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By K Saito, M Hasegawa

In steelmaking processes, it is known that P2O5 in dephosphorisation slags often exists in solid solutions between Ca2SiO4 and Ca3P2O8, <C2S-C3P>SS, and thus the solid solutions play an important role in the dephosphorisation reaction. Hence, the knowledge of thermochemical properties, ie phase relations and activities of components, in slags containing <C2S-C3P>SS are necessary for the effective removal of phosphorus from hot metal. In this study, the P2O5 activities in <C2S-C3P>SS were measured through the gas equilibrium method. In the present experiment, oxide samples were equilibrated with Cu-P liquid alloys at 1573 K under a stream of Ar + H2 + H2O or Ar + H2 + CO2 gas mixture in which oxygen potential was fixed and then equilibrium phosphorus concentrations in the Cu-P alloys, [mass%P]Cu, were analysed with ICP-OES.

Aug 21, 2024

By M Ranjan, C R. Borra, P Palai, P P. Sahoo

Change in mould slag composition during casting of medium alloy steel is caused by the redox reaction between molten steel and mould flux. Mould flux generally contains a certain amount of SiO2, but elements such as Al, Mn and Ti in high/medium alloy steels reduce SiO2 in the mould flux, causing remarkable changes in the composition of the mould slag. As a result, the properties of the mould slag change greatly as continuous casting proceeds. This causes casting instability, process abnormality and casting defects. Effect of Ti as an alloying element in steel on mould slag is studied extensively through high temperature laboratory measurements and plant measurements. TiO2 gets picked up by the mould slag up to 3 per cent during casting a steel grade containing 0.1 per cent Ti. This changes the mould slag composition and results in decreasing the slag viscosity by up to 10 per cent and decreases slag break temperature by 30–40°C.

Aug 21, 2024

By R G. Reddy, A Yahya

The sulfur distribution ratio (Ls) is an expression of the amount of sulfur in slag to the amount of sulfur in molten metal. The sulfide capacities calculated from Reddy-Blander (RB) model were used to calculate the sulfur distribution ratio (Ls). A new Reddy model for sulfur distribution ratio (Ls) was developed for modelling Ls for ironmaking, steelmaking, and secondary steelmaking conditions. Besides calcium oxide, the major component in the ladle furnace (LF) slags is alumina. The Ls was calculated for typical LF slags as a function of temperature and composition. The model calculated Ls values are in good agreement with the experimental and industrial slags data. The extremely low oxygen potential in these furnaces after fully-killed steel is favourable for desulfurisation. For any given slag’s composition and temperature, its sulfide capacity can be calculated a priori. The equilibrium sulfur distribution ratio between this slag and liquid metal in a particular vessel can also be calculated a priori. The Ls for ladle furnace (LF) slags is about twice those for blast furnaces (BF) slags and ten times those of basic oxygen furnace (BOF) slags. The desulfurisation of pig iron in BF and desulfurisation of steel in LF during secondary steelmaking are recommended. Steel desulfurisation in steelmaking furnaces is not effective. Since the model used to calculate the sulfur distribution ratio (Ls) is a priori, it is a useful tool for the iron and steel makers in improving the product quality and optimisation of the industrial furnace operations.

Aug 21, 2024

By A Nigam, K Biswas, R Sarkar

Because of the problems with 1st and 2nd generations of Advanced High-Strength Steels (AHSS), a 3rd generation of AHSS steels has become prominent and these steels have properties in between the 1st and 2nd generations of AHSS. However, although the 3rd generation of AHSS is a promising candidate as a replacement for its predecessors, there remain some challenges in processing these steels which are essentially medium Mn (Mn content ~ 5–7 wt per cent) and high Al (Al content ~ 1– 3 wt per cent) steels. The use of conventional casting powders based on the CaO-SiO2 system is unsuitable for high and medium Mn/Al steels. This work investigates the development of CaO-Al2O3- based mold fluxes for casting third-generation AHSS steel. Mold fluxes, with otherwise similar compositions but different C/A ratios, are tested and their crystallisation behaviour is examined using differential scanning calorimetry (DSC). A calcium aluminate phase having a composition Ca12Al14O33 was found to be the main crystalline phase in the mold fluxes. A decrease in crystallisation temperature was observed as the CaO/Al2O3 ratio increased from 1.00 to 1.33. The effective crystallisation rate constant exhibited an increase with decreasing crystallisation temperature, indicating a potential influence of nucleation rate on the overall crystallisation rate and suggesting an anti-Arrhenius behaviour in the crystallisation process of these mold fluxes.

Aug 21, 2024

By Z Li, Z Yan, T Htet, S Zhang

During the pyrometallurgical processes, a substantial quantity of high-temperature ironmaking and steelmaking slags, generated at temperatures ranging from 1400 to 1600°C, is wasted, as the heat contained in these slags is released into the environment during the tapping process without effective utilisation. On the other hand, a significant amount of energy is required to reheat the cold materials for the manufacturing of glass and mineral-wool, often necessitating the addition of high-silica materials to facilitate the production process. In this study, an innovative approach is presented to harness the heat present in molten metallurgical slags to directly produce new raw materials for glass and mineral-wool manufacturing while simultaneously reducing energy consumption and mitigating CO2 emissions. The theoretical amount of waste glass that can be effectively added in the process has been estimated via thermodynamic calculation. Experimental assessments were conducted to examine the impact of high-silica waste materials on the dissolution, melting and fluidity. Potential recipes for glass and mineral-wool manufacturing were suggested and an assessment of the energy savings, and reduction in CO2 emissions with manufacturing of glass and mineral-wool using this innovative approach were included. It was determined that the processes could lead to a reduction of over 26 kg of CO2 emissions per 100 kg of new material used, primarily due to the utilisation of heat from slag and the accelerated smelting process.

Aug 21, 2024

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 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 H Zhang, S Li, J Song, Z Lv

In this paper, a method for extracting and refining metallic molybdenum using low-temperature ZnCl2- NaCl-KCl molten salt was proposed. The electrochemical behaviour of molybdenum ions in ZnCl2- NaCl-KCl molten salt was investigated in detail, and pure metallic molybdenum was collected on the cathode. The reduction and diffusion processes of Mo(V) ions in ZnCl2-NaCl-KCl molten salt were determined through a series of electrochemical methods. The diffusion coefficients and nucleation modes of Mo(V) ions were also studied, and electrolysis was conducted for a prolonged period at a constant current density. The results indicated that the electrode reduction of Mo(V) ions in ZnCl2- NaCl-KCl molten salt proceeds through a three-step reaction: Mo(V) → Mo(IV) → Mo(III) → Mo at 250°C. The Mo(V) → Mo(IV) reaction was reversible and diffusion-controlled, with a Mo(V) diffusion coefficient of 6.02 × 10-6 cm2 s-1. Additionally, the nucleation mode of Mo(V) ions was instantaneous nucleation. The products electro-deposited were confirmed of metallic molybdenum with a particle size of less than 1 μm.

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 Karosiya, A Sharma, M Jain, N N. Viswanathan, M M. Pande, D Kumar, S Kumar

Desulfurisation of steel during ladle refining is governed by both thermodynamics and kinetics. For effective desulfurisation, thermodynamically, a low partial pressure of oxygen at the steel-slag interface and highly basic slag which possess a large sulfide capacity are desired. Kinetically, the mass transfer coefficient of sulfur in the liquid steel and in the slag determines the rate of desulfurisation. A fast desulfurisation rate is achieved by maintaining sufficiently strong argon stirring of the melt. In the present work, sulfur mass balance for steel and slag was performed after the desulfurisation treatment for several industrial heats. The decrease in the sulfur quantity of the liquid steel was more than the increase in the sulfur quantity of the slag. The discrepancy in the sulfur mass balance suggests that the sulfur could be transferred to: (a) the gas (via slag) phase; or to (b) the refractory (crucible) phase. The preliminary investigation of the refractory samples taken at slag-refractory and steel-refractory interface showed no interaction of sulfur with the refractory. Therefore, the possibility of sulfur transfer to the gas phase was verified by carrying out melting experiments of sulfur containing slag in an argon/air atmosphere. Sulfur containing slag was initially melted in an MgO-C crucible under an argon atmosphere followed by creating the air atmosphere just above the melt. Careful sampling and analysis from the cold spots of the crucible, much above the melt surface, revealed formation of a fibrous structure. Scanning electron microscopy energy dispersive X-ray spectroscopy (SEM-EDS) analysis of these fibrous deposits confirmed the presence of oxides and sulfides. Oxidation of sulfur containing slag under air atmosphere was also performed using a thermogravimetric analysis (TGA) set-up. It showed a constant sulfur loss in the range of 1300– 1500°C. Thermodynamic calculations carried out using FactSage™ ver 8.3 for these experimental conditions are in good agreement with the observed results.

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 X Yang

White phosphorus (P4) is a critical element in industry, but its current production from phosphate rock using the carbothermal reduction method raises significant environmental and health concerns. This pressing issue necessitates the development of new technologies that facilitate the sustainable production of P4. In response, my team is actively developing an innovative, coke-free approach for white phosphorus production. This method involves the dissolution of phosphate rock in molten CaCl2, followed by the extraction of P4 through electrochemistry at relatively low temperatures. Moreover, this approach has the potential to utilise phosphate-bearing solid wastes as raw materials, further enhancing its environmental benefits. By employing this cutting-edge technique, we aim to revolutionise the phosphorus chemical industry towards greener and more sustainable practices. This paper provides evidence of the feasibility and effectiveness of our proposed approach.

Aug 21, 2024

By R E. Gerald II, B Zhang, T Sander, J D. Smith, J Huang, R J. O’Malley, H Tekle

In the steelmaking process, mold fluxes are essential for ensuring thermal insulation, refining, and the efficiency of continuous casting. Real-time understanding of the in-service composition of slags and fluxes are crucial for optimising the steel production process and improving the quality of the final product. An in situ fibre-optic Raman probe that enables the study of the structure, composition, and viscosity of molten slags and fluxes at steelmaking temperatures has been developed and demonstrated both in the lab and in foundry scale experiments. The focus of this study is on the structural, compositional, and property analysis of molten fluxes in a laboratory setting, with the aim of applying this technology for in situ monitoring during industrial production. Raman spectra were successfully collected at various temperatures from 1000°C to 1400°C in real-time and analysed using a deconvolution algorithm to isolate and quantify peaks in the spectra associated with the specific structures of molecular components in molten and solidifying flux. The research successfully combines in situ Raman spectroscopy with high-temperature viscosity data, specifically targeting CaO-CaF-SiO2-Al2O3 based mould flux systems. Specified ratios of the deconvoluted Raman peaks, such as Al-O-Al/Si-O-Si ratio, shows good correlation with the flux chemistry, while the Q3/Q0 peak ratio shows good correlation with viscosity. A ruggedised Raman probe system was also developed and demonstrated in an 80 kg induction furnace. Ultimately, the goal of this work is to demonstrate in situ slag and mould flux analysis in industrial processes, such as in the continuous caster or electric arc furnace (EAF).

Aug 21, 2024