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By Pengfu Tan

In order to understand and control the formation of dioxins and furans in iron ore sinter plants and to possibly avoid expensive end-of-pipe removal stages, thermodynamic calculations on the stability of PCDD/Fs have been combined with sinter process modeling by means of kinetic simulations and computational fluid dynamics. Three thermodynamic databases of PCDD/Fs, derived using the Group Additivity approach and two computational molecular modeling methods, MNDO and PM3, respectively, combined with the SGTE database have been used to model the PCDDIF formation and the PCDD/F isomer distributions in iron ore sintering. The results show very similar conditions for the PCDD/F formation using the different databases. Concerning the isomer distributions of toxic PCDD/Fs, the calculated data derived from the MNDO method showed optimum agreement with measured values from industrial furnaces. The thermodynamic calculations also proved that the isomer distributions found in combustion processes are equilibrium values, while the concentration ratio of PCDDs and PCDFs in the wind boxes does not represent an equilibrium state. A CFD model of iron ore sintering was developed including the kinetics of 15 relevant chemical reactions with the aim of describing the temperature fields and the gas flow patterns in the sintering bed. On the basis of these information and experimental observations reported in the literature possible pathways for the PCDD/F formation in sinter plants have been identified: PCDD/Fs are formed in the critical temperature region of 250 to 450 °C below the combustion zone, are then carried downwards with the gas and condensed close to the bottom of the sinter bed. Transported to the discharge end with the solid mixture, they are again released into the gas phase when the flame front approaches the bottom. PCDD/Fs are also formed in the last wind boxes when the hot off-gases cool down and reach the critical temperature range. Consequently, methods to reduce the dioxin formation reactions are proposed including inhibitor addition to the sinter feed and off-gas quenching.

Jan 1, 2003

By Magnus Ek

After the installation of three new converters as part of the recent expansion of the Rönnskär smelter completed in 2000 work continues to further improve the converter operation. The converter upgrade led to an increase in blister copper taps from 150 tons per batch to more than 300 tons. The total cathode copper production increased from 130,000 tons in 1999 to 230,000 tons in 2001, the first year in full production. In recent years focus has been to improve operating practise, maximize the blowing time, extend the converter campaigns hence to reduce the specific brick consumption and improve the converter slag composition.

Jan 1, 2005

"Mechanical alloying (MA) synthesizing technology and thennohydrogen processing (THP) were utilized to produce nanocrystalline Ti-MMC's reinforced by TiB intermetallic compound by using TiH2-B powder mixtures. Powders MA'ed up to 8 hours were examined by X-ray diffraction and SEM study. All MA'ed powders afterwards were HIP'ed at 700, 800 and 950EC for 1 hour. Detailed XRD, SEM and TEM study of the samples were carried out to determine the structure and micrography of the Ti-TiB MMC material processed by MA+THP approach followed by HIP'ing at high temperatures.IntroductionThe fiber reinforced titanium base composites [1,2] which possess a great resistance to high temperature have been investigated. In these studies fibers of C and SiC were used as reinforcing materials. However, these fibers react with Ti-matrix at elevated temperature resulting in product formation at the interface between the matrix and the fiber. Because of the chemical reactions, strength of the product MMC material diminishes.In conventional techniques of whisker reinforced composite material production, the mixtures of matrix metal powders and dispersed fibers are consolidated by hot pressing, HIP and/or hot extrusion. These techniques, however, have some shortcomings. Hard and brittle fibers could be broken during mixing cycle of the processing. Consolidation techniques could also be the cause for fiber breakdown. Attaining of the uniform dispersion of fibers into the metal matrix is not an easy process. The chemical reactions at elevated temperature exposures in the interface between the matrix material and fiber reinforcement cause product formations leading to poor mechanical properties."

Jan 1, 1998

By Batric Pesic

Solvent extraction of nickel and cobalt from the real leach solutions was studied by using a novel extraction system. The extraction system was a mixture of 2,6-bis-[5-n-nonylpyrazol-3¬y]] pyridine (BNPP) and dinonylnaphthalene sulfonic acid (DNSSA). The BNPP represents a novel molecule, which was designed and synthesized in our laboratory. Real solutions for the study were prepared by leaching of two different cobalt-nickel bearing concentrates, cobaltite [CoAsS] concentrate from Blackbird Mine, Idaho, and siegenite [(Ni,Co)3S4] concentrate from Missouri Lead-Belt. The major strength of the system was the selectivity of extraction toward nickel and cobalt from iron containing solutions. Other metals such as Mn, Mg, Ca, Al and As were not extracted. Due to the irreversibility of copper extraction, its removal from solution was required prior to the extraction of nickel and cobalt. Zinc was not as strongly extracted (i.e. its stripping was readily achieved) as was copper . Flowsheets for the recovery of nickel and cobalt were also developed.

Jan 1, 1997

By Atul Kurnar

In the present research a two-cell polymer electrolyte membrane fuel cell stack (PEMFCS) with SS-316 bipolar plates has been tested. Different flow field designs were studied and a modified multi-parallel channel design is proposed. The stack is stable within ±3 mV even after 1000 hours of continuous operation, indicating efficient water management and effective removal of any metal ions from the stack. Also no iron is detected in membrane electrode assembly (MEA) by EDAX analysis after 1000 hours of cell operation. Results indicate that high operating pressures beyond 138 kPa didn't significantly increase the performance of cell, however added much to the pressurization cost of the system. Tests at different temperatures showed that at temperatures below 80°C, external humidification could be completely removed. The prototype stack is also tested under variable load conditions simulating highway-driving schedule. The experimental efficiency of PEMFCS is 48%, which is in good agreement with the model predicted efficiency of 53.8 %. Results show that 59% of the total losses are due to ohmic polarization in the cell. Further analysis on applications of the stack in automotive transportation system is in progress.

Jan 1, 2002

By Taiping Lou

The effects of slag composition, additive agents, and heat treatment conditions on the perovskite (CaO ? TiO2) crystal morphology, the precipitation behavior, the crystal growth and the volume fraction (VF) in the Ti-bearing blast furnace slags were investigated. The morphology of perovskite is dispersed dendriform in molten slags. The crystal growth mechanism of the remelting of fine dendrites and the coarsening of larger grains exists throughout the solidification of molten slags. With the temperature decrease, the VF was increased and Perovskite transformed from fine dendrites to coarsening ones or equiaxed grains. The lower cooling rate can increase the VF and coarsen the grain obviously, while higher cooling rate will decrease the VF and reduce the average equivalent diameter (AED) of Perovskite. When .increasing the content of CaO and Fe20}, the VF can increase obviosly. However, high basicity will give rise to the increasing of viscosity of slag, which result in the reducing of the AED. The experimental results showed that additive CaF2 and MnO can efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promote growth.

Jan 1, 2000

By Mehmet Bu daycı, Onuralp Yücel, Ahmet Turan, Murat Alkan

In this study, iron based alloys (Fe, Fe-Cr-Ni-Mo, etc.) were produced by using metallothermic methods starting from Mill Scales obtained continuous casting processes. During the process, the combustion was realized by ignition and the produced wave propagates throughout the reactant mixture yielding the desired product. In this work, Mill scale used as an iron source, which includes +2, +3 values iron oxides. Aluminum, Magnesium and Silicon were used as reductants. In these metallothermic experiments, different ratios of reductants were examined, and their effects on the metal recovery and alloy compositions were investigated. The samples were characterized by using chemical analysis (AAS), XRD and XRF techniques.

Jan 1, 2016

By R. G. Reddy

Reduction of different chromite ores with carbon was studied as a function of C/FeO ratio and temperature in the range 700 °C to 1100 °C by thermogravimetry (TGA) analysis. Powders of chromite ore(-150 mesh) and carbon(-150 mesh) were thoroughly mixed in a desired proportions and were placed in the reaction crucible. The reduction rates of reactions were determined by continuously monitoring the weight loss as a function of time at constant temperature using TGA set up. The analysis of results suggest that FeO present in the chromite ores is reduced to Fe involving gaseous intermediates CO and CO2. The overall rate of FeO reduction is controlled by the oxidation of carbon. A kinetic equation, that of random nucleation, was proposed. The activation energies for the reduction of FeO, present in Roast Movat and Transvaal ores, with carbon were determined to be 55800 and 23000 J/mole, respectively. The results of the present study are compared with the data available in literature. The low activation energy values as determined in this study suggest that the carbon oxidation reaction is catalyzed. It is concluded from the present investigation that the low grade chromite ores can be significantly upgraded to higher value added chromite that can be used as a feed source for economical smelting.

Jan 1, 1998

By Thomas P. Battle

Titanium is the ninth most common element in the Earth's crust, yet only in this century has titanium come into use as an engineering material, particularly in aircraft structures, as the metal, and in pigments, as the dioxide. In this presentation, the metallurgical aspects of processing titanium-containing raw materials will be reviewed. Particular emphasis will be given to the ores and beneficiation techniques which lead to the production of titanium dioxide pigment, which accounts for over 90% of world titanium production.

Jan 1, 1993

By Flavio Begazo, William A. Enrico

"Southern Peru Copper Corporation's Ilo Refinery, the largest in Peru, began operations in 1975 with a production capacity of 165,000 stpy. Southern Peru bought the Refinery from the state owned Minero Peru SA on June 1, 1994.The Refinery processes blister from Southern Peru's I/o Smelter. Blister copper is processed in an anode plant equipped with two 365 st tilting reverberatory furnaces, a 26 mold casting wheel and an anode press machine. Copper is electrorefined in a tank house equipped with 768 commercial cells, 44 stripper cells, and 40 liberator cells, utilizing two electrolyte circuits and a 21,000 Ampere rectifier.During 1989 through 1994 a program for improving productivity was carried out by increasing the number of cells and increasing current density to the total rectifier capacity. As a result, a capacity 215,000 stpy of refined copper, 2 million tr. oz silver and 6,000 tr. oz gold per year was achieved. In 1994 Southern Peru announced plans to increase capacity to 250,000 stpy of cathode with a US$ 18 million investment and a US$ 2 million investment in environmental improvement projects, as part of the purchase agreement with the Peruvian government.This paper outlines the scope of the SPCC lio Refinery modernization and environmental program. It describes the implementation of the Electrolytic Plant expansion based on instaliation of polymer concrete cells, a new rectifier, a new selenium roaster and a Precious Metal Plant upgrades."

Jan 1, 1997

By W. G. Davenport

Changes in copper extraction from 1960 till today are documented. The top ten changes have been: (a) replacement of reverberatory smelting by high intensity oxygen rich smelting (b) growth of the Outokumpu flash smelting to over 50% of the world's smelting capacity (c) successful development of single furnace coppermaking but only for low slag fall concentrates (d) replacement of the batch Peirce-Smith converter by continuous converting, but only in a few cases (e) increased SO2 capture throughout the industry, mainly-as sulfuric acid (f) development of low initiation temperature `big bight' Cs catalysts for treating the continuous high-SO2 strength gases from continuous smelting/converting (g) complete replacement of reverberatory anode scrap and cathode melting furnaces by the Asarco shaft furnace (h) adoption of stainless steel permanent cathodes and automated stripping technology for electrorefining and electrowinning (i) complete elimination of wire bar casting by continuous bar casting/rod rolling (j) development and adoption of extractants for turning weak impure leach solutions into strong pure electrolytes. It is postulated that the biggest possible change over the next 20 years would be complete replacement of smelting/converting by hydrometallurgical processing. However, this seems unlikely due to copper purity, precious metal recovery, and economic concerns. The increasing value of sulfuric acid to many copper companies gives chalcopyrite smelting/oxide-supergene leaching a nice synergy especially with the energy credits now coming from continuous smelters, and their acid plants.

Jan 1, 1999

By Hiroyuki Matsuura

The effects of P2OS or Na2O addition on the reaction rate of CO2 dissociation on the surface of FexO-base molten oxides was investigated at I 773K by isotope exchange method 1-6. The rate constant decreased with increasing P2Os content of molten oxides and the residual rate constant was observed at high P2OS content. On the other hand, the rate constant increased with increasing Na20 content for FexO-SiO2 melts, The rate constant was evaluated by the composition of oxides and the rate controlling step of CO2 dissociation was discussed.

Jan 1, 2003

By Ali Hasham

Reduction rates of FeO in CaO-SiO2-Al2O3 slags by Fe-C melts have been investigated experimentally at 1723 K. The rates were estimated using experimentally determined CO(g) evolution rates. Flash X-ray images were employed to visualize the behavior of the melt-slag interface during the reactions. The influence of melt interface was examined by conducting two types of experiments - (i) dropping one (or several) Fe-C droplet(s) weighing 2 g into the molten slag bath, and (ii) dropping a small amount (10-30 g) of slag onto a Fe-C melt weighing 400 g. The rates from both types of experiments were compared and analyzed to determine the rate limiting steps. It was established that neither the carbon transport in the Fe-C melt, nor the transport of gas species in the gas film adjacent to Fe-C melt was responsible in limiting the reaction rate. It is possible that the slag phase mass transport may be controlling the initial reduction rate in the droplet experiments. However, a, different mechanism was responsible in limiting the reduction reaction when the overall %C in the droplets fell to about 2-3.

Jan 1, 1992

By Takaaki Shibata

The Tamano Refinery has developed two new processes for removing the impurities, arsenic, antimony, and bismuth from an electrolyte. The first process involves bleeding the surface electrolyte in the electro-refining cells. The copper concentration level in the outermost layer is lower than that in any of the other layers, while the impurity levels are almost the same in all layers. Bleeding the surface electrolyte increases the amount of impurities removed in the liberator by approximately 20%. The second process involves adsorbing antimony and bismuth from the electrolyte by means of chelating resin. As the electrolyte passes through the packed column of chelating resin, antimony and bismuth are selectively adsorbed. They are then desorbed by means of hydrochloric acid, and then recovered in the form of a highly concentrated antimony chloride solution by means of evaporation. This process almost doubles the capacity for removing antimony from an electrolyte.

Jan 1, 1987

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,(Cu2S) 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 I. S. Blair

The introduction of the 36 MVA smelting furnace at Mufulira, and the experience gained during the first five years of operation have been described previously (6). Based on this experience the furnace was rebuilt in 1977., Details of the modifications made during this rebuild are described. Subsequent to the rebuild, refractory failures, particularly in the electrode ring bricks of the sprung arch roof, continued to cause concern, and repair and improved roof control methods are described. Electrode breakages continued, but developments in casing design and electrode preparation have resulted in significant improvements. Modifications in the electric furnace gas handling system are outlined, together with details of further changes to be implemented in the near future. The systems developed for metallurgical control of the furnace and the thermo-dynamics of the process are discussed. The electric furnace at Mufulira is now operating at above design production levels, and has decisively justified the choice of this technology in situations with inexpensive electric power. The potential for further increases in production capacity from the Mufulira unit, and improvements in design for new units are discussed.

Jan 1, 1983

By Sharif Jahanshahi

Calcium ferrite slags are often associated with Professor Yazawa due to his pioneering work on the thermodynamics of this type of melts. Over the past years CSIRO has invested some effort in studying physico-chemical properties of such melts to fill in some gaps in our knowledge and explore opportunities for application of the understanding developed. These investigations cover thermodynamics, transport properties of calcium ferrite based slags, as well as the kinetics of reactions of such slags with refractories. The present paper provides an overview of some of these studies and highlights some of the interesting behavior of such melts, The oxidation state of copper and arsenic in calcium ferrite based slags are predominantly Cu+ and As3+, respectively, at oxygen potentials below 10-7 atm. The concentration of CU2+ in such slags becomes significant at oxygen potentials of greater than 10-7 atm at 1300 °C. The activities of CuO0.5 and AsO1.5 in calcium ferrite slags show strong deviations from the Raoultian Law, while that of CoO is very close to ideal behaviour with respect to pure solid CoO. Addition of SiO2 to calcium ferrite slags can have significant effects on the activities of FeO and Fe2O3 and hence the stability of magnetite phase. Transfer of oxygen in calcium ferrite slags is fast with diffusivity of 2x 103 cm2/s at 1350 °C and activation energy of 16 kcal/mol. Presence of solid phases, such as magnetite, has pronounced effect on the viscosity of calcium ferrite slags. The observed dependence on solid loading and shear rate indicates deviation from Newtonian behaviour. The interfacial tension between copper mattes and calcium ferrite slags is strongly dependent on the matte grade, with the determined values being much lower than the corresponding ones for interfacial tension between similar mattes and iron silicate slags. MgO, Cr2O3 and MgCr2O4 have low solubility in calcium ferrite slags and their solubility increases with increasing copper oxide content of the slag at 1300°C. The oxidation state of the slag has strong effects on phase transformation, dissolution rate and disintegration of refractories in calcium ferrite slags. Other key factors with major impact on slag-refractory interactions include viscosity and surface tension of slags as well as the contact angle between slag and refractory material,

Jan 1, 2003

By Mitsutaka Hino

The contents of gangue minerals, such as Al2O3. P2O5, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year. Though the increments of such gangue contents arc approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly Al2O3. on the blast furnace operation, the dripping behavior of Fe,O-CaO-SiO2-Al2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, Fe2O and MgO contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper. It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When Fe2O content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Ah03. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant Fe2O and Al2O3 contents, This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

The cleaning of copper containing fayalite slag using a CuFe alloy was studied under an oxygen pressure ranging from 10-7 to 5 X 10-11 atm at 1200º c. The reduction of copper from fayalite slags by Cu-Fe alloys was found to be very effective. For example, at a P 02 of 10-7 atm, the copper content in the slag was reduced from 4.1 to 0.402 wt. percent after 90 min. of reaction time using a Cu- 5.27 wt. percent Fe alloy. The copper reduction rates were found to be independent of P02 in the gas phase when using Cu-Fe alloys which exhibit an iron activity of greater than 0.4. A mechanism for slag c1eaning is proposed based on the concept that the Cu-Fe alloy lowers the oxygen potential of the slag according to Eq.1 1, fol1owed by the reduction of cuprous oxide by wustite as shown in Eq.2. Here X represents element X in the alloy phase while (X) represents the element in the slag phase. The copper and iron transfer behaviour obtained in this study are explained by a ?Stepwise equilibrium model.

Jan 1, 1985

By George Oprea, Tom Troczynski, Joe A. Rigby, Waiman Lo

The refractory lining of the tuyere line in Peirce Smith converters have usually much shorter life in service than the rest of the lining, above or below it. There are already recognized chemical, thermal and mechanical factors which contribute to the wear of the lining. Our study presents the experimental results on microstructural changes occurring on these tuyere line bricks in a nickelcopper converter. The experimental bricks, after use at the tuyere line, were investigated using SEM/EDS and XRD techniques, to identify the mineralogical changes due to interactions with the nickel-copper matte or fayalite type slag at the process temperatures. The microstructural changes were correlated with physical and mechanical properties of the brick before and after use and a wear mechanism was suggested. Although the matte does not theoretically react with the mineralogical components of the brick, a partial oxidation of the Ni-Cu sulphides was identified using a line analysis by SEM/EDS in the densified layer at the hot face, which allows for mineralogical changes at the matte-refractory interfaces, with a high probability of microcrack formation due to the thermal cycling during use. These microcracks were also identified to open through inter-granular fractures parallel to the hot face, which appeared to be the main cause of lost lining during use. The reactions between the fayalite slag and refractory brick could eventually play a role in chemical dissolution of the brick only in the superficial layer at the hot face, as no slag components were identified deep into the brick.

Jan 1, 2009