The growing demand for lithium-ion batteries (LiBs) for energy storage has intensified the need for the critical raw materials (CRMs) they contain, including Li, Co, Ni, and Mn. Consequently, the incentive to recycle LIBs is increasing. However, the commonly used hydrometallurgical processes often have a significant environmental footprint. Moreover, the relatively low value of certain battery materials (e.g., LiFePO₄, LFP) results in a limited incentive for their recycling. This study explores the simultaneous recycling of LFP with various types of LiNi_xMn_yCo_zO₂-containing Black Mass (BM). Leaching studies over time were conducted using stepwise additions of LFP and H₂O₂ solution (1 vol%) to a mild lixiviant of 0.63 mol/L H₂SO₄ at 50°C_. For pristine NMC 532, ± 95% leaching of Li, Ni, Co, and Mn was achieved. The Fe(II) present in LFP, as well as H₂O₂, acts as a reductant for the dissolution of Ni, Co, and Mn, later precipitating as FePO₄ to the leaching residue. The Al and Cu present in industrially treated BM further enhanced the dissolution of the transition metals via a catalyzed reaction with the iron from LFP. This resulted in complete leaching of Li, Ni, Co, and Mn for mechanically pre-treated industrial black mass samples. However, the leaching residues acquired from these samples were highly contaminated with graphite. Also, while pyrolysis of the black mass benefits the leaching of Co and Mn, it results in difficulties in subsequent removal of Fe from the pregnant leach solution. The chemical processes and their performance are described in this work.

Ironmaking is a crucial step for integrated steelmaking, which consumes a significant amount of energy and is the main CO₂ emission source for the whole steelmaking industry. In the Netherlands, Tata Steel, previously known as Koninklijke Hoogovens and Corus, runs an integrated steel plant and produces high-quality flat steel with more than 100 years of history (since 1918). TU Delft, the oldest technical university in the Netherlands with over 180 years of history, holds the education and research program in process metallurgy, to support the technology innovations in the metallurgical industry. Close cooperation between TU Delft and Tata Steel in process fundamentals and technology developments has a long history. This paper focuses on the cooperation in the recent 25 years from the new millennium in ironmaking research: from the blast furnace (BF) process, the “HIsarna” smelting reduction, to the future H₂-based technologies. Tata Steel has its own R&D center, focusing more on applied research to support production now and in the future. The research at TU Delft focuses more on the process fundamentals and supports process optimization and new process development. Long-term and continuous industry-academic-national funding schemes with the assistance of Materials Innovation Institute (M2i) are instrumental in supporting the academic industry alliance. Joint EU-funding applications as partner pair is another cooperation path. A recently awarded 8-year program as part of the Dutch national growth funds: Growing with Green Steel (GGS) is a good example, where the H₂-based ironmaking is an important part of the program. The paper will highlight the flagship projects in ironmaking technologies: BF cohesive zone simulation, nut-coke in BF, suspension pre-reduction and H₂-enrichment in HIsarna, H₂-based direct reduction, as well as the industrial decarbonization technology pathways. It is believed that fundamental research with a long-term funding scheme will facilitate a more rapid green transition of the steelmaking industry.

A hyphenated optical-electrochemical set-up was used to investigate the early-stage dissolution mechanism of NdFeB permanent magnets immersed in acetic, citric, and formic acids at concentrations of 0.01 and 0.1 M. This approach enabled a direct correlation between quantifiable surface changes and dissolution behaviour under open-circuit potential (OCP) conditions. Despite minimal OCP variation (180 mV) across all conditions and rapid stabilisation within approximately 300 s, significant optically-detectable surface changes continued throughout the measurement period (1 h). This emphasises that surface dissolution kinetics, rather than thermodynamics, predominantly control the early-stage dissolution of NdFeB. Kinetic parameters obtained by fitting mean activity-level curves with a sigmoidal model revealed that higher acid concentrations result in shorter induction periods and faster surface activation. In-situ optical analysis indicated a consistent dissolution mechanism characterised initially by localised activation, followed by the progressive expansion of active sites across the surface. Post-immersion analysis confirmed preferential dissolution of rare-earth-rich phases at grain boundaries and triple points, alongside intragranular dissolution observed in 0.01 M citric acid. Among the tested conditions, dilute citric acid (0.01 M) emerges as particularly suitable medium for practical control, as its relatively long induction period (∼1378 s) allows monitoring and controlling local dissolution before rapid surface activation begins. The combined optical-electrochemical approach also revealed that, while rare-earth-rich sites are preferentially activated, early signs of matrix activation are detectable, underscoring the value of in-situ optical analysis for advancing process control in NdFeB recycling.

Recycling of rare-earth elements (REEs) from NdFeB magnets is an important strategy to mitigate the risks associated with the REE supply chain. In this article, we propose an electrochemical process to recover REEs wherein all the reagents required for both leaching of REEs as well as the precipitation are generated in situ electrochemically. A three compartment electrochemical reactor was used in which a rare-earth containing salt along with an additive salt, ammonium sulfamate, was fed into the middle compartment. Upon electrolysis, the salts were split into acid and rare-earth hydroxides. The acid generated in the anolyte compartment was used to leach the NdFeB magnet waste. The rare-earth hydroxides were collected in the catholyte compartment and calcined to obtain rare-earth oxides. More than 95% of REEs and cobalt were extracted into the solution, and more than 85% of iron was removed as Fe(OH)₃precipitate in the same step. Subsequently, the leachate was oxidized and neutralized to remove more than 99% of iron. By using electrons as green reagents, this process combines leaching and precipitation in a single reactor enabling process intensification. The leachate produced at the end is rich in REEs and can be fed again into the middle compartment, forming a completely closed-loop process. Overall, the process consumes no acid, only electricity, ammonium hydroxide for neutralization, and an additive salt, ammonium sulfamate.

Steel is an important product in many engineering sectors; however, steelmaking remains one of the largest CO2 emitters. Therefore, new governmental policies drive the steelmaking industry toward a cleaner and more sustainable operation such as the gas-based direct reduction–electric arc furnace process. To become carbon neutral, utilizing more scrap is one of the feasible solutions to achieve this goal. Addressing knowledge gaps regarding scrap heterogeneity (size, shape, and composition) is essential to evaluate the effects of increased scrap ratios in basic oxygen furnace (BOF) operations. This review systematically examines heat and mass transfer correlations relevant to scrap melting in BOF steelmaking, with a focus on low Prandtl number fluids (thick thermal boundary layer) and dense particulate systems. Notably, a majority of these correlations are designed for fluids with high Prandtl numbers. Even for the ones tailored for low Prandtl, they lack the introduction of the porosity effect which alters the melting behavior in such high temperature systems. The review is divided into two parts. First, it surveys heat transfer correlations for single elements (rods, spheres, and prisms) under natural and forced convection, emphasizing their role in predicting melting rates and estimating maximum shell size. Second, it introduces three numerical modeling approaches, highlighting that the computational fluid dynamics–discrete element method (CFD–DEM) offers flexibility in modeling diverse scrap geometries and contact interactions while being computationally less demanding than particle-resolved direct numerical simulation (PR-DNS). Nevertheless, the review identifies a critical gap: no current CFD–DEM framework simultaneously captures shell formation (particle growth) and non-isotropic scrap melting (particle shrinkage), underscoring the need for improved multiphase models to enhance BOF operation.

In the pre-reduction cyclone of the HIsarna process, both thermal decomposition and gas reduction of the injected iron ores occur simultaneously at gas temperatures of 1723–1773 K. In this study, the kinetics of the thermal decomposition of three iron ores (namely OreA, OreB and OreC) for HIsarna ironmaking were analysed as an isolated process with a symmetrical thermogravimetric analyser (TGA) under an inert atmosphere. Using various methods, the chemical and mineralogical composition, particle size distribution, morphology and phase distribution of the ores were analysed. The ores differ in their mineralogy and morphology, where OreA only contains hematite as iron-bearing phase and OreB and OreC include goethite and hematite. To obtain the kinetic parameters in non-isothermal conditions, the Coats–Redfern Integral Method was applied for heating rates of 1, 2 and 5 K/min and a maximum temperature of 1773 K. The TGA results indicate that goethite and hematite decomposition occur as a two-stage process in an inert atmosphere of Ar. The proposed reaction mechanism for the first stage of goethite decomposition is chemical reaction with an activation energy ranging from 46.55 to 60.38 kJ/mol for OreB and from 69.90 to 134.47 kJ/mol for OreC. The proposed reaction mechanism for the second stage of goethite decomposition is diffusion, showing an activation energy ranging between 24.43 and 44.76 kJ/mol for OreB and between 3.32 and 23.29 kJ/mol for OreC. In terms of hematite decomposition, only the first stage was analysed. The proposed reaction mechanism is chemical reaction control. OreA shows an activation energy of 545.47 to 670.50 kJ/mol, OreB one of 587.68 to 831.54 kJ/mol and OreC one of 424.31 to 592.32 kJ/mol.

The demand for lithium-ion batteries (LiBs) is rising, resulting in a growing need to recycle the critical raw materials (CRMs) which they contain. Typically, all spent LiBs from consumer electronics end up in a single waste stream that is processed to produce black mass (BM) for further recovery. It is desired to design a recycling process that can deal with a mixture of LiBs. Hence, this study investigates the structure and composition of battery modules in common appliances such as laptops, power banks, smart watches, wireless earphones and mobile phones. The battery cells in the module were disassembled into cell casing, cathode, anode and separator. Then, the cathode active materials (CAMs) were characterized in detail with XRD-, SEM-, EDX- and ICP-OES-analysis. No direct link was found between the chemistry of the active materials (NMC, LCO, LMO, LFP etc.) and the application. Various BM samples were submitted to a leaching procedure (2 M H2SO4, 50 °C, 2 h, 60 g BM/L) with varying concentration (0–4 vol%) of H2O2 to study the influence of their chemical composition on the dissolution of Li, Ni, Mn and Co. Only a part of the BMs dissolved completely at 4 vol% H2O2, which was attributed to the oxidation state of the transition metals (TMs). Exact determination of H2O2 consumption by redox titration confirmed this hypothesis.

In this study, different existing methods to remove alloyed and coated copper from steel are summarized, compared, and discussed. None of these methods have been scaled up industrially so far. Characterization of industrial steel scrap will indicate in which forms and quantities copper is present. Based on environment, economics and process efficiency, the most promising techniques will be selected for further investigation. The study will then focus on ways to bring the process efficiency to the level required for industrial application, by better understanding of thermodynamic limits and the reaction kinetics. Possible removal of other undesired elements from the scrap will be taken into account as well.

An evaluation of neodymium‑iron‑boron permanent magnets (NdFeB PMs) from different end-of-life products, as a secondary resource of rare-earth elements (REEs), is presented. De-coating of PM was investigate as pre-treatment to facilitate efficient direct magnet recycling. Thus, critical aspects from disassembling to the de-coating of the magnets were addressed. A challenge for the de-coating process is that the magnets have different sizes, weights, and their coating compositions are not known beforehand. It was shown that ammonia-based solutions was thermodynamically suitable to dissolve nickel and zinc coatings selectively, while keeping the bulk magnet stable. Nevertheless, the dissolution of Zn was much faster than the Ni one, and more efficient.

The HIsarna off-gas system wall is a cooling jacket made of cooling pipes arranged in the radial direction and in a circular pattern. Part of the off-gas system cooling pipes are isolated using a low-thermal-conductivity refractory material to protect the cooling pipe from melting and thermal stresses. During long runs and due to thermomechanical stresses, the refractory material is lost, and its thickness is reduced. It is possible to measure the thickness of the refractory layer only during shutdown, which is a disadvantage during long runs. The aim is to investigate the possibility of predicting the thickness of the refractory material by using other parameters that are possible to measure during the operation. A combination of FEM and CFD modeling is used to develop a methodology for detailed wall modeling and refractory material loss prediction. Finite element method (FEM) analysis is used to obtain the thermal properties of the wall using detailed geometries for variable refractory thickness. The obtained properties are then used to build CFD models to study the effect of refractory thickness on wall heat loss, temperature and composition profiles. The proposed procedure is validated against the plant measurement, and according to the findings, it is possible to relate the wall thickness to measured parameters such as heat loss through the walls, temperature and carbon conversion.

In this paper a CFD analysis of HIsarna off-gas system for post combustion of CO-H2-carbon particle mixture is presented to evaluate the effect of different sub-models and parameters on the accuracy of predictions and simulation time. The effects of different mesh type, mesh grid size, radiation models, turbulent models, kinetic mechanism, turbulence chemistry interaction models, including and excluding gas-solid reactions, number of reactive solid particles are investigated in detail. Based on the accuracy of the predictions and agreement with counterpart measured values, the best combination is selected and conclusions are derived. It was found that radiation and turbulence chemistry interaction model have a major effect on the temperature and composition profile prediction along the studied off-gas system, compared to the variations in other models. The effect of these two models becomes even more evident when the temperature and fuel content of the flue gas are high.

In order to take full advantage of the secondary resources, in this paper, we reported a template-free process to prepare porous Co microfibers from spent lithium-ion batteries (LIBs). First, the waste LiCoO₂ powders were leached by oxalic acid at a suitable temperature, and rod-like cobalt oxalate powders were obtained. Second, the porous Co microfibers were prepared by using the cobalt oxalate as precursors through a thermal decomposition at 420 °C under nitrogen atmosphere. The prepared Co microfibers possess diameters of 1–2 μm, and each microfiber consists of small particles with size of 100–200 nm. The Co microfibers (25 wt%)/paraffin composite exhibited excellent microwave absorption performance. When the sample thickness is 4.5 mm, the reflection losses reach − 36.14 and − 38.20 dB at 4.16 and 17.60 GHz, respectively, and the effective bandwidth reaches up to 5.52 GHz. This indicates that the Co microfibers can be used as a promising microwave absorber. Therefore, this paper demonstrates a novel process to make a high value-added product through recycling from the spent lithium-ion batteries. In addition, it is advantageous to eliminate the hazard of spent lithium-ion batteries and electromagnetic radiation to environment and human health. Graphical abstract: [Figure not available: see fulltext.].

HIsarna reactor is characterized by a high raw materials versatility and is therefore attractive for processing secondary iron sources. Among the materials that can be recycled through HIsarna, zinc-bearing material has drawn a special attention. Based on the plant data, once dust-containing Zinc was injected into the main reactor, a final collected dust with a zinc content of 16% was achieved which opened up possibilities of higher enrichment for direct reuse in Zn smelting as a secondary source and an alternative for Zn ore (the primary source). However Zn vapor can react with iron oxide to form zinc ferrite (ZnFe₂O₄), which is an undesired product. Hence, the main focus of this study is to minimize the formation of ZnFe₂O using thermodynamic (FactSage) and computational fluid dynamic tools. After detecting regions with high potential of ZnFe₂O₄ formation, proper geometrical and operational modifications of the off-gas system is proposed to minimize the formation of zinc ferrite.

Cobalt is considered a key metal in the energy transition, and demand is expected to increase substantially by 2050. This demand is for an important part because of cobalt use in (electric vehicle) batteries. This study investigated the environmental impacts of the production of cobalt and how these could change in the future. We modeled possible future developments in the cobalt supply chain using four variables: (v1) ore grade, (v2) primary market shares, (v3) secondary market shares, and (v4) energy transition. These variables are driven by two metal-demand scenarios, which we derived from scenarios from the shared socioeconomic pathways, a “business as usual” (BAU) and a “sustainable development” (SD) scenario. We estimated future environmental impacts of cobalt supply by 2050 under these two scenarios using prospective life cycle assessment. We found that the environmental impacts of cobalt production could likely increase and are strongly dependent on the recycling market share and the overall energy transition. The results showed that under the BAU scenario, climate change impacts per unit of cobalt production could increase by 9% by 2050 compared to 2010, while they decreased by 28% under the SD scenario. This comes at a trade-off to other impacts like human toxicity, which could strongly increase in the SD scenario (112% increase) compared to the BAU scenario (71% increase). Furthermore, we found that the energy transition could offset most of the increase of climate change impacts induced by a near doubling in cobalt demand in 2050 between the two scenarios.

Galvanized steel scrap flow and injection into the HIsarna reactor are investigated using discrete element method (DEM). The scrap particle is fed into the reactor through an inclined chute and hits the slag surface where the zinc content is evaporated and solid particles melt. A DEM model is setup and validated using experimental data obtained from the exact plant-scale chute geometry and scrap particles. Using the DEM model, the effect of chute inclination, injection elevation, injection mode (batch and continuous), batch size, and flowrate on particle distribution and exerted pressure on the slag surface are investigated. It is found that continuous mode of injection is the most suitable method to increase the spread of particles and also to reduce the exerted pressure on the slag surface. Placing dent-like obstacles at the tip of the chute significantly increases the impact area, especially for batchwise injection, thus reducing force and pressure on the slag surface that minimizes the risk of liquid splash. Larger particle impact area is also beneficial to obtain higher zinc evaporation rate from particle surface and also to minimize the slag surface temperature disturbance.

HIsarna is a novel ironmaking process with great raw materials versatility that is attractive for various secondary resources. Among the materials that can be recycled, there is steel scrap which is fed to the furnace bath through an inclined chute. The velocity distribution of the scrap particles along the chute affects the particles’ distribution on the liquid slag and, thereupon, the efficient operation of the reactor. In this study, the flow of steel scrap particles along an inclined chute with the same dimensions as those of the actual chute of the HIsarna plant is investigated experimentally and numerically. The simulations are validated using chute tip velocity and mass fractions collected at the different compartments of a sampling device. Translational and angular velocity distributions along and across the chute are reported, and the effect of different parameters are investigated. The impact of the shape of the particles on the simulation process is found to be negligible. The angular velocity distribution in cross-sections of the chute exhibited a V-shaped orientation, whereas the translational velocity displayed similar values across the cross-sections. Moreover, translational velocity appeared to increase with increasing inclination angles, whereas angular velocity increased with decreasing batch size.

Silicon [Si] in hot metal is an impurity acting in the steel shop as an energy source that is released by oxidation during oxygen blowing in the converter. Preferred silicon concentration in hot steel is typically 0.4 wt-% (± 0.1 wt-%), helping predictable and low-cost processing. In practice, the Si concentration is difficult to control and may occasionally reach levels higher than 1 wt-%. The authors studied data from observations, samples and autopsies of a chilled blast furnace, a core drill and a furnace in operation. In addition, production data from a melting reduction pilot plant (HIsarna) and FactSage® calculations were used. The amount of FeO in the raceway, the area in which hot gas and powdered coal (PCI) are introduced in the blast furnace, in relation to [Si] in hot metal, is observed. The goal of this paper is to contribute to a better understanding about the mechanism of the dissolution of silicon in hot metal.

Exploring more efficient and low-cost electrocatalysts to replace platinum (Pt) is highly desired to promote the practical hydrogen production through water splitting. Herein, a facile and effective strategy is proposed to fabricate self-standing Al₃Ni₂/Ni electrode with controlled phase composition and surface morphology, which is obtained by one-step electrochemical reduction of Al³⁺ on commercially available nickel in eutectic NaCl-KCl melt. Different from previously reported approaches, uniform Al₃Ni₂ monolith catalyst can directly grow onto Ni substrate. The deposit possesses unique three-dimensional (3D) cauliflower-like morphology comprising of nano- and microparticles due to the rapid nucleation rate during molten salt electrolysis. The as-fabricated Al₃Ni₂/Ni electrode can be directly used as the cathode to catalyze Hydrogen evolution reaction (HER). Impressively, it exhibits remarkable HER activity comparable to commercial Pt, including a low overpotential of 83.4 mV for a current density of 10 mA cm⁻², a small Tafel slope of 40.7 mV dec^-1, and excellent long-term stability over 36 h of continuous HER operation in 0.5 M H₂SO₄ solution. The intrinsic catalytic ability of Al₃Ni₂ with the unique hierarchical structure of nano/microsized grains can offer multiple effects, including massive exposed active sites, enhanced charge transfer and mass transport, and fast gas releasing that synergistically contribute to improving the electrocatalytic performance of HER. This work represents a highly promising approach to the design and one-step controllable fabrication of efficient and self-standing base metal electrode for electrocatalytic hydrogen production.

A three-dimensional computational fluid dynamics (CFD) model for the HIsarna off-gas system is set up and validated by real plant data. In the model detailed reaction mechanism and kinetic data for post-combustion of CO-H2 mixture and carbon particles are incorporated. The results are presented and discussed in another study (Part 1) by the same authors. In the present paper, the focus will be on geometry modification of the off-gas system and the effects on the operating parameters. The effect of this modification on heat loss, temperature profile, carbon conversion and gaseous phase composition across the off-gas system is investigated. It is shown that the modified geometry leads to a higher heat loss through the reflux chamber walls which can change the temperature profile and consequently species composition. The modified geometry also offers possibility of higher CO-H2 mixture and carbon particles conversion rate and reduce unwanted emission from the reflux chamber.

Within the steelmaking industry, a large amount of zinc-bearing waste is produced which cannot be effectively treated through integrated steel mills. Concurrently, zinc smelters generate waste residues containing significant amounts of iron and zinc which are stored or landfilled. The zinc concentration of iron and steelmaking residues inhibits its recycling to the blast furnace but is insufficient to be sent directly to the zinc producers. Consequently, a means of up-concentration is required. The pilot HIsarna ironmaking furnace has shown potential for processing secondary iron-bearing resources. Furthermore, zinc can be concentrated in the off-gas flue dust, providing an enriched input for zinc smelters. The potential recyclability of blast furnace (BF) and basic oxygen furnace (BOF) dust and ‘goethite’ residue from the zinc industry has been studied. The input materials have been comprehensively characterized and their reduction–vaporization behavior, has been investigated. Individual samples were tested at temperatures of up to 1300 °C. Here, it was shown that minimal reduction of iron and volatilization of zinc occurred in the goethite and BOF samples. Conversely, even at 1000 °C, the BF dust showed complete reduction of iron and removal of zinc within 30 min. This was due to its high carbon content (40 wt%) which can act as a reductant. Consequently, mixtures of BOF dust and goethite with BF dust were studied. It has been shown that mixtures of 30:70 BF dust to goethite and 20:80 BF dust to BOF dust are suitable for recovering zinc to the gas phase and fully reducing the contained iron. Graphical Abstract: [Figure not available: see fulltext.]