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2016 | Book

Celebrating the Megascale

Proceedings of the Extraction and Processing Division Symposium on Pyrometallurgy in Honor of David G.C. Robertson

Editors: Phillip J. Mackey, Eric J. Grimsey, Rodney T. Jones, Geoffrey A. Brooks

Publisher: Springer International Publishing

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Table of Contents

Frontmatter

Keynote Session

Frontmatter
David Gordon Campbell Robertson: A Biographical Sketch

Emeritus Professor David Robertson of the Missouri University of Science and Technology was born in Dublin Ireland on 29 December 1941. His father was a merchant navy Captain who served during WWII and during David’s early years his family lived in Dublin and Donegal where David went to the local elementary school. In 1954 he moved to London with his parents and attended Highgate School before commencing metallurgy at the Royal School of Mines, Imperial College, London in 1960.

J. B. See
Evolution of the Large Copper Smelter — 1800s to 2013

Over the course of Dr. Robertson’s career, the ferrous and non-ferrous plants have seen enormous changes in technology and increases in plant capacity, essentially amounting to a “technological revolution”. In iron and steel, the “mega” blast furnace of some 6,000 m3 working volume is now standard (~10,000 tonnes (mt) of pig iron/day). Similar huge changes in process technology and plant size have occurred in the non-ferrous industry. As an example, the fuel-fired reverberatory furnace, once the mainstay of the copper industry, has disappeared — replaced by large capacity flash and bath smelting technologies. The energy consumption per unit mass of metal produced has also been reduced considerably. Our understanding of the thermodynamics and mechanisms of metallurgical reactions, a field to which Dr. Robertson has significantly contributed, has made great strides. This paper reviews these changes with particular reference to the copper smelting industry, providing also comments on expected future trends.

P. J. Mackey
Evolution of the Mega-Scale in Ferro-Alloy Electric Furnace Smelting

The historical progression in installed electric furnace smelting capacity of some 1650 calcium, chromium, manganese, nickel and silicon ferro-alloys furnaces is reviewed. Key increases in the inherent installed electrical capacity, often achieved through uprating furnaces, are identified.Possible factors facilitating such advances are explored, including: specific process engineering and pyrometallurgical enhancements (e.g., improved control over the consistency, size and chemical form of raw materials, extents of preheating and pre-reduction delivered into the furnace; and patterns of feed distribution); furnace electrical configuration (AC or DC; immersed, submerged-, shielded- or open-arc); form of electrode (graphite, self-baking or composite); furnace configuration (circular or rectangular; closed or open and 1-, 3- or 6-electrodes); better engineering and equipment designs (e.g., high-intensity cooling) and state of furnace electrical and metallurgical control systems. A view is presented on the prevailing state of evolution of the Mega-scale in ferro-alloy smelting and opportunities for still further improvements.

Lloyd Robert Nelson
From Sulfide Flash Smelting to a Novel Flash Ironmaking Technology

A novel flash ironmaking technology is under development at the University of Utah under the support of U.S. Department of Energy (DOE) and American Iron and Steel Institute (AISI). The history of the development from the conception of the idea to the current status will be discussed. The flash ironmaking process produces iron directly from fine iron ore concentrates without requiring cokemaking and pelletization/sintering, which will enable the technology to significantly reduce energy consumption and carbon dioxide emissions compared with blast furnace ironmaking. Unlike other gas-based ironmaking processes, this technology will not suffer from the problems of solid sticking and fusion. Current work is focused on the method of supplying the energy required to maintain the necessary temperature, as an intermediate step to determine the scalability for larger, industrial-scale pilot trials.

Hong Yong Sohn
Fostering Minerals Workforce Skills of Tomorrow through Education and Training Partnerships

The Minerals Council of Australia (MCA), through its Minerals Tertiary Education Council (MTEC), builds capacity in higher education in the core disciplines of mining engineering, metallurgy and minerals geoscience. Over the past fourteen years, this all-of-industry approach in securing the long-term supply of these critical skills (which remain a chronic skills shortage for the Australian minerals industry) through nationally collaborative programs across sixteen Australian universities delivers spectacular and sustainable results for the industry. These unique, world-first programs are built on a healthy platform of dedicated industry funding and in-kind support and forms part of the MCA’s broader uninterrupted, sustainable education and training pathway to increase workforce participation, workforce diversity and workforce skills, regardless of the business cycle in the industry. This paper will highlight the origins, iterations and current successful programs of MTEC, including its future vision, and presents a mechanism for industry and academia to collaborate to address future professional skills needs in the minerals industry globally.

Gavin Lind
Modeling of Ladle Metallurgy in Steelmaking

Ladle or secondary metallurgy in steelmaking is an essential process step for the production of high-quality steel. Professor David Robertson was a pioneer in the modeling of these processes, in particular gas-metal fluid dynamic interactions and the rates of slag-metal reactions. This is now a highly active area of research, and some of the recent developments in this area will be reviewed.

Gordon Irons, Krishnakumar Krishnapisharody, Kevin Graham
Process Metallurgy an Enabler of Resource Efficiency: Linking Product Design to Metallurgy in Product Centric Recycling

In this paper the link between process metallurgy, classical minerals processing, product centric recycling and urban/landfill mining is discussed. The depth that has to be achieved in urban mining and recycling must glean from the wealth of theoretical knowledge and insight that have been developed in the past in minerals and metallurgical processing. This background learns that recycling demands a product centric approach, which considers simultaneously the multi-material interactions in man-made complex ‘minerals’. Fast innovation in recycling and urban mining can be achieved by further evolving from this well developed basis, evolving the techniques and tools that have been developed over the years. This basis has already been used for many years to design, operate and control industrial plants for metal production. This has been the basis for Design for Recycling rules for End-of-Life products. Using, among others, the UNEP Metal Recycling report as a basis (authors are respectively Lead and Main authors of report), it is demonstrated that a common theoretical basis as developed in metallurgy and minerals processing can help much to level the playing field between primary processing, secondary processing, recycling, and urban/landfill mining and product design hence enhancing resource efficiency. Thus various scales of detail link product design with metallurgical process design and its fundamentals.

Markus Reuter, Antoinette van Schaik
Horizontal Single Belt Casting (HSBC) of Ca-Based Bulk Metallic Glass (BMG) Strips

The HSBC is an ideal process for the production of BMG strips. The purpose of the present work was to investigate the casting of Ca-based, bulk amorphous strips. The possibility of casting three Ca-based alloys (60Ca-20Mg-20Al, 60Ca-15Mg-10Al-15Zn and 55Ca-15Mg-10Al-15Zn-5Cu (at.%).) was investigated, using the HSBC simulator. Numerical simulation and mathematical modeling were used to predict temperature variations and cooling rates, under different interfacial gaseous atmospheres (helium and air) near the meniscus region. Given the critical cooling rates and glass temperatures needed to be reached for the vitrification of the respective alloys, this leads to predictions of the critical thicknesses possible with this novel casting process. To validate our predictions, these alloys were then prepared and cast onto the sand-blasted, solid copper substrate mould of the HSBC simulator. The possibility of producing Ca-based metallic glassy strips via the HSBC processes was confirmed, using optical microscopy, X-ray diffraction and Scanning Electron Microscopy, to characterize the glassy properties of the cast strips. It was found that the HSBC process would be able to provide sufficient cooling to form amorphous strips for the 60CA-15Mg-10Al-15Zn and 55Ca-15Mg-10Al-15Zn-5Cu alloys, but not the 60Ca-20Mg-20Al alloy.

Roderick I. L. Guthrie, Mihaiela Isac, Donghui Li, Luis Calzado

Ferro-Alloys

Frontmatter
Developments in Manganese Ferroalloy Research and Production in the Last 25 Years

Ferromanganese production in electrical furnaces is quite an old process. However, as the furnaces are getting bigger, the requirements of cost, yield, product quality, emissions and security are raised. With the increased expectations, the fundamental knowledge must follow. Within the last 25 years there has been a great effort both in the industry as well as the academic environment to push the limits of this process. This article will show some examples of improvements within fundamental data, reaction mechanisms and emissions over this time period.

Merete Tangstad, Ragnar Tronstad
DC Arc Furnaces — Past, Present, and Future

DC arc furnaces were first used industrially for the reductive smelting of chromite fines to produce ferrochromium thirty years ago. Since then, they have been used for a variety of applications, including the smelting of ilmenite to produce titania slag and pig iron, the recovery of cobalt from non-ferrous smelter slags, and the smelting of nickel laterite ores to produce ferronickel. The power of these furnaces has increased from 12 MW to 72 MW for ferrochromium, and to 80 MW for ferronickel. The largest of these furnaces requires two electrodes to carry sufficient current to generate this much power. A review is presented of various DC arc furnaces in use, along with a discussion of the likely ways in which furnace power might be increased further in the future.

Rodney T. Jones
Recent Developments in Factsage Thermochemical Software and Databases

The FactSage® package consists of a series of information, database and calculation modules that enable one to access pure substances and solution databases and perform thermochemical equilibrium calculations. FactSage was originally founded by process pyrometallurgists and has since expanded its applications to include hydrometallurgy, electrometallurgy, corrosion, glass technology, combustion, ceramics, geology, environmental studies, etc. With the various modules one can perform a wide variety of thermochemical calculations and generate tables and graphs of complex chemical equilibria and phase diagrams for multicomponent systems.This paper presents examples of recent and current developments in FactSage in areas of particular interest to Dr. David Robertson. These include both ferrous and non-ferrous processing, as well as solidification and refining simulation. The paper also includes reference to the Internet Fact-Web education package.

Christopher W. Bale, E. Bélisle, P. Chartrand, S. A. Decterov, G. Eriksson, A. Gheribi, K. Hack, I.-H. Jung, J. Melançon, A. D. Pelton, S. Petersen, C. Robelin
Reduction of Agglomerated Manganese Ores in a 150 kW Pilot Scale Furnace

Manganese ore fines cannot be added to the submerged arc furnace directly as they will prevent even gas flow through the burden. Low gas permeability in the burden will lower the degree of pre-reduction of ore subsequently increase the carbon and energy consumption of the process. In order to utilize manganese ore fines in the furnace, they are typically agglomerated into sinter. In this work, the melting and reduction properties of Gabonese sinter and Gabonese ore have been investigated in pilot scale experiments. Two experiments were conducted, one with 100% sinter as manganese source and one with 50/50 sinter and ore. Lime was used to achieve a charge basicity of 0.72 in both experiments. The composition of slag samples from the excavation of the furnace was established using EPMA(WDS), and the composition of the tapped slag and metal was found using XRF. It was found that while the coke-bed size would determine the tapped slag composition, the melting behavior of the Mn source would determine the mixing with lime.

Merete Tangstad, Thomas Brynjulfsen, Eli Ringdalen
Arc Detection in DC Arc Furnaces

A direct-current (DC) plasma arc furnace is a type of electric furnace used for metallurgical operations. The successful operation of DC furnaces depends to a large extent on gaining a fundamental understanding of the arc phenomenon itself, and ensuring its presence in the furnace at all times. A method for detection of the presence of the arc in a DC circuit is presented, along with discussion of why this may be of value for certain modes of furnace operation such as brush-arc. The theoretical development of the method is presented along with supporting experimental work conducted on large-scale pilot-plant facilities.

Quinn G Reynolds, Christopher J Hockaday, Dominic T Jordan, Ian J Barker
An Electromagnetically Stirred Slurry Model for the Smelting Zone of a Ferroalloy Furnace

For certain ferroalloy furnaces, such as ferrochrome or ferromanganese, there is still doubt about the mechanisms operating under the electrode tips. In this paper a model is built that does not call upon an arc. The medium is best described as an electrically conducting slurry, a mixture of liquids, solids and gas. There are two sources of propulsion, the Lorentz force within the conducting part and buoyancy generated by CO bubbles, creating two opposed poloidal circulation loops, downward below the electrode axis and upward further out.

Ben Bowman
Roles of Mn Carbides in Carbothermic Processes for Mn Alloys

The reduction of Mn oxides at pre-smelting steps is an integral part of smelting processes for Mn alloys, and an understanding of its reaction mechanism is expected to contribute to the improvement of processing efficiency for Mn alloys smelting. The phase diagram shows that five Mn carbides are operative in the Mn-C system. Although they are expected to participate in the reduction of Mn oxides, no specific information is available yet to clarify their roles in pre-smelting carbothermic reaction of Mn oxides.Experiments with composite pellets prepared with Mn oxides and graphite powders show that Mn3O4 is reduced initially to MnO at about 1130°C and, subsequently, to Mn7C3 carbide as temperature increases further. At 1331°C, Mn7C3 carbide dissociates to Mn alloy and carbon. The degree of reducing reaction increases with increasing carbon balance in composite pellets and increasing temperatures.

Byeong Deok Lee, Hyun Kyu Shin, Young Eun Lee

Non-Ferrous Smelting, Converting, and Refining

Frontmatter
Redoubling Platinum Group Metal Smelting Intensity — Operational Challenges and Solutions

The 2003 redoubling in power to 68MW on the Polokwane Smelter furnace represented a significant intensification in platinum group metal (PGM) smelting. Combined with onerous ‘green’ PGM concentrate smelting requirements, this yielded conditions unusually corrosive to copper coolers and refractories. This presented unexpected operational and design challenges to reliable crucible operation and maintenance.Combined with specific operational control intervention, development of protective coatings has led to the life of water-cooled copper components improving from 9 to 40 months. The furnace matte endwall was extended in 2010 to address accelerated wear of refractories and the potential risk for contact of copper components by superheated matte. An 18 month planned endwall rebuild cycle has been demonstrated (versus catastrophic failure within 9 months).Finally, benefits including lower energy consumption, improved metal recoveries and higher productivity resulting from operational and in-house design developments will be described, that justify “Celebrating the Mega-scale” in PGM smelting.

Rodney Hundermark, Lloyd Nelson, Bertus de Villiers, July Ndlovu, Diale Mokwena, Phillimon Mukumbe, Bart Pieterse, Whitey Seyanund, Paul van Manen
Pyrometallurgical Processing Technologies for Treating High Arsenic Copper Concentrates

Various pyrometallurgical methods for treating copper concentrates that contain appreciable arsenic are reviewed. Various aspects of the engineering of these treatment methods are discussed. The methods discussed include: complete oxidation with arsenic fixation; selective volatilization of arsenic; acid baking, soda ash roasting, and others methods. Methods for the ultimate disposal, or marketing, of the arsenic are discussed.

Patrick R. Taylor, Teuku A. R. Putra
Arsenic and Antimony Capacities in Ni-Cu Mattes and Slags

A thermodynamic model for a priori predictions of arsenic and antimony impurity capacity in Ni-Cu mattes and slags was developed based on the Reddy-Blander (RB) capacity model. The As and Sb capacities were calculated a-priori considering the RB capacity model in Ni-Cu mattes and FeO-FeO1.5-MgO-CuO0.5-NiO-SiO2 slag at 1573 K and 0.1 to 1 atm partial pressure of SO2. The results showed an excellent agreement between the model calculated and experimental data of arsenic and antimony capacities between the mattes and slag. The impurity capacity model developed here, can be extended for prediction of impurity capacities in multi-component base metal slags and base metal mattes. Such a priori predictions of impurity capacities can lead to develop or improve the efficiency of impurity removal from the base metal smelting, converting and refining processes.

Ramana G. Reddy, Jonkion M. Font
Quartz-Cristobalite Transformation and Its Effect on Reactions in Si Production: Initial Studies

In Si and FeSi production, the main Si source is SiO2, in the form of quartz. Reactions with SiO2 generate SiO-gas that further reacts with SiC to Si. During heating, quartz will transform to other SiO2 modifications with cristobalite as the stable high temperature phase. Transformation to cristobalite has been investigated and shown to be a slow process where the rate varies between the investigated quartz types.The effect of quartz versus cristobalite as SiO2 source has been studied for reaction (1) 2SiO2 + SiC = 3SiO + CO, by heating of pellets with SiO2 + SiC in Ar-gas. The reaction was faster with cristobalite than with quartz. Initial experiments indicates that this is the case only in Ar and not in CO-atmosphere The higher specific surface area of cristobalite is believed to contribute to the higher rate. The industrial consequences of the observed difference between quartz types are discussed.

Eli Ringdalen, Dian Adisty, Leiv Kolbeinsen
Modifications to a Smelter to Accommodate Recycled Materials

The Columbus Processing Complex of the Stillwater Mining Company began operations at Columbus, Montana in 1990 based on electric furnace smelting treating a precious metals concentrate from the nearby Stillwater mine and mill. Since that time, the smelter plant has been expanded in stages in order to treat recycled materials in addition to the concentrate. This paper describes a number of changes made at the plant to effectively handle recycled materials.

Greg Roset, Dayle Flynn, Katie Schumacher
Removal of Pb from Molten Copper by FetO-SiO2 (-CaO, Al2O3) Slag Treatment in Mitsubishi Process

The distribution behavior of Pb between molten copper and FetO-SiO2 (-CaO, Al2O3) slags was investigated at 1473 K (1200 °C) and p(O2)=10-10 atm in view of the reaction mechanism of Pb dissolution into the slag. The distribution ratio of Pb (LPb) decreases with increasing CaO content (~6 mass pct) irrespective of Fe/SiO2 ratio (1.4~1.7). However, the addition of alumina into a slag with Fe/SiO2=1.5 linearly decreases the LPb, whereas a minimum value is observed at about 4 mass pct Al2O3 at Fe/SiO2=1.3. The log LPb continuously decreases with increasing Fe/SiO2 ratio, and the addition of Al2O3 (5 to 15 mass pct) into the silica-saturated iron silicate slag (Fe/SiO2 > 1.0) yields the highest Pb distribution ratio. The log LPb linearly decreases by increasing the log (Fe3+/Fe2+) value. The Pb distribution ratio increases and the excess free energy of PbO decreases with increasing Cu2O content in the slag. However, from the viewpoint of copper loss into the slag, the silica-saturated system containing small amounts of alumina is strongly recommended to stabilize PbO in the slag phase at a low Cu2O content.

Soo Sang Park, Joo Hyun Park
Simulation of the Gas Flow in a Peirce-Smith Converter

In the pyrometallurgical production of copper from its sulfides, converting in the Peirce Smith (P-S) Converter is still the most widespread method to obtain white metal and blister copper from the matte. Despite the fact of being a century-old process, it is still possible to achieve improvements in the process, by the use of modern tools, one of the most valuable being numerical calculation and computer-aided simulation. The present study presents three cases in which the angle for the gas injection and the number of working tuyeres are changed during the slag blow phase of the converting process. It was noticed that a decrease of the number of tuyeres, followed by an increase in the injection gas velocity, results in improved reaction volume and less stress to the refractory lining. However, an increase in the amount of copper lost to the slag as oxide is likely to occur.

Wagner Moulin Silva, Bruno Augusto Batista Ribeiro, Felipe Terra Elias
From Phase Equilibrium and Thermodynamic Modeling to Freeze Linings — The Development of Techniques for the Analysis of Complex Slag Systems

Modern analytical tools, such as electron probe X-ray microanalysis (EPMA), are used in experimental characterization of phase equilibria and micro structure s of complex slags. Integrated thermodynamic computer packages, such as FactSage, are used to provide more accurate descriptions of complex slag systems. These advanced methodologies have been applied to characterize dynamic steady state freeze linings in slag systems using submerged cold finger probes at controlled laboratory conditions, establishing the effects of bath chemistry, temperature, heat extraction rate and bulk fluid flow.It has been found that stationary freeze lining deposit interface temperatures at steady state conditions can be lower than the bulk slag liquidus temperature, and that stable operation below the liquidus is possible. A conceptual framework has been developed to explain the phenomenon and the range of interface temperatures that can be obtained in dynamic steady state conditions. These findings have important implications for the design of freeze linings and possible improvements to high-temperature metallurgical operations.

Ata Fallah Mehrjardi, Peter Hayes, Evgueni Jak
Modelling Simulation and Comparison of Refractory Corrosion at RHI’s Technology Center

In order to determine the most suitable refractory products and improve the lining lifetime for the diverse furnaces used in the nonferrous metal industry, corrosion tests are performed at RHF’s Technology Center. The practical facilities include the cup test, induction furnace, rotary kiln, and drip slag test described in this paper, which enable a comprehensive understanding of the chemo-thermal brick wear on a pilot scale. The corrosion trials are performed with actual slags generated during operations at a customer’s plant. To determine the highest influencing wear parameter, every single test is combined with a detailed mineralogical investigation and thermochemical calculations performed using FactSage. Based on the results, tailored refractory solutions for the nonferrous metal industry can be provided in combination with trials conducted at the customer’s site.

Dean Gregurek, Angelika Ressler, Anna Franzkowiak, Alfred Spanring

Iron and Steel Production

Frontmatter
Sustainability in Ironmaking: The Rise of Direct Reduction

Modern-day direct reduction of iron first developed as a small-scale, low capital and operating cost alternative to the blast furnace. Since commercialization of continuous DR technology in the late 1960s, the market for the products of direct reduction has grown to more than 74 million tonnes in 2012. The initial advantages of DR plants over BF facilities have grown over the years, for several reasons, including the increased size of DR modules, lower energy and emissions (particularly CO2), along with the flexibility to use a number of different reductants. The development of DR technology over the past forty years will be emphasized in this presentation, including recent developments that allow for even more direct sustainability comparisons with the iron blast furnace — and even combine the two technologies for improved synergies. Also briefly discussed will be the possibilities of using direct reduction for non-ferrous ores.

Thomas P. Battle
Kinetics of Reaction Important in Oxygen Steelmaking

Recent work on modeling of BOF steelmaking is reviewed, highlighting the critical aspects of each approach. It is concluded that the most successful models should be based on a deep understanding of the mechanisms and kinetics of the critical reactions. The importance of the decarburization mechanism is discussed with particular reference to its role in droplet swelling or bloating which has a profound influence on the droplet residence time in the slag. Conditions which cause bloating are discussed and the rate determining step is proposed to be primarily nucleation of CO bubbles inside the metal droplet with some influence from growth by reaction at the bubble/metal interface. The discrepancy in the super-saturation ratio required for classical nucleation is discussed and an approach using a surface tension modifying parameter is illustrated. Finally, the role of CO nucleation in controlling the driving force for dephosphorization is discussed.

Kenneth S. Coley, Elaine Chen, Michael Pomeroy
Current Status and Future Direction of Low-Emission Integrated Steelmaking Process

In 2006 the Australian steel industry and CSIRO initiated an R&D program to reduce the industry’s net greenhouse emission by at least 50%. Given that most of the CO2 emissions in steel production occur during the reduction of iron ore to hot metal through use of coal and coke, a key focus of this program has been to substitute these with renewable carbon (charcoal) sourced from sustainable sources such as plantations of biomass species. Another key component of the program has been to recover the waste heat from molten slags and produce a by-product that could be substituted for Portland cement.This paper provides an overview of the low-emission Integrated Steelmaking Process, progress made over the past seven years and the program’s future direction which includes proposed demonstrations of the technologies developed including large scale piloting and full scale plant trials.

S Jahanshahi, A Deev, N Haque, L Lu, J G Mathieson, T E Norgate, Y Pan, P Ridgeway, H Rogers, M A Somerville, D Xie, P Zulli
Analysis of Steelmaking Reactions by Coupled Reaction Model

Kinetic modeling is very important to understand steelmaking reactions. The coupled reaction model proposed by Prof. D.G.C Robertson is the best suited program, and therefore, the author has applied it to the various steelmaking reactions, a few examples of which are discussed. Hot metal dephosphorization occurs under non-equilibrium conditions as it takes place between the slag, which has a high oxygen potential, and the hot metal, which has a low oxygen potential. A process simulation model based on the coupled reaction model was constructed. This model considers the solid and liquid slag, liquid metal phases, and the reaction between the solid and liquid slag, besides the reaction between the liquid slag and liquid metal. Using this model, the ruling factor to increase the reaction efficiency of dephosphorization has been verified. In the secondary refining process, the values of inclusion composition calculated by the thermodynamic model, under the assumption of equilibrium with the metal composition, were found to be different from those observed in practice. A kinetic model, incorporating the reactions between slag, metal, inclusion, and refractory has been postulated, and the composition change of inclusion during treatment has been analyzed.

Shin-ya Kitamura
Cold Modelling of Splashing Phenomena in Oxygen Steelmaking

In oxygen steelmaking, splashing and droplet formation play a key role in the kinetics of the process. Though splashing has been studied by previous investigators, there is only limited understanding of how different cavity modes affect splashing. Therefore, a cold model study (at various lance heights and gas flow rates) has been carried out focusing on the issue of cavity modes and how it affects splashing phenomenon. Analysis using Fast Fourier Transform (FFT) was carried out on cavity oscillation that showed that frequency and amplitude of oscillation was highest in penetrating mode. Measurements of splashing over a range of conditions showed splashing greatly reduced when cavities went from splashing to penetrating mode. The results were validated and compared with plant data and previous model investigations.

Shabnam Sabah, Geoffrey Brooks
Lean Operations Strategy to Combat Uncertainties in Temperture at BOF End Point, Tapping, Deoxidation, Alloy Addition and Thermal History

Steel plants generally employ static BOF end point control models to arrive at a given temperature and chemistry at the end of blow. These end point models have now been supplemented with chaos control models to steer the blowing process in the right direction while the blow is in progress. Merely arriving at the correct end point temperature is however not adequate because in the subsequent stages as well the temperature variations can be large and unpredictable. The present paper deals with an integrated model to take into account the effect of all parameters affecting temperature and composition from tapping to the start of casting to minimize the use of LF or aluminum heating, and also minimize grade mixing. The application of lean operations strategy is explained in which the previous “Push System” is changed to a “Pull System”, minimizing the use of ladle furnace or aluminum heating during steelmaking.

Ishani Shukla, G Rajesh, Pratik Agarwal, Ajay Kumar Shukla, Deepu Philip
Ladle Metallurgy Kinetics: Inclusion-Inclusion Reactions

An example is presented to illustrate the joint effect of local reaction equilibria and mass transfer limitations, for reactions during ladle refining of steel. The example relies on some of the kinetic principles that David Robertson has employed to quantify many metallurgical processes. In calcium treatment of alumina inclusions in aluminum-killed steels, solid CaS forms as an intermediate reaction product. During subsequent reaction, CaS disappears and calcium aluminate forms; at the same time, aluminum and sulfur dissolve in the steel. Kinetic analysis shows that the rate of this reaction is not limited by mass transfer of dissolved aluminum and sulfur away from the reacting inclusions. The reaction rate is likely limited by transport of dissolved calcium. This example also illustrates the use of FactSage macros for kinetic modeling.

P. Chris Pistorius
Valorization of Electrical Arc Furnace Oxidizing Slag

Valorization of the electrical arc furnace oxidizing slag by coke was carried out by the reduction of iron oxide in the slag. Since the reduction of iron oxide by solid carbon is an endothermic reaction, supply of heat energy is required. In addition, slag has a low thermal conductivity; traditional fuel injection is not suitable for this reaction. Microwave can be used to supply heat energy to the system. Commercial oxidizing slag was reduced by coke under the microwave irradiation (1.7 kW, 2.45 GHz). The maximum recovery ratio of iron was 87%. In addition, slag composition modification was attempted to use the remaining slag for a mixture in cement clinker. Free-CaO in the slag was successfully suppressed, and the use of the remaining slag as a potential mixture was confirmed.

Joonho Lee, Sung Beom An, Minsoo Shin, Ki Joo Sim

Process Modeling and Simulation

Frontmatter
Computational Modelling of Metallurgical Processes: Achievements and Challenges

Extractive metallurgical processes rate amongst the most complex from the perspective of computational modeling. They typically involve multi-phase and multi-component fluid flow in very complex geometries, heat transfer driven by a number of interacting phenomena, solid-liquid-gaseous phase change and mass transfer together with complex thermodynamics and associated chemical reactions. Beyond the model building itself, key challenges have always involved being able to identify the phenomena present together with interactions to characterize processes and experimental laboratory and plant data to parameterize the arising models — it is in this milieu, which require considerable process understanding and subtlety of thought, that David Robertson has made his contributions.We will review the achievements, over the last couple of decades, in computational modeling of extractive metallurgical processes and address some of the remaining challenges to enable simulation based process design, as we move through the 21th century.

Mark Cross, Diane McBride, Nick Croft
Metallurgical Plant Optimization Through the use of Flowsheet Simulation Modelling

Modern metallurgical plants typically have complex flowsheets and operate on a continuous basis. Real time interactions within such processes can be complex and the impacts of streams such as recycles on process efficiency and stability can be highly unexpected prior to actual operation. Current desktop computing power, combined with state-of-the-art flowsheet simulation software like Metsim, allow for thorough analysis of designs to explore the interaction between operating rate, heat and mass balances and in particular the potential negative impact of recycles. Using plant information systems, it is possible to combine real plant data with simple steady state models, using dynamic data exchange links to allow for near real time de-bottlenecking of operations. Accurate analytical results can also be combined with detailed unit operations models to allow for feed-forward model-based-control. This paper will explore some examples of the application of Metsim to real world engineering and plant operational issues.

Mark William Kennedy
Chemsheet as a Simulation Platform for Pyrometallurgical Processes

ChemSheet is a thermodynamic multi-phase multi-component simulation software, which is used as an Add-in in Microsoft Excel. In ChemSheet, the unique Constrained Gibbs free energy method can be used to include dynamic constraints and reaction rates of kinetically slow reactions, yet retaining full consistency of the multiphase thermodynamic model. With appropriate data, ChemSheet models can be used to simulate reactors and processes in all fields of thermochemistry. The presentation will cover off-line modeling of Cu-flash smelters and advanced thermochemical simulation coupled with on-line process control of Cu-Ni smelting. The presentation will describe an off-line model of Cu-smelter based on critically assessed properties of the Al-Ca-Cu-Fe-O-S-Si -system (slag, matte and liquid metal) by using the quasichemical model. A four-stage reactor model (shaft, settler, uptake and bath) is used for optimizing process parameters and feed particle distribution. As a second example, an advanced thermochemical model of a Ni-Cu sulphide smelting plant will be given. The on-line model covers the operation of treating Ni-Cu-S concentrate via roasters, electric furnace and converters, producing a high grade Bessemer matte product for further refining. The model integrates the thermochemistry of the roasters and electric furnace, and predicts important process parameters such as degree of sulphur elimination in the fluid-bed roasters, matte grade, iron metallization, slag losses and the iron to silica ratio in the electric furnace slag. Both models can be used to assist process engineers and operators in calculating the addition rates of coke, flux and air for different feed scenarios.

Karri Penttilä, Justin Salminen, Nagendra Tripathi, Pertti Koukkari
A Computational Fluid Dynamic Model for a Novel Flash Ironmaking Process

A computational fluid dynamic model for a novel flash ironmaking process based on the direct gaseous reduction of iron oxide concentrates is presented. The model solves the three-dimensional governing equations including both gas-phase and gas-solid reaction kinetics. The turbulence-chemistry interaction in the gas-phase is modeled by the eddy dissipation concept incorporating chemical kinetics. The particle cloud model is used to track the particle phase in a Lagrangian framework. A nucleation and growth kinetics rate expression is adopted to calculate the reduction rate of magnetite concentrate particles. Benchmark experiments reported in the literature for a nonreacting swirling gas jet and a nonpremixed hydrogen jet flame were simulated for validation. The model predictions showed good agreement with measurements in terms of gas velocity, gas temperature and species concentrations. The relevance of the computational model for the analysis of a bench reactor operation and the design of an industrial-pilot plant is discussed.

Silvia E. Perez-Fontes, Hong Yong Sohn, Miguel Olivas-Martinez
Application of the Combined Reactors Method for Analysis of Steelmaking Process

A new integrated CFD-combined reactors approach is proposed for the description of processes in metallurgical vessels. CFD simulations were used to obtain the melt flow pattern in the vessels (ladle, tundish, and continuous caster mold). From these simulations, the characteristic curves were derived: (i) the residence time distribution curves (RTD) for flow-through systems (at tundish exit or at dendrite coherency surface in the mold) and (ii) the mixing curves for closed systems (ladle). In the next step, the melt flow was represented in a “combined reactors” system consisting of a combination of unit reactors (Plug Flow, Mixer, and Recirculated Volume). An inverse simulation was used to define the volumes of the reactor units and the melt flow rates between them by fitting to the characteristic curves from both methods (CFD and combined reactors). The suggested approach is demonstrated for multiple designs of Ar-stirred ladles, tundish, and SEN. This methodology can be used to enhance traditional post-processing CFD analysis and also as a tool for on-line process control.

Simon N. Lekakh, D. G. C. Robertson
Modelling of Slag Foaming Coupled with Decarburisation

CFD models have been developed and numerical simulations have been carried out to predict the formation of foam in oxygen steelmaking. Foam was considered as a separate phase comprising a mixture of gas and liquid. Bubble break up and coalescence models have also been incorporated in a CFD model to predict the number density of individual bubble classes. A population balance equation was used to track the number density of each bubble class. Decarburization with heat generation from chemical reactions was integrated in the process. User subroutines were written in FORTRAN to incorporate the foam formation, the bubble break up and coalescence rate and decarburisation in the main program. The model predicted the foam height, bubble number density, velocity of phases, decarburization, and turbulence. The result from the model has been compared with available data from literature and found to be in reasonable agreement with the experimental and plant data.

M. A. Sattar, J. Naser, G. Brooks
A Methodology for Modeling Electromagnetic Confinement Systems: Application to Levitation Melting

A modeling strategy is presented for computing the electromagnetic field and the shape of the molten metal in electromagnetic confinement systems. This strategy involves the use of a hybrid finite element/integral technique to calculate the electromagnetic field and force distribution in the melt. The free surface shape is determined from minimization of electromagnetic, gravitational and surface tension energies using the Lagrange method of multipliers. This approach was applied to model the electromagnetic levitation melting process. The model was found to accurately predict the measured shape of levitated droplets.

Nagy El-Kaddah, Thinium T. Natarajan
Electrochemical Characterization and Modeling of a Solid Oxide Membrane-Based Electrolyzer for Production of Magnesium and Oxygen

This paper reports a solid oxide membrane (SOM) electrolysis experiment using an LSM-Inconel inert anode current collector for production of Mg and O2 at 1423K. The electrochemical performance of the SOM cell was evaluated by using various electrochemical techniques including electrochemical impedance spectroscopy, potentiodynamic scans, and potentiostatic electrolysis. The effects of Mg solubility in the flux on the current efficiency and the YSZ membrane stability during SOM electrolysis were discussed and examined through experiment and modeling. The electronic transference number of the flux were measured to assess the Mg dissolution in the flux during SOM electrolysis. A negative correlation between the electronic transference number of the flux and the current efficiency of the SOM electrolysis was observed.

Xiaofei Guan, Uday B. Pal, Srikanth Gopalan, Adam C. Powell
Phenomenological Models and Animations of Welding and their Impact

Professor Robertson’s recognized research on metallurgical thermodynamics and kinetics for over 40 years facilitated the emergence of rigorous quantitative understanding of many complex metallurgical processes. The author had the opportunity to work with Professor Robertson on liquid metals in the 1970s. This paper is intended to review the advances in the quantitative understanding of welding processes and weld metal attributes in recent decades. Over this period, phenomenological models have been developed to better understand and control various welding processes and the structure and properties of welded materials. Numerical models and animations of melting, solidification and the evolution of micro and macro-structural features will be presented to critically examine their impact on the practice of welding and the underlying science.

Tarasankar DebRoy

Metallurgical Education

Frontmatter
Current and Suggested focus on Sustainability in Pyrometallurgy

The production of iron and steel and non-ferrous metals by pyrometallurgical processes will remain a critical element in meeting the demand for materials in both developed and developing nations. Given the important need to reduce and minimise greenhouse gas emissions the technological focus of future pyrometallurgical R&D by universities and industry alike must concentrate on sustainability issues such as improved energy efficiency, recycling and waste minimization. Continued efforts are also needed on process optimization and new process development with a view to reducing capital and operating costs of the new large “mega” plants. Using the academic and industrial backgrounds of the authors, the present paper reviews the current status of R&D in pyrometallurgy in university departments with a particular emphasis on sustainability issues. The role of industry and government laboratories is also reviewed although primarily for developed countries. The paper also includes comments and suggestions on the future requirements for education and R&D in pyrometallurgy in developed countries to maximise sustainability. It is also suggested that future R&D in pyrometallurgy will be even more concentrated in developing countries — most notably China.

J. B. See, D. G. C. Robertson, P. J. Mackey
Teaching Process Simulation in Eleven Easy Lessons Using Excel and Its Tools

The primary market driver for improving process technology is innovation, which requires a skilled and educated workforce. However, many Materials Science and Engineering departments have eliminated extractive metallurgy and chemical thermodynamics from their curricula, yet these topics contain the necessary fundamentals for process innovation. As a result, most MS&E students are ill-prepared for careers in processing. The dearth of process-oriented MS&E curricula has prompted some Universities to develop a “shared” effort to offer distance education between multiple institutions [1]. A target audience for a shared process simulation course would not only benefit students, but also be a basis for an on-line course for practicing engineers faced with new or changing career choices. To fill the gap, the basics of a process simulation course was developed in an abbreviated form as series of eleven articles and Excel workbooks published in Industrial Heating magazine between July 2012 and July 2013.

Arthur E. Morris
Enhancement of Pyrometallurgical Teaching Using Excel Simulation Models

Steady state Excel models for a copper flash smelter and an iron blast furnace are used to enhance the teaching of pyrometallurgical smelting principles within a fourth year level process engineering unit delivered at the Western Australian School of Mines. A lecture/workshop approach has been adopted in which student teams undertake process simulation assignments that illustrate the multifaceted responses of process outputs to variation of inputs, the objectives being to reinforce their understanding of smelting principles. The approach has proven to be popular with students, as evidenced by the consistently high ratings the unit has received through student feedback. This paper provides an overview of the teaching approach and process models used.

Eric J Grimsey
The Engineering Design Sequence and Materials Development: 990 Gold-Titanium as a Case Study

Engineering design follows a six-step sequence. Demonstration of this sequence in materials engineering is less common. A case study is presented, using the 1989 paper by Gafner on the development of 990 gold-titanium alloy. This paper identifies a need, develops the problem, identifies alternatives, demonstrates the use of metallurgical principles to identify alternative responses, and shows how more favorable options are selected. The paper can also be used to illustrate engineering design as an iterative process. The paper is also useful as a starting point for more in-depth examination of specific elements of the design process, and lends itself to the creation of student exercises.

Mark E. Schlesinger
The Challenges for Professional Metallurgical Education

The changes that are happening in the world of metallurgy, and with it university education, are generational and require generational responses. Some of the key issues facing metallurgical education and ongoing professional training are explored.What will be required of metallurgical engineering professionals in the coming decades? What knowledge and skills will be needed? How to provide the educational and learning pathways, and how to attract smart young people into this profession? These are issues more readily addressed by tertiary institutions in conjunction with industry; perhaps the greater challenges lie in building and maintaining competencies post-graduation. There is a need to establish and maintain a system that supports graduates and enables them to develop further into competent expert engineers able to successfully address complex engineering challenges.

Bob Hannah, Peter C. Hayes
Sustainability Education for Minerals and Materials Industry Professionals

The finite and non-renewable nature of mineral resources poses unique challenges for sustainability: How can mineral and material needs of society be satisfied indefinitely? How can the benefits of exploitation of minerals best be captured for present and future generations? How can the environmental problems caused by large scale mining and processing best be ameliorated? These issues are rarely addressed, or if so only incidentally, in traditional courses in geology, mining, metallurgy and materials yet addressing them will increasingly be a major role for professionals in the minerals and materials industry and related sectors and agencies. This paper describes a framework for examining these and other sustainability issues related to meeting future material needs from non-renewable resources. The framework may be useful for educational purposes, either as the basis of a dedicated subject or by including the elements of it throughout a traditional course in relevant subjects.

W. John Rankin
Delivering a National Process Design Unit with Industry Support

Supported by the Minerals Council of Australia (MCA) through the Minerals Tertiary Education Council (MTEC), three Australian universities-Curtin University, Murdoch University and the University of Queensland-have formed the Metallurgical Education Partnership (MEP) to jointly develop and deliver an engineering design capstone unit-Metallurgical Process and Plant Design-in their respective undergraduate programs in extractive metallurgy, in order to enhance the students’ educational experience. A unique feature of the program is the close interaction of the students in all three universities and a significant involvement of industry professionals. Now in its sixth year, it is clear that this unit is achieving its objectives.

Don Ibana
The MetSkill Program — Rapidly Developing Effective Young Engineers in the Workplace

MetSkill is a professional development program for metallurgical engineers that integrates with normal duties in their first one or two years of service. Graduates work together on a structured technical project, facilitated by specialists and supported by formal learning, and ultimately reported to their technical managers. The program enables graduates to “fill the gaps” in their undergraduate education, which is increasingly pertinent as engineering degrees become more general. Participants report that they enjoy the focus on more challenging (rewarding) aspects of their jobs and feel more confident about problem solving. Sponsor companies add that the relationships developed with external technical specialists enhances opportunities for innovation and development. MetSkill was delivered to two major resource companies in Australia in 2012. This paper provides an outline of the program and the reasons for its success, and demonstrates how the learning model could be applied to groups of graduates in other engineering disciplines.

Diana Drinkwater, Nina Bianco

Pyrometallurgy Process Fundamentals I

Frontmatter
Oxidation of Flash Reduced Iron Particles in Various Gas Mixtures Under the Conditions of a Novel Flash Ironmaking Process

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5–21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Zhixue Yuan, Hong Yong Sohn, Miguel Olivas-Martinez
A New Approach to Investigating Coke Reactivity

The coke analogue is a new research tool that has been developed to quantify and characterize the effect minerals in coke have on coke reactivity. The analogue material is made from a number of different carbon or carbon containing materials and minerals to in part replicate real industrial coke’s reactivity behavior. Elucidation of the effects of minerals on coke reactivity has proved difficult due to the complex and heterogeneous nature of industrial coke and the potential non-additive effects of minerals on coke reactivity. The coke analogue addresses this complexity and heterogeneity through control of its mineralogy, mineral size and mineral dispersion through the analogue, porosity and carbon structures. Initial studies using the analogue were focused on coke dissolution kinetics in liquid iron but recent work has focused in characterization of its porosity, carbon structure and rate of reaction.

Brian J Monaghan, Raymond J Longbottom, Mark Reid, Oluwatosin A Aladejebi, Apsara S Jayasekara, Marc in het Panhuis
The Use of Natural Gas for Reduction of Metal Oxides: Constraints and Prospects

Industrial pyrometallurgical processes in ferrous metallurgy are based on carbothermal reduction of metal oxides. Carbothermal reduction of stable oxides requires high temperatures. Low-temperature reduction can be implemented by using methane-containing gas with high carbon activity, or by carbothermal reduction under reduced CO partial pressure. Under standard conditions, methane is thermodynamically unstable above 550 °C and decomposes to solid carbon and hydrogen. At appropriate CH4/H2 ratio and temperature, carbon activity in the methane-containing gas phase can be well above unity relative to graphite, which provides favorable thermodynamic conditions for reduction. To maintain these conditions, the rate of reduction/carburisation should be higher than the rate of solid carbon deposition. The paper discusses reduction of pure manganese and chromium oxides at relatively low temperatures, and constraints in reduction of manganese and chromium ores. Reduction of metal oxides by carbon in hydrogen as an alternative use of natural gas is also discussed.

Oleg Ostrovski
Decomposition of Methane During Oxide Reduction with Natural Gas

The decomposition of methane has been studied experimentally in contact with various oxides at elevated temperatures. For each oxide, the temperature at which the cracking starts has been determined. No correlation was found to exist between the temperature for the onset of cracking for a given oxide and the affinity for carbon of the oxide’s metallic component. In terms of potential for using methane as a reducing agent, calculations are presented that indicate that the suitability of an oxide for such reduction depends on the desired methane+oxide reaction being more energetically favourable than the methane+methane=ethylene/acetylene reactions.

Halvor Dalaker, Pål Tetlie
Reduction of Mixtures of Ni-Oxide and Ti-Oxide Powder in a Natural Gas Containing Atmosphere

Natural gas has been used as reductant in the production of iron for several decades. Recently, the use of natural gas as reductant for other metals has been drawing attention because of the low price of natural gas, as well as the reduction of CO2 emissions compared to the use of coke and coal. In this work, the reduction of a mixture of Ti- and Ni-oxides by natural gas has been studied. Within the Ni-Ti system, the intermetallic compound Ni3 Ti is thermodynamically the most stable one. Therefore, powders of Ni-oxide and Ti-oxides were mixed in an atomic ratio of three to one and subsequently pelletized. Reduction was performed in a TGA furnace at constant temperature with varying reducing gas atmospheres.In a natural gas containing atmosphere, the Ni-oxide was easily reduced to metallic nickel while the Ti was reduced to Ti-oxycarbides or Ti-oxynitride when nitrogen was present. Depending on the process parameters, several percent of Ti was dissolved in the nickel-based solid phase.

Casper van der Eijk, Kai Tang
Kinetic and Thermodynamic Analysis of the Reduction of Oxides of Cu and Co in a SiO2-CaO-(Al,Fe)2O3 Slag

The investigation focuses on a low temperature recovery of Cu and Co from a 40 wt% SiO2-(30 wt%Fe,6 wt%Al)2O3-10wt% CaO-7wt%CuO-7wt%CoO slag over a temperature range of 1173K to 1323K. The alloy phases containing Cu-Co and Fe-Co alloy formed via the carbothermic reduction of oxides: MO + C = M + CO(g), where M represents metallic copper, cobalt or iron. In the direct reduction of oxides, the recovery of metallic phase was well below 90% at 1323K, due to the kinetic barrier which was analysed and attributed to oxygen and metal-ion transport in the slag. This barrier was overcome by adding CaSO4 and carbon, which yields a matte (MS) phase via MO + CaSO4 + 4C = MS + CaO + 4CO reaction. Lime thus produced in situ participates in metal oxide/metal sulphide reduction reactions, which are analysed with the help of X-ray powder diffraction, scanning electron microscopy, and thermogravimetric analysis.

Yotamu Stephen Rainford Hara, Animesh Jha
Carbothermic Reduction of Ilmenite Concentrate with Coke Assisted by High Energy Ball Milling

The electric arc furnace process is a common method to produce high TiO2 slag from ilmenite. The pre-reduction process was proposed in recent years in order to reduce electricity consumption. In order to enhance the pre-reduction degree, high energy ball milling was proposed to improve the specific surface area of the ilmenite prior to reduction. In this study, the carbothermic reduction behavior of milled ilmenite concentrate was investigated. It was found that the ball milling method can result in a higher reduction rate and improved metallization of iron. The metallization of iron increased with increasing the time of ball milling. The metallization of iron with milling reached 89.49% when the time of ball milling was 70 min., while the FeO content decreased with 70 min. of milling from 11.84% to 4.76%.

Bing Song, Kai Zhang, Fei Xi, Xuewei Lv

Pyrometallurgy Process Fundamentals II

Frontmatter
Electricity-Independent Generation of Silicon Based on the Use of Rice Husk: A Concept Process

The present paper is based on a term project for final year undergraduate students, requiring them to evaluate a process for producing silicon from rice husk. The traditional method for production of silicon involves carbothermal reduction of quartz in electric arc furnaces at temperatures exceeding 2000 °C. The technology consumes a considerable amount of electrical energy as well as fossil fuels, resulting in significant CO2 emissions. A flowsheet for production of silicon metal from rice husk is laid out in this paper. The technology will consist of combustors, which will generate steam using the rice husk biomass, power generator, and electric furnace for reduction of the rice husk. Materials and energy balance calculations presented here indicate that such process can be operated independent of external electricity.

Mansoor Barati
Electrically Enhanced Metal Purification Using Slag

A novel electrically-enhanced metal purification using slag has been developed. This was achieved by applying DC potential between liquid metal and slag phases. The concept was demonstrated through small-scale experiments at temperatures of 1500–1600°C for the removal of boron from Si-B melt using CaO-SiO2-16wt%Al2O3. Silicon (containing B) and slag were reacted in an alumina crucible in a resistance tube furnace. A circuit was produced by immersing graphite rods into the silicon bath and the slag layer. Electrical potential differences of up to 3.5 V were applied during the reactions. The reaction rates, the open-circuit voltages and short-circuit currents (in the case when the potential was applied) were then measured and determined for various slag to silicon ratio. It has been shown from this study that both the apparent rate and the boron partition ratio were increased by a factor of approximately 1.6.

Md Saiful Islam, M Akbar Rhamdhani, Geoffrey A. Brooks
Crystallization Behavior of Molten Blast Furnace Slag Using Confocal Scanning Laser Microscope

Extracting perovskite from high titanium-bearing blast furnace (BF) slag is a green and potential method to recover the second titanium resource. The non-isothermal crystallization process of perovskite in synthesized high titanium-bearing slag was studied in situ by confocal scanning laser microscope (CSLM) with cooling rate of 20 K/min. The results showed that perovskite was the primary phase formed during cooling process in the titanium-bearing synthesized slag (TiO2=23%). Perovskite started to precipitate at 1719 K and finally presented an orthogonal straight lines morphology.

Liu Lu, Hu Meilong, Bai Chenguang
Viscosity-Structure Relationship in the CaO-SiO2-MnO-CaF2 Slag for the Production of Manganese Ferroalloys

The viscosity of the CaO-SiO2-xMnO-yCaF2 slags (C/S=1.0; x=10, 40%; y=0 to 15%) was measured to clarify the effect of CaF2 on the viscous flow of molten slags at high temperatures. Furthermore, the Raman spectra of the quenched glass samples were quantitatively analyzed to investigate the structural role of CaF2 in a depolymerization of silicate networks. The critical temperature of the slags abruptly increased at 15%CaF2, which was confirmed to originate from a crystallization of cuspidine using XRD analysis. The viscosity of the slags continuously decreased by CaF2 addition in the 10%MnO system, whereas the viscosity of the 40%MnO system was not significantly affected by CaF2 addition. The effect of CaF2 on the viscosity of the slags was quantitatively analyzed using micro-Raman spectra of quenched glass samples accompanying with a concept of silicate polymerization index, Q3/Q2 ratio. A polymerization index continuously decreased with increasing content of CaF2 in the 10%MnO system, whereas it was not affected by CaF2 in the 40%MnO system. Consequently, the bulk thermophysical property of the CaO-SiO2-MnO-CaF2 slags was quantitatively correlated to the structural information.

Joo Hyun Park, Kyu Yeol Ko
Recovery of Vanadium from a High Ca/V Ratio Vanadium Slag Using Sodium Roasting and Ammonia Leaching

In order to seek an effective extraction process for vanadium, the recovery of vanadium from a high Ca/V ratio vanadium slag was studied by sodium roasting and ammonia leaching. In the present paper, the oxidation and leaching process of vanadium slag was investigated by X-ray diffraction (XRD), scanning electron microscopy and energy dispersive X-ray spectrometry (SEM/EDS) techniques. The effects of ammonium carbonate concentration, leaching temperature and leaching time on the leaching ratio of vanadium were discussed. As indicated in the experimental result, the optimal (NH4)2CO3 concentration was 120g/L, leaching temperature was 60°C and leaching time was 20 min. Approximately 92% of the vanadium was recovered under the optimal conditions. Furthermore, by means of X-ray diffraction analysis, the phase transformations of the vanadium slag during roasting and leaching processes were analyzed and discussed.

Song Xu, Mujun Long, Dengfu Chen, Helin Fan, Yuting Chen, Xue Sun
Sintering Process for Limonitic Nickel Laterite

Land-based nickel resources include nickel sulfide and nickel laterite. With the consumption of high grade nickel sulfide, use of nickel laterite has received more and more attention. The mineralogy and sintering behavior of limonitic nickel laterite with high iron and low nickel and silica was studied to offer technical support for producing ferronickel through sintering-blast furnace route. The mineralogy results showed that the main phases in this kind of nickel laterite are goethite (FeO(OH)), gibbsite (Al(OH)3) and NiFe2O4. The TGA (Thermogravimetric Analysis) and DSC (Differential Scanning Calorimetry) revealed hydroxide minerals in addition to absorbed water. After the sintering experiments the chemical composition, phases present (XRD analysis) and physical properties of the sinter were studied. The content of FeO in the sinter increased with increasing basicity up to 1.3, and then decreased with further increase in basicity. The yield of sinter increased (from 73% to 80%) with increase in the basicity from 1.1 to 1.7, and then the yield decreased with the further increase in basicity. Mg(Ni)(Fe,Al)2O4 is the main phase in the sinter while MgCaSiO4 and Fe2SiO4 is the main binder phase when the basicity is 1.1~1.5, and MgCaSiO4, Fe2SiO4 and SFCA is the main binder phase when the basicity is 1.7~2.1.

Enguang Guo, Mei Liu, Cheng Pan, Qiugang Yuan, Xuewei Lv

Pyrometallurgy Process Fundamentals III

Frontmatter
Development of a Thermodynamic Database for Mold Flux Applications to the Continuous Casting Process for Steelmaking

A thermodynamic database for the oxyfluoride system CaO-MgO-Al2O3-SiO2-Na2O-K2O-Li2O-MnO-FeO-F has been developed based on the critical evaluation and optimization of all available experimental thermodynamic and phase diagram data. The developed database can be used for phase diagram and equilibrium solidification calculations for multicomponent systems and for understanding the solidification behavior of mold fluxes. Based on this thermodynamic database, a simple kinetic model was developed to simulate the interactions between the mold flux and molten steel using effective equilibrium reaction volumes combined with the thermodynamic database.

Marie-Aline Van Ende, In-Ho Jung
Thermodynamic Optimization of Mn-Si-C System

The critical evaluation and thermodynamic optimization of Mn-Si-C and its sub-binary systems have been carried out over the whole composition range from room temperature to above the liquidus temperature. The solution properties of the liquid systems have not been clearly described because the liquid solution exhibits a high degree of short-range-ordering. In order to predict the thermodynamics of the liquid solution, the liquid phases were optimized by the modified quasichemical model. The model parameters of the solid phases were also optimized by the compound energy formalism to best reproduce the phase diagram and important thermodynamic properties in Mn-Si-C system. Using the model parameters, various thermodynamic calculations were carried out. The present database will be a part of larger thermodynamic database for the ferromanganese alloy database.

Min-Kyu Paek, Youn-Bae Kang, Jong-Jin Pak
Removel of Non-Metallic Inclusions from Molten Steel Using a High Frequency Magnetic Field

This paper is to discuss the removal of non-metallic inclusions from molten steel using a high frequency magnetic field. In experiments, a certain amount of aluminum was added to the molten steel in a crucible to generate aluminum inclusions. A layer of aluminum clusters were observed close to the wall of the crucible after the electromagnetic (EM) field was imposed. Three dimensional EM field and fluid flow simulation were performed and showed that over 91% inclusions transported to the skin depth (2.31 mm) of the molten steel. The calculation of inclusion removal agreed well with the experimental observation. The separation mechanisms of inclusions from the molten steel by the high frequency EM field were discussed.

Shengqian Wang, Lifeng Zhang, Yue Tian
Fluid Flow, Alloy Dispersion and Inclusion Motion in Argon-Stirred Steel Ladles

In this work, a multiphase mathematical model for the fluid flow in argon-stirred steel ladles was established and validated by experimental measurement of wood’s metal. Alloy dispersion in the molten steel was calculated. The melting and mixing of alloy was faster with smaller size of the alloy particles, larger superheat and bigger slip velocity. The current mixing time is approximately 300 s with 30 mm alloy diameter and 91.5 K superheat.

Yanlong Li, Lifeng Zhang, Ying Ren

Poster Session

Frontmatter
Nitrogen Solubility in Liquid Mn-Fe-Si-C Alloys

The nitrogen solubility in liquid Mn-Si, Mn-Si-Fe, Mn-Si-C and Mn-Si-Fe-C alloys has been measured by the gas-liquid metal equilibration technique in the temperature range of 1673–1773 K. The additions of silicon, iron and carbon significantly decreased the nitrogen solubility in liquid manganese alloys. The experimental results were thermodynamically analyzed by the Wagner’s formalism to determine the first- and second-order interaction parameters of silicon, iron and carbon on nitrogen in liquid manganese. The thermodynamic parameters can be used to predict the nitrogen solubility in ferromanganese and silicomanganese alloy melts as functions of the melt composition and temperature at given nitrogen partial pressures.

June-Yong Eom, Jung-Mock Jang, Min-Kyu Paek, Jong-Jin Pak
Study on Dezincification and De-Lead of Blast Furnace Dust by Fluidized Reduction Experiment

In the blast furnace process, the dust entrained in the blast furnace gas enters into the down-comer, flows through the gravity dust separator (to eliminate coarse particles) and then is collected in a bag-house. The powder collected by the baghouse is called bag dust, while both fractions are called blast furnace dust whose main components are C and Fe. The dust also contains small amounts of nonferrous metals such as Zn and Pb, which have some value. Also, due to the small particle size and low density the dust is easily suspended in air and so can endanger human health. Therefore it is necessary to develop a process to both treat the dust to recover the metal values and to dispose of the residue — preferably by recycling to the blast furnace itself via the sinter strand. These objectives will result in good economic, environmental and social benefits [1].

Shufeng Yang, Chengsong Liu, Xiaojie Gao, Jingshe Li
Backmatter
Metadata
Title
Celebrating the Megascale
Editors
Phillip J. Mackey
Eric J. Grimsey
Rodney T. Jones
Geoffrey A. Brooks
Copyright Year
2016
Publisher
Springer International Publishing
Electronic ISBN
978-3-319-48234-7
Print ISBN
978-3-319-48591-1
DOI
https://doi.org/10.1007/978-3-319-48234-7

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