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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 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

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 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

By W Y. Kim, Y B. Kang, Y J. Park

The phase equilibria in the Al2O3–TiOx system were investigated in wide ranges of temperature and oxygen partial pressure: 1300~1600°C and 10-16.6~10-8 atm, respectively. The equilibrium phases and their compositions were identified using X-ray diffraction (XRD) and electron probe microanalysis (EPMA), respectively. Most noticeably, a wide range of pseudobrookite solid solution was found in equilibrium with almost pure alumina. At each temperature, the cationic ratio expressed as RTi = nTi/(nAl + nTi)) of the pseudobrookite solid solution showed a noteworthy dependency on the oxygen partial pressure. This resulted in the formation of a broad range of pseudobrookite solid solutions, ranging from Al2TiO5 (RTi = 1/3) to Ti3O5 (RTi = 1.0). Complete miscibility within the pseudobrookite solid solution was observed at 1600°C, with only a minor miscibility gap becoming evident below 1500°C. Based on the results obtained in the present study, the behaviours of Al2TiO5 pseudobrookite have implications in two key domains: (1) understanding changes in the physical properties of the materials, and (2) elucidating the evolution of Al–Ti complex oxide inclusions in liquid steel which can deteriorate the steel cleanliness.

Aug 21, 2024

By M Suzuki

Although several models for the surface tension of molten oxide slag have been proposed, suitably accurate predictions of this property are not yet possible. The surface tension, or surface excess free energy, of molten oxides is largely determined by the ionic coordination induced by surface relaxation. However, the associated mechanism of surface structural relaxation for molten oxide mixtures such as slag is complex and not yet fully understood. To allow a better evaluation of surface relaxation characteristics, the present work analysed the ionic coordination associated with the surface-relaxed states of several oxide mixtures. This work especially focused on calcium aluminate slags because these materials exhibit complex relationships between composition and surface tension. The effects of incorporating low concentrations of SiO2 as a surface active component on the surface ionic coordination were also examined. X-ray absorption techniques were used to assess oxygen and cationic elements in glassy samples after surface relaxation treatments, and molecular dynamics simulations based on a polarisable ion model of molten slag with vacuum/melt interfaces were also performed. The X-ray absorption techniques provided data related to electron yields (which are primarily associated with surface features) and fluorescence yields (which evaluate the bulk material). Thus, the ionic coordination characteristics of both regions were investigated. The results of molecular dynamics calculations allowed statistical analysis of the distributions of Al- or Sicentred polymorphs as well as the bond angles between cations and oxygen anions in the vacuumexposed and bulk regions in the equilibrated melt. The results indicated that bridging oxygen ions were preferentially distributed in the relaxed surface region rather than non-bridging oxygens. These bridging oxygen ions represented vertex connections between AlO4 or SiO4 tetrahedra. In the case of the calcium aluminate slags, the addition of one Ca2+ ion as charge compensation for two Al3+ ions was found to be necessary to form two AlO4 tetrahedra. This specific feature of surface ionic coordination could be responsible for the complex trends observed in surface tension data. The incorporation of low concentrations of SiO2 reduced the proportion of tetrahedrally-coordinated Al ions such that higher coordination states become dominant in the bulk of the material, whereas AlO4 tetrahedra were preferentially distributed in the surface region. SiO4 tetrahedra were the preferred Si-centred polymorph and were likely connected to one another to form bridging oxygen ions at the surface. On the basis of these results, a model to predict slag surface tension was proposed, and the energy of the formation of the ionic clusters resulting from surface relaxation was taken into account.

Aug 21, 2024

By E Jak, M Shevchenko, E Nekhoroshev, D Shishin

In the field of pyrometallurgy, the presence of multiple molten phases with distinct chemical compositions, such as slags, mattes, speiss liquids, metals and molten salts, is a well-known phenomenon. These phases exhibit strongly non-ideal solution behaviour and are mutually miscible to varying degrees. To describe these complex molten liquids, the Modified Quasichemical Model (MQM) has proven effective and has been applied to numerous binary, ternary and several higher-order multicomponent systems related to pyrometallurgy. In recent decades, the complexity of high-temperature processes has escalated due to increased impurity concentrations in primary ores, the incorporation of recycled consumer products and the integration of metallurgical plants through by-product and waste exchanges. To address these issues, PYROSEARCH laboratory has been developing large 20-component thermodynamic database using a generalised CALPHAD (CALculation of PHAse Diagrams) methodology integrated with experimental investigations. Over the past decade, strategic decisions were made balancing the ability to generate experimental data, prediction power, accuracy, stability of calculations, as well as computational time, which are discussed in the paper. Examples provided for issues of >3 liquid immiscibility, non-ionic behaviour and exaggerated ‘sharp’ enthalpies of mixing in silicate slags, dealing with multiple oxidation states, as well as comparative analysis of pair and quadruplet approximation in MQM.

Aug 21, 2024

By E Jak, M Shevchenko, D Shishin

One of the key aspects to develop sustainable metallurgical production is to ensure that the predictive power of thermodynamic tools is brought up to a new level of accuracy and reliability. Exploring new polymetallic processes, integrating primary and recycled materials, means utilising the uncharted areas within the Cu-Pb-Zn-Fe-Ca-Al-Mg-Si-O (major) – Cr-Na (slagging) – As-Sn-Sb- Bi-Ag-Au-Ni-Co (minor) slag-solids-metal-matte-speiss-sulfate system. This requires extensive integrated experimental and thermodynamic modelling study, which is underway at PyroSearch at the University of Queensland (UQ).

Aug 21, 2024

By G Tranell, E Pastor-Vallés, A Vallejo-Olivares, J B. Pettersen

Metals are essential for the sustainability transition and decarbonisation of society. Yet, it will be paramount to produce them sustainably and minimise the affiliated resource and energy use and the associated emissions. In the circular economy, the metallurgical industry should recycle existing material stocks, and improve its utilisation of wastes, residues and side streams. This increases the complexity of processes, as they become both (often multi-fraction) waste treatment as well as material production processes and brings complexity to the assessment of environmental benefits. Assessing the environmental impact of technological developments frequently is supported by life cycle assessment (LCA). While the method is well documented, its implementation involves several methodological choices that deserve reasoning and analysis, such as how to define the product when former wastes are turned into new products, the selection of impact methodology when converting emissions to environmental indicators, the definition of system boundaries and co-product allocation and the interpretation of sensitivity and uncertainty in final outcomes. In this exploratory study, we investigate how the variation of LCA set-up affects the environmental burden of the system. We consider a metallurgical process where a mix of hard-to-recycle aluminium-containing streams is used to produce aluminium cast alloys in a rotary furnace. Remelting with salt-fluxes allows recovering metals from partly oxidised/contaminated streams, such as dross, bottom ash and industrial shavings, but at the expense of generating significant amounts of salt-slag/salt-cake hazardous waste. The study considers different system alternatives such as landfilling the salt-slag residues versus valourising them into salts, aluminium concentrates, ammonium sulfate and non-metallic-compounds to be used by the metallurgical, construction or chemical industries. Practical recommendations are outlined to facilitate the implementation of LCA in assessing the potential benefits of the circular economy in the metallurgical sector.

Aug 21, 2024

By Q Shu, T Deng, B Yan, B Song, D Wang

In view of the lack of phase equilibria data of vanadium-bearing oxide system and the desirability of them for design or optimisation of vanadium extraction process, the phase equilibria relationships of V2O3-FeO-SiO2-CaO(15 mass per cent) system were determined experimentally and then an isothermal section phase diagram of this system was constructed. Totally, 81 samples of different composition were equilibrated at 1623 K for 48 hours in iron crucible under Ar atmosphere. The equilibrated samples were quenched quickly in cold water, and then the phase constituents of all the samples were identified by X-ray diffraction (XRD) combined with electron probe microanalysis (EPMA) measurements.

Aug 21, 2024

By H Zhang, Y Wang, S Sukenaga, H W. Ni, H Shibata, W Z. Mu

The crystallisation behaviour of low melting point CaO-SiO2-Al2O3-MgO inclusions greatly affect the deformability of inclusions during the rolling process. The crystallisation characteristics of CaO-SiO2- Al2O3-MgO melts representing the oxide inclusions in Si-Mn killed steel were systematically investigated. The effect of Al2O3 and MgO contents on the crystallisation change were analysed under a fixed CaO/SiO2 in the complex inclusions. The continuous-cooling-transformation (CCT) and time-temperature-transformation (TTT) experiments were conducted. The results showed that the increase of MgO content increases the crystallisation ability of CaO-SiO2-Al2O3-MgO inclusions, while the increase of Al2O3 content has the opposite effect. The viscosity, liquidus temperature of oxide melt and also the initial crystallisation potential might be the reasons for the change in crystallisation behaviour. Also, the crystallisation activation energy could semi-quantitatively characterise the crystal growth during the crystallisation of inclusions. To obtain low melting point plasticized CaO-SiO2-Al2O3-MgO (CaO/SiO2=1) system inclusions, the Al2O3 content of the system needs to be controlled larger than 15 wt per cent and the MgO content should be kept at a small amount.

Aug 21, 2024

By A Specht, A Müller, V Montenegro, S Winkler, E Klaffenbach, A Schmidt

In the process of primary copper smelting in flash smelting furnace (FSF), the ratio of iron to silica (Fe/SiO2 mass ratio) primarily determines the slag viscosity and magnetite formation. Viscous slag does not only cause difficulties in daily operation, such as in tapping, it also increases the copper losses to slag. Thus, keeping the Fe/SiO2 mass ratio at the desired level is an important aspect of FSF and slag cleaning furnace (SCF) operation. In this study, the improvement of the Fe/SiO2 mass ratio was conducted in two steps: First, the optimal Fe/SiO2 mass ratio was derived based on thermodynamic data. Based on this analysis, appropriate control limits were determined. Second, this range of favourable Fe/SiO2 mass ratios was implemented into operation by an advice-based control system, which suggests the addition of silica based on the analysis of SCF slag. As this approach was successful, the same advice-based control system principle was adapted for the coke addition to the SCF. After testing the new advice-based control for several months, the production data confirm the predictions by thermodynamics: since the prediction was implemented as an advisor, the copper and magnetite content in SCF slag is significantly reduced and viscous slag is reported less often by operations.

Aug 21, 2024

By A D. Pradana, D R. Pradana, Y H. Putra, Z Zulhan, T Hidayat

The high temperature processing of nickel laterite ore is currently dominated by the Rotary Kiln- Electric Furnace (RKEF) technology. The ratio of SiO2/MgO (S/M) in the ore is one of the critical parameters that determines the success of the RKEF process. Incompatible S/M ratios in the ore can cause aggressive chemical interaction between the slag and MgO refractory. The slag-refractory interaction at conditions relevant to nickel laterite ore smelting was investigated in the present study. Synthetic mixtures representing the slag compositions of nickel laterite ore smelting were prepared by mixing MgO, SiO2, Al2O3, CaO, Fe2O3, and Fe and heating the mixtures in steel containers at 1300°C under an argon atmosphere for 3 hrs. Pure MgO crucible were used as containment material in the melting process of the mixtures to represent the MgO refractory. The kinetics of the slagrefractory reaction were investigated using samples with selected initial S/M ratios of 2.0 and 3.0 (wt/wt) (with constant CaO = 3 wt per cent, Al2O3 = 5 wt per cent, FeO = 10 wt per cent) by performing melting at 1500°C in MgO crucibles for 5, 30, and 120 mins under an argon atmosphere. The effect of the S/M ratio in slag on the slag-refractory interaction was also investigated by performing melting of mixtures with different initial S/M ratios of 1.75, 2.0, 2.5, and 3.0 (wt/wt) in MgO crucibles at 1500°C for 120 mins under an argon atmosphere. After the melting process, each sample was quenched in water, mounted in resin, ground, polished, and coated. The interaction between the slags and MgO refractory was then evaluated by analysing the polished samples using a scanning electron microscope equipped with an energy dispersive spectroscopy (SEM-EDS). Thermodynamic simulations using FactSage™ 8.0 thermochemical software were performed based on the experimental slag compositions, refractory, and conditions to support the evaluation process. The results show that a higher S/M ratio in slag leads to a higher tendency for the refractory component to dissolve into the slag. A higher S/M ratio in slag also leads to an increasing extent of solid-state diffusion of iron oxide into the remaining refractory grains. The dissolution of MgO into the slag is rapid; the MgO concentration in the final slag increased by 2.4 wt per cent and 5.7 wt per cent at initial S/M ratios of 2.0 and 3.0 wt/wt, respectively, within 5 and 30 mins of the melting process.

Aug 21, 2024