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By Katsutoshi Inoue

The sulfuric acid leaching of spent hydrodesulfurization catalysts yields an acidic solution rich in rare metals such as molybdenum, vanadium, cobalt, and nickel in addition to aluminum. For the purpose of separating and recovering the rare metals from the solution, basic solvent extraction characteristics of the metals involved with commercially available acidic organophosphorus reagents like TR-83, PC-88A, PIA-8 and CYANEX 272 as well as aliphatic alpha-hydroxyoxime LIX 63 from sulfuric acid media were investigated in the present work. It was demonstrated that CYANEX 272, PIA-8 and LIX 63 possessed excellent selectivity for molybdenum and vanadium over the other metals at comparatively low pH. Further, recovery of molybdenum and vanadium from the total leach liquor by the selected extractants was discussed. Additionally, in order to achieve preferential separation and recovery of cobalt and nickel over an appreciable amount of aluminum from the raffinate obtained after recovering molybdenum and vanadium, a systematic investigation was conducted on synergistic extraction behaviors of the mixed solvents of LIX 63 in combination with a series of acidic extractants such as CYANEX 272, PIA-8, PC-88A, D2EHPA, TR-83 and OPEHPA for cobalt, nickel and aluminum. It was elucidated that all of these mixtures could exhibit a good synergistic effect for extraction of cobalt and nickel, and that the lower the pKa of the acidic extractants, the greater the synergism. Contrarily, the extraction of aluminum, was considerably suppressed by LIX 63. Effective extraction of cobalt and nickel away from aluminum was accomplished from the sulfate solution at low pH (1.0 - 2.5) with the mixtures. In particular, the mixtures consisting of LIX 63 and CYANEX 272 or PIA-8 appeared to be the most feasible and economic from an industrial point of view, yielding acceptable separation efficiency for cobalt and nickel over aluminum and .a low acidity requirement for stripping cobalt and nickel as well as negligible degradation of LIX 63. Aluminum can be readily recovered as sulfate salt from the raffinate obtained after recovering molybdenum, vanadium, cobalt and nickel as outlined above by conventional crystallization method.

Jan 1, 1995

"Hematite pellets were electro-deoxidized to iron in molten sodium hydroxide to produce iron containing about 10-wt % oxygen. The anodic reaction was the evolution of oxygen on an inert nickel anode. Before the electrochemical reaction, there is a reaction between sodium hydroxide and ferric oxide to form sodium ferrite and, in order to compensate for the reduction in sodium oxide content, 1 wt % sodium oxide is added to the melt. In a laboratory cell, the cell voltage was 1.7 V with a current density of 5000 A m-2, a current efficiency of 90% and an energy consumption of 2.8 kWh kg-1.Introduction The iron and steel industry contributes about 2.3 bn tonnes/annum of the carbon dioxide to the atmosphere, which is about 10% of the total, and some believe that, in order to prevent a catastrophic rise in the earth’s temperature, carbon dioxide emissions must be reduced by 50% come 2050. However, by 2050, it is likely that the iron and steel industry would have grown significantly so that the production may have risen to 2 or 3 bn tonnes/year so in order to meet the 50 % reduction on today’s figure, the carbon dioxide may have to be reduced to 25% or less, which is a very demanding requirement. There are probably three ways of reducing the carbon dioxide output:1. By capture and sequestration, but this may be technically very demanding.2. Reduction using hydrogen in place of carbon."

Jan 1, 2009

By Li. Jiarong, Zuojian Liang, Qingyan Xu, Baicheng Liu, Shizhong Liu, Hailong Yuan

Single crystal solidification of turbine blades is a key technology for the production of reliable and high efficiency gas turbines. The solidification process of single crystal investment castings causes a number of problems that have to be solved such as the increase of casting defects and complexity of production process. Computer modeling and simulation is helpful to predict the defects and improve the process design. In the paper, a mathematical model for three dimensional simulation of solidification and single crystal growth of investment castings was developed based on CA, mechanism of crystal growth and basic transfer equations such as heat, mass transfer equations. Many factors including constitutional undercooling, curvature undercooling and anisotropy, which had vital influences on microstructure evolution, were considered in the model. Temperature, crystal growth interface and structure defects of investment castings of single crystal superalloy were investigated at withdrawal rates of 4.5mm/min and 7mm/min. Simulated results showed that microstructure evolution and structure defects were predicted reasonably and calculated results were coincident with experimental ones. The study indicated that three dimensional solidification simulation technique is a powerful tool for understanding the fundamental of solidification and the formation of structure defects in single crystal investment castings and finally for optimizing process design.

Jan 1, 2004

By Jenq-Gong Duh, Jyh-Wei Lee

"Hard chromizing process is a method for developing a surface modified coating providing wear, corrosion resistance and high temperature surface protection. Two carbon steels with 0.45 wt% and 0.95 wt% carbon contents, respectively, were chromized with pack cementation process at 950'C for 4 and 9 hours, respectively. The phase transformation and microstructure phenomena of chromized coating layer and matrix of two steels were studied with X-ray diffractometer and electron probe microanalyzer. (Cr,Fe)23C6 and (Cr,Fe)7C3 carbides and (Cr,Fe)2N1-x nitride phases were observed on the chromized surfaces. The thickness of chromized layers obeyed the parabolic rate law. The mechanism and diffusional kinetics of the chromizing process were proposed. The diffusivity of chromium in the (Cr,Fe)7C3 carbide phase was calculated using the moving boundary method.IntroductionChromizing process is one of the surface treatment technologies that can produce a chromium contained surface layer with sufficient corrosion and wear resistance on the steel matrix [1-7]. The relatively low cost and no ""line-of-sight"" restrictions are main advantages of chromizing. Adequate bonding strength of these coatings to the substrate was reported [7]. Chromizing process can be classified into soft chromizing and hard chromizing [2]. Soft chromizing is applied to steels containing less than 0.1wt% carbon through which chromium will be diffused. High temperature oxidation resistance improvement is the main purpose of soft chromizing process. On the contrary, the hard chromizing can be applied to steel containing more than 0.3wt% carbon, and very hard chromium nitride and carbide layers will be formed on the surface, which are very resistant to wear, corrosion and temperature [5-7]. In the previous studies on the Fe-Mn-Al-Cr alloy [5,7] and carbon steels [6], the thickness (X) of chromizing layers was analyzed and found the parabolic rate Jaw prevailed:"

Jan 1, 2004

By D. C. Azubike

Wolframite (FeWO4) usually having cassiterite (SnO2) as a major impurity is a primary source of tungsten. Its direct reduction/carburisation with carbon in the temperature range 1000-1400°C, and with hydrogen at 600-900°C followed by carburisation with CO at 900°C are described. Depending on the conditions and reactants employed, Fe, Fe2W, B-Sn,WC, W2C, Fe3W3C and Fe6W6C are the products. Tin was found to inhibit the overall reduction and carburisation reactions significantly. The potential for either efficient separation of iron and tungsten or a one-stage production of an iron-based metal carbide composite is discussed.

Jan 1, 1992

By Lamar S. Todd

The direct production of metal from a sphalerite concentrate is an attractive route for primary zinc. A series of operations and conditions have been selected to efficiently cause the following overall exothermic reaction. The process uses a continuous circulation of molten copper for material and energy transfer between the unit operations. Sulfide concentrate is reduced with an excess of superheated copper to make a copper alloy and white metal. The alloy is stripped of volatile metals under vacuum and some metals can be separately condensed. The residual copper and the white metal are fed into a copper converter to be blown with oxygen for desulfurizing and the superheated copper is recycled. The paper will include a detailed material flow sheet for the process, discussion of the operating conditions of the individual units, behavior of minor elements, and zinc quality.

Jan 1, 1999

By K. Kalgraf

The motion and stability of the metal/electrolyte interface is determined by Navier-Stokes equation. The equation may be decomposed into two independent equations by taking the divergence and curl of Navier-Stokes equation. The divergence determines the motion and stability of magneto-gravitational waves. The curl of Navier-Stokes equation gives an equation containing only velocity and magnetic field, and states that the magnetic field is driving a circulation pattern in the cell, and this magneto-flow has its own stability conditions. The waves are called Alfven waves, and their stability properties are related only to magnetic field and geometry.

Jan 1, 2001

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By F. J. J. van Loo, A. A. Kodentsov, J. A. van Beek, M. R. Rijnders

"A periodic layered morphology of the reaction zone has been observed in several annealed solid/solid diffusion couples, including metal/metal and metal/ceramic couples. This morphology is characterized by a regular array of alternating layers, which are either single-phase layers or bands of particles embedded in an intermetallic matrix phase. A description of several systems showing periodic layer formation is given. It is shown that the periodic layered structure with the single phase layers and the one with the bands of particles have a different mechanism of formation.IntroductionSolid state reactions in ternary systems can produce a variety of reaction zone morphologies if there are two or more reaction products. Three types of morphology have been described in detail: 1) simple layered; 2) isolated precipitates in a singlephase layer; 3) interpenetrating columnar (lamellar) or interwoven structure. Understanding the factors that govern the formation of different morphologies is of importance in many fields of engineering. For solid state displacement reactions the conditions governing the formation of these morphologies are well understood [1-4]. For example, the development of a layered or aggregate reaction zone depends on the relative diffusivities of the components through the reaction products.This paper is concerned with the periodic layered morphology which has been observed in various solid state systems. We consider this to be a fourth type of reaction layer morphology. Two manifestations of periodic layered morphology may be distinguished. One form consists of regularly spaced layers of particles of one reaction product embedded in a matrix phase (another reaction product). The other form consists of single-phase layers embedded in a matrix phase. It will be shown that each manifestation has its own mechanism of formation. In section A we consider a system (Ag/Ti-foil/Si) in which periodic layer formation will be explained as a special case of the Liesegang phenomenon. In section B we consider systems where the periodic layered structure has a different origin."

Jan 1, 1996

By D. E. Woolley

The rate of reduction of iron oxide from calcia-silica-alumina slag by carbon in liquid iron has been measured over the temperature range 1400-1600°C by monitoring the rate of carbon monoxide (CO) evolution. Slags containing ferric iron have been used in order to study the reduction of both ferric and ferrous cations. Results show that ferric iron is reduced before ferrous iron, so that the ferrous iron concentration increases initially. It is also shown that the rate constant, k, decreases at low reaction rates, or, equivalently, at low concentrations. The authors conclude that the reaction occurs in two periods. During the first period, ferric iron is reduced to ferrous iron. During the second period, ferrous iron is reduced to metallic iron, and the rate-limiting step during the second period is the mass transfer of ferrous cations in the slag phase to the slag-metal interface.

Jan 1, 1998

By Rui-Qing Li, John G. Peacey, Peter J. Hancock

"Noranda has been investigating a pyrometallurgical process for the direct recovery of zinc from zinc concentrate and zinc and iron containing residues. The process consists of injecting dry zinc concentrate and secondary zinc materials into a molten iron oxysulphide bath, volatilizing metallic zinc into furnace off gas essentially free of sulphur or S02, fixing sulphur contained in the feed materials as iron oxysulphide matte which is disposed, and recovering metallic zinc in an ISP type lead splash condenser. Combustion of petroleum coke with air or oxygen enriched air inside the oxygen containing matte supplies part of the heat, and the products of combustion dilute the zinc-laden gas to a desired level.This paper describes the process concept, thermodynamic background, experimental tests, mass and heat balance calculation for a conceptual flowsheet, environmental stability of the residue and advantages and disadvantages of the process. Experimental tests have successfully proved the process concept and thermodynamic predictions. Direct smelting of zinc concentrate and residues inside an iron oxysulfide bath has a great potential to become a cost effective and flexible zinc smelting process.1. INTRODUCTIONZinc is mainly produced by a roast-leach-electrowinning process route, which accounts for about 80% of the world primary zinc production. This process produces high quality zinc with very high zinc recovery (>95%) but suffers from several major drawbacks such as using high cost electricity as reductant, producing environmentally problematic iron containing leach residue (jarosite or goethite) and the difficulty in treating secondary zinc feed materials containing high impurity levels, such as electric arc furnace dusts from the steel industry, and other complex sources. Also in some areas, markets for sulphuric acid are distant resulting in negative realizations on acid sales.The Imperial Smelting Furnace (ISF) process is the major pyrometallurgical process to treat zinc-lead concentrate. The advantage of this process over the electrolytic zinc process is its flexibility in treating high-lead, bulk concentrates with high recoveries of lead, copper and precious metals. However, this is a two-stage process involving sintering of Zn-Pb concentrates followed by blast furnace reduction. The process requires large amounts of high-quality coke which is a major operation cost, and the sintering process which results in serious environmental problems."

Jan 1, 1996

By C. J. Newman

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to improve gas cleaning capability. The acid plant is reviewed with references to changes? made to accommodate the increased SO2 gas strength resulting from the higher smelting rates.

Jan 1, 1992

By R. J. St. Eloi

The Kidd Creek Copper Smelter has been expanded from its original design of 59,000 tonnes of copper per year to over 120,000 tonnes per year .. Modifications to the process gas handling system and acid plant have been made to accommodate this higher production rate and to .generally optimize the operation. The gas handling system associated with the continuous smelting process is discussed in terms of boiler accretions and modifications to minimize their impact on operations; design changes to effect reductions in high pressure drop duct configurations; material changes to overcome corrosion and plant additions to 'improve gas cleaning capability. The acid plant is reviewed with references to changes made to accommodate the increased S02 gas strength resulting from the higher smelting rates;

Jan 1, 1992

By P .. R. Ammann

A two-stage pyrometallurgical process has been developed for the recovery of copper (and other non-ferrous metals) from copper smelter slags. All types of slags, including highly oxidized, converter-type slags, are cleaned in an electric furnace which employs mechanical mixers to promote magnetite reduction and copper extraction at high rates. In a 10-ton pilot furnace, it has been demonstrated that slags can be cleaned to 0.2-0.3 per cent copper with economically acceptable usage of raw materials and energy; copper is recovered as a high-grade matte. Pilot plant data have been scaled up to a commercial furnace and engineering designs have been made for a furnace to treat 60 tons per hour of slag from a Noranda Reactor and the associated converters. Plans are being formulated for the construction of a prototype slag cleaning furnace.

Jan 1, 1976

By Tor Lindstad

Specific C02-emissions are given for the production of silicon-metal, ferrosilicon, ferromanganese and silicomanganese. Emissions taken into account come from reduction materials, from coke production and generation of electric energy. C02-emissions can be abated by direct and by indirect methods. A direct method is to replace fossil carbon as reduction material wholly or partially by endogenous carbon (biocarbon, charcoal). Another possibility is to produce metals by electrolysis instead of the present electric smelting furnace. Indirectly CO2-emissions can be reduced by energy recovery, thus saving coal, oil or natural gas for heat generation. Some reduction in global C02-emissions can be obtained by giving credit for the use of silica dust partially replacing cement in concrete. In addition to give an overview of possible methods, costs will be discussed.

Jan 1, 1999

Sanes are utilized to make molds for metal castings in the foundry industry. Approximately a half ton of sand is disposed of for each ton of metal cast in this country. The purpose of this investigation was to study and develop a process to separate chromite sand and silica sand from reclaimed sands for a steel foundry. Physical separations were utilized to yield silica and chromite sands with desirable molding properties. Several different separation methods, including electrostatic, magnetic, and various gravitational approaches were examined. Experimental results are presented. A method was developed to separate chromite sand from silica sand after mechanical or thermal reclamation. The reclaimed sands are passed through a rare earth magnetic separator to separate chromite sand and magnetic impurities from non-magnetic silica sand. Chromite sand can be recovered from magnetic silica sand or magnetic impurities very effectively using a wet concentrating table. The applicabilities of the separation methods are discussed.

Jan 1, 1995

By P. M. Prasad

The last two decades have witnessed the emergence of numerous hydrometallurgical and direct processing techniques for the extraction of some metals from pocketed/lean/complex sulfide ore deposits. A new approach with some inherent technological merits, investigated in recent years, is the lime-enhanced reduction of metal sulfides. Thermodynamic aspects relevant to the lime-enhanced reduction of metal sulfides by H2,C0 and C are discussed. A survey of the researches on the basic features of and factors influencing the lime-scavenged reduction of selected sulfides and sulfide concentrates reveals that lime tremendously enhances the sulfide reduction rates (up to 100 times) and drastically reduces the sulfur emission into off-gas to negligible levels. Further successful practice of lime-enhanced reduction requires only a moderate temperature of reduction (characteristic of each sul¬fide) and, in the case of gaseous reduction, relatively low gas flow rates. Relevant kinetic aspects of the concerned reactions that have a bearing on process development and its understanding are also briefly discussed. A conceptual scheme of general applicability for the processing of sulfide concentrates by the lime-enhanced reduction technique consists of three main steps: (0 lime-enhanced reduction by a suitable reagent (e,g., H,2, CO, gasified coal, water gas), (ii) separation of the product metal from the dry slag (CaS + unused CO) by mechanical separation, magnetic/gravity concentration or flotation and (iii) melting and refining by standard procedures. This novel approach, which is patently less complex, is expected to employ basically simpler flow sheets at comparatively lower operational temperatures and aid in pollution abatement. Potential for developing such a route for the small scale extraction of metals like copper, molybdenum and antimony is indicated. Possibility of utilizing this technique for the production of fibers/ filaments of some metals is also outlined.

Jan 1, 1983

By Kimio Itagaki

The distribution behaviours of the VA elements between the gas, slag and matte phases in copper smelting were evaluated on the basis of the thermodynamic data, most of which were determined by the authors. The distribution is basically dependent on the process factors such as temperature, the content of the element in charge, the amount of the waste gas and degree of vapour saturation with the elements. The thermodynamic quantities such as the activity coefficients of the VA elements in matte, the activities of iron and copper, SO2 or 02 potential and the distribution ratio of the elements between the slag and matte phases seriously affect the distribution, and the behaviours in various smelters could be explained systematically and reasonably by considering the changes in these quantities, In oxidation smelting at PSO2= 0.1 to 1 atm, the proportion of arsenic and bismuth in gas is predomi22t for the arsenic and bismuth distributions in both smelting and converting stages. The degree of vapour saturation has serious effect on the distribution, and sufficient contact between gas and matte phases is desirable for transferring arsenic and bismuth into gas phase.The elimination of antimony by means of vaporization is not significant. In reduction smelting at po2 = 10-11 atm, the proportions of arsenic and antimony in the gas phase are quite small, but the proportion of bismuth does not change significantly.

Jan 1, 1983

By K A. Pericieous

"Magnetic fields have many actual applications in the metals processing industry. Externally applied magnetic fields give rise to electromagnetic (Lorentz) forces formed by the cross product JxB, between the induced current density J and the magnetic field density B. When the metal is in liquid form, the Lorentz force generates motion in the fluid which in applications of practical interest becomes turbulent. In modelling terms, the Lorentz force appears as a source in the momentum equations. In addition, the induced current generates heat (Joule heating) in the metal that is in proportion to J2, with a corresponding source of heat in the energy equation. Whether as heat or as a force, these effects represent action at a distance - a most useful attribute when dealing with hot metal. The Lorentz force is used to stir solidifying alloys, pump liquid metal in conduits, dampen the flow in the meniscus of a continuous caster, levitate metal drops, induce artificial gravity conditions in suspensions or contain liquid metal. Elsewhere, the Lorentz force may be a by-product of some other operation, so leading to wave excitation in aluminium electrolysis cells, or altering the shape of the weld pool in arc welding. Joule heating is most commonly used with applied AC fields, to melt metal in induction furnaces.The author and his colleagues have been involved in the modelling of most of these processes in the past decade. Modelling is not however straightforward, since most of the examples mentioned represent genuine multi-physics challenges. There is a strong coupling between the flow field and electromagnetic field. The addition of a dynamically varying metal free surface and the moving solidus front means the flow, heat and electromagnetic fields need to be computed simultaneously. In situations involving metal containment, the metal free surface position is governed by the interplay of gravity, Lorentz force, surface tension and fluid inertia. Since all the interesting effects often happen in thin boundary layers at the surface due to the skin effect, mesh generation and mesh control during the computation become non trivial problems that need to be addressed. This paper presents a review of numerical methods used to model droplet levitation, semi-levitation melting and cold crucible induction melting of metals. The first method is based on spectral collocation techniques and the second is the traditional FV approach. Steps taken to validate the computations and typical transient results are also given."

Jan 1, 2001

By Y. Y. Liu, H. M. Domanus, W. T. Sha

"Casting is fundamental to manufacturing of many types of equipment and products. Although casting is a very old technology that has been in existence for hundreds of years, it remains a highly empirical technology, and production of new castings requires an expensive and time-consuming trial-and-error approach.In recent years, mathematical modeling of casting has received increasing attention; however, a majority of the modeling work has been in the area of heat transfer and solidification. Very little work has been done in modeling fluid flow of the liquid melt. This paper presents a model of fluid flow coupled with heat transfer of a liquid melt for casting processes. The model to be described in this paper is an extension of the COMMIX code and is capable of handling castings with any shape, size, and material. A feature of this model is the ability to track the liquid/gas interface and liquid/solid interface. The flow of liquid melt through the sprue and runners and into the mold cavity is calculated as well as three-dimensional temperature and velocity distributions of the liquid melt throughout the casting process.IntroductionBower et al. (1), in their 1969 review of the evolution of some of the casting techniques, stated that:""The evolution of technology requires alternatives to be available so that choices can be made that lead to changes. The role of solidification science and other disciplines related to casting technology is to develop a better understanding of process and product, so that a wider range of alternatives is possible.Alternatives, whether from science or from invention, must lead to improvements in casting ""utility."" Utility, or economic advantage, must include consideration of total system costs, and final product value. The cost of materials, melt processing and finishing should be optimized with casting costs, since all are part of the production system. It is the favorable relationship between total processing costs and product value that makes a change in casting technology viable, but the best change is not possible unless technology has provided an understanding."""

Jan 1, 1986