionIn high temperature metallurgical melts mixing is carried out by injection of a gas either from top or bottom of the vessel in order to accelerate the rates of chemical reactions and to promote bath homogenization. When a gas is injected into a liquid through a submerged lance, porous plug or nozzle, the gas, rising as a two phase plume to the surface, imparts momentum to the surrounding liquid and causes gross circulation in the bath which promotes mixing."

Jan 1, 1997

By D. L. Yopps

Platinum-group metal (PGM) flotation .. concentrate from the Stillwater Complex, MT, was subjected to biooxidation using Thiobacillus ferrooxidans in an effort to break down the sulfide minerals and liberate the ? associated PGM's for subsequent chemical leaching. Bacterial treatment oxidized up to 94 pct of the sulfide present, destroyed the PGM-bearing pentlandite [ (Ni,Fe),9Ss) mineralization, and dissolved most of the nickel in the concentrate. Results showed that increased sulfide oxidation during the biological stage led to improved PGH recovery in the subsequent. chemical leaching stage. cyanidation at 80° c proved to be the best chemical leachant tested. It removed 7.6 pct of the palladium, 94 pct of the rhodium, 97 pct of the gold, but only 34 pct of the platinum from the biooxidized concentrate.

Jan 1, 1991

By Y. Ono

In lightweight metal processing such as aluminum (AI) and magnesium (Mg), metal cleanliness is a crucial process parameter for refining, part manufacturing and recycling in order to obtain high quality parts and products. In this paper, techniques for cleanliness evaluation of molten AI and Mg using ultrasonic probes with clad steel buffer rods having high signal-to-noise ratio (SNR) are presented. Due to the high SNR of the ultrasonic probes used, backscattered ultrasonic signals from inclusions, which may be oxide films and/or particles, in molten Mg and those from silicon carbide particles, having an average size of 50f.Ull, added in molten AI are successfully detected with reflection configurations of pulse-echo and/or pitch-catch modes at an ultrasonic frequency of 10 MHz. In addition, relative cleanliness evaluation of molten Al and Mg is demonstrated. In order to establish the procedure and to investigate the optimum system configurations for cleanliness evaluation of molten metals, particle flow simulation system using water and polyvinyl chloride (PVC) particles has been constructed. Counting the number and measuring the size distribution of the PVC particles, having an average diameter of 128um, suspended in water with the PVC volume concentrations of 5ppm and 10ppm are performed with ultrasonic pitch-catch mode. The counted numbers of particles by the presented method and system have good agreement with the calculated results with a count error of less than 10% or two counts. Based on the results obtained with water simulation experiments, the prototype system for cleanliness evaluation of molten Mg by counting and sizing inclusions has been developed. Keywords: Ultrasound, Clad buffer rod, Molten metal, Aluminum, Magnesium, Inclusion detection, Cleanliness measurement, Counting, Sizing

Jan 1, 2003

By M. J. Bagshaw, J. D. Hunt, R. M. Jordan

"Continuous casting processes, and the roll casting process in particular, offer considerable potential to the Aluminium industry, both meatallurgically and economically.The three major limiting process problems that occur during roll casting are Centre Line Segregation', 'Sticking' where metal adheres to the rolls during casting, and 'Heat Line' formation. 'Heat Lines' are localised semi-continuous longitudinal defects, usually a few cms in width, where the cast metal leaves the roll bite partially molten. These defects occur at relatively low casting speeds when the mean slab exit temperature remains several hundred degrees below the solidus temperature. The objective of the work described here is to develop a better understanding of the roll casting process in general, and in particular, to understand the phenomenon of 'Heat Line' formation.A steady state two dimensional finite difference model has been developed to describe the roll casting process, incorporating a variable heat transfer coefficient through the roll bite. In the model the difference equations are formulated using a control volume method and latent heat is incorporated according to the Scheil equation. A Gauss-Seidel type technique is used to obtain the solution. Because the rate of heat evolution is non-linear the temperature in each box is determined by using a Newton-Raphson method. The solution for a box can be multi valued and therefore lead to instability particularly near the vicinity of the front. A stability 'criterion is presented which shows that to obtain a stable solution it is better to have long narrow boxes rather than boxes with small dimensions in both directions.The model explains why heat lines form in terms of the variable slab/roll heat transfer coefficient.Experimental measurements of slab exit temperatures are also presented. These were obtained on a Hunter twin roll caster for the binary AI-Cu system, at two compositions over as wide a range· of casting speeds as possible. The experimental results are compared with the predicted ones."

Jan 1, 1986

By N. M. Komkov

The main operation of obtaining zinc from sulfide raw materials by hydrometallurgical technologies is the oxidation roasting of zinc concentrates in fluidized bed furnaces. The technical-economic parameters are determined by the parameters of the roasting process, which depend on the composition of the initial raw materials, the temperature of the bed and on other factors. The predetermined roasting temperature is maintained due to the change of specific efficiency as well as to the quantity of the heat removed from the bed. The efficiency of caissons depends at a high degree on the composition and the thickness of the accretion formed on the surface of the caissons. Forecasting the roasting results is impossible unless we know the mechanism of the accretion formation. The aim of the present paper is the thermodynamic analyses of the behavior of the charge compositions under roasting and the determination of the potential mechanism of the accretion formation. The thermodynamic analyses show that under conditions of the oxidation roasting the thermodynamic probability of the formation of zinc sulfate is higher than the probability of the oxide formation until a temperature of 873°K is reached. The thermodynamic probability of the formation of the lead sulfate is higher than the probability of oxide formation in the entire temperature range of roasting. The probability of formation of ferrites and silicates of zinc decreases only insignificantly the sulfate stability. The results of the investigation of the accretions composition formed under roasting of concentrates with particle sizes less than 0.02 um (60%), containing 65% of sphalerite (ZnS), 12% of pyrite and chalcopyrite (FeS2 and CuFeSz2 each, 3% of galenite (PbS), 7% of silica and other non-ore minerals, have shown that the composition of accretion varies depending on the depth of the accretion layer. The accretions on the caissons and the thermo-siphons consist mostly of zinc sulfate (more than 50%). The accretions of forchamber consist mostly of zinc oxide. They also contain ferrites and silicates. The formation of the sulfate zinc accretion in the cold parts of the fluidized bed furnace (the caissons and thermo-siphons) may be explained by a lower temperature on the surface and probably by a catalytic influence of the present oxides in the formation of S02 and sulfates. The nature of the structure of the accretion in the hotter parts of the furnace may supposedly be explained by the formation of elemental vaporous zinc during roasting.

Jan 1, 2003

By Bora Derin

This work deals with the recovery of valuable metals from the ancient copper smelting slags located in Küre-Turkey. In this process, copper and cobalt were recovered in metallic form and/or as their compounds, whereas iron was recovered as magnetic oxide or pigment. Abrasive grit material was produced using reduced final slag. The process stages involved carbothermal reduction in a DC arc furnace, granulation, leaching, chemical precipitation, selective sulfidizing roasting and product preparations. In this paper, the process stages were described as theoretically and experimentally whereas slag and products were characterized in detail.

Jan 1, 2003

By Klaus Bauckhage

Phase-Doppler-anemometry (PDA)-measurements have to be taken from representative measuring positions from inside the spray cone, helping - with the support of simulated data of improved process models - to describe the multiphase flow situations within the spray cone - and accordingly to that - the heat transfer conditions for the rapid cooling and (partly) solidifying melt droplets before their impact onto the substratddeposit. Simulations and PDA-measurements thus give the base to confirm the hypothesis of the existence of a semisolid mixed-layer and it's influence on the resulting material structure during compaction. The dispersed particles in the spray cone exhibit a cooling and solidification process within a split of a second, which leads - as far as the particles solidify - to a dendritic structure with very short dendritic arm spacings. This causes within the particles extremely short distances for the following equalizing diffision processes taking place on a high temperature level (between liquidus and solidus) in the semisolid mixed-layer of the deposit and explaining the short residence times within this zone of only seconds up to a few minutes. This and the fact that the globular structure of the mushy zone (in the semisolid mixed-layer) leads to an unidirectional crystallization process over very short distances also explains the chemical and morphological ,homogeneity of the sprayed material. The dynamics of these process steps, the very special buffer function of the mixing layer during parameter variations as well as the controlled cooling process of the preform in order to avoid hot cracks influence the quality of the material. Due to the necessity of measuring and controlling the particle bound mass-, momentum- and enthalpy- fluxes to the deposit the PDA-technique has been adapted and modified in order to receive in-line and (in the future) also on-line data from the dynamics of the multiphase flow conditions within the spray chamber.

Jan 1, 1999

By Bo Zhou

During secondary aluminum recovery, complex aluminum scraps are melted and refined often in a rotary melting furnace and the aluminum metal has to pass through a molten salt layer and melt down in a bottom aluminum bath. Previous experimental study and industrial observations have indicated that salt shell formation and re-melting on the metal solids in the early stage plays a critical role in the overall melting process of the scrap. In the present paper, mathematical models are developed to simulate the process of salt shell formation and its re melting, as well as aluminum melting in the molten melt. Influence of the salt layer properties, the residence time of the metal particles in the salt layer, the particle size, the temperature of bulk melt were investigated. Reasonable agreement with the measurement data was reached. The developed melting model will be used to construct a population balance model of the scrap melting behavior for a rotary melting furnace, taking into account the distributed characteristics of the scrap. Finally, an overall process model based on Computational Fluid Dynamics (CFD) for the rotary furnace will be constructed, coupling with the population balance model for the scrap melting.

Jan 1, 2003

By Guy Xueyi

The environmental impact assessment of the Imperial Smelting Process for metallic zinc and lead production in Shaoguan Smelter, China, was carried out by the life cycle assessment method. The detailed inventory analysis of the Input/Output in the process during 1998-2000 was conducted and the allocation was done among the main products of zinc, lead and sulfuric acid, according to the system expansion and substitution principle, The environmental impacts were assessed by using the following five Eco-indicators: Gross Energy Requirement (GER), Global Warming Potential (GWP), Acidification Potential (AP), Heavy Metal Toxicity' (HMT) and Solid Waste Burden (SWB). The results from this study are useful to address the environmental situation of the technology practice in this smelter, and provide a scientific basis for the further improvement.

Jan 1, 2003

By Yasumasa Hattori

An extensive study including fluid dynamic calculations, cold model tests, pilot plant tests as well as measurements in a commercial flash furnace was carried out in order to develop a new Sumitomo flash smelting concentrate burner. The pressure measurements in the commercial burner indicated that the premixing of the concentrate and reaction air in a burner was insufficient. Pilot plant tests showed that enhancement of the premixing of the concentrate and reaction air is very effective for improving the burner performance. Using the additional pressure drop of the reaction air as an indicator of the premixing, a new type Sumitomo premixed concentrate burner was developed.

Jan 1, 2003

By Milorad Cirkovic

Kinetics of copper concentrate oxidation in roasting processes in a fluidized bed reactor has been studied at temperatures between 600°C and 720°C using particles of 0.038 to 2.5 mm in average size. The analysis of composition of samples has been done by chemical methods. Phase composition has been determined by Siemens X-ray equipment with Cu anticathode and Ni filters at a voltage of 40 kV and a current of 18 mA. The content of sulphur has decreased from 33.23 to 19.02 mass percent with the increase of temperature, but the content of Fe304 has increased from 0.15 to 17.14 mass percent. The new mechanism of copper concentrate oxidation in a fluidized bed reactor is proposed in this study. It has been shown from the mathematical model that the velocity of oxidation of copper concentrate between 600°C and 720°C is virtually controlled by the rate of diffusion of 02 through the layer of reaction product.

Jan 1, 1999