Search Documents

By D Stepanenko, G Stovpchenko, L Lisova, D Togobitskaya, L Medovar

Classical electroslag remelting of consumable electrodes is a drop-by-drop melt feeding through a slag layer into a renewing molten metal bath, slowly solidifying into a homogeneous, dense, defectfree ingot in a copper water-cooled mould. The new look at the additive nature of the electroslag remelting (ESR) process in a protective atmosphere allowed us to formulate the principles of a comprehensive thermodynamic-based model that can predict dynamic changes in slag and metal composition at certain ingot remelting. The model considers drastically different slag-to-metal mass ratios at the beginning and end of remelting and predicts gas, slag and metal composition in a chain of thermodynamic subsystems. Despite consisting of calcium fluoride and stable oxides, the ESR slag can oxidise main and active elements from steel and alloys (primarily aluminium, titanium and silicon) due to chemical reactions between slag and metal. ESR is not an electrochemical process in its nature. However, slags are ionic melts and deviation in their composition causes a change in their properties, affecting both operation mode and ingot quality. Another important understanding derived from the modern metallurgy technological route is that the ability to refine metal from impurities is not a priority for the ESR because consumable electrode has already passed all stages of refining and deep degassing at ladle treatment that changes ESR slags engineering principles. The critical importance became slag’s ability to generate process heat and keep the melting composition in the metal bath unchanged (except for non-metallic inclusions assimilation). Slag engineering for ESR required a compromise between chemical inertness to a metal composition and desired physical properties deriving from technological reasons. The Directed Chemical Bonds Concept (DCBC) in a multicomponent oxide system was used to build predictive models of electric conductivity and the melting temperature of fluoride-oxide slag based on their chemical composition. Both models help to design a customised composition of effective slags for steel and alloy groups or individual grades, and they are significant steps in the development of a comprehensive model of electroslag remelting.

Aug 21, 2024

By B A. Webler, P Su, P C. Pistorius

Advanced high-strength steels (AHSS) typically have much higher aluminium concentrations (by an order of magnitude or more) than conventional low-carbon aluminium-killed steels. The resulting lower oxygen activity at the steel-slag interface changes the kinetics and thermodynamics of steelslag reactions. Previous work showed that the rapid transformation of alumina inclusions to spinel inclusions, and spinel to periclase, occurs because of the relatively high concentration of dissolved magnesium. In this paper, experimental results on nitrogen removal by ladle slag are compared with predictions based on the available thermodynamic databases. As in previous work, the kinetics was modelled by assuming mass transfer control, with steel or slag mass transfer limiting. The results show that significant removal of nitrogen by steel-slag reaction is possible.

Aug 21, 2024

By H Kim, M J. Sun

Global steel companies are actively combating climate change by reducing carbon emissions. Traditional steel production, using the blast furnace (BF) – basic oxygen furnace (BOF) process, heavily depends on coal and emits substantial CO2. To mitigate this, companies are transitioning to the more eco-friendly DRP (direct reduction plant) – EAF (electric arc furnace) process, which lowers CO2 emissions. This study quantitatively evaluates the impact of increased hydrogen consumption on the carbon footprint of product (CFP) through an analysis of direct reduction process heat and mass balances. The study prioritises a comprehensive material balance based on mass conservation principles. The heat balance is calculated using differences in enthalpy through state energy properties, avoiding heat consumption. Validation using operational data from Hyundai Steel Dangjin works’ blast furnaces shows close alignment between calculated results and actual data, with less than 1 per cent error. This methodology facilitates a detailed analysis of the direct reduction process, offering insights into its feasibility and efficiency. Analysis of the operational impact by increasing the hydrogen ratio demonstrates reduced CO2 emissions and increased heat requirements due to the endothermic nature of hydrogen reduction, in contrast to the exothermic CO reduction. Possible solutions include raising reducing gas temperature or enhancing flow rate. The study effectively utilises designed heat and mass balances to assess material quantities and thermal balance under different operational conditions. It lays the foundation for the initial direct reduction process design, aiding in deriving and optimising operational parameters. Additionally, it provides valuable insights into the challenges of increased hydrogen, contributing to the production of greener steel by addressing these issues.

Aug 21, 2024

By A Vickerfält, J Huss, J Martinsson

The European Union has listed vanadium (V) as one of the critical raw materials for the transition to a future green society, as stated in the Critical Raw Material Act, written by Grohol and Veeh (2023). In the steelmaking industry based on V-containing iron ore, V is a possible by-product from the slag. A requirement for slags to be suitable for V extraction is a V content preferably above 8 wt per cent as V2O3 and a phosphorus (P) content below 0.1 wt per cent as P2O5. Hence, it is important to keep V in the slag phase while the P is moved to the metal phase during the steelmaking process.

Aug 21, 2024

By J Coveney, A Rich, D Grimsey, J Wood, S Creedy

In 2021, BHP and Metso examined processing of high-MgO nickel sulfide concentrates using Metso’s Ausmelt Top-Submerged-Lance (TSL) technology. Test work was conducted in Metso’s pilot test work facility in Dandenong, Australia to explore operability of the SiO2-FeO-MgO-CaO-NiO slag system across a wide range of compositions, temperatures and bath oxygen potentials. Pilot-scale testing aimed to define slag ‘operability limits’, representing the lowest bath temperature at which stable process and equipment operation could be maintained. This work was supported by FactSage™, version 8.2 (by Thermfact/CRCT and GTT-Technologies) thermodynamic modelling, slag viscosity measurements, physical characterisation of quenched slag samples performed by the University of Queensland and benchmarking of commercial-scale TSL nickel smelting operations. A wide range of slag compositions were examined, with Fe/SiO2 ratios varying from 0.4–1.1, CaO content from 0.8–7.0 wt per cent and MgO content from 6–19 wt per cent. Slag SiO2/MgO ratio, wt per cent CaO and matte grade were found to have the greatest impacts on identified operability limits. Operability limits were found to be influenced by both the solids content in slag and viscosity of the remaining liquid slag phase, with the relative contribution of these parameters heavily influenced by the slag composition. In the majority of trials, limits were defined by a theoretical solids content of 40–50 per cent, however in trials with a low Fe/SiO2 ratio and/or low wt per cent CaO, limits were characterised by a much lower solids content due to the increased effect of the liquid slag viscosity in determining the behaviour of these slags. The test work highlighted inherent flexibility of the Ausmelt TSL process to operate across a wide slag range of slag compositions and recover from process disturbances without an interruption to feeding. The trials also demonstrated the possibility for Ausmelt TSL technology to process concentrates with an Fe/MgO ratio as low as 1.4, which has important implications to the commercial-scale processing of high MgO feeds. Arsenic rejection across the trials was very good, with only 30 per cent of arsenic in the feed inputs reporting to the matte phase. Such high levels of arsenic removal provide the Ausmelt TSL process with a notable advantage over alternative smelting technologies.

Aug 21, 2024

By A Kamaraj, M Mohanasundaram, R Kumar, P Tikare

This study presents a comprehensive thermodynamic optimisation and sustainability analysis of the secondary copper smelting process for Waste Printed Circuit Board (WPCB) recycling. The study investigates various scenarios with different proportions of WPCB in the input stream, ranging from 0 per cent to 100 per cent. Through thermodynamic modelling using FactSage™ version 8.1, the optimisation process is conducted in three stages. The results of the thermodynamic modelling indicate that the best-case scenario for WPCB recycling is achieved with a 40 per cent proportion of WPCB in the input stream. This case exhibits a maximum copper recovery of 99.93 per cent while minimising the formation of other waste. In addition to the thermodynamic analyses, environmental factors such as the carbon emission index and resource utilisation efficiency are studied. The 40 per cent WPCB recycling case exhibits a resource utilisation efficiency of 93.055 per cent and a carbon emission rate of 0.133. The present investigation highlights the significant benefits of a 40 per cent WPCB recycling scenario through a secondary copper smelting process in terms of base metal recovery and energy efficiency, thus emphasising its potential for sustainable PCB waste management and resource utilisation.

Aug 21, 2024

By M Kim, J Park, I-K Suh, E Kim, J Lee

One of the key technologies in developing hydrogen-enriched ironmaking operations is the control of the carburisation, melting, and dripping behaviour of the iron ore burden materials. When a hot compacted iron (HCI) is charged in the blast furnace or the FINEX Melter-Gasifier, iron oxide reduction, the reduced iron’s carburisation, and the melting of iron and slag occur successively. This study investigated the reduction, carburisation, melting and dripping behaviour of HCI under a COH2 gas mixture using the high-temperature X-ray radiographic technique. Under 100 per cent CO gas atmosphere, the dripping temperature was 1410°C. When 5 per cent H2 was introduced, the dripping temperature slightly decreased to 1400°C. Furthermore, the dripping temperature gradually increased as the H2 gas composition increased. As 30 per cent H2 was introduced, the dripping temperature reached 1414°C. The carbon concentration in the drained metal samples gradually increased with increasing H2 composition. It is considered that H2 decreased FeO content in the slag, yielding the increased melting temperature and viscosity of the slag. On the other hand, H2 accelerated the carburisation of the reduced iron by CO gas, enabling the homogenisation of the oxide materials to form a liquid phase. Therefore, it is considered that introducing H2 in the reactor is helpful to increase productivity and energy efficiency by accelerating the liquid phase’s formation.

Aug 21, 2024

By R G. Reddy, Z Zhang

Viscosities of CaO-aluminosilicate ternary melts were estimated using a structure-based model. The model considers depolymerisation effects and related breakdown of the silicate network structure on the addition of metal oxides to the melts. The predicted values are in good agreement with the experimental values over the whole temperature and composition range.

Aug 21, 2024

By G M. Zhomin, A S. Arkhipin, A Kondratiev

Viscosity of multicomponent slags is one of the crucial physicochemical properties for many industrial processes and technologies. While the viscosity-temperature relationship of completely molten slags can well be described by an Arrhenian-type law, the compositional dependence of viscosity is still not fully understood, especially in compositional regions with the lack of experimental data (eg at the glass-former concentration of 90 molar per cent or higher). In the present work major compositional relationships of the activation energy of viscous flow have been revised for numerous binary and ternary slag systems on the basis of experimental data collected and stored in the viscosity database OxiVis. For example, it has been found that the activation energy relevant to the polymerisation effect in binary systems of the MO-GFO type, where MO is the modifier oxide (ie monovalent K2O, Na2O, Li2O and bivalent CaO, MgO, BaO, MnO, PbO etc) and GFO is the glass-forming oxide (SiO2 or B2O3) is not always proportional to the third power of XGFO (contrary to the Urbain formalism) and can vary significantly dependent on the slag system. Also, the activation energy of the charge compensation effect has been revised for ternary systems of the AO-MO-GFO and AO-MO type, where AO is the amphoteric oxide (Al2O3, Fe2O3 or other). A simple polynomial model has been proposed on the basis of the carried-out analysis for estimation of viscosities of multicomponent slag systems. The model has been optimised against the experimental viscosities in the selected binary, ternary, and higher-order oxide systems and has been shown reasonable agreement with the experimental data.

Aug 21, 2024

By S L. Nicol, B J. Hogg, O J. Mendoza, S Nikolic, A Burrows

The top submerged lance (TSL) technology, developed in the 1970s, is now widely used for the processing of a range of materials. The key advantage the ISASMELT™ TSL technology provided was the ability to process feed materials in a highly turbulent bath, reaching close to equilibrium conditions, uniquely allowing for operation below the liquidus of the molten slag phase. The details on what happened below the liquidus line in the phase diagram became critical for the successful operation of the technology. During the development of the ISASMELT™ technology this led to a collaboration between the Process Technology group of Mount Isa Mines, now part of Glencore Technology, and the Pyrometallurgy Research Centre (PYROSEARCH) at The University of Queensland. The fusion of the phase equilibria research into the technology development allowed for understanding of the behaviour of molten splash, reliable tapping of the furnace, and the ability to operate the furnace with a refractory lining and achieve a year campaign life in excess of four years. The outcome has allowed for the highly successful adaption of the ISASMELT™ technology to recycling of complex feed streams necessary to drive circularity in our modern global economy.

Aug 21, 2024

By A Van den Bulck, K Verbeken, O Vergote, I Bellemans

Viscosity is one of the most important physicochemical properties during pyrometallurgical operations. In the sub-liquidus regime, an important factor is the presence of suspended solid particles, yet its influence is not well-described in earlier literature, despite the significance of this factor. This project aims to determine the influence of spinel particles (Zn(Al,Fe)2O4) on the rheology of a multiphase synthetic PbO-SiO2-ZnO-Fe2O3-CaO-Al2O3 slag system. Three data sets with a wellcontrolled methodology and three different spinel sizes (small (13 μm), medium (34 μm) and large particles (76 μm)) were published previously, using a custom-built high-temperature rheometer. This study presents an additional data set of slag viscosity measurements, performed using a different apparatus, the Anton Paar FRS 1800, to verify the consistency of the earlier determined viscosity behaviour. Within this data set, no consistent trend could be found between the predicted wt per cent spinel and the relative viscosity. Therefore, additional quenching experiments were conducted to identify the morphology and experimentally determined volume fraction of the spinel particles in the slag. These measurements revealed a difference in spinel size across the samples and corresponding viscosity behaviour, emphasizing the importance of spinel particle size on slag viscosity. Once the spinel size was taken into account, consistent viscosity results (relative apparent viscosity and flow index) were observed across the two devices. This study confirms that, once all parameters affecting slag viscosity are considered, the viscosity behaviour of a heterogeneous slag can be uniquely determined. The resulting optimised slag viscosity models can be used to predict viscosity before processing, addressing relevant phenomena such as slag tapping, slag foaming and copper droplet settlement.

Aug 21, 2024

By G Sartor, A Rich, D Grimsey, R Forzatti, M White

An in-depth process model was developed for the pyrometallurgical, off-gas systems and water balance of the Kalgoorlie Nickel Smelter. This model was used to assess plant capacity with changing concentrate grades, increased throughput and tighter environmental emissions under a range of potential future operating conditions. Comparison of modelled results allowed for flow sheet optimisation across a range of metrics including sustainability, processing capacity and costs. Process modelling software, METSIM® (ver 2020.06 by METSIM International), was used to simulate the flash furnace, integrated electric slag cleaning furnace, Pierce-Smith converters, matte granulation, waste heat boiler, hot gas handling equipment, wet gas cleaning plant and acid plant. The METSIM® model was divided into three separate, yet interconnected models: metals, off-gas and water balancing. This allowed for improved modelling efficiency and traceability while minimising manual error. The METSIM® model was supported by inputs from other specialised software. Chemical thermodynamics software, FactSage™ (ver 8.2 by GTT Technologies), was used to establish relationships for the flash furnace fluxing strategy and determine the operating temperature. Arena® (ver 16.0 by Rockwell Automation), a discrete event modelling software, was used to simulate material movements within the aisle as well as Pierce-Smith converter operation, allowing for integration with upstream and downstream systems. A dynamic data exchange (DDE) was used to connect the results of each software package, interfacing through Excel® (version 4203 by Microsoft). The integration between models provided a streamlined approach to test capacity, bottlenecks, water consumption and emissions under a range of operating conditions, enabling a more robust process. Further downstream modelling techniques were used to assess mechanical equipment. METSIM® outputs provided key parameters for combustion assessments using computational fluid dynamics and finite element analysis for the furnace mechanical design.

Aug 21, 2024

By R Atmuri, W Liang, R Prasad, Y Liu, E Wingate

Yellow phosphorus (YP) has been commercially produced since the 1920s. First in the USA by the Tennessee Valley Authority (TVA), next in Russian (Kazakhstan) in the 1950s, and finally in China in the late 1970s and early 1980s. There are operations in Vietnam and Sarawak on a smaller scale. YP has become very in vogue due to its use in the production of lithium iron phosphate battery cathode precursor materials by the Chinese and other western battery manufacturers. The YP is also used to produce purified phosphoric acid and higher grades of acid using a thermal oxidation process after smelting. This paper will look at the basics of the smelting including slag chemistry, alloy chemistry and offgas chemistry. The paper will look at the design of the furnaces used in the YP production process as well as the downstream recovery of phosphorus from the smelter off-gas stream to YP. The next part of the discussion will focus on the operations of a YP smelter with regards to control of the furnace to optimise phosphorus recovery to YP. Will discuss tapping cycles for alloy and slag with a view to optimal phosphorus recovery. The discussion will close out with a review of operational challenges in the smelter and a brief description of the downstream conversion of YP to high purity phosphoric acid.

Aug 21, 2024

By M-A Van Ende, N Kumar, I-H Jung

In order to utilise the powerful thermodynamic databases for process simulations, a concept called Effective Equilibrium Reaction Zone (EERZ) was introduced to couple thermodynamic database calculations and reaction kinetics. Using the EERZ concept, many process simulation models for steelmaking processes have been developed within the FactSage steelmaking consortium. After validation of the simulation results by comparing with plant data, the simulation models have been applied to improve plant operations. Several success stories of the improvement of real steelmaking operations are shared. A new user-friendly FactProSim software developed for building process simulations is introduced.

Aug 21, 2024

By R G. Reddy

The complexity in treating environmentally harmful impurities such as As, Sb, Bi from the base metal matte or metal in the smelting stage are responsible for the high cost of the refining process. The impurity capacities (such as arsenic, antimony and bismuth) of slags were calculated a priori using Reddy-Blander (RB) model. The capacity predictions were for a wide range of matte and slag compositions in copper smelting conditions. The calculated impurities capacities and impurity distribution ratios results are in good agreement with the available experimental and industrial slags data. The a priori knowledge of impurities is useful for reduction of energy consumption and enhanced environmental control in the current and future non-ferrous metal processes.

Aug 21, 2024

By S Gezgin, F Beckstein, M Müller, D Rapp, D Sergeev, J Qi, A Lichtinger

Salts and their mixtures play an important role for industrial and energy sectors, eg metallurgy, biomass gasification and combustion, nuclear and solar powerplants and electrochemical processes. Depending on the composition of salts (eg Li+, Na+, K+, Mg2+, Ca2+ // NO3-, F-, Cl-, CO32-, SO42-, etc), the temperature range for different applications can vary starting from room temperature and going up to 1500°C. For the proper design and modelling of heat exchangers and other equipment, it is necessary to have reliable and validated data sets of thermophysical properties. The 50 mol per cent NaNO3 – 50 mol per cent KNO3 salt mixture as a well-studied composition was selected for validation of relevant thermophysical properties (heat capacity, enthalpy of phase transitions, thermal expansion, viscosity and thermal conductivity). To study these properties of the liquid phase, special crucibles and approaches should be implemented. Verification of these crucibles for different methods (differential scanning calorimetry (DSC), thermomechanical analysis (TMA), laser flash analysis (LFA) and rheometers) has been performed. The low thermal conductivity of salts is one of the main problems in implementing latent heat storage. In this project, the authors intend to develop a fundamental solution to this problem using chemically bonded metals with salts. These are known as metal-salt solutions. To fit the main parameters of new phase change materials to the requirements of thermal energy storage, a wide variety of possible combinations should be considered. CALPHAD modelling is used together with thermal analysis for the development of a consistent thermodynamic database including chloride salts (Li, Na, K, Mg, Ca // Cl) and corresponding metals (Li, Na, K, Mg, Ca). The results of the study of quasibinary and multicomponent metal-salt (eg Mg-KCl and Ca-KCl) systems as well as the selection of suitable crucible materials and challenges by studying of these systems will be discussed.

Aug 21, 2024

By R A. Pakhomov, L V. Krupnov, P V. Malakhov, I M. Dymov

The article presents results of thermodynamic calculations and laboratory studies, focusing on the cobalt behaviour during oxidative smelting of copper-nickel mattes. The compositions of the studied solutions are related to the products formed during the second stage of the converting process of copper-nickel matte at the Nadezhdinsky Metallurgical Plant (NMP) of MMC Norilsk Nickel company. These sulfide products typically contain from 1.5 to 12 wt per cent of iron. The obtained experimental results and thermodynamic calculations indicate that adjusting the CaO ratio to increase the proportion of CaO or complete replacement of SiO2 with fluxes containing CaO leads to a significant increase in cobalt recovery rates in the matte phase (with an iron concentration of 2.5 wt per cent) raising them from 30 per cent to 45 per cent. Meanwhile, the recovery rates of copper and nickel remain constant.

Aug 21, 2024

By S Wan, F Zhang, J You, K Tang, X Tang, C Bessada, A Canizarès, Q Zhang, L Lu

Microstructure of CaO-SiO2-based glassy samples with various Al2O3 contents were examined quantitatively by Raman spectroscopy and 27Al MAS NMR (magic-angle spinning nuclear magnetic resonance). Sequence of multiple cluster models of aluminosilicate system modified with Ca2+ and Na+ cations have been designed, and Raman spectra simulation were carried out after geometric optimisation by quantum chemistry (QC) ab initio calculation. The functional relationship between Raman scattering cross-section (RSCS) and stress index of silicon-oxygen tetrahedron (SIT) for aluminosilicates was established, which was applied to the calibration of experimental Raman spectra. Some five-fold coordinated aluminium (AlV, around 5 per cent) and less than 2 per cent sixfold coordinated aluminium (AlVI) were detected by 27Al MAS NMR, while most of aluminium remained in tetrahedral sites (AlIV). The hyperfine quantitative results of Raman spectroscopy and NMR showed a gradually production of AlIV with addition of Al2O3, along with the significant adjustment of Qi species distribution, in which Q1, Q2 reduced and fully polymerised Q4 increased while Q3 showed a non-monotonic variation and obtained the maximum at Al2O3 = 18 mol per cent. Furthermore, the effects of aluminium to bridging oxygen bond types (T-Ob, T = Si, Al) and the degree of polymerisation were also discussed in detail. The evolution of microstructure and its correlation with the viscosity of CaO-SiO2 based melts, incorporating various Al2O3 additives, have been investigated by employing in situ high temperature Raman spectroscopy at 1823 K and viscosity model. These structural features related to composition are essential theoretic foundation to understand their properties. The average Qi evolution culminates in an overall enhancement of the degree of polymerisation. Viscosity was determined utilising a rigorously selected viscosity model, elucidating a consistent upward trajectory as Al2O3 content is incrementally added. Furthermore, a quantitative analysis of the relationship between viscosity and structure was conducted based on the average number of non-bridging oxygen per network-forming tetrahedron (NBO/T). It provides valuable insights for examining and predicting viscosity behaviour of aluminosilicate systems.

Aug 21, 2024

By K S. Park, J K. Kim, J H. Park, Y Su

The present study investigates the possibility of the direct removal of oxygen from the Ti-30Ni (wt per cent) alloy melt through the thermodynamic equilibrium reactions at 1623 K in the vertical tube furnace. The deoxidation efficiency of Ti-Ni alloy melt by adding different contents of metallic calcium (Ca) as a deoxidant was evaluated with the binary CaF2-MgCl2 flux. The thermodynamic equilibrium experiments showed that the total oxygen content in the alloy decreased from about 650 ppm to 350 ppm when 3.5 wt per cent Ca was added to the Ti-30Ni (wt per cent) alloy. Alternatively, the effect of flux composition in the CaF2-MgCl2 flux on the oxygen content was also investigated at 1623 K. Therefore, the effect of binary flux systems on the deoxidation ability was compared at 1623 K. According to the results, the flux system with 80 per centCaF2– 20 per centMgCl2 exhibited the best deoxidation capability, ie total oxygen content in the alloy reduced from 1450 to 550 ppm.

Aug 21, 2024

By S K. Michelic, M Schickbichler, A Kharicha, E Karimi-Sibaki

The requirements for the controllability of metallurgical processes are increasingly becoming the focus of both industry and research. Advances in this field of research not only impact the stability of processes but often also influence the quality of the final product. One important way to examine processes in-depth, and thus show potential for improvement, is to describe them using physicsdriven models. In metallurgy, thermodynamic and kinetic descriptions of interactions between individual components of a system are often used to describe and analyse important metallurgical phenomena across the entire process. However, for the creation of physics-based models, boundary conditions and process variables must be implemented to enable a description that is as realistic as possible. The collection and generalisation of boundary conditions and process variables is, therefore, an important step towards functional models. The focus of this study is the determination of mass transfer coefficients between all components in a steel/slag/refractory system. For this purpose, experimental and theoretical methods are applied. Laboratory scale experiments are carried out in an induction furnace, and the mass transfer coefficients of the defined steel/slag/refractory system are calculated from changes in the chemical composition of the various components. Additionally, a calculation of the mass transfer coefficients based on dimensionless quantities is carried out. By comparing the values of the mass transfer coefficients determined theoretically and those determined experimentally in the trials, the suitability of the calculation is examined. The collection of mass transfer coefficients provides essential findings for future kinetic descriptions of inclusion modification based on the effective equilibrium reaction zone (EERZ) approach.

Aug 21, 2024