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Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite / Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

Based on experimental and computer simulation results from our group, we report a systematic, atomic level analysis of carbon dissolution from carbonaceous materials in molten iron. Experimental results on graphite/Fe-C-S system were obtained using carbon dissolution studies, XRD and FESEM investigations and were supplemented with Monte Carlo simulations. Three basic mechanisms, namely carbon atom dissociation rate, interfacial phenomena and mass transfer in the melt were found to be responsible for the overall dissolution process. While mass transfer in the melt is governed by the concentration gradients, melt composition and temperature; impurities present in ash play a significant role in the interfacial phenomena. For less ordered forms of carbonaceous materials, carbon atom dissociation rate depends strongly on the degree of long-range order and is an important rate controlling mechanism in the overall dissolution process. A systematic comparison of dissolution rates for a variety of coal-chars, natural and synthetic graphites has been carried out in an attempt to identify rate-controlling mechanisms. The structure of the carbonaceous material appears to be an important underlying factor in the carbon dissolution process.

Jan 1, 2003

By E. Burgos Cruz

The behaviour of S, N and P during refining of Fe-18 wt%Cr-10 wt%Ni with calcium carbide was investigated. The effects of the initial contents of C and N in the metal phase, as well as the supply method of calcium carbide to the melt on the removal degrees of S and P were evaluated. Heats were carried out at 1873K, in MgO crucibles, using a laboratory induction furnace. It was observed that simultaneously with S and P, N and O have also participated in the reactions. It seems that, in fact, O governs the behaviour of the other elements dissolved in the melt and that N is had to the removal of P with calcium carbide. It was also noticed that high C content in the metal phase have not altered the dephosphorization and desuffirization degrees, but that the supply of calcium carbide done by injection led to a lower dephosphorization degree than the one obtained by dumping it.

Jan 1, 1995

By Pekka Taskinen

The converter-less nickel matte smelting technology (DON) adopted more than 20 years ago in Boliden Harjavalta smelter has been since that applied successfully to the processing of large number of nickel sulphide concentrates of various Ni-to-Cu ratios and MgO contents. The operational point of the technology is far from the conventional primary nickel smelting in the smelting-converting route. Therefore, a careful scouting of distribution equilibria of the base and trace elements in the smelting conditions of DON process has been conducted, in order to obtain quantitative information about the equilibria and thermodynamic properties of the nickel mattes at low iron concentrations, less than 10 wt% [Fe] in matte. The series of investigations has included novel experimental and analytical techniques for increasing the reliability and sensitivity of the phase equilibria as well as the element distribution observations carried out in typical high-grade nickel matte smelting conditions.

By Shihan Zhang, Qingguo Xue, Jingsong Wang, Yaxing Du, Guang Wang

The rotary hearth furnace iron nugget process is in line with China’s energy and resource condition. It has the advantages of short reaction time and high quality iron nugget. The fundamental study on the novel ironmaking process is meaningful. Based on CaO-SiO2-Al2O3-FeO quaternary slag system, the effects of slag basicity and Al2O3 content on the melting of slag were studied. Using the iron concentrate as raw material, the effects of different slag basicity and Al2O3 content on the reduction and melting separation behaviors of carbon composite pellets, such as the starting temperature of melting separation and the morphology of melting separation were studied. Then, the relationship between the properties of slag and melting separation quality was established, which could provide standard for the selection of iron ore for the rotary hearth furnace iron nugget process.

Mar 1, 2018

By Edouard Asselin, Guikuan Yue

"In the present study, electrochemical measurements, especially cathodic potentiodynamic polarization (CPC) and cyclic potentiodynamic polarization (CPP), have been employed to study the kinetics of ferric reduction on chalcopyrite in aqueous Fe( II )-Fe(III)-H2S04 solution at 25°C and 70 °C. Results from the calculation ofspeciation in the above solution reveal that, at both 25 °C and 70 °C, the real Fe3+/Fe2+ ratio is much lower than the nominal ratio, which leads to smaller values for the reversible potential of the ferric/ferrous couple based on the Nemst equation. Exchange current densities of the ferric/ferrous couple were obtained by extrapolating the cathodic linear Tafel line to the reversible potential and are on the order of 10-7·10-6 A/cm2 at 25°C and 10·6-10-5 A/cm2 at 70 °C, respectively. The transfer coefficients were about 0.35-0.38 at 25°C and 0.35-0.45 at 70 °C. Polarization plots of CPC and CPP under different nominal Fe3+/Fe2+ ratios are in good agreement at 25 ·c and at 70 °C. Based on the obtained exchange current densities, the rate constant k, was calculated and is on the order of 10-1 cm/s at 25 °C and 10 1 cm/s at 70 °C.IntroductionChalcopyrite is the most abundant copper mineral in nature, accounting for about 70% of copper reserves in the world [I]. In recent years, the metallurgical industry has been searching for a hydrometallurgical process as an alternative to pyrometallurgical treatment due to high emissions of S02 and capital costs associated with smelting. Activity in this area has increased recently due to some inherent advantages associated with hydrometallurgical processing, such as the possibility of treating low-grade ores (increasingly more abundant in the case of copper) and easier control of waste, with the attendant benefits to the environment [I]. Chalcopyrite is highly refractory under most hydrometallurgical conditions, owing to the formation of an anodic passivation layer on the chalcopyrite surface which renders the process kinetics very slow. Most of the currently proposed processes are based on sulfuric acid with ferric ions and/or dissolved oxygen as oxidants. Sulfuric acid is preferred over all other leaching reagents in terms of cost, environmental friendliness, and ease of its regeneration during electro-winning. Some of these processes have been piloted in attempts to implement these technologies on an industrial scale,"

Jan 1, 2012

By Luben Savov

This paper presents recent research works on the removal of the tramp elements Cu, Sn, Zn and Pb from steel. The evaporation of Cu and Sn in iron-based melts treated at reduced pressure of the gas phase was studied in a vacuum induction melting furnace. The effect of chamber pressure, temperature and melt composition was investigated. Since the main source of contamination of steel with Sn and Zn is the recycling of tinplate and zinc coated steel, respectively, possibilities for the removal of meta1ic coatings in a scrap pre-treatment stage were studied, too. Tin was removed in the temperature range 400-5S0°C by treatment with reactive gases featuring high sulphur potential. Zinc can be removed by evaporation or by a combination of thermal and mechanical treatment. The paper discusses the thermodynamics of Pb in carbon-saturated iron melts, too.

Jan 1, 2001

By H. Jiang, S. Yang

"The main processes for nickel metallurgy in China consist of electric arc furnace smelting to produce low grade nickel matte and converter to high grade nickel matte, grinding and flotation to separate nickel sulfide from copper sulfide and direct electrolysis of nickel matte. Systematic studies on the properties of electric furnace slag, smelting process for nickel matte, anodic process of nickel matte, cathodic process of nickel electrolysis have been done in our labs. In addition, an approach to a new hydrometallurgy process for nickel matte has been done. The feature of the new process is one stage acidic leaching of high grade nickel matte. The leaching solution could be purified by deposition way or by solvent extraction way. There are two leaching rate-determing steps, chemistry reaction-determing one at temperatures below 600C and diffusion-determing one at temperatures higher than 600 c. The acidic leaching fraction reacted dvaties with leaching time t according to the equation 1-(1- a ) 1/3=kt. The experimental data also show that the leaching reaction rate varies with concentrations of H+, Cl-, and it is also effected by copper sulfide and Cu++. The Cu++ ion can retard the leaching reaction due to forming a copper sulfide layer on the matte surface and the equation 1- 2/3 a. - (1- a: ) 2/3 akt can be used for the case. However the copper sulfide added into nickel matte can facilitate the leaching process. The research work for nickel metallurgy done by others in China has also been mentioned in this paper.Large scale production of nickel in China started in 1960s.The main processes consist of electric arc furnace smelting to produce low grade nickel matte and converter to high grade nickel matte grinding and floatation to separate copper sulfide from nickel sulfide and direct electrolysis of nickel matte.To reduce nickel loss in slag a reseaech group organized by Jinchuan Company and Central South Institute of Mining and Metallurgy (now the Central South University of Technology) measured the viscosity surface tention density conductance melting point and structure of the slag(I).lt has been found that the physico-chemical properties of the slag depend on the components SiO2 ,MgO and FeO but FeO in the slag is too high and the statistic analysis of data from industry gave an equation to correlate the content of Ni in slag with the content of Ni in matte and the composition of slag again it was pointed out that the content of FeO in slag effected the loss of Ni in slag very much (2). The ratio (FeO+MgO) to SiO2shouid be less than 1.13 and the content of Fe3O4should be as low as possible but the reaction"

Jan 1, 1988

A rotating-discelectrode system was used to evaluate the electrochemical behaviour of Eu(III) during its reduction in NaCl solutions. The solution pH and NaCl concentration have a great effect on the reduction kinetics. The thermodynamic modelling study also revealed that Eu(III) exists in various forms in NaCl solutions. At a low concentration of NaCl, the predominant species is the free Eu3+. Other Eu-chloro complexes become more predominant when the NaCl concentration increases.

Jan 1, 1992

By Junji Shibata

Waste solution from the Ni non-electric plating process contains 4.0 kg/m3 Ni, 0.1 kglm3 Fe, 0.0 I kg/m3 Zn, 48 kg/m3 S042-, 98 kg/m3 HP032-and 31 kg/m3 laetic acid as a typical composition. Solvent extraction, cementation, ion exchange resin and precipitation methods are possible to use for the treatment of this kind of solution. In this study, solvent extraction of Ni was investigated using two kinds of extractants to clarify the relation between extraction percent and pH for various extractant mixtures. As Ni ion has an octahedral structure with ligands, the synergistic effect for Ni extraction is considered to take place in solvent extraction using two types of extractants. The investigation of the synergistic effect for Ni extraction was carried out in case of various extractant systems.

Jan 1, 2003

By T. Ikeda, M. Maeda, K. Mita

Galvanized steel sheet is the major product for the automobile industry. Therefore, automotive recycling results in zinc-containing scrap that should be remelted in EAFs. Naturally, the EAF dust is a very important source of zinc for zinc recycling processes. The thermodynamic properties of the Fe-Zn intermetallic compounds formed on the surface of galvanized steel sheet should be clarified to make clear the evaporation mechanism of zinc; however, there are few reports on these compounds because of difficulties in their synthesis. There are various intermetallic compounds in the Fe-Zn system. We synthesized them at about 673K. A specimen was examined chemically and X-ray diffraction was applied to ensure the formation of intermetallic compounds. Material containing two phases was placed in a Knudsen type effusion cell and the mass spectrum studied to evaluate the vapor pressure of zinc. The thermodynamic property of intermetallics was then evaluated through measured intensity.

Jan 1, 2000

By Run-boWang, Fan-yi Meng, Jian-Liang Zhang, ZheWang

To elucidate the influence of high Al2O3 content on sinter softening and melting behavior, heating-up reduction test under load was carried out. In addition, microstructure study of sinter bed structure change at a different temperature was also made and the mechanism that the effect of Al2O3 content on sinter softening and melting property was discovered. SEM results showed that the increase of Al2O3 content favored the formation of Al2O3-rich slag phase, such as the eutectic (2CaO·SiO2-2CaO·Al2O3·SiO2-FeO) and gehlenite (2CaO·Al2O3·SiO2), resulting in the decrease of sinter Ts temperature. Further, high Al2O3 content improved the concentration of metallic iron and lowered the dripping temperature due to the decrease of slag liquidus temperature and viscosity. At a fixed basicity, it was indicated that there was a relationship between Al2O3 content and sinter softening-melting property. Based on the results, counter strategies to cope with the adverse effect of high Al2O3 content on the cohesive zone property were also proposed. It could provide guidance for the blast furnace operation of sinter with high Al2O3 content.

Jan 1, 2015

By J. L. Sanchez

Using a special double-zone transpiration reactor, the vapor transport chemistry of vanadium pentoxide in the presence of water vapor has been investigated. Three possible volatile hydroxides above V,O,(s) are reported in the literature: VO,(OH),, V,O,(OH),, and VO(OH),. In the present study, it was established that VO(OH), is the principal gaseous hydroxide species formed. The predominant reaction was found to be: { } The vapor pressure of VO(OH), was measured as a function of temperature, water pressure, oxygen pressure and flowrate. The results have been used to determine the Gibbs free energy of the above reaction as a function of temperature: { } The results of the present work were combined with thermodynamic data reported in the literature to obtain expressions for the AGO for the reaction above V,0,(1) and the AGO of formation (units in cal/g-mole).

Jan 1, 1993

By Dave Tahija

"Many investigations are being performed with the goal of removing carbon dioxide from the atmosphere and permanently storing it in geologically stable settings. At the same time, carbon dioxide in the form of dissolved carbonate is steadily accumulating in the world's oceans. Both carbon dioxide sequestration and oceanic accumulation are constrained by the aqueous thermodynamics of the carbonate system. These constraints are illustrated using the STABCAL computer model to generate potential-pH and aqueous distribution diagrams of seawater in contact with various pressures of carbon dioxide gas. STABCAL diagrams and titration simulations are also used to model some potentially useful cation-carbonate sequestrationsystems.IntroductionAtmospheric carbon dioxide concentrations have risen dramatically in the past couple of centuries and are rising still, primarily as a result of human activities, especially the burning of fossil fuels. Increased atmospheric carbon dioxide concentrations have been implicated as a main cause of global warming but have other effects as well.Rising levels of atmospheric carbon dioxide result in increased concentrations of dissolved carbonate complexes in water, including the oceans. These dissolved carbonates interact with other dissolved substances, altering overall seawater chemistry, most noticeably causing lowered pH levels.Some of these chemical changes are observed directly, for instance the general drop in oceanic pH, [1], while others can be inferred and predicted using thermodynamic modeling. The chemistry of dissolved carbonate in seawater is not especially intricate, as such chemical systems go, but neither is it simple enough to be worked out on the back of an envelope. Interactions between the several simple carbonate species and all the major dissolved cations in seawater should be considered, as well as the effects of competing anions, especially chloride and sulphate, since they are much more abundant than carbonate in seawater."

Jan 1, 2011

By Stephanie Trant

Montana Tech has been engaged in fundamental research on the processing of critical materials for more than a decade. Efforts include examining novel reagents for the flotation of Rare Earth Minerals (REMs). For this paper, research results on a collector, salicyl hydroxamic acid (SHA), are presented. Various REMs were examined and include the rare earth oxides (REOs), carbonates (RECs), and phosphates (REPs) of a suite of Rare Earth Elements (REEs). Differences are attributed to solution and surface chemistry, coordination number, and ionic diameter. SHA adsorption follows an ion-exchange process that leads to chemisorbed and surface-precipitated states, depending mostly on pH. Many effects are directly attributed to lanthanide contraction. Results should also be applicable to other REM/collector systems and further suggest that REM flotation should consider dual collectors.

By Rainer Schmid-Fetzer

"Isothermal solidification can be used to form strong bonds at low temperature which remain solid at much higher temperatures. The exploitation of this principally known technique for new high temperature processing steps and applications in electronic assemblies is the aim of this study. Three basically different variants of this bonding process are given. A comprehensive metallurgical screening is performed and the feasibility of binary material systems is given on a quantitative scale. Very attractive systems are spotted that have never been studied before. Detailed examples for the realization of bonding with complex ternary and multilayer systems are given. A highly innovative example is the chip stack or wafer to wafer bonding of unmetallized Si or SiC at 250°C. The proposed bond remains stable above the melting point of Si and enables entirely new semiconductor manufacturing steps. An improved die bonding process was proposed and verified experimentally.1. IntroductionIsothermal solidification can be applied to form strong bonds at relatively low temperature which remain solid at higher temperatures. The general principle of this type of joining processes is illustrated in Fig. 1. An interlayer of a low melting component, Lo, is provided as a foil or a thin film coating between the high melting joint components, Hi. The assembly is heated under moderate pressure to the bonding temperature, T 8 , and a liquid filler forms, either because the melting point of Lo is exceeded or due to a eutectic reaction between Lo and Hi. This molten filler initiates a rapid interdiffusion or reaction diffusion between Lo and Hi and the subsequent approach to an equilibrium state results in isothermal solidification. The solid phases formed at T 8 in the joint region exhibit a remelt temperature above T8 •"

Jan 1, 1996

By Florian Kongoli

The overall productivity and efficiency of sulfide smelting plants depends considerably on the productivity and efficiency of each unit furnace operations. Furthermore, the efficiency and productivity of each furnace affects and dictates to a certain degree the process of managing the flow of materials from one unit to another. A furnace with low productivity, several technical problems or high frequency of accidental shut downs can easily become a temporary or a permanent bottle neck in the entire flowsheet and can be the cause for a low productivity and efficiency of the entire plant. As a result, controlling, optimizing and automating the individual furnace operations in order to assure a stable process but at the same time to increase productivity is an indispensable need. In this paper, the authors discuss their recent work in effectively controlling acute industrial furnace problems such as magnetite build-up and accretions, eliminating unnecessary slag foaming, decreasing slag losses etc. as well as the intensification, optimization and automation of a series of furnaces in sulfide smelting through a unique physical process modeling that correctly simulate the industrial furnace operations and avoid guessing and uncertainties. The advantages of this new approach have been discussed.

Jan 1, 2006

The increasing need for robust pyrometallurgical furnace construction is driven by two trends in the copper and other base metals smelting industry: ? the desire for increased production within a single furnace line by greatly increasing smelting intensities, which generates high heat fluxes to the crucible. walls, and ? the operational and economic imperatives of maintaining high percentage on- line times and long campaign lives between rebuilds. A key feature of furnaces capable of producing at high rates, while containing intense processes, is a strong, thermally robust wall cooling system. Equally important design aspects include the furnace steel structure, refractories, a cooling water supply and piping arrangment for safety from leaks and disruptions, and instrumentation/controls for monitoring and rapid mitigation of process excursions. Integration of the cooling elements into these furnace systems is essential for optimum performance of the cooling elements, and indeed the entire furnace. This paper discusses the development of a composite copper / refractory water- cooled design, which has been successfully implemented on several copper smelting and converting furnaces, including Kennecott's flash converting furnace, INCO's MK reactor, and Kidd Creek's converting furnace.

Jan 1, 1999

By Karel Verscheure

Reliable furnace cooling technology is a domain of increasing concern to the pyrometallurgical industry as it can significantly increase process intensities, productivity and campaign times of furnaces. Although there are many advantages in using cooling systems, they also impose a variety of problems mainly related to safety, heat losses and sustainability of the operations. The choice of cooling system is hence a matter of trade-offs and differs for every metallurgical application. This paper gives a review of different cooling designs used in the ferrous, non-ferrous and alloying industries. Additionally, the paper systematically reviews aspects of materials selection, manufacturing, installation, water quality and furnace monitoring when using water cooled refractories.

Jan 1, 2006

By Roberto Parra

The wear and corrosion phenomena in the furnace lining of the ferrous and non ferrous pyrometallurgical processes are complex problems where chemical, interfacial and mechanical phenomena are presents. The characteristics of the processes determine the conditions to which these materials are submitted, where the thermal conditions reached during the operation is one of the most important parameter. Assuming that all the degradation phenomena are thermal activated, the rate of the different steps of the wear mechanism will depend on the thermal field in the lining. In view to apply the independent physicochemical knowledge of degradation mechanisms to the analysis and design of furnace lining the methodology of the Nodal Wear Model (NWM) was done. It combines the mathematical modelling of the heat transfer in the lining with the physicochemical control equation for the wear-corrosion phenomena. The NWM has been applied to different examples: theoretical analysis, laboratory scale test and industrial applications. We present in this paper the theoretical background of the model and two examples of applications: the sole of an electric furnace and the earth of a blast furnace.

Jan 1, 2006