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By X Hu, J Björkvall, L Sundqvist Ökvist

The metal production industry is a significant contributor to global CO2 emissions due to the use of fossil fuels such as coal and coke. To mitigate these emissions and meet climate goals, innovative and sustainable technologies are required. Molten salt electrolysis is a promising technology that directly produces metals from their precursor sulfides or oxides using electricity. When combined with renewable electricity and an inert anode, the electrolysis process can be carbon neutral. This paper presents the results of two pilot-scale studies on the electrolytic reduction of metal oxides and sulfides in molten salts. The first study focuses on the electrolytic reduction of chalcopyrite in molten NaCl-KCl salt. The results demonstrate that in situ separation of copper, iron, and sulfur is possible, enabling the extraction of all valuable elements without CO2 emissions. Furthermore, the findings underscore the capability to eliminate impurities like zinc, antimony, arsenic, and mercury from the electrolysis product. The second study investigates the electrolytic reduction of pure/synthetic chemicals of wüstite, hematite, and magnetite, as well as a magnetite-type iron ore in molten NaOH salt. The findings reveal a stepwise reduction of iron oxides from high valence to low valence, ultimately leading to the production of metallic iron electrolytically. Notably, this study underscores the challenges associated with the selection of an economically viable and durable inert anode material for efficient oxygen generation. These results indicate that molten salt electrolysis provides a sustainable and green route for base metal production. The use of this technology has the potential to significantly reduce CO2 emissions in the metal production industry, contributing to achieving climate goals.

Jun 19, 2024

By S Basu, P M. Midhun

Electro-Slag Remelting (ESR) is a process capable of producing ingots with much lower centre-line segregation and better internal soundness than conventional ingot casting processes, as well as lower inclusion and sulfur concentrations. This process is commonly used for alloyed steels intended for critical applications like components of marine turbines, supercritical powerplants and rocket motor casings. It involves melting a metal electrode using electrical resistive heating in a slag pool and re-solidification of the resulting metal droplets beneath the slag layer, forming an ingot. Conventional ESR fluxes consist primarily of CaF2, Al2O3 and CaO, along with minor concentrations of SiO2, MgO etc. The emission of fluoride vapour from the molten slag causes several environmental and health problems, triggering a need to develop and reduce the fluoride content in the ESR flux. The present study aims to develop low-CaF2 alternatives to commercial ESR fluxes without compromising on productivity and the surface quality of the refined ingot. Thus, the modification in chemical composition needs to satisfy properties like electrical resistivity, viscosity and liquidus temperature, essential for efficient ESR operation. Since electrical resistivity and viscosity are highly dependent on the ionic structure of the molten slag, it is important to understand the effect of compositional modification on the structure of the flux. The present study employs Fourier-transform infrared spectroscopy (FT-IR) and Raman spectroscopy to investigate the structural variations in the modified fluxes, especially the effect of changing SiO2 concentration, in comparison with conventional CaF2-rich fluxes. Additionally, thermal analysis (Differential Thermal Analysis (DTA) and Thermogravimetric Analysis (TGA)) has been carried out to characterise the melting behaviour of the fluxes. The findings are compared with simulations carried out using the FactSage™ software, ver 8.3 (GTT Technologies, Aachen, Germany). Simultaneous analysis of liquidus temperature and the structure is expected to help in identifying the practical suitability of modified ESR flux compositions for industrial implementation.

Jun 19, 2024

By J H. Park, M J. Lee

Because the environmental problems are occurred by greenhouse gases such as CO2, the industries have tried to increase electric motor efficiency to reduce CO2 emissions. A core material of electric motor is high-silicon electrical steel. The ferrosilicon (FeSi) alloy, a raw material for the production of electrical steel, affects the electric properties of silicon steel. The main impurities such as Ca, Al and Ti make inclusions or precipitates that causes core loss. The slag treatment has been widely used to remove impurity elements. Thermodynamic principles for the refining of several impurities, specifically Ca and Al, have been investigated, whereas thermodynamic behaviour of Ti has not been fully understood yet. Therefore, in the present study, the titanium distribution ratio () between ferrosilicon and CaO-SiO2-Al2O3 slag system at 1773 K was investigated. The results show that is influenced by both the basicity and stability of titanium ion in the slag. Specifically, exhibits a minimum value at about C/S=0.7 indicating a shift in the titanate structure unit from [TiO5]-square pyramid to [TiO4]-tetrahedron because of lack of Ca2+ ions in a C/S<0.8 region, contributing to an increase in titanate capacity and .

Jun 19, 2024

By L Klemettinen, A Jokilaakso, D Attah-Kyei, P Taskinen, M Tiljander, D Sukhomlinov, D Lindberg

In this study, the use of carbon neutral biochars as reducing agents in the pyrometallurgical treatment of nickel slag was investigated at 1400°C in order to recover valuable elements such as copper and nickel from the slag. A large amount of slag is generated during the nickel matte smelting. Nickel slag contains valuable elements such as copper, nickel and cobalt, which can be recovered. Disposal of this slag results in loss of resources and may cause pollution of the environment. It is important to retrieve these metals for environmental and economic reasons. In this study, the slag was reacted with non-fossil reducing agents (biochar) which were produced from hydrolysis lignin and black pellet biomass pyrolyzed at 600 and 1200°C and with metallurgical coke for comparison. The reduction experiments were done at 1400°C for 15, 30 and 60 mins under inert gas atmosphere. The samples were quickly quenched and analysed with Electron Probe X-ray Microanalysis (EPMA). The results showed that the use of biochar resulted in faster reaction kinetics in the reduction process compared to coke. The fast reaction kinetics is attributed to the relatively high content of volatiles in this biochar, leading to gas formation and thus mixing of the sample material. Moreover, thermodynamic modelling was also performed using FactSage™ to simulate equilibria with different amounts of biochar. The metal to slag distribution coefficient calculated from the results of thermodynamic modelling were consistent with experimental results. In addition, thermodynamic calculations confirmed that nickel is reduced rapidly and it deports to the metal alloy phase. As the reduction progresses or extra reductant is available for reactions, more iron is deported to the metal phase. The calculations also revealed that Zn vaporises into the gas phase.

Jun 19, 2024

By W Polkowski, M Tangstad, M Wallin, J Jiao

Fe-26Si-9B (wt per cent) alloy has been identified as a potential high-temperature phase change material (PCM) due to its attractive properties, such as its high latent heat of fusion and low volumetric change during solid/liquid transition. For the successful utilisation of this alloy into thermal energy storage (TES) systems, the development of a cost-effective production method is essential. Presently, the Fe-26Si-9B alloy is produced by mixing FeSi alloys with either pure boron element or FeB alloys. However, the use of pure boron is financially prohibitive, and the carbothermic reduction results in high greenhouse gas emissions and high energy consumption in the production of FeB alloys. In this regard, our study proposes a silicothermic reduction method to produce Fe-26Si-9B PCM by using FeSi alloys and B2O3-based oxides. Accordingly, the influence of various parameters on the production process was investigated, including operating temperature, holding time, B2O3 content in the added oxides, and initial Slag/Metal (S/M) ratio. Based on the experimental results, the optimal parameters for producing FeSiB alloys with over 9 wt per cent boron were determined. Consequently, it was documented that the FeSi alloys and the added oxides enriched with 50– 65 wt per cent B2O3 should be subjected to temperatures ranging from 1550–1650°C, maintain an initial S/M ratio exceeding 1, and ensure a holding duration beyond 1 hr. Moreover, the energy consumption of this process was estimated to be ~1.86 MWh/t metal and the mass loss was lower than 7 per cent. Therefore, silicothermic reduction offers a sustainable approach for producing FeSiB alloys with a boron content above 9 wt per cent.

Jun 19, 2024

By G H. Park, Y J. Jun, J H. Park

The carbon solubility of the CaO-Al2O3-FeO-SiO2-MgO slag, the main system formed in the Ruhrstahl-Heraeus (RH) vacuum degasser, was measured at 1873 K to understand the effect of slag compositions on the carbon contamination in the ultra-low carbon (ULC) steels. The stable form of carbon was demonstrated to be carbonate by plotting the log [(wt%C)/aC] ratio against the log p(O2) which ranged -11 < log p(O2,atm) < -9. The carbon solubility of the CaO-Al2O3-FeO-SiO2-MgO slag can be estimated using thermodynamic model. The distribution ratio of carbon increased with increasing concentration of FeO due to the FeO reduction reaction and increased basicity of slag. The carbonate capacity of the CaO-Al2O3-FeO-SiO2-MgO slag can be expressed as a linear function of the activity of lime and the optical basicity.

Jun 19, 2024

By L Scheunis, A Van den Bulck, E Jak, K Verbeken, M Shevchenko, R Starykh, I Bellemans, P-J Boeykens

As a result of the globally increasing consumer use of electronic devices, it is expected that pressure will increase on the supply chain of precious metals. Hence, recycling of these electronics becomes increasingly important, as well as optimising the current processes. One major issue in metallurgical processes is the amount of metal that is lost into the slag. This metal loss is inherent to the production process and therefore, additional processing steps such as slag cleaning may be required. Slag cleaning can be done in electrical resistance furnaces where heat is produced using the Joule effect, making the slag’s electrical conductivity an important operating parameter. Since slags are ionic liquids, the electrical conduction happens via the movement of ions which is called ionic conductivity. However, within the presence of transition metal oxides, a second mechanism of conductivity occurs as electrons are able to hop from one transition state to another, which is known as electronic conductivity. As ‘FeO’ is a common slag component in the non-ferrous pyrometallurgical industry, both mechanisms are present, but their proportions vary with the respective amounts of the two forms of the multi-valent ions and hence, with the oxygen partial pressure. The goal of the present study is to develop an experimental set-up and methodology for measuring the electrical conductivity of synthetic SiO2 – CaO – AlO1.5 – ‘FeO’ slags at various oxygen partial pressures.

Jun 19, 2024

By S-C Shim, H-R Lee, Y Kang, H Shin

Since iron oxide and silicon oxide are major gangue components in various types of ore, FeO-SiO2 base slag, ie fayalite slag, has been often encountered in pyrometallurgical processes of non-ferrous metals. During most matte production processes such as the smelting of Cu, Pb, and Ni, the FeOSiO2 based slag is inevitably formed and plays an important role in refining crude metal as well as engineering aspects. Recently, similar pyrometallurgical approaches have been attempted in the recovery of valuable metals (Ni, Co, Cr) from wasted secondary batteries. Thus, the viscosity of the FeO-SiO2 based slag has great significance in properly controlling smelting processes. However, when molten metal or matte does not coexist with the slag during the measurement, there has been a serious difficulty in maintaining Fe valance and consequently, the slag composition. In the present research, the viscosity of molten FeO-SiO2 slag was measured in 1573~1673 K using a rotational viscometer. In order to keep the state of iron oxides, the oxygen partial pressure was controlled using CO/CO2 gas mixture. The optimised ratio of CO/CO2 could be calculated using Fe/Fe2+ and Fe2+/Fe3+ equilibria at each temperature. The composition of the slag, particularly Fe valance, after the measurement was analysed with the aid of an inductively coupled plasma – optical emission spectroscopy (ICP-OES) and an automatic potentiometric titrator. The measurement showed that the FeO-SiO2 slag has considerably low viscosity values in the molten state, and it sharply increases as the temperature decreases. In spite of the careful oxygen partial pressure control, a part of Fe2+ was found to be oxidised to Fe3+, with a maximal case reaching about 20 per cent. The increase in viscosity of FeO-SiO2 at low temperatures can be attributed to the composition change due to an unavoidable Fe2+ oxidation. In addition, the relationship between the change in the viscosity and the liquidus temperature of FeO-SiO2 based slag was discussed to understand the composition dependence of viscosity.

Jun 19, 2024

By P Hayes, D Fadhlurrahman

Molten slags, fluxes and salts play key roles in a wide range of the high temperature industrial process applications, including metals production, refining and recycling, metal manufacturing processes, electrochemical metal production cells, batteries, and efficient heat transfer media. Recognising the importance and significance of fundamental scientific knowledge of these systems, the International MOLTEN Conference series was established to provide a forum to bring together leading academic researchers and industrial engineers to present and discuss the latest scientific ideas and findings, and their application in their respective fields. This article presents an analysis of the research carried out in this field over time in terms of the number of journal articles, fields and slag systems studied and geographical origin of the research.

Jun 19, 2024

By S H. Li, H Z. Gu, A Huang

High aluminium steel is a promising advanced steel known for its exception properties and holds significant economic and strategic importance. However, the CaO-Al2O3-SiO2 based slag with high alumina content reacts vigorously with alumina refractories during the smelting process at high temperature, seriously affecting the safe and efficient production of furnaces and resulting in the formation of Al2O3-MgO non-metallic inclusions within the molten steel. This is a bottleneck problem for high-quality steel refining, and the key reaction path during the corrosion remains unclear. The dissolution reaction mechanism of alumina refractories in high alumina CaO-Al2O3-SiO2 slags under a weak static magnetic field was investigated in this work, using high temperature laser confocal microscopy and in situ radiation spectroscopy techniques. The results indicate that the interaction between the high alumina slags and the alumina refractories is governed by free radical reactions. The dissolution of alumina forms AlO and AlO2 radicals. The reaction rate increases with the C/S ratio of the slag due to its low polymerisation. The reaction between non-bridging oxygen and AlO2 free radicals accelerates the generation of AlO and O2ꞏ- radicals. The reaction layer composed of calcium aluminate is formed through the recombination of AlO, Caꞏ+ and O2ꞏ- radicals. The weak static magnetic field induces the Zeeman splitting of free radical pairs and intersystem crossing occurs, promoting the formation of triplet free radical pairs through the hyper-fine coupling effect. The reaction can be significantly inhibited as the triplet free radical pair does not meet Pauli’s incompatibility principle. This discovery perfects the structure theory of molten slags with radicals and provides supplement to the design of the highly slag-resistant refractories, and provides the theoretical basis for the development of external field protection technologies for high-quality steel refining.

Jun 19, 2024

By C Chen, T Kan

The distribution ratio of Pb (LPb s/m) between three types of slags (FeOx–SiO2, CaO–FeOx and FeOx– CaO–SiO2) and molten copper after equilibrium was measured at 1300°C and oxygen partial pressure (pO2) of 10-10–10-6 atm. Results showed that for FeOx–SiO2 slag, the LPb s/m increased from 0.024 to 2.57 with pO2 increased from 10-10 to 10-6 atm. The LPb s/m with CaO–FeOx slag was lower than the FeOx–SiO2 slag at the same pO2, ranging between 0.015 and 0.53. Using the FeOx–CaO– SiO2 slag generated LPb s/m values (0.02–1.6) in between. The oxygen partial pressure in the investigated range had no obvious effect on the activity coefficient of PbO (γPbO) which was averagely 0.44, 1.70 and 0.71 for FeOx–SiO2, CaO–FeOx and FeOx–CaO–SiO2 slags, respectively. The increases in the (CaO+MgO)/SiO2 mass ratio of the FeOx–CaO–SiO2 slag induced the decrease in the LPb s/m and the increase in the γPbO value. However, the variation in the Fe/SiO2 mass ratio didn’t exert obvious effects.

Jun 19, 2024

By S Jayakumari, E Ringdalen, V Canaguier

Silicomanganese (SiMn), containing approximately 16–30 per cent Si, is produced in submerged arc furnaces using various Mn sources and quartz as the primary raw materials, along with fluxes and reductants. In the high-temperature zone known as the coke bed, a silica-rich slag is formed. SiMn is produced through the reduction of SiO2 from the slag. Dissolution of quartz into slags with different compositions, the primary slag formed from the Mn sources and flux before any MnO reduction occurred, representing conditions at the top of the coke bed, and dissolution of quartz into a partially reduced slag to simulate conditions inside the coke bed has been investigated. Experimental investigations were carried out to study the dissolution of quartz particles of varying sizes, 5 mm and 25 mm in synthetic slags with different compositions at temperatures between 1400°C and 1600°C, with varying holding times. Observed results are compared with liquidus compositions and equilibrium phases for original and formed slags. Particle size has been shown to be of little importance for the dissolution. Quartz dissolved more easily in slag at top of the coke bed than slag in the coke bed. Complete dissolution was observed after 30 mins at 1600°C in all cases, but not after 0 mins.

Jun 19, 2024

By B J. Monaghan, P Zulli, X F. Dong

In the lower zone of blast furnace (BF), slag trickles down through a packed bed of carbonaceous particles in the form of films, rivulets or droplets. During its downward flow, there are significant interactions occurring between slag and other phases, ie gas and packing particles. In particular, the interaction between gas and slag is closely associated with the key flow phenomena such as loading, flooding or channelling in the lower zone of the BF. With gas introduced laterally through tuyeres and slag flowing downward from the cohesive zone to the hearth, this interaction varies throughout the lower zone and in the cohesive zone:  strong cross-flow of gas relative to the slag occurs in front of the raceway  counter-current flow of gas and slag occurs in the upper parts of the lower zone  both strong cross- and counter-current flow of gas and slag around and within the cohesive zone. These interactions can be linked to furnace irregularities, affecting smooth operation and limiting production. Therefore, understanding the gas-slag interaction and its influencing factors remains critical for BF process control. In the current review, the physical behaviour and key influencing factors of gas and slag flow are initially examined. Numerical models describing gas and slag flows in a packed bed at micro-, mesoand macro-scopic levels, are reviewed. Each simulation approach has its advantages and limitations, as well as unique assumptions when used in BF process modelling. Applications of these approaches to gas-slag flow in key identified functional zones will highlight the differences between approaches and modelling outcomes. As no single approach can fully address all aspects of gasslag interactions, an integration of different approaches is considered an effective and beneficial method in providing a more complete understanding of gas-slag flow in the BF process.

Jun 19, 2024

By S Natsui, Y Goto, S Kawanishi, J Takahashi, H Nogami

The demand for copper increases yearly, and further improvements in copper smelting efficiency using flash furnaces are required. This study was conducted to understand and promote the interfacial reaction associated with the collision of silica flux and iron oxide particles, ie the formation reaction of fayalite slag, in the reaction shaft of the flash furnace. High-temperature microscopy was used to observe the reaction behaviour of a 2 mm granular SiO2 reagent in contact with micrometreorder- sized FeO reagents in situ. When the amount of FeO was lower than the stoichiometric amount with SiO2, the molten slag formed at the interface between FeO and SiO2 diffused into the SiO2 particle before dissolving the remaining FeO particles. It did not contribute to the subsequent reaction, and despite having the lowest amount of FeO among the samples in this study, many unreacted FeO particles remained on the surface of the samples after testing. On the other hand, under conditions with high FeO content and close to the eutectic composition of the FeO-SiO2 system, a liquid phase formed from low temperatures, gradually increasing in volume and eventually completely dissolving the 2 mm SiO2 grain. These results indicate that the early-stage slag is essential in increasing the interfacial area between FeO and SiO2 and facilitating the supply of FeO to SiO2. In other words, the FeO/SiO2 determines the amount of liquid phase and significantly influences the subsequent interfacial reaction rate between FeO and SiO2. Therefore, the local FeO/SiO2 of the particles falling down the reaction shaft should also be optimised to ensure early slag formation. Meanwhile, the time required for 2 mm SiO2 to complete the reaction for the temperature history employed in this study was significantly longer than the particle residence time in the reaction shaft. Further detailed investigation of the effects of silica flux particle size, composition, and reaction temperature on the reaction time will help find the conditions under which the reaction of silica flux can be completed in the reaction shaft. These kinetic approaches could contribute to future innovations in the copper smelting process using flash furnaces.

Jun 19, 2024

By L Klemettinen, J Biswas, W Malan, D Sukhomlinov, D Lindberg

In order to mitigate the effects of climate change, our society must be able to drastically reduce its CO2 emissions. As the metallurgical industry is a considerable contributor to these emissions, new greener technologies must be invented and developed. One option could be the direct production of metals from oxides using renewable electricity. The aim of this study was to investigate the possibility of using high-temperature molten oxide electrolysis (MOE) for iron and ferrochrome production. FactSage™, ver 8.2 (by Thermfact Ltd and GTT-Technologies) was utilised for estimating a feasible equilibrium electrolyte composition, and the experiments were conducted at 1550–1580°C in conical alumina crucibles with iridium wire as the cathode and platinum wire as the anode. The sources of iron and chromium were either pure FeO powder or industrial chromite pellets. Voltage was applied to the electrolysis cell for 6 hrs and the resulting current was measured, along with oxygen concentration in the off-gas line. The electrolyte comprised of SiO2, Al2O3, MgO and CaO. First, the effect of FeO concentration on iron reduction efficiency was investigated using only pure oxide powders as starting materials. The results indicated that 10 wt per cent FeO mixed with the electrolyte resulted in more efficient iron reduction compared to 20 wt per cent. In further experiments, industrial chromite pellets were ground and mixed with the CaO-free electrolyte. Iron and chromium reduction efficiencies were higher when approximately 19 wt per cent of the total sample mass consisted of pellets compared to increasing the pellet amount to 37 wt per cent. Generally, the chromium solubility in the liquid electrolyte was relatively low, and most of the chromium was confined to the spinel solid solution, from where its dissolution to the liquid electrolyte was very slow, resulting in slow reduction kinetics. For larger scale applications, economically more viable electrode materials should be investigated.

Jun 19, 2024

By G Brooks

The control of phosphorus in steelmaking is one of the famous challenges of pyrometallurgy. It is well established that highly basic slags, the presence of FeO in the slag and lower temperatures (less than 1650°C) are favourable for phosphorous removal. The thermodynamics of this reaction have been extensively studied under laboratory conditions and the general trends confirmed through industrial trials. However, in general, phosphorus slag/metal distributions measured in industry are far from equilibrium and quite specific to the oxygen steelmaking technology being used. This variability was quantified by Urban, Weinberg and Cappel (2015), who found that the phosphorus partition ratio measured in plants varied with blowing practice, stirring intensity and even converter life. Some recent kinetic studies by Gu, Dogan and Coley (2017) have shown how the kinetics of these reactions vary with FeO content and dissolved sulfur at the droplet scale. A global kinetic model by Rout et al (2018) provides meaningful predictions of where dephosphorisation occurs in an industrial basic oxygen furnace (BOF) and some recent heat transfer modelling by Madhavan et al (2021, 2022) implies that temperature difference between droplets and slag has a role to play in explaining why equilibrium is not achieved. This paper will review the current state of knowledge and provide suggestions on predicting phosphorous removal for industrial operations and how greater removal could be achieved.

Jun 19, 2024

By H Fukaya T Miki, J Gamutan

Molybdenum disilicide (MoSi2) is a promising material for thermal applications due to its excellent heat and oxidation resistance. It can operate at temperatures of up to 1800°C as furnace heating elements and protect refractory metals such as molybdenum from rapidly reacting with air to form volatile molybdenum oxides at elevated temperature. In this work, the feasibility of forming MoSi2 on a molybdenum substrate by hot dipping in a silicon-saturated molten metal bath was investigated. This method is simple, predictable and can be used to coat large components and complex parts. It was found that tetragonal MoSi2 can be successfully synthesised on the surface of the substrate after dipping for 15 mins at 1000°C using molten tin (Sn), bismuth (Bi) and copper (Cu) baths. The growth of the MoSi2 layer was fast within the first 15 mins and then gradually slowed down with time. After dipping for 60 mins at 1000°C, the thickness of the MoSi2 layer were measured as 441.5, 19.5 and 13.1 μm for the copper, tin, and bismuth baths, respectively. The MoSi2 coating synthesised in this study provided oxidation resistance at 1150°C by forming a protective SiO2 layer on the surface. The SiO2 layer prevented the sample from rapidly oxidising by inhibiting direct contact between the molybdenum substrate and oxygen in the atmosphere. Compared to conventional methods, the proposed hot dipping method produces a MoSi2 layer more rapidly and at much lower operating temperatures. This makes it a more attractive option for coating large and complex components, with the potential to enable the use of MoSi2 in a wider range of applications.

Jun 19, 2024

By F Diaz, G Hovestadt, B Friedrich, D Latacz, M Sommerfeld

The metallurgical sector significantly contributes to the global carbon footprint and encounters the challenge of developing more sustainable production methods. This study introduces novel approaches aimed at reducing CO2 emissions within the industrial sector, some of which have been developed up to the demonstration scale. In two case studies, urban waste from the agricultural sector (corn, olives, coconut etc) and waste electrical or electronic equipment (WEEE) recycling residues (shredder light fractions (SLF)) were subjected to thermal treatment. The resulting materials were then used as substitutes for conventional fossil-based reducing agents in both the copper and ferroalloy industries. Furthermore, hydrogen was employed at different scales to assess its efficacy as a reducing agent for recovering metal oxides from fayalitic copper slags. Our findings reveal promising prospects and defined specific challenges for the integration of these alternative reducing agents in the industry. The synergistic use of pyrolysed SLF, bio-coke, and hydrogen presents a viable pathway to significantly diminish CO2 emissions while simultaneously improving the sustainability of the metallurgical sector.

Jun 19, 2024

By M A. Rhamdhani, K Avarmaa, A Putera, J Chen, G Brooks

Silicon-based photovoltaic cells are currently the most dominant types applied to convert solar energy to electricity. In solar-grade silicon (SG-Si), the control of boron (B) and phosphorus (P) is very critical. Generally, these elements are difficult to remove into acceptable sub-ppm levels from lower grade Si. This study investigates slag treatment as a process for Si refining, focusing on the behaviour of P and B. The experiments were conducted by equilibrating Si-B-P alloys with 43 wt per cent SiO2 – 47 wt per cent CaO – 10 wt per cent Al2O3 slag under inert atmosphere at 1500°C. Different crucible materials were used (Al2O3, SiO2 and MgO), which determined the primary saturation phase for the system and modified the final slag composition accordingly. The samples were equilibrated and analysed with microanalysis techniques (EPMA (electron probe microanalysis) and LA-ICP-MS (laser ablation inductively coupled plasma mass spectrometry)). New standards were prepared and applied in the LA-ICP-MS analyses. Experimental results show that silver is essentially fully dissolved in silicon, as well as most phosphorus with LP ( = wt per cent P in slag/wt per cent P in Si) between 0.1–0.3. The distribution coefficient of boron was measured to be between 1 and 2. The crucible material used had an influence on the phase compositions and slight influence on the distribution coefficients of boron and phosphorus. The experimental results provided new accurate data when considering applicability of slag treatment as a technique for Si refining and Si PV cell recycling.

Jun 19, 2024

By B J. Monaghan, R J. Longbottom, D J. Pinson, S J. Chew

Recycling steel plant by-products is a critical issue for achieving both environmental and economic sustainability of integrated steel plants. A key steel plant by-product stream is dust from basic oxygen steelmaking (BOS), which can be recycled back to the BOS vessel as iron units and to aid slag formation. The major limitations for its recycling are zinc and the uncertainty in zinc speciation of the dust. This uncertainty affects the amount of dust recycled and how it interacts with the slag during processing. BOS dust in stockpiles can undergo self-sintering reactions that oxidise the iron-bearing components. As this occurs, zinc (or oxide) may combine with iron oxides to form a zinc-iron spinel solid solution phase. Knowing which zinc-bearing species are present in the BOS dust is a key aspect in understanding and developing an efficient recycling process for the dust. To overcome difficulties associated with phase identification in the BOS dust (both fresh and selfsintered), particularly the magnetite-zinc ferrite spinel solid solution using X-ray diffraction (XRD) / scanning electron microscopy (SEM) / energy dispersive spectroscopy (EDS), high end characterisation tools, transmission electron microscopy (TEM) and Mössbauer spectroscopy, were also used. Such an approach allowed improved phase identification of key zinc- and iron-bearing phases that were not previously resolvable. The zinc in fresh BOS dust was mostly present as extremely fine separate particles of zinc oxide, attached to the iron particles. These extremely fine particles were <10 nm in size. Additionally, a small amount of zinc ferrite was also identified within the sample (most likely contained within a magnetite-zinc ferrite spinel solid solution). However, the zinc in the self-sintered BOS dust, was found to be present entirely in a magnetite-zinc ferrite spinel solid solution. While this spinel phase had been previously identified by XRD, it was not clear that it contained zinc. The Mössbauer results provided definitive evidence of zinc within the spinel phase.

Jun 19, 2024