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Funding Information: The authors are grateful to Akkuser Oy (Finland) for providing the battery scrap. The authors would like to thank Lassi Klemettinen and Anna Klemettinen for their training on working with the furnace and SEM. The authors are also grateful to the Academy of Finland for providing financial support for this project (GOVERMAT, grant 346728). This study utilized the Academy of Finland’s RawMatTERS Finland Infrastructure (RAMI), based jointly at Aalto University, GTK Espoo, and VTT Espoo. Publisher Copyright: © 2023 by the authors. The extraction of cobalt from secondary resources has become crucial, as cobalt has been identified as a strategically important and critical raw material due to the high risks of supply chain disruptions. In this work, selective sulfation roasting was investigated as a potential recycling strategy to extract cobalt and lithium from an industrial lithium cobalt oxide (LCO)-rich black mass. Additionally, the effect of graphite on metal extraction was studied. In the first set of experiments, the sieved black mass fraction containing both cathode and anode materials was directly roasted in a predetermined composition of gas mixtures of SO2, O2, and Ar for 1 h at 850 °C. The gas composition was determined from Kellogg’s diagram to allow for the selective sulfation of Co and Li. In another set of experiments, the carbon present in the black mass was first removed by roasting the material in Ar for 2 h and then in an Ar and O2 gas mixture for five hours at 600 °C. Afterward, selective sulfation roasting was performed in mixtures of SO2, O2, and Ar gas similar to the previous set of experiments. For comparison, similar experiments were performed at 800 °C. The sulfation roasted black mass was leached in water to study the efficiency of Co extraction into the solution. Interestingly, the presence of carbon was found to be beneficial for Co extraction. The extraction efficiency for the first case (with carbon present in the raw material) was observed to be more than three times higher than in the second case (with carbon removed) for sulfation at 850 °C. The extraction efficiency and purity of the extracted Co were found to be better for higher temperature sulfation roasting conditions due to faster reaction kinetics. It was also found that almost all of the Li could be recovered while extracting Co. The maximum efficiency of the extraction was 99.51% Li and 61.21% Co for roasting under a gas flow of 10% SO2-10% O2-Ar at 850 °C for 60 min. These results suggest that Co and Li can be selectively extracted from the black mass by sulfation roasting pre-treatment followed by leaching in water. In holistic processing, the leach residue can then be further subjected to battery metal processing by state-of-the-art methods.

Publisher Copyright: © 2022 by the authors. As the electrification sector expands rapidly, the demand for metals used in batteries is increasing significantly. New approaches for lithium-ion battery (LIB) recycling have to be investigated and new technologies developed in order to secure the future supply of battery metals (i.e., lithium, cobalt, nickel). In this work, the possibility of integrating LIB recycling with secondary copper smelting was further investigated. The time-dependent behavior of battery metals (Li, Co, Ni, Mn) in simulated secondary copper smelting conditions was investigated for the first time. In the study, copper alloy was used as a medium for collecting valuable metals and the distribution coefficients of these metals between copper alloy and slag were used for evaluating the recycling efficiencies. The determined distribution coefficients follow the order Ni >> Co >> Mn > Li throughout the time range investigated. In our study, the evolution of phases and their chemical composition were investigated in laboratory-scale experiments under reducing conditions of oxygen partial pressure p(O2) = 10−10 atm, at 1300 °C. The results showed that already after 1 h holding time, the major elements were in equilibrium. However, based on the microstructural observations and trace elements distributions, the required full equilibration time for the system was determined to be 16 h.

Funding Information: Funding: This research was funded by the Kaute Foundation and grant number was 20210327 Optimization and dynamic modelling of slag-matte interactions in an industrial scale continuous flash smelting settler. The APC was funded by the Aalto University. Funding Information: Acknowledgments: Financial support from the Kaute Foundation is deeply appreciated, and the Aalto School of Chemical and Metallurgical Engineering is also gratefully acknowledged for providing the proper research environment and research facilities. The computational resources for this project were provided by CSC Finland. Publisher Copyright: © 2022 by the authors. Licensee MDPI, Basel, Switzerland. A mathematical modeling approach was used to test different design modifications in a flash smelting settler to reduce the copper losses in slag, which is economically disadvantageous for copper processing using the pyrometallurgical route. The main purpose of this study was to find ways to reduce copper losses in slag by improving the settling and coalescence of copper matte droplets, in particular, the smallest droplet sizes of ≤100 µm. These improvements inside the flash smelting (FS) settler were targeted through different settler design modifications. Three different design schemes were tested using the commercial computational fluid dynamics (CFD) software, Ansys Fluent. These settler design modification schemes included the impact of various baffle types, positioning, the height inside the settler, and settler bottom inclinations. Simulations were carried out with and without coalescence and the results were compared with normal settler design. The results revealed that the settling phenomenon and coalescence efficiency were improved significantly with these design modifications. It was concluded that a single baffle design was optimal for reducing copper losses and increasing coalescence efficiency instead of using multiple baffle arrangements. The top-mounted baffle outperformed the bottom-mounted baffle and inclined settler design.

This research has been funded by The Ministry of Economic Affairs and Employment financed project OXCOR (The effect of oxide layer on copper corrosion in repository conditions) in the Finnish Research Programme on Nuclear Waste Management (KYT2022). This study utilized the Academy of Finland’s RawMatTERS Finland Infrastructure (RAMI) based jointly at Aalto University, GTK, and VTT in Espoo. The aim of this study was to investigate the oxidation kinetics of copper at low temperatures (60 °C to 100 °C) in air by isothermal thermogravimetric analysis (TGA) and quartz crystal microbalance (QCM). The weight change in thermogravimetric tests showed periodic weight increase and decrease. In thermogravimetric tests the mass of the copper sample increased until the oxidation gradually slowed down and finally started to decrease due to cracking and spalling of the oxide formed on the surface. In QCM tests using electrodeposited copper film, the weight change was rapid at the beginning but slowed to a linear relationship after few minutes. Temperature and exposure time appeared to have a large effect on oxide film thickness and composition. With QCM, oxidation at 60–80 °C produced less than 40 nm films in 10 days. Oxidation at 90–100 °C produced 40 nm thick films in a day and over 100 nm films in a week. Although SEM-EDS analyses in TGA tests indicated that oxygen was adsorbed on the copper surface, neither XRD patterns nor Raman spectroscopy measurements showed any trace of Cu2O or CuO formation on the copper surface. Electrochemical reduction analysis of oxidized massive copper samples indicated that the oxide film is mostly Cu2O, and CuO develops only after several days at 90–100 °C.

Funding Information: Open access funding provided by Aalto University. This work was supported by the China Scholarship Council, and School of Chemical engineering, Aalto university. Publisher Copyright: © 2021, The Author(s). Copyright: Copyright 2021 Elsevier B.V., All rights reserved. The emerging bottom blown copper smelting (SKS) technology has attracted growing interest since it came into production. To further reveal the agitation behavior inside the bath and optimize the variable parameters, CFD simulation was conducted on a scaled down SKS furnace model with different tuyere arrangements. The Multi-Fluid VOF model was used for the first time in SKS furnace simulation and the simulated results show good agreement with an experimental water model reported in the literature, in terms of plume shape and surface wave. It was found that a low velocity region would appear on the opposite side of the bubble plume and persisted for a long time. To enhance the agitation in the low velocity region and reduce the dead zone area, an arrangement with tuyeres installed at each side of the furnace was recommended. Results suggested that a smaller tuyere angle difference would help to strengthen the agitation in the system. However, further investigation indicated that the difference in tuyere angle between two rows of tuyeres should be limited within a certain range to balance the requirements of higher agitation efficiency and longer lining refractory lifespan.

Computational methods have become reliable tools in many disciplines for research and industrial design. There are, however, an ever-increasing number of details waiting to be included in the models and software, including, e.g., chemical reactions and many physical phenomena, such as particle and droplet behavior and their interactions. The dominant method for copper production, flash smelting, has been extensively investigated, but the settler part of the furnace containing molten high temperature melts termed slag and matte, still lacks a computational modeling tool. In this paper, two commercial modeling software programs have been used for simulating slag&ndash, matte interactions in the settler, the target being first to develop a robust computational fluid dynamics (CFD) model and, second, to apply a new approach for molten droplet behavior in a continuum. The latter is based on CFD coupled with the discrete element method (DEM), which was originally developed for modeling solid particle&ndash, particle interactions and movement, and is applied here for individual droplets for the first time. The results suggest distinct settling flow phenomena and the significance of droplet coalescence for settling velocity and efficiency. The computing capacity requirement for both approaches is the main limiting factor preventing full-scale geometry modeling with detailed droplet interactions.