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By S. Goto, S. Yamashita, K. Hata

"The average consumption of zinc dust for purification of zinc leaching solution is more than 25 kg per tonne of electrolytic zinc. Authors proposed to remove impurities in zinc leaching solution by electrolysis instead of cementation by zinc dust. The effects of copper and arsenic on electrodeposition of cobalt in zinc sulfate solution were examined fundamentally using a potentiostat. It is observed that cobalt is easily deposited on a cathode at potentials under -480mV with arsenic. Mesh cathodes of stainless steel and lead anodes were used in a small electrolytic cell and the electrolyte was circulated through 'the electrodes during the electrolysis. The effect of electrolyte circulating rate , pH, cell temperature, current density, and concentration of copper and arsenious ions on removal of cobalt were studied. Removal of Cd and Ni are also examined.IntroductionCobalt is difficult to remove from a zinc leaching solution by a simple cementation reaction using zinc dust. However, it is easily precipitated by zinc dust with co-addition of arsenious or stibinous oxide and copper ion in practical operations(I), (2), (3). The consumption of zinc dust for purification is 16-152 kg per tonne of electrolytic zinc and 65% of this zinc dust consumption is used for cobalt purification. The average retention time for purification of cobalt is 4.5 hours (1). A more economical process for purification is desired instead of zinc dust. The mechanism of this acceleration effect of copper and arsenious oxide on removal of cobalt are explained by the authorsas follows; a galvanic cell is formed between zinc dust and copper which is precipitated firstly, and cobalt is reduced on copper as Co-As alloy by this galvanic current(2). This assumption was confirmed in experiments using a galvanic cell with a membrane( 4). The following galvanic reactions occur between zinc dust and copper precipitate; on copper cathode,2H+ + 2e -= Hz(g)2Coz+ + 2HAs02 + 6H ++ 10e -= 2CoAs + 4HzOand on zinc anode,Zn = Zn = 2+ 2e –This galvanic current becomes almost zero in a zinc sulfate solution which includes only cobalt and no arsenious oxide, and cobalt is weakly deposited on a copper cathode. Cobalt deposition requiers a high degree of cathodic polarization. However, the galvanic current flows almost constantly in an electrolyte, which includes arsenious oxide, and the cathode potential is kept at about -500mV. Cobalt is precipitated as Co-As on the cathode.The authors assumed that cobalt may be removed by electrolysis at a very low current density instead of zinc dust and the following experiments were carried out. In the first part of this paper, the fundamental experiments using a potentiostat on the behaviour of cobalt in zinc sulfate solution are described. In the second part, the results of the electrolysis are reported. Cobalt is removed by a new type of an electrolytic cell, which was desigoed to <Iccelerate the rate of deposition of cobalt. The removal of cadmium and nickel in a solution which includes cobalt and arsenic are also examined."

Jan 1, 1997

By R. Shimpo

Equilibrium calculations by a computer may sometimes fail in giving solutions when the system includes a large number of components and more than three phases, and especially when no definite information about stable phases is given. An improved method of calculation is presented in which the number of phases need not to be initially fixed, phases can appear or disappear in the course of&apos; calculation and a new method is combined with the Newton-Raphson method to obtain solutions easily. The improved method is applied to the copper smelting operation and all the successive stages of the operation are successfully simulated.

Jan 1, 1983

By F. Shahbazian

attempt to systematize the knowledge on slag viscosities, the present work was carried out. The Among the physical properties of slags, viscosity is very important in understanding the mass out in the temperature range 1438-1762 Q The rotating cylinder method was used in the viscosity measurements. Crucibles and spindles made out of pure iron were employed. The transfer phenomena in metallurgical processes. The viscosities of fayalitic slags are of great interest in the non-ferrous metal industry, with special reference to copper production. In an slags were prefused before the measurements. In order to take into account the vaporization reactions involving CaF2, pre- and post measurement samples of the slags were chemically analysed and the compositions were ascertained. The results show that in the case of the CaO-SiO2 system, CaF2 additions tend to decrease the viscosity, in accordance with the expectations. In the case of the "FeO"-SiO2 system, at higher "FeO" / SiO2 ratios in the slags, a reverse trend was observed. The results are discussed on the basis of a viscosity model for silicate melts developed in the present laboratory as well as the structural considerations of silicates.

Jan 1, 2000

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 &apos;solvent&apos; or &apos;transport agent&apos; 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 Gerald Onyedika, Tochi Onwumere, Martin Ogwuegbu

"The kinetic study for the leaching of iron from cassiterite ore in KOH solution was studied. The effects of KOH concentration, particle size and reaction temperature on the leaching rate of iron were also examined. The results of leaching studies showed that the leaching of iron from cassiterite ore in KOH solution is significantly influenced by the reaction temperature, KOH concentration, and decrease in particle size. The study showed that 90.62% of iron ore was leached in 8M KOH solution at 80°C within 120 minutes. The experimental data were well evaluated using the shrinking model for surface chemical reaction and diffusion control through the product layer. The activation energies for the iron ore dissolution using the two models were calculated to be 32.06KJmor1 and 97.97 KJmor' respectively.IntroductionIn recent times, there has been increasing attention on the kinetic study of mineral dissolution. In most of these studies, the experimental results were analyzed with a suitable shrinking core model under the assumption that the ore is a homogeneous spherical solid phase [1-4]. A study of the dissolution kinetics of a Nigerian cassiterite ore by hydrochloric acid showed that increase in the hydrochloric acid concentration is accompanied with increase in the amount of cassiterite ore dissolved at various times [4]. The optimal concentration was found to be 4.0M HCl, after which there was a decline in the amount of the ore dissolved, which showed that the concentration of the reagent has a significant effect on the leaching rate of the ore. Also in studying the effect of stirring speed on the rate of cassiterite ore dissolution while keeping other conditions constant for 120 minutes, the result showed that the rate of cassiterite ore dissolution was dependent on the stirring speed over a range of 0 to 630 rpm. Above 360 rpm, the stirring speed no longer had any effect on the solid dissolution. The dissolution rates of cassiterite were analyzed using a suitable shrinking model. The results showed that the reaction was controlled by the diffusion of tin through the porous product layer, a reaction order with respect to hydrogen ion concentration of 0.92 M and activation energy of 50.05KJmor'. In another kinetic study on the leaching of a low grade niobium-tantalum ore with concentrated KOH solution the effect ofreaction temperature, KOH concentration, agitation speed, particle size and alkali-to-ore mass ratio on the dissolution rate of niobium were examined [5]. The result of niobium leaching from low grade niobium-tantalum ore with concentrated KOH, solution at different agitation speeds showed that the dissolution rate increased with increase in agitation rate. In the case of particle size effect, the results show that small particles require much shorter time for complete dissolution than the large ones."

Jan 1, 2013

By Peter Brown

The present work involves the study of Chemical Vapor Deposition (CVD) of silicon carbide from the methyltrichlorosilane (MTS) - hydrogen system. A computer program, SOLGASMIX has been employed to calculate the equilibrium compositions of the gaseous and condensed phases in the MTS - H2 system. The results indicate the range of parameters such as temperature, pressure and species concentrations, required to deposit the single phase Sic under thermodynamic equilibrium conditions. A mathematical model for describing the transport phenomena and the rate of deposition of Sic onto a thin rod in a vertically-oriented hot-walled CVD reactor has been developed. Exper iments were conducted using the same operating conditions as those used in the model in order to validate the mathematical predictions. The predicted rates of deposition were found to be in good agreement with those obtained experimentally. The model can be used to study the effects of various operating parameters on the rate of Sic deposition on a fiber.

Jan 1, 1992

By Avijit Moitra

The behavior of the solidifying shell in the early stages of solidification has an important influence on the final quality of continuously-cast steel slabs. In order to understand the thermal and mechanical behavior of the shell, a two-dimensional transient piecewise-coupled finite-element model has been developed. The model simulates a transverse section of the slab as it moves down through the mold and incorporates the effects of heat conduction, solidification, shrinkage, turbulent fluid flow, thermal distortion of the mold and the visco-plastic behavior of the steel. Coupling between the thermal and the mechanical model is based on the mutual dependence of heat transfer across the interface between the shell and the mold and the size of the gap. The effects of mold distortion and taper on the gap size are also included. The effect of fluid flow has been incorporated via a heat flux imposed at the solid-liquid interface, which is obtained from a separate fluid flow model. The high temperature creep and plasticity of the steel is incorporated through a unified constitutive law defining the inelastic strain rates as a function of temperature, time and stress state. The model can be applied to various problems in continuous casting, such as the formation of surface defects and the design of mold taper.

Jan 1, 1992

By Pengfu Tan

NiModel, a thermodynamic model, database and computer program, has been developed to predict the distribution behavior of Ni, Cu, Co, Fe, S, O, As, Sb and Bi, and heat balance in the nickel pyrometallurgical processes such as Outokumpu flash smelting, Outokumpu direct high-grade matte smelting, INCO flash smelting, and Peirce-Smith converting processes. In this model, as much as 16 elements (Ni, Cu, Co, Fe, As, Sb, Bi, S, O, Al, Ca, Mg, Si, N, C and H) are considered. The compositions of matte, slag and gaseous phases, and heat balance are calculated using the thermodynamic data and the activity coefficients of the components derived from the experimental data. The model predictions were compared with the known industrial data from Kalgoorlie Nickel Smelter in Australia, Outokumpu Harjavalta Nickel Smelter in Finland and INCO Metals Company in Canada, and an excellent agreement was obtained. In this paper, the applications of NiModel in the nickel pyrometallurgical industries have been presented. NiModel has been used by Jinchuan Group Limited in China.

Jan 1, 2004

By Fumitaka Tsukihashi

Increasing amounts of steel scrap are being used as resources for steelmaking. Therefore, there has been a growing interest in the removal of harmful tramp elements such as antimony, zinc, tin, arsenic, bismuth, lead and copper from the molten steel. The problem that should be solved is the economic removal treatment of residual tramp elements in the steelmaking processes and the production of high quality steel by reducing the effect of the contaminated tramp elements and satisfying the environmental regulations. In this paper, the available thermodynamic data of the residual tramp elements in the molten steel arc summarized and the possibility of the removal of residual tramp elements from the molten steel is thermodynamically estimated.

Jan 1, 2003

By Y. A. Chang

The objective of the present study is to evaluate and compile the relevant phase equilibria and thermodynamic data reported in the literature for the ternary system Cu-Fe-S. It is hoped that the results presented here will be useful to practising engineers and scientists in industry who are attempting to improve continually the existing processes of copper extraction and refining. At the same time, the present work will undoubtedly reveal the lack of some basic data which are important for the improvement of our existing extractive processes. Lastly, this work will also show that the development of theoretical models for the alloy phases in the Cu-Fe-S system is essential before complete consistency between the phase equilibria and the thermodynamic data can be achieved.

Jan 1, 1976

By John C. Taylor

With growing emphasis on energy conservation and increased concern over the presence of heavy metals in the environment, it is fortunate that most metals are readily recycled. In this respect, metals have a significant advantage over plastics and similar materials used as metal substitutes. For many years a secondary industry has processed scrap copper, nickel, lead and zinc to produce refined metal which has, to varying degrees, influenced the price and displaced the production of primary metal. This paper reviews some of the challenges the industry will face and the changes in process technology which will be required as pressure mounts to increase the amount of metal recycled. In the case of most base metals, this will have an impact on primary metal production; as the tonnage of metal recycled increases, the requirement for primary production, or new metal, will depend more and more on the growth in consumption.

Jan 1, 1993

By S. G. Kumar, R. G. Reddy

"Niobium aluminides offer the advantage of higher high temperature capability compared to other intermetallic aluminides due to the refractory nature of niobium. However, the reaction sequence in Nb-Al system is sluggish and currently there is a great interest in the processing aspects of these materials. In the present study, a systematic investigation was undertaken to compare the effect of different powder metallurgy processing routes on the phase relations and microstructure of 66Nb-22AH2Ti (in atom percent) alloy. The three different process routes adopted were: (i) cold pressing followed by reaction sintering; (ii) cold pressing and hot pressing followed by sintering; and (iii) arc melting, hydride-dehydride process to make the alloy powder followed by cold pressing and then sintering. The samples are analyzed by XRD, Optical Microscopy, SEM-EDS and EPMA. The analysis showed that alloy pellets made from pre-alloyed powders i.e., arc melting followed by hydride-dehydride process, gave good densification and more Nb3Al formation.1. IntroductionTo improve the performance standards of turbine engines, materials scientists are challenged to develop materials that have· high thrust-to-weight ratio with high specific strength, high specific modulus and good environmental properties at elevated temperatures. The conventional high temperature materials like nickel based superalloys are high in density and hence many of the high temperature materials scientists have focussed their attention on intermetallic aluminides like Fe-AI, Nb-AI, Ni-AI and Ti-AI in recent years. The phase relations and properties of alloys based on Fe-AI, Ni-AI and Ti-AI are fairly well known whereas little is known about the alloys based on niobium aluminides."

Jan 1, 1996

By J. P. Hager

The formation of the vapor complex AgFeC14 (g) baa been identified and its thermodynamic properties determined. The vapor pressure of silver chloride can be enhanced by a factor of 15-20 due to the formation of the vapor complex. The vapor pressure of both AgCl (g) and AgFeC14(g) were measured using a double-zone transpiration .technique. Gibbs free energies have been determined for the vapor transport reactions. Laboratory kiln tests were conducted to confirm the enhanced recovery of silver through the formation of the AgFeC14(g) vapor complex and to indicate the opportunities for process development using this new vaporization chemistry.

Jan 1, 1985

By Boxun Lu, Juan Wei, Kun Chen, Wanlin Wang, Lejun Zhou

"Slag system is an indispensable part during the continuous casting process, and playing various important roles like absorbing inclusions, modifying heat transfer rate, preventing oxidation of molten steel, etc. to ensure the smooth process and excellent slab quality. However most slags contains more than 8% fluorides which tend to introduce a series of environmental and health problems. This study involves the research of the removal of fluorine through the chemical composition optimization. Through the studies of CCT, DHTT, XRD and SEM, it has been successfully founded that the crystalline phase of Ca11Si4B2O22 discovered in this study shows very similar crystallization property as Cuspidine (Ca4Si2O7F2), which is the most important crystalline phase in the current fluorine bearing slags. Moreover, the optimized free/low fluorine slag shows the opportunity to replace conventional high-fluorine mold slag for casting medium carbon steels that is regarded as the bottleneck of green slag development for continuous casting.IntroductionMold flux has been widely used in continuous casting to control heat transfer, lubricate the strand, absorb inclusions, provide insulation and prevent oxidation of the molten steel[1-3]. It usually contains fluorides, like CaF2, NaF etc., which are used to control the viscosity and solidification temperature of mold fluxes [4-5]. However, the presence of fluoride leads to corrosion of equipment, serious environmental pollution (toxic volatiles and water pollution), and high processing cost of cooling water[6-7]. Therefore, the study of low or free fluorine mold flux is of interest and attracts worldwide attention.S. Y. Choi et al. [4] used B2O3 as a substitute for cuspidine in steel B2PB2) however, B2O3 content was extremely high (up to 30 w%). Other studies have investigated F-free mold flux by adding or optimizing components as MgO, Li2O, B2O3 et al[8-11]. However, most of these focused on the melting and viscosity issues or for low or ultra-low carbon steels, where crystallization tendency is not significantly strong. Very few studies regarding to the development of low/free Fluorine mold flux for casting medium carbon (MC) steels have been conducted, due to the difficulty of the crystallization and heat transfer control without the formation of cuspidine."

Jan 1, 2014

By Masaru Imaizumi, Hiroyuki Nomura, Mitsuharu Takita

"Cast iron possesses many superior characteristics caused from precipitated graphite structure, for example, castability, wear resistance, solid lubrication, damping capacity. But the more graphite hyper-eutectic cast iron contains, the lower its mechanical strength becomes, because graphite gives a negative effect to strength of cast iron. In addition, primary graphite tends to segregate during solidification, so uniform materials are difficult to be produced.In this study, authors introduced semi-solid processing in developing new and high quality cast iron. A series of semi-solid processing experiments were carried out to clarify the effect of stirring condition; solidification temperature and etc. on microstructures and characteristics of cast iron. In particular much attention is paid to the appearance of ternary eutectic zone at the final stage of solidification. As the results advanced hyper-eutectic cast iron was obtained with high quality of both the mechanical strength and wear resistance. As for the mechanical strength, 300MPa and 0.60% are obtained as the tensile strength and the elongation values, respectively, under the controlled stirring condition. This indicates that semi-solid processed hyper-eutectic cast iron is used prospectively without spheroidization.IntroductionCast iron has various good properties such as wear resistance, solid lubrication, damping capacity and machinability. The characteristics of cast iron are mainly decided by graphite structure, namely graphite shape and its distribution in the matrix. Mechanical strength of cast iron is large in the case of small quantity of graphite particles which are precipitated uniformly, however, it becomes small in the case of large quantity of graphite precipitated flakily."

Jan 1, 2000

By N. A. Warner

To filly secure the environmental and social acceptability benefits of making a sulphide smelting facility and its ancillary sulphuric acid plant or other means for fixing sulphur, a virtually zero gas emission operation, it will be necessary to utilise exclusively technically pure oxygen. The strategy proposed for preventing the smelter from overheating involves highly efficient energy transfer by promoting sulphur trioxide formation at a relatively higher temperature than normal. A closed-loop gas circuit uses an eductor system actuated by the process oxygen to recirculate sulphur trioxide and unconverted sulphur dioxide back to the smelter, the endothermic dissociation of sulphur trioxide becoming a major contributor to the removal of excess heat. The only gases leaving the system relate to the bleed of nitrogen impurity introduced in the tonnage oxygen.

Jan 1, 1998

By Jillian Spindura

This work investigates the carbothermic reduction of the complex sulphide mineral, pentlandite, in the presence of lime. The effects of change in temperature and the use of different carbon sources are studied and the role of these variables on the reducibility of pentlandite mineral is discussed. The microstructures of the heat-treated pellets are examined using X-ray diffraction and scanning electron microscopic techniques. The latter analytical method also allows any variation in the morphology and composition of the metallic phases formed, with temperature, to be considered. The kinetics of the reduction process is studied and the magnitude of the overall activation energy is determined from the plots of percentage reduction versus time.

Jan 1, 1996

By D. Bruce Wilson

The reaction of oxygen and solid aluminum produces the well-known surface coating of aluminum oxide, Al2O3. Thermodynamic properties and kinetic mechanisms of this reaction are extensively documented. Less well-defined are the corresponding liquid phase reaction and reactions which would be characterized. as &apos;burning&apos; of aluminum. This paper reviews the solid aluminum-oxygen reaction as a foundation for discussing the flammability of aluminum in oxygen-enriched atmospheres. Appropriate thermodYDan3ic analysis and kinetic reaction mechanisms are developed. Available models of aluminum burning are reviewed and evaluated, The appropriate information for design of engineering applications of aluminum in oxygen atmospheres? is summarized.

Jan 1, 1996

By M. Kawakami

In relation to the designing of a new-type blast furnace, the reaction of carbonaceous materials with C02 is expected to occur at as low temperature as possible. In order to get a highly reactive carbonaceous material at low temperature, the reaction kinetics was investigated by measuring such quantities as the reaction rate from weight loss, the amount of CO adsorption and specific surface area by BET method. The reaction rates were large in the order of the Bintyo char, metallurgical coke, graphite and glassy carbon. If the rate was converted to the rate per unit area, however, those of the Bintyo char was smaller than that of graphite. Thus, it is suggested that the rate of the Bintyo char is influenced by the pore diffusion of C02. The rate had a positive relation with the amount of CO adsorption, showing that the rate determining step would be the desorption of CO from the active side on the surface. The rate independent of surface area was derived, combining al\ the obtained data.

Jan 1, 2003

By Kotaro Ogura

"The electrolysis process in which CO2 is selectively reduced to C2H4 at a three-phase(gas/solution/metal) interface on a copper-mesh electrode has been developed in a concentrated solution of potassium halide. At open-circuit potential, CO2 is captured on the electrode by being inserted into the double-layer consisting of halide anions specifically adsorbed and potassium cations which are located in the Helmholtz inner and outer layers, respectively. CO2 thus activated is subjected to the electrochemical reduction. In the early stage of reduction, CO2 is converted to formate radicals that are adsorbed on the electrode by taking the place of halide anions. The reductive coupling of these radicals results in the formation of intermediates such as -CH2C(O)- and CH2=CH-, and C2H4 is finally produced. The catalytic activity of the electrode process involving the insertion of CO2 into the double layer is not deteriorated at all during the electrolysis, and the continuous reduction of CO2 to C2H4 is possible with the addition of inorganic acid under the assistance of natural energy.Carbon dioxide is a serious pollutant released from fossil fuel power station, internal combustion and many industrial operations. The easy release of CO2 to the air has caused the global warming, and the technique which intends to curtail CO2 by pushing it back into the ground has been suggested. However, this problem should be greatly mitigated if CO2 can be converted to innocuous substances. Especially, the reuse of CO2 as fuels and chemicals is extremely effective not only for the mitigation of the global warming but also against the depletion of the fossil fuel reserves. Several processes for converting CO2 to valuable compounds have been proposed including hydrogenation over heterogeneous catalyst at high temperature and electrochemical and photochemical reduction. In the conversion and cutback processes of CO2, however, it is of importance that the process is feasible under mild conditions, because the secondary generation of CO2 is feared if high energy is required and supplied with a fossil fuel. In this meaning, the electrochemical reduction of CO2 taking place at room temperature, which is similar to photosynthesis, is promising. From the practical point of view, it is further necessary that the conversion rate is high enough and the product is satisfactorily valuable."

Jan 1, 2008