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By Qinmeng Wang

The oxygen bottom blown copper smelting process is a new technology which has been widely applied to the copper production in China. In this work, a computational thermodynamics model for this technology has been established, based on smelting mechanism and theory of Gibbs free energy minimization. The calculated results from the model agree well with the actual industrial data, indicating that the model can be used for the predictions under different operating conditions. The tendencies of the key parameters (such as Cu losses and Fe3O4 content in slag) and the distribution ratios of the minor elements (such as Pb, Zn, As, Sb and Bi) can be predicted by adjusting the oxygen/ore ratio charged into the bottom blown copper smelting furnace. The model can be used to monitor and optimize the industrial operations of the oxygen bottom blown copper smelting process.

By Richard D. Hagni

Polished sections of pyrometallurgical intermediate products from a simulated commercial flash furnace were examined by reflected light microscopy, scanning electron microscopy-energy dispersive spectrometry and electron backscatter analysis, and microprobe analysis for phase and textural relationships. The smelter feed is a copper concentrate from a porphyry copper deposit. The concentrate consists primarily of chalcopyrite, bornite and pyrite with smaller amounts of covellite, chalcocite, molybdenite, magnetite, galena, and sphalerite. The flash furnace reactions for pyrite and chalcopyrite can be observed by reflected light microscopy. Reacted angular particles of pyrite exhibit successive rims of fibrous pyrrhotite and hematite or magnetite. Reacted angular chalcopyrite particles show successive rims of bornite, digenite, and chalcocite. Spherical particles, formed by the complete melting of former pyrite particles, consist of variable amounts of granular pyrrhotite with magnetite rims and minor hematite. Spherical particles, formed by the complete melting of former chalcopyrite particles, exhibit exsolution intergrowths with varying proportions of intermediate solid solution, bornite, digenite, and chalcocite and have rims of hematite, magnetite, and copper-iron spinel. Sphalerite and molybdenite do not show evident mineralogical reactions.

Jan 1, 1987

By J. Méndez-Nonell

The thermodynamic and chemical properties of SrSO4 and SrS in a gaseous flow of CO and CO2 at high temperature are discussed. The thermodynamic analysis of the system was made using data from the literature. The results obtained from the thermodynamic analysis were experimentally verified using the thermogravimetric technique. The experimental results suggest the formation of a complex compound between SrO and SrSO4. It was also found a change in the chemical mechanism of the process between SrSO4 and CO-CO2 and in the chemical mechanism of the process between SrS and pure CO2.

Jan 1, 1995

By L. J. Davies

Refractories usage in furnaces for the extraction of nickel from both sulphides and lateritic ores is reviewed. Recent changes in raw materials and basic brick qualities developed to meet the increasing demands of existing and new processes are outlined. Examples of used brick examinations to establish mechanisms of wear are given. The importance of physical and chemical properties are discussed. The use of simulative laboratory testing to aid in refractories development and selection is described.

Jan 1, 1988

By G. J. Abbaschian, A. B. Gokhale, M. M. Kunjapur

"A laboratory scale model furnace was constructed for obtaining radially inward oriented columnar grains in disc shaped castings. The furnace consisted of eleven circular, concentric, equispaced resistance heaters on each half of a split graphite mold. Water or air flowing through a copper pipe along the periphery of the disc constituted the heat sink. After filling the mold, the heaters were turned off consecutively in top and bottom pairs from the rim towards the center, causing the temperature gradients to move inward. Equiaxed structure was obtained at the center by turning off the inner coils together when desired. Sn:15%Pb alloy was used to cast integral blade disc castings using the above technique to obtain dual-property discs with a central equiaxed structure and an outer columnar grain structure projecting inwards from the blades to the rim. A numerical technique was used to predict the temperature profile in the disc during solidification, and good correlation was obtained with the experimentally measured temperature profiles. The corresponding heat transfer coefficient values obtained were h = 544 Wm- 2k-1 (0.013 cal/cm2- ° C-sec) for cooling between metal and chill and h' = 71 Wm- 2k-1 (0.0017 cal/cm2- ° C-sec) for the heat input from the hot mold to the liquid metal. BackgroundHigh temperature alloys used in the current generation of gas turbine engines have evolved through two main stages of development: in 1950's, the increase in the efficiency of gas turbines was paced by improvements in alloy design, which led to the development of Ni and Co-based superalloys (1). By mid-1960's, it was realized that improved alloy chemistry alone was inadequate in meeting the increasingly stringent service requirements. The focus of research then shifted from alloy development to process development, and resulted in the introduction of directional solidification (DS) techniques for the production of turbine blades and vanes (1,2).Under typical operating conditions, the blades and vanes are subjected to aerodynamic loading, while the blades are additionally subjected to high centrifugal loading and vibratory stresses. The primary material requirements for blades may be summarized as follows (1,3):•,High creep resistance•,Good high temperature tensile strength (typically in the range of•,275 to 550 MPa at temperatures in excess of 750°C)•,Resistance to both low cycle and high cycle fatigue (LCF and HCF)•,Resistance to erosion, corrosion, and oxidation•,Resistance to thermal fatigue"

Jan 1, 1986

By C. Flores

A novel process using solid metals for the direct reduction of more noble metal ions from solvent extraction organics has been developed. Base metals recovery has been the principal focus of investigations to date but feasibility tests have now also been made on galvanically stripping selected precious metals. In this study gold (III) was loaded from an aqueous HAuCI4 .3H20 solution into a mixed organic 40 vol.% TBP, 10 vol. % D2EHPA in kerosene. The direct precipitation of metallic gold from the loaded organic phase using zinc powder and iron, aluminum and copper slabs at 70 °C was successfully demonstrated. The gold reduction rates were relatively fast even though the conductivity of the organic solutions is very low. The reaction rates were studied as a function of the variables zinc particulate size, oxygen and nitrogen atmosphere, water content in the organic phase, organic ratios and temperature. The gold morphology was usually powdery or dendritic in nature but continuous films were obtained in some instances. Activation energies were calculated and possible reaction mechanisms are discussed. In general, the results obtained were very promising and showed that gold can be successfully cemented from selected organic solvents by galvanic stripping using less noble solid metal reductants.

Jan 1, 1995

By Derek J. Fray

"A need exists for fast and accurate analysis of species in various phases at elevated temperatures. Although modern analytical techniques are very efficient, the equipment is usually situated some distance from the industrial operation and time is spent taking the sample and sending it to the analytical facility. Several minutes can easily lapse and, during this time, heat must be supplied in order to keep the system molten and, if the composition is changing rapidly due to a refining process or reaction with the environment, the information may only be of retrospective use. Perhaps more important reasons for the use of on-line sensors are that instantaneous analysis gives better control, process optimisation and the minimisation of energy losses and pollution. To date oxygen has been the only element which is measured widely using solid electrolytes. However, the analysis of many more elements is required and possible electrolytes for other species are discussed. For some elements, ~here is no suitable conducting electrolyte and, therefore, a different approach is adopted where the electrolyte, in which one species is mobile, comes to equilibrium with another species. IntroductionThere is an ever increasing demand for the development of sensors for on-line measurements in most areas of technology and, in particular, metal processing. This is especially relevant in situations where greater control can be achieved by monitoring the chemical composition of the melt during processing and where a minor constituent in the melt can have a major effect on the properties of the finished alloy. Although modern analytical techniques are fast and reliable, the equipment due to its complexity, is frequently situated away from the process area and valuable time may be spent in sampling and transportation. During this period, heat may have to be supplied to prevent solidification and the refining reactions may be continuing, and, therefore, the analytical information may not be of direct use."

Jan 1, 1988

By Ravi Vancheeswaran

The consolidation of ceramic fiber reinforced metal matrix composites is a key process step in the synthesis of high performance composite systems. A simulation tool has recently been developed for predicting the evolution of the composites internal state microstructural variables (eg. relative density, fiber microbendinglfracture, and chemical reaction layer thickness at the fiber-matrix interface) during the consolidation processing of spray deposited composite mono-tapes. A Generalized Predictive Control (GPC) scheme is used in conjunction with the simula-tion tool to design near optimal process paths that minimize fiber damage and reaction product thickness while simultaneously maximizing the composites relative density. The microstruc-tural evolution depends nonlinearly on the process conditions and therefore the scheme uses a constantly updated linearization of the model to optimize the input process variable vector. A control simulation is presented to illustrate the performance of the design scheme and to assess the feasibility of its use for the achievement of goal state microstructures at the completion of consolidation cycles.

Jan 1, 1996

By Jing Zhan

The fibrous precursor can be obtained by coordination precipitation process, using oxalate, cobalt chloride and ammonia. The composition and morphology of fibrous precursor were characterized by XRD, IR, DTA/TGA and SEM analysis. The results show that XRD pattern and composition of the precursor with fibrous morphology precipitated at pH=9.0 were different from that of ß-CoC2O4?2H2O precipitated at pH=1.0. The mechanism on the thermal decomposition of fibrous precursor was addressed. The influences of various conditions in pyrolysis, including the temperature, time, atmosphere, and the morphology of the precursor, on the morphology, average size and specific surface area of the Co powders were investigated in detailed. At last, the final product, fibrous cobalt powders with diameter about 0.3~0.5µm in size and 40~60 in aspect ratio, were produced by thermal decomposition at 400~500? in the weak reducing atmosphere. The structure of pores in cobalt powders was capillary tube with open ports and the majority was mesoporous.

Jan 1, 2009

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 'burning' 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 Bowen Li, Matthew D. Andriese, Jiann-Yang Hwang, Zhiwei Peng

"Magnetic iron sulfide ore particles heat rapidly by microwave (MW) irradiation generating plasma during oxidation of surfaces. The high temperatures produced by the exothermic event decompose local portions of samples forming a differentiated flux of partially melted silicate (si-mt) with entrained metal-sulfide (sul-mt) droplets. The si-mt forms crystals of olivine (01) in Ca-rich pyroxene (Cpx) melt that resorbs a portion of iron sulfide (Po). The immiscible sul-mt droplets of (Fe,Ni,Cu)1-xS contain magnetic subsolidus Ni-pyrrhotite (Ni-Po) with Cr-bearing ferrospinel (Mag). Sub-micron sized flecks of Au are found on the surface of a sul-mt droplet with scanning electron microscope (SEM).IntroductionSulfide ore deposits supply the world's mineral resource in the production of non-ferrous metals. Particularly, Cu-Ni deposits are chemically enriched in metals from high sulfur saturation during magmatic formation that creates the proper geochemical environment for metals enrichment [1, 2]. The sulfur and oxygen fugacity control redox conditions of a differentiated silicate/sulfur magmatic melt with the concentration of iron playing a dominate role in the chemical partitioning of metals in sulfide liquid [3, 4]. The initial magnetic crystallization of (Fe,Ni)i-xS monosulfide solution (mss) from metal-sulfide liquid has an exclusive effect on the fractionation of mineral assemblages (zoning) [5].Phase equilibria of sulfide melt (sul-mt) components are related by a miscibility gap with mss forming Ni-rich pyrrhotite (Ni-Po) followed by the crystallization of (Fe,Cu)1-xS intermediate sulfide solution (iss) [6]. Precious metals form stable chacogenides and are retained in solution until the final liquid solidifies. The redistribution of metals now occurs by subsolidus cooling of mss and iss that exsolve low-temperature Fe-Cu-Ni bearing mineral assemblages [7]. The proper interpretation of ore genesis increases processing capabilities by isolating chemically enriched zones during extraction and should be used to aid in sustainable mine site development [8-11]."

Jan 1, 2013

By Arsenio Enriquez, Adrian Deneys

"Rio Tinto through its subsidiary Kennecott Utah Copper Corporation (KUC) and Praxair have implemented the CoJet® gas injection system for copper anode refining. The system provides the capability to melt on average 60 to 70 tons of scrap copper per heat (with acceptable NOx emissions). The system has demonstrated the potential for tuyere-less sulfur and oxygen removal using coherent jet technology.This paper describes the process concept, system development, laboratory testing, implementation, current operation and ongoing developments."

Jan 1, 2009

By Fei Ruan, Chang Jie, Jieyu Zhang, Jifang Xu, Kuochih Chou

"Viscosity is an important physical parameter of slag in metallurgical processes. Most studies of aluminosilicate and aluminate systems assume that aluminum occurs in tetrahedral coordination. In this case, the O/Al value was utilized to describe the slag structure in terms of the network character of aluminosilicate and aluminate systems. Composition and viscosity data from the literature and the trends were analyzed according to the O/Al value and temperature. It is shown that the O/Al value explains the trends in more than ten systems, containing more than 200 data points. In aluminosilicate system, the trend that viscosity value changed with the O/Al value which implies that alumina works as network modifier such as basic oxides or works as network former. In aluminate system, irrespective of the system and temperature, viscosity decreased steadily when O/Al value increased.IntroductionMetallurgical slags, which are made of oxides and many also contain fluorides, play an important role in metallurgical processes such as iron making, steel making and secondary refining processes. Aluminosilicate slags are applied in a wide range in metallurgical processes. A polymerizing effect of the addition of aluminum and an association of aluminum with low-field strength cations is further supported by the physical variations in aluminosilicate and aluminate systems. The behavior of alumina in silicate melts has been studied by various authors [1-6]. It is generally accepted that Al2O3 is amphoteric [7] because Al3+ ions can behave in profoundly different ways in a silicate melt. When added to a pure silica melt, Al2O3 acted as a network modifier, breaking the bridging oxygen of the pure silica network, thereby decreasing the viscosity in a similar manner to other network modifiers, such as CaO, MgO etc. to form [1/2Ca (AlO4)]4- complexes. However, when added with alkali or alkali-earth metal oxides, some of the Al3+ ions assumed tetrahedral coordination and replaced Si in the liquid network, the missing charge was compensated by Me+ or Me2+ ions. Therefore Al2O3 acted as network former [8, 9]."

Jan 1, 2011

By Huyang Xie, Rishi Raj, Vera A. Versteeg

"A new method for MOCVD has been developed in which a precursor solution is directly injected into a reaction chamber. The vaporization of short pulses of liquid is facilitated by atomization with a piezoelectrically-operated nozzle. The system has been used successfully to grow oriented, thin Ti02 (rutile) films on sapphire substrates with the crystalline relationship (101)[010]R I (1120)[0001]s. A growth rate of approximately 2 monolayers per pulse was achieved at 650°C for a reactant impingement rate of about 800 monolayers per pulse. Also, epitaxial LiTaO3 thin films were grown on (0001) sapphire from a single source, bimetallic precursor, lithium tantalum hexa-t-butoxide as the precursor. X-ray diffraction shows that the LiTaOa c-axis is normal to the sapphire surface. The x-ray pole figure and crosssection TEM diffraction show that the films were also in-plane oriented, with sapphire [1010] parallel to lithium tantalate [1010]. These films are shown to have extremely low optical attenuation, and refractive index that compares well with bulk values.IntroductionMetalorganic chemical vapor deposition (MOCVD) techniques have come into increasing use in recent years, due to the growing versatility and availability of precursors and improved environmental advantages over the halogenated compounds used for conventional CVD. Most commonly, the films are deposited by dissolving the metalorganic reactant (typically a metal alkoxide) in a carrier gas, which is carried through heated lines to a heated substratel . The metal alkoxides decompose by pyrolysis, leaving the films on substrates. While this method has been used to produce excellent epitaxial and heterepitaxial films, it has the disadvantages of complexity: the precursor must be heated to fix its vapor pressure, the gas flow rate carefully controlled, and the carrier lines heated to prevent condensation before reaching the reactor. Additionally, this conventional method cannot be used with certain low-volatility precursors that decompose upon heating."

Jan 1, 1994

By Christiana Mystrioti

Greece is the only EU country with extensive nickel laterite deposits. Since the 1960s, the Greek laterites are treated for ferronickel production via a pyrometallurgical route, which involves pre-reduction of the ore in rotary kilns and reduction smelting in electric arc furnaces. Due to the rising cost of energy and the decreasing grade of mined laterites, the pyrometallurgical treatment is economically marginal. For this reason, alternative treatment processes are currently under investigation. Potential applicability of hydrometallurgical treatment, using either H2SO4 or HCl, under atmospheric pressure conditions, for Ni and Co extraction from two low grade laterite ores, was examined in the present work. The two samples were selected to represent the different mineralogical composition of the saprolitic and limonitic ore deposits of the Greek laterites. The investigated parameters were temperature (65–90 °C), acid concentration (1–4 N) and solid to liquid ratio (10–30% w/v). The results indicated that HCl was more efficient than H2SO4 for the treatment of the saprolitic ore; Ni and Co extractions were very high for both elements, up to 98% and 96% respectively, while H2SO4 could leach efficiently Ni, up to 100%, but extracted only 34% of Co. Hydrochloric acid was also more efficient for the treatment of the limonitic ore, with Ni and Co extractions up to 98.3% and 87.6% respectively. With H2SO4 the maximum extractions were 71.3% for Ni and 52.1% for Co.

By Nagahiro Saito, Takahiro Ishizaki, Mituhito Hirota, Akio Fuwa

"Owing to their extremely high toxicity in the environment, the dioxins have been attracting social, technical and scientific attention in recent years. The authors theoretically had predicted the thermodynamic properties of all the dioxins via quantum chemistry and statistical thermodynamics and elucidated the generation-decomposition behavior of dioxins in the equilibrium calculation· of C-H-0-Cl system. In actual combustion processes, it is said that metallic compounds have much influences on the dioxins behavior. The aim of this study is to reveal the roles of metallic compounds the generation-decomposition behavior of dioxins is revealed from the viewpoints of quantum chemistry. Especially, the catalytic effect of copper has been investigated for the reaction, 2HCl(g)--H2(g}+Cl2(g) and for the etherification reaction from precursors, which is Phenol(g) here, to dioxins. The catalytic role of Cu is shown to have much influence on the generation -decomposition of dioxins.1. IntroductionIt is well known that dioxins are very harmful not only for our health but also for that of our children and grandchildren because they are very stable substance and their reaction rates of decomposition are considerably low. On the other hands, it is not well know how dioxins are generated and decomposed; the generation-decomposition conditions and paths as well as the catalysts to decompose them'1l. The authors believe that the thermodynamic and kinetic study of dioxins is useful to find a solution to these issuers. The authors have been investigating the following problems to reveal the generation-decomposition behavior of dioxins; (a) the prediction of the thermodynamic parameters of dioxins (2), (3), (b) the generation -decomposition behavior of non-chlorinated dioxins by the thermodynamic equilibrium calculations in C-H-O system(4) and (c) the generation-decomposition behavior of dioxins by the thermodynamic equilibrium calculations in C-H-O-CI system(5). Summaries of these thermodynamic researches are as follows.(I) The thermodynamic parameters for dioxins, which had been unknown and/or inaccurate'6 l, could be predicted and are available within the scientific accuracy."

Jan 1, 2000

By Joerg Hammerschmidt, Marcus Runkel, Andreas Wirtz, Kent Pope

"Fluidized bed reactor systems in the minerals industry have been progressively developed and widely implemented over a period of more than sixty years for a multitude of process applications. Their versatility is manifested in calcining, roasting and combustion treatment of minerals including solid fuels. Experiences from metallurgical processes have expanded to new applications in the oil shale processing, biomass combustion and renewable energy sector. This paper focuses on the most important aspects of fluidized bed technology for a variety of Outotec processes. Energy recovery is a major topic for all applications and will be addressed, as well as environmental aspects, particularly regarding the off-gas treatment. Outotec is one of the pioneers of roasting and the fluidized bed process including gas cleaning and sulphuric acid production where applicable. Process development is strongly supported by significant investment in R&D, thus enabling process adaptation and scale-up to meet specific customer/market requirements.Introduction to Fluidized Bed TechnologyThe early days of fluidized bed technology were characterized by the use of bubbling fluidized bed reactors (BFB). This technology was popular for roasting zinc and copper ores. The introduction of circulating fluidized bed technology led to increased plant capacities and improved process control for the traditional processes. Furthermore, the technology has been applied in many other industries, including the renewable energy industry, which will be part of this design and process comparison. The paper starts out with the fundamentals on particle fluidization as the main common design parameter, leading to the importance of heat recovery and offgas treatment.In fluidized reactor systems, the particle concentrations can reach several hundred kilograms per cubic meter of fluidization gas. This high solid concentration leads to large surface areas and enables direct contact of gas molecules with particle surface molecules. Excellent conditions for enhanced heat and mass transfer thus provide nearly ""ideal"" heat exchange conditions and better reaction kinetics. The bubbling bed exhibits a better heat transfer coefficient within the bed in comparison to the circulating fluidized bed (CFB). The different conditions of gas velocities and solid concentrations allowing the classification of fluidization reaction regimes are shown in the Reh diagram in Figure 1."

Jan 1, 2014

Carbon injection into metallurgical slag is important in electric arc furnace (EAF) steelmaking for foamy slag practices and in nonferrous slag cleaning operations. The current publication presents kinetic data for coal injection into EAF slag to understand the interaction between injected carbon and metallurgical slag. Coal particles were injected into EAF slag and the kinetics were followed by gas and slag analysis. The results were analyzed, in terms of fundamental rate equations for each possible reaction step, as a function of temperature and slag composition.

Jan 1, 2003

By A. E. M. Warner

In co Limited has long and extensive experience in converting nickel-copper primary smelting mattes over a broad range of nickel/copper weight ratios and combined nickel-copper-cobalt contents. At the Copper Cliff Smelter, the composition of the converter product matte has to meet the requirements of the matte separation process; at the Thompson Smelter, converter matte of a different composition is cast into anodes for nickel electrorefining; and in Soroako, Indonesia, a very low copper product matte is granulated for the Japanese market. Recently, Inco has conducted pilot plant testing of three possible nickel-copper matte continuous converting routes, namely flash converting, oxygen top blowing-nitrogen bottom stirring, and tuyere blowing. This test work has generated substantial new information on nickel-copper matte converting chemistry. This overview paper reviews the metallurgy of nickel-copper matte converting, in particular the behaviour of cobalt and the operating conditions required to meet the iron and sulfur specifications of the product matte. The relevant thermodynamic information is used to discuss the industrial data.

Jan 1, 2003

By S. M. Hay

The zinc content of blast furnace and basic oxygen furnace dusts is low compared with electric arc furnace dusts and it is generally not economical to treat the dusts to recover zinc. However, they have a high iron content and removal of the zinc would allow recovery of the iron values. A literature review and thermodynamic analysis was undertaken and, as a result, several smelting options were identified. This paper describes experiments undertaken to develop understanding of metallurgical aspects of these processes which are not amenable to theoretical analysis. Dusts from an Australian steelworks were characterised in order to determine their mineralogical make-up and the form of the iron. The processing aspects investigated in the laboratory were slag-metal equilibrium and solid-state pre-reduction using reducing gases of compositions expected from bath-smelting processes. Particular attention. was paid to the deportment of zinc, sodium, potassium, phosphorous and sulfur between the phases formed during smelting and pre-reduction. The smelting results indicate that less than 10% of the zinc, sulphur, sodium and potassium report to the metal. About 99% of the zinc and potassium and about 80% of the sodium could be volatilised from the dusts by reducing them at 1,000°C with mixtures of CO, CO2, H2 and H2O even when metallic iron was not formed. The experiments indicate that smelting of blast furnace and basic oxygen furnace dusts should produce hot-metal of a composition which can be blended into the main stream of hot-metal in the steelworks.

Jan 1, 1994