Slags from the metallurgical recycling process are an important source of resources classified as critical elements by the EU. One example is lithium from Li-ion battery recycling. In this context, the thermodynamic properties of the recycled component system play a significant role in the formation of the Li-bearing phases in the slag, in this case, LiAlO2. LiAlO2 crystal formation could be engineered and result in varying sizes and occurrences by different metallurgical processing conditions. This study uses pure ingredients to provide a synthetic model material which can be used to generate the valuable phase in the slag, or so-called engineered artificial minerals (EnAMs). The aim is to investigate the crystallisation of LiAlO2 as an EnAM by controlling the cooling conditions of the model slag to optimise the EnAM formed during crystallisation. Characterisation of the EnAMs is an important step before further mechanically processing the material to recover the valuable element Li, the Li-bearing species, respectively. Investigations are conducted using powder X-ray diffraction (XRD), X-ray fluorescence (µXRF), and X-ray Computer Tomography (XCT) on two different artificial lithium slags from MnO-Al2O3-SiO2-CaO systems with different cooling temperature gradients. The result shows the different EnAM morphology along the height of the slag, which is formed under different slag production conditions in a semi-pilot scale experiment of 5 kg. Based on the different EnAM morphologies, three defined qualities of the EnAM are identified: granular, dendritic, and irregular-shape EnAM.
Pyrometallurgical processes produce slags that may contain valuable elements because of their high oxygen affinity. However, the concentration is extremely low, which causes losses. In fact, these elements, for example, tantalum and rare earth elements, are less than 1% recycled. To return such technologically important elements to the material cycle, pyrometallurgically is used to enrich them in the simplest possible compounds within the slag, which have favorable properties for recovery (morphology, crystal size, magnetic properties), allowing further mechanical separation. The purpose of modification of the slag system is to obtain engineered artificial minerals” (EnAM), a process in which targeted minerals with high element concentration are formed. In this article, this approach is investigated using tantalum-rich fayalitic slag, since this slag is commonly found in the industry for the pyrometallurgical treatment of waste electric and electronic equipment. Synthetic fayalitic slags in reducing environment under different cooling rates were produced with Ta addition. The characterization of the produced samples was carried out using powder X-ray diffraction (PXRD) and electron probe microanalysis (EPMA). Additionally, the speciation of Fe and Ta was accessible through X-ray absorption near-edge structure (XANES) spectroscopy. EPMA also provided a semiquantitative assessment of the Ta distribution in these individual compounds. In these slags, tantalum accumulated in perovskite-like oxidic and silicate compounds as well as in magnetic iron oxides. The enrichment factor is highest in tantalite/perovskite-type oxides (FexTayO6, CaxFeyTazO3) with up to 60 wt.% Ta and ‘tantalomagnetite’ (FeII(FeIII(2-5/3x)Tax)O4) with a maximum of ~30 wt.% Ta (only fast cooling). This is followed by a perovskite-like silicon containing oxide (XYO3) with 12–15 wt.% Ta (only slow cooling), and a hedenbergite-like compound (XYZ2O6) with a varying content of 0.3–7 wt.%. The Ta concentration in pure Fe, Fe(1-x)O, hercynitic spinel and hematite is negligible. Despite the very low phase fraction, the most promising EnAM compound is nevertheless perovskite-like tantalum oxide, as the highest enrichment factor was obtained. Tantalum-rich magnetite-like oxides also could be promising.
Direct emissions due to the use of carbon-based fossil-reducing agents contribute to the overall CO2 emissions of pyrometallurgical production processes. This study investigated the replacement of fossil coke by silicon-rich cutting waste from the solar wafer cutting process to produce ferrochrome in an electric arc furnace. Laboratory test work and thermochemical simulation were carried out to examine the product quality at various additions of cutting waste and lime. The experimental trials resulted in products in accord with international standards, however, adjusting the slag composition by the addition of lime was necessary, otherwise high silicon contents in the alloys were obtained. Due to the highly exothermic reaction of silicon with iron- and chromium oxides, the silicothermic reduction results in a decreased specific electric energy consumption compared to the carbothermic reduction according to the thermochemical simulation. Low phosphorus and sulfur contents in the alloy might result in premium prices, aiding the economic viability of the process. Graphical Abstract
With the continuous development of easily accessible resources, the exploitation of complex mineral resources, metallurgical waste slag containing high-value metals, and secondary resources is gradually becoming a mainstream trend. Due to the complex distribution characteristics of elements in these resources, efficient recycling is difficult to achieve. A phase reconstruction strategy has been proposed to address the distribution forms of elements. The phase reconstruction strategy employs pyrometallurgical methods to subject complex resources to high-temperature smelting and cooling crystallization. In the cooling crystallization process, the target elements in melt are selectively enriched into engineered artificial minerals (EnAMs). Then, the target elements can be recovered by subsequently separating these EnAMs. However, the concept of and design strategies for EnAMs are still unclear. In this review, the concept of EnAMs is proposed based on previous studies. This review explores how to design EnAMs by phase equilibrium studies and utilizing geochemical behaviors. Additionally, the application cases of EnAMs in treating challenging tantalum–niobium and rare earth element (REE) resources, secondary resource recycling, and metallurgical slag were collected. Furthermore, the challenges and future perspectives of EnAMs for complex resources are discussed.
The increasing use of lithium-containing materials highlights the urgent need for their recycling to preserve resources and protect the environment. Lithium-containing slags, produced during the pyrometallurgical process in lithium-ion battery recycling, represent an essential resource for lithium recovery efforts. While multiple methods for lithium recycling exist, it is crucial to emphasize environmentally sustainable approaches. This study employs dry forced triboelectrification (FTC) to recover valuable components from slag powder, commonly known as engineered artificial minerals (EnAMs). The FTC method is used to change the charge of the target material and achieve a neutral state while other materials remain charged. The downstream electrostatic separator enables the charged particles to be separated from the target material, which in this study is lithium aluminate. The results show that the method is effective, and lithium aluminate can be successfully enriched.