Lithium aluminum oxide has previously been identified to be a suitable compound to recover lithium (Li) from Li-ion battery recycling slags. Its formation is hampered in the presence of high concentrations of manganese (9 wt.% MnO₂). In this study, mock-up slags of the system Li₂O-CaO-SiO₂-Al₂O₃-MgO-MnO_x with up to 17 mol% MnO₂-content were prepared. The manganese (Mn)-bearing phases were characterized with inductively coupled plasma optical emission spectrometry (ICP-OES), X-ray diffraction (XRD), electron probe microanalysis (EPMA), and X-ray absorption near edge structure analysis (XANES). The XRD results confirm the decrease of LiAlO₂ phases from Mn-poor slags (7 mol% MnO₂) to Mn-rich slags (17 mol% MnO₂). The Mn-rich grains are predominantly present as idiomorphic and relatively large (>50 µm) crystals. XRD, EPMA and XANES suggest that manganese is present in the form of a spinel solid solution. The absence of light elements besides Li and O allowed to estimate the Li content in the Mn-rich grain, and to determine a generic stoichiometry of the spinel solid solution, i.e., (Li_(2x)Mn²⁺_(1−x))_1+x(Al_(2−z),Mn³⁺_z)O₄. The coefficients x and z were determined at several locations of the grain. It is shown that the aluminum concentration decreases, while the manganese concentration increases from the start (x: 0.27; z: 0.54) to the end (x: 0.34; z: 1.55) of the crystallization.

The recovery of critical elements in recycling processes of complex high-tech products is often limited when applying only mechanical separation methods. A possible route is the pyrometallurgical processing that allows transferring of important critical elements into an alloy melt. Chemical rather ignoble elements will report in slag or dust. Valuable ignoble elements such as lithium should be recovered out of that material stream. A novel approach to accomplish this is enrichment in engineered artificial minerals (EnAM). An application with a high potential for resource efficient solutions is the pyrometallurgical processing of Li ion batteries. Starting from comparatively simple slag compositions such as the Li-Al-Si-Ca-O system, the next level of complexity is reached when adding Mg, derived from slag builders or other sources. Every additional component will change the distribution of Li between the compounds generated in the slag. Investigations with powder X-Ray diffraction (PXRD) and electron probe microanalysis (EPMA) of solidified melt of the five-compound system Li₂O-MgO-Al₂O₃- SiO₂-CaO reveal that Li can occur in various compounds from beginning to the end of the crystallization. Among these compounds are Li_1−x(Al_1−xSi_x)O₂, Li_1−xMg_y(Al)(Al_3/2y+xSi_2−x−3/2y)O₆, solid solutions of Mg_1−(3/2y)Al_2+yO₄/LiAl₅O₈ and Ca-alumosilicate (melilite). There are indications of segregation processes of Al-rich and Si(Ca)-rich melts. The experimental results were compared with solidification curves via thermodynamic calculations of the systems MgO-Al₂O₃ and Li₂O-SiO₂-Al₂O₃.

Rare earth-bearing gypsum tailings from the fertilizer industry are a potential source for an economically viable and sustainable production of rare earth elements. Large quantities are generated inter alia in Catalão, Brazil, as a by-product in a fertilizer production plant. Hitherto, the gypsum has been used as soil conditioner in agriculture or was dumped. The cooperative project, “Catalão Monazite: Economical exploitation of rare earth elements from monazite-bearing secondary raw materials,” intends to extract rare earth elements from these gypsum tailings. In this paper, a chemical process route to obtain a mixed rare earth carbonate from a monazite concentrate, was investigated. The results of the digestion, leaching, and precipitation experiments are presented and discussed herein. This includes reagent choice, process parameter optimization through experimental design, mineralogical characterization of the feed material and residues, purification of the leach solution, and precipitation of the rare earth as carbonates. The results showed that a rare earth extraction of about 90% without the mobilization of key impurities is possible during a sulfuric acid digestion with two heating stages and subsequent leaching with water. In the following purification step, the remaining impurities were precipitated with ammonium solution and the rare earth elements were successfully recovered as carbonates with a mixture of ammonium solution and ammonium bicarbonate.

Municipal waste incinerator bottom ashes contain copper contents comparable to those of low-grade ores in addition to other valuable metals. While the processing of coarse fractions (>2 mm) is state of the art, the fines with their residual metal content are landfilled. This paper presents the results from a mineralogical characterization of fine fractions from the processing of municipal solid waste incinerator bottom ashes. From the results, possible approaches for a recovery of copper from the fine fraction are derived. Spatially resolved phase analysis reveals that the material contains a very heterogenic mixture of naturally occurring compounds as well as particles of alloys, metals, artificial oxides, and sulfides. The most interesting element to recover is copper. Copper can be found in the form of alloys, simple sulfides (XS), and oxides (XO). During the incineration process, new phases are generated that differ from natural ones and therefore can be called artificial minerals. Additionally, several components are partially altered due to oxidation, especially after the prolonged outside storage of the bottom ash. Crystalline silicate and glass particles are only sporadically enriched in Cu. Based on these results, different processing techniques are discussed. Due to the small particle size distribution and the physical and physico-chemical properties of the particles, flotation seems to be the most promising technique for the enrichment of copper from municipal solid waste incineration bottom ash (MSWI-BA) fine fractions.

In the future, it will become increasingly important to recover critical elements from waste materials. For many of these elements, purely mechanical processing is not efficient enough. An already established method is pyrometallurgical processing, with which many of the technologically important elements, such as Cu or Co, can be recovered in the metal phase. Ignoble elements, such as Li, are known to be found in the slag. Even relatively base or highly redox-sensitive elements, such as Zr, REEs, or Ta, can be expected to accumulate in the slag. In this manuscript, the methods for determining the phase formation and the incorporation of these elements were developed and optimized, and the obtained results are discussed. For this purpose, oxide slags were synthesized with Al, Si, Ca, and the additives, P and Ti. To this synthetic slag were added the elements, Zr and La (which can be considered proxies for the light REEs), as well as Ta. On the basis of the obtained results, it can be concluded that Ti or P can have strong influences on the phase formation. In the presence of Ti, La, and Ta, predominantly scavenged by perovskite (Ca_1−wLa_2/3wTi_1−(x+y+z)Al_4/3xZr_yTa_4/5zO₃), and Zr predominantly as zirconate (Ca_1−wLa_2/3wZr_4−(x+y+z)Al_4/3xTi_yTa_4/5zO₉), with the P having no effect on this behavior. Without Ti, the Zr and Ta are incorporated into the pyrochlore (La_2−xCa_3/2x−yZr_2+2/4y−zTa_4/5zO₇), regardless of the presence of phosphorus. In addition to pyrochlore, La accumulates primarily in britholite-type La oxy- or phosphosilicates. Without P and Ti, similar behavior is observed, except that the britholite-like La silicates do not contain P, and the scavenging of La is less efficient. Lithium, on the other hand, forms its own compounds, such as LiAlO₂(Si), LiAl₅O₈, eucryptite, and Li silicate. Additionally, in the presence of P, Li₃PO₄ is formed, and the eucryptite incorporates P, which indicates an additional P-rich eutectic melt.

Due to the increasing demand for electromobility, the recovery of technologically relevant elements from spent Li-ion batteries is becoming increasingly important. Pyrometallurgical processing can deal with a broad range of input materials. Unfortunately, ignoble elements such as Li and Mn enter the slag. A novel approach to facilitate this processing is the Engineered Artificial Minerals (EnAM) strategy for the recovery of critical elements. The aim of this study is to investigate whether it is possible to stabilize Li in Li-manganates as the first crystallizate. For this purpose, synthetic oxide slags (Li, Mg, Al, Si, Ca, Mn) of varying compositions were made. The constituting compounds were identified using inductively coupled plasma optical emission spectrometry, powder X-ray diffraction, X-ray absorption near-edge structure analysis, and electron probe microanalysis. These results provide an understanding of the solidification process and the behavior of the elements of concern. Lithium-manganate(III) (LiMnO₂) crystallized first, next to hausmannite (Mn²⁺Mn³⁺₂O₄) in a matrix consisting of wollastonite (CaSiO₃) and larnite (Ca₂SiO₄). Within the structure of LiMnO₂, Li and Mn can replace each other in certain proportions. By adding Al and Mg spinel, solid solutions between Mn²⁺Mn³⁺₂O₄, MnAl₂O₄, MgAl₂O₄ and LiMnO₂ are expected and described by the stoichiometry formula: (Li_(2x),Mg_(1x),Mn_(2+(1–x)))_1+x(Al_(2–z),Mn³⁺_(z))₂O₄.