In this study, waste-derived hematite pigments were modified with nano-oxides (TiO2, SiO2, and Al2O3) using a mechanical coating process to enhance their functional properties. Hematite base pigments were synthesized via a microwave-assisted method at varying pH levels, resulting in distinct morphological characteristics. To prevent secondary agglomeration and tailor surface reactivity, the hematite particles were modified with nano-oxides (TiO2, SiO2, and Al2O3) using a mechanical coating process. The resulting modified systems were characterized by Scanning Electron Microscopy (SEM), X-ray diffraction (XRD), Dynamic Light Scattering (DLS), oil absorption measurements, and zeta potential analysis. The results confirm the successful deposition of nano-additives on the hematite surface, leading to a significant reduction in average particle size and improved dispersion stability. Specifically, the mechanical coating allowed for precise control over the specific surface area, with BET values ranging from 4 to 49 m2/g and total pore volumes between 0.014 and 0.255 cm3/g. The dispersion stability was remarkably improved, as demonstrated by the shifting of the isoelectric point and zeta potential measurements, where modified systems showed enhanced surface charge density. These quantitative improvements in particle characteristics resulted in a reduction in oil absorption and enhanced color stability, confirming the effectiveness of the nano-oxide coating in tailoring the functional properties of hematite-based pigments.
The increasing demand for lithium-ion batteries (LIBs) and the critical need for lithium make the efficient recycling of secondary resources essential. Synthetic Li-bearing phases, some with lithium contents greater than natural sources (e.g., spodumene), can occur in slags produced by the pyrometallurgical recycling of end-of-life LIBs. This study investigates both the composition of synthetic model slags reproducing LIB recycling and the recovery potential of Li-bearing phases using SEM-based automated mineralogy and batch flotation tests, respectively. In particular, the efficacy of a novel zwitterionic collector, punicine, in contrast to the conventional collector, oleic acid, was evaluated with a focus on recovering Li-aluminate as a key engineered artificial mineral (EnAM). The flotation tests demonstrated that punicine provided a higher degree of selectivity for Li-aluminate over gehlenite, along with improved recovery of fine and well-liberated particles. The enhanced performance is attributed to punicine’s unique frothing properties and phase-specific interactions. Our findings highlight punicine’s significant potential as a collector for lithium-bearing EnAMs to advance lithium recovery from complex slag materials. The applied unique methodology supports the study of reagent regimes in relation to the flotation behavior of EnAM phases and the sustainable recycling of LIBs.
Microwave-based reactions have gained traction in recent years due to their ability to enhance reaction rates and yield while reducing energy consumption. Also, according to the conception of ‘waste to materials’, various waste feeds are intensively sought to be tested. The experimental setup of this study involved varying pH levels, oxidation agents, and precipitation agents to optimize the synthesis process of iron red based on waste iron sulfate. The selection of oxidation and precipitation agents was found to significantly influence the pigment synthesis process. Various oxidizing agents, including hydrogen peroxide and atmospheric air, were evaluated for their effectiveness in promoting the oxidation of ferrous ions to ferric ions, essential for pigment formation. Additionally, different precipitation agents such as sodium hydroxide and ammonia solution were assessed for their ability to precipitate iron hydroxides and facilitate pigment particle formation. The characterization of synthesized pigments revealed promising results in terms of quality and color properties. Helium Ion Microscopy (HIM) analysis confirmed the formation of well-defined pigment particles with controlled morphology. X-ray diffraction (XRD) studies provided insights into the crystalline structure of the pigments, indicating the presence of characteristic iron oxide phases. By improving this technology, waste iron sulfate can be efficiently transformed into valuable iron pigments, offering a sustainable solution for waste management while meeting the growing demand for high-quality pigments.
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.
Emerging concepts from scientific deep machine learning such as physics-informed neural networks (PINNs) enable a data-driven approach for the study of complex kinetic problems. We present an extended framework that combines the advantages of PINNs with the detailed consideration of experimental parameter variations for the simulation and prediction of chemical reaction kinetics. The approach is based on truncated Taylor series expansions for the underlying fundamental equations, whereby the external variations can be interpreted as perturbations of the kinetic parameters. Accordingly, our method allows for an efficient consideration of experimental parameter settings and their influence on the concentration profiles and reaction kinetics. A particular advantage of our approach, in addition to the consideration of univariate and multivariate parameter variations, is the robust model-based exploration of the parameter space to determine optimal reaction conditions in combination with advanced reaction insights. The benefits of this concept are demonstrated for higher-order chemical reactions including catalytic and oscillatory systems in combination with small amounts of training data. All predicted values show a high level of accuracy, demonstrating the broad applicability and flexibility of our approach.
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.
The inherent complexity of underground mining requires highly selective ore extraction and adaptive mine planning. Repeated geological face mapping and reinterpretation throughout mine life is therefore routine in underground mines. Hyperspectral imaging (HSI) has successfully been applied to enhance geological mapping in surface mining environments, but remains a largely unexplored opportunity in underground operations due to challenges associated with illumination, wet surfaces and data corrections. In this study, we propose a workflow that paves the way for the operational use of HSI in active underground mines. In a laboratory set‐up, we evaluated different hyperspectral sensors and lighting set‐ups as well as the effect of surface moisture. We then acquired hyperspectral data in an underground mine of the Zinnwald/Cínovec Sn‐W‐Li greisen‐type deposit in Germany. These data were corrected for illumination effects, back‐projected into three dimensions and then used to map mineral abundance and estimate Li content across the mine face. We validated the results with handheld laser‐induced breakdown spectroscopy. Despite remaining challenges, we hope this study will help establish hyperspectral sensors in the extractive industry as a means to increase the volume and efficiency of raw material supply, advance digitalisation, and reduce the environmental footprint and other risks associated with underground mining.
In this work, the extraction of vanadium (V) ions from an alkaline solution using a commercial quaternary ammonium salt and the production of metal vanadates through precipitation stripping were carried out. The crystallization of copper vanadates from the extracts was performed using a solution containing a copper(II) source in concentrated chloride media as a stripping agent. In an attempt to control growth, a stabilizing polymer (polyvinylpyrrolidone, PVP) was added to the stripping solution. The structural characteristics of the crystallized products, mainly copper pyrovanadate (volborthite, Cu3V2O7(OH)2·(H2O)2) nanoflakes and nanoflowers and the experimental parameter influencing the efficiency of the stripping process were studied. From the results, the synthesis of nanostructured vanadates is a simple and versatile method for the fabrication of valuable three-dimensional structures providing abundant active zones for energy and catalytic applications.
The present study aimed to investigate the genesis and characteristics of some of the world-famous agate deposits in the state of Chihuahua, Mexico (Rancho Coyamito, Ojo Laguna, Moctezuma, Huevos del Diablo, Agua Nueva). Geochemical and textural studies of host rocks showed that all the studied deposits are related to the same rock type within the geological unit of Rancho el Agate andesite, a quartz-free latite that shows clear indications of magma mixing. As a result of their large-scale distribution and various differentiation processes, as well as transport separation, different textures and local chemical differences between rocks of different localities can be observed. These differences have also influenced the properties of SiO2 mineralization in the rocks. The mixing of near-surface fluids from rock alterations with magmatic hydrothermal solutions led to the accumulation of various elements in the SiO2 matrix of the agates, which were, on the one hand, mobilized during secondary rock alteration (Fe, U, Ca, K, Al, Si) and, on the other hand, transported with magmatic fluids (Zn, Sb, Si, Zr, Cr). Different generations of chalcedony indicate a multi-stage formation as well as multiple cycles of filling the cavities with fluids. The hydrothermal fluids are presumably related to the residual solutions of a rhyolitic volcanism, which followed the latitic extrusions in the area and probably caused the formation of polymetallic ore deposits in the Chihuahua area. The enrichment of highly immobile elements indicates the involvement of volatile fluids in the agate formation. The vivid colors of the agates are almost exclusively due to various mineral inclusions, which consist mainly of iron compounds.
<p>Future mining will increasingly require rapid and informed decisions to optimise ore extraction and valuation. In this context, the use of hyperspectral imaging has been proven to be effective for geological mapping in surface mining operations. The potential of hyperspectral methods in underground mining environments, however, remains underexplored due to challenges associated with illumination and surface water. Our contribution addresses this gap by evaluating different lighting setups and the effect of moisture on the spectral quality of hyperspectral data in a laboratory setup. We also compared three commercially available, visible-near infrared to shortwave infrared sensors to assess their suitability for underground hyperspectral scanning. As a demonstration, we acquired hyperspectral data from three adjacent outcrops in the visitor&#8217;s mine of Zinnwald, Germany, where rocks of a Late Variscan Sn-W-Li greisen-type deposit are exposed in representative underground mining conditions. A photogrammetric 3D digital outcrop model was used to correct for illumination effects in the data. We then estimated mineral abundance and lithium content across the mine face employing an adapted workflow that combines quantitative XRD measurements with hyperspectral unmixing techniques. Laser-induced breakdown spectroscopy was used to validate the results. While there are still challenges to overcome, this study proves that hyperspectral imaging techniques can be applied underground to yield rapid and accurate geological information. This application will pave the way for the safe, digital and automated underground mine of the future.</p>
In this study, synthetic pure cassiterite and cassiterite doped with two different Fe contents were successfully recrystallized by means of sintering. Their crystal structure and chemical compositions were characterized by X-ray powder diffraction (XRD) as well as scanning electron microscopy (SEM) combined with energy-dispersive X-ray (EDX) analysis. Their floatability was studied by microflotation with a diphosphonic acid surfactant named Lauraphos301 as a collector. Unlike the addition of ferric ions in solution, which strongly depressed the floatability of all of the cassiterite samples, a much higher flotation efficiency of the Fe-doped cassiterite samples was found especially at lower collector concentrations. The cassiterite floatability is proportional to the Fe content in cassiterite at a broad range of pH, and the recovery has the following order: cassiterite with 1417 ppm Fe > cassiterite with 1165 ppm Fe > pure cassiterite. The electrokinetic behavior of the cassiterite samples with and without the collector was studied by electrophoretic measurements and revealed that the chemical interaction dominated the adsorption. With the help of the particle shape analysis, a more angular shape was found for the Fe-doped cassiterite samples. Moreover, without the influence of particle shape, much abundant adsorption of Lauraphos301 was found on the Fe-doped cassiterite samples by AFM topography imaging. The minor amount of Fe in the cassiterite lattice and a more angular shape of the Fe-doped cassiterite samples were believed to enhance floatability collectively. The study reveals that the influence of the chemical composition of the minerals on flotation was almost inextricably bound up with particle morphology and emphasizes the importance of considering both factors and investigating them individually for the flotation study.
Cobalt, nickel, manganese and zinc vanadates were synthesized by a hydrometallurgical two-phase method. The extraction of vanadium (V) ions from alkaline solution using Aliquat® 336 was followed by the production of metal vanadates through precipitation stripping. Precipitation stripping was carried out using solutions of the corresponding metal ions (Ni (II), Co (II), Mn (II) and Zn (II), 0.05 mol/L in 4 mol/L NaCl), and the addition time of the strip solution was varied (0, 1 and 2 h). The time-dependent experiments showed a notable influence on the composition, structure, morphology and crystallinity of the two-dimensional vanadate products. Inspired by these findings, we selected two metallic vanadate products and studied their properties as alternative cathode materials for nonaqueous sodium and lithium metal batteries.
With the increasing demand for metalliferous and mineral raw materials and the consequent depletion of the global natural resource base, the possible utilization of secondary raw material sources is receiving more and more attention. In the present study, we present results from a detailed vanadium deportment study of three basic oxygen furnace slag (BOS) samples known to containing elevated bulk concentrations of vanadium. Complementary analytical methods that were used to quantify the abundance and composition of V-containing phases include SEM-based automated mineralogy, X-ray fluorescence analysis, and X-ray powder diffraction as well as electron probe microanalysis. The vanadium deportment was quantified using Monte-Carlo simulations of the data obtained from automated mineralogy and electron microprobe analysis. The total V concentrations identified by XRF are between 1.7 and 2.2 wt.% V. The most important hosts of vanadium are larnite-, brownmillerite- and portlandite-solid solutions. In two samples Ca carbonates also significantly contribute to the V deportment, while wuestite, lime, and native iron do not contribute significantly to the vanadium deportment. A thorough consistency check identifies considerable uncertainties in the density of the V-bearing phases as the most likely reason to explain remaining discrepancies between measured and calculated V values.
The South Namxe deposit in Vietnam contains unusually high quantities of parisite, in addition to minor quantities of other fluorocarbonates, such as synchysite and bastnaesite. Together these minerals constitute the main REE-bearing minerals. This carbonatite-related deposit presents tabular (dykes) or lens-form ore bodies, up to several tens of meters wide and tens to hundreds of meters in length, that are hosted in Permian limestone and Triassic basalts. The main gangue minerals in the ore bodies are from the barite-celestine solid solution series, ankerite and calcite. It was considered necessary to assess the different grain characteristics presented by the presence of parisite intergrowths and its association with minerals of the barite-celestine solid solution series to structure a probable initial beneficiation strategy. Mineral liberation analysis revealed that an optimal liberation particle size between 45 mu m and 90 mu m could be achieved without overgrinding the material. Additionally, it showed a strong mineral association between fluorocarbonates, baryto-celestine, and calcite. Grinding below 100 mu m is necessary. One substantial energy saving potential is removing the host rock prior to grinding. The potential for pre-concentration with sensor-based sorting and selective comminution is investigated in a prestudy. Sensor-based sorting using X-ray transmission resulted in an enrichment of REE by a factor of 4, a reduction of the mass stream down to approximately 30%, and a loss of rare earths below 2%. Selective comminution using a pin mill, at a circumferential speed of 20 m/s, yielded a recovery of 96.5% of REE minerals and allowed rejection of 27% of barren material. This shows that both selective comminution and sensor-based sorting can be considered as complementary beneficiation steps when processing these REE ores.
Enhanced digital outcrop models attributed with hyperspectral reflectance data, or hyperclouds, provide a flexible, three-dimensional medium for data-driven mapping of geological exposures, mine faces or cliffs. This approach facilitates the collection of spatially contiguous information on exposed mineralogy, and so helps to quantify mineralising processes, interpret 1-D drillhole data, and optimise mineral extraction. In this contribution we present an open-source python workflow, hylite, for creating hyperclouds by seamlessly fusing geometric information with data from a variety of hyperspectral imaging sensors and applying necessary atmospheric and illumination corrections. These rich datasets can be analysed using a variety of techniques, including minimum wavelength mapping and spectral indices, to accurately map geological objects from a distance. Reference spectra from spectral libraries, ground or laboratory measurements can also be included to derive supervised classifications using machine learning techniques. We demonstrate the potential of the hypercloud approach by integrating hyperspectral data from laboratory, tripod and unmanned aerial vehicle acquisitions to automatically map relevant lithologies and alterations associated with volcanic hosted massive sulphide (VHMS) mineralisation in the Corta Atalaya open-pit, Spain. These analyses allow quantitative and objective mineral mapping at the outcrop and open-pit scale, facilitating quantitative research and smart-mining approaches. Our results highlight the seamless sensor integration made possible with hylite and the power of data-driven mapping methods applied to hyperclouds. Significantly, we also show that random forests (RF) trained only on laboratory data from labelled hand-samples can be used to map appropriately corrected outcrop scale data.
Bioleaching has been a well-established technique for the extraction of various metals since the 1990s. In particular, leaching in continuously stirred tank reactors (CSTR) facilitates the rapid and environmentally friendly extraction of different metals. This work investigates the economic feasibility of this technology when carried out using a suitable process and sulphide concentrate from a mining operation in the Erzgebirge region of Germany. The process is based on assumptions and tests are pending. The focus is on recovering zinc, copper and, in particular, indium from zinc sulphide. Based on the defined process characteristics of the bioleaching step as well as down- and upstream processes, investment costs and operating costs of the necessary plant structure were determined. After determining the potential profits based on given metal concentrations and current market prices of zinc, copper and indium, a net present value (NPV) and the corresponding internal rate of return (IRR) were calculated to ensure comparability with other investments. Both values are positive, showing that an investment in the proposed bioleaching plant pays off even with low process volumes.
Better quality control for alloy manufacturing and sorting of post-consumer scraps relies heavily on the accurate determination of their chemical composition. In recent decades, analytical techniques, such as X-ray fluorescence spectroscopy (XRF), laser-induced breakdown spectroscopy (LIBS), and spark optical emission spectroscopy (spark-OES), found widespread use in the metal industry, though only a few studies were published about the comparison of these techniques for commercially available alloys. Hence, we conducted a study on the evaluation of four analytical techniques (energy-dispersive XRF, wavelength-dispersive XRF, LIBS, and spark-OES) for the determination of metal sample composition. It focuses on the quantitative analysis of nine commercial alloys, representing the three most important alloy classes: copper, aluminum, and steel. First, spark-OES is proven to serve as a validation technique in the use of certified alloy reference samples. Following an examination of the lateral homogeneity by XRF, the results of the techniques are compared, and reasons for deviations are discussed. Finally, a more general evaluation of each technique with its capabilities and limitations is given, taking operation-relevant parameters, such as measurement speed and calibration effort, into account. This study shall serve as a guide for the routine use of these methods in metal producing and recycling industries.
The depletion of ore deposits, the increasing demand for raw materials, the need to process low-grade, complex and finely disseminated ores, and the reprocessing of tailings are challenges especially for froth flotation separation technologies. Even though they are capable of handling relatively fine grain sizes, the flotation separation of very fine and ultrafine particles faces many problems still. Further, the flotation of low-contrast semi-soluble salt-type minerals with very similar surface properties, many complex interactions between minerals, reagents and dissolved species often result in poor selectivity. This study investigates the flotation beneficiation of ultrafine magnesite rich in dolomite from desliming, currently reported to the tailings. The paper especially focuses on the impact of the depressant sodium hexametaphosphate (SHMP) on the following: (i) the froth properties using dynamic froth analysis (DFA), (ii) the separation between magnesite and dolomite/calcite, and (iii) its effect on the entrainment. As a depressant/dispersant, SHMP has a beneficial impact on the flotation separation between magnesite and dolomite. However, there is a trade-off between grade and recovery, and as well as the dewatering process which needs to be considered. When the SHMP increases from 200 g/t to 700 g/t, the magnesite grade increases from 67% to 77%, while recovery decreases massively, from 80% to 40%. The open circuit with four cleaning stages obtained a concentrate assaying 77.5% magnesite at a recovery of 45.5%. The dolomite content in the concentrate is about 20%, where 80% of dolomite was removed and importantly 98% of the quartz was removed, with only 0.3% of the quartz in the final concentrate. Furthermore, the application of 1-hydroxyethylene-1,1-diphosphonic acid (HEDP) as a more environmentally friendly and low-cost alternative to SHMP is presented and discussed. Using only 350 g/t of HEDP can achieve a similar grade (76.3%), like 700 g/t of SHMP (76.9%), while obtaining a 17% higher magnesite recovery as compared to 700 g/t of SHMP. Interestingly, the proportion of hydrophilic quartz minerals ending up in the concentrate is lower for HEDP, with only 1.9% quartz at a recovery of 21.5% compared to the 2.7% of quartz at a recovery of 24.9% when using SHMP. The paper contributes in general to understanding the complexity of the depressant responses in froth flotation.