Molecular Design and Spodumene Flotation-A Review.

Spodumene flotation stands as the most commonly used method to concentrate lithium minerals. However, it faces significant challenges related to low collector recoveries and similarity in the surface characteristics of the minerals, which make the effective separation of this valuable mineral difficult. For this reason, numerous researchers have conducted studies to address and confront this problem. In this work, an exhaustive bibliographic search was carried out using keywords and search queries, and the results were structured in three sections according to temporal, methodological, and thematic criteria. The first section covers the period from 1950 to 2004, focusing on experimental tests. The second section covers from 2004 to the present and focuses on flotation tests and measurement analysis. Simultaneously, the third section spans from 2011 to the present and is based on molecular dynamics simulations. Topics covered include spodumene surface properties, the influence of metal ions, pre-treatment techniques, and the use of collectors. Ultimately, molecular dynamics simulations are positioned as a tool that accurately represents experimental phenomena. In this context, specialized software such as Materials Studio or Gromacs prove to be reliable instruments that allow a detailed study of mineral surfaces and other elements to be carried out, which justifies their consideration for future research in this scientific field.

Experimental and Simulation Studies on Hematite Interaction with Na-Metasilicate Pentahydrate.

Iron ore is a fundamental pillar in construction globally, however, its process is highly polluting and deposits are becoming less concentrated, making reusing or reprocessing its sources a sustainable solution to the current industry. A rheological analysis was performed to understand the effect of sodium metasilicate on the flow curves of concentrated pulps. The study was carried out in an Anton Paar MCR 102 rheometer, showing that, in a wide range of dosages, the reagent can reduce the yield stress of the slurries, which would result in lower energy costs for transporting the pulps by pumping. To understand the behavior observed experimentally, computational simulation has been used by means of quantum calculations to represent the metasilicate molecule and the molecular dynamics to study the adsorption of metasilicate on the hematite surface. It has been possible to obtain that the adsorption is stable on the surface of hematite, where increasing the concentration of metasilicate increases its adsorption on the surface. The adsorption could be modeled by the Slips model where there is a delay in adsorption at low concentrations and then a saturated value is reached. It was found that metasilicate requires the presence of sodium ions to be adsorbed on the surface by means of a cation bridge-type interaction. It is also possible to identify that it is absorbed by means of hydrogen bridges, but to a lesser extent than the cation bridge. Finally, it is observed that the presence of metasilicate adsorbed on the surface modifies the net surface charge, increasing it and, thus, generating the effect of dispersion of hematite particles which experimentally is observed as a decrease in rheology.

Clay Tailings Flocculated in Seawater and Industrial Water: Analysis of Aggregates, Sedimentation, and Supernatant Quality.

High-molecular-weight anionic polyacrylamide was used to analyze the effect of kaolin on the structure of particle aggregates formed in freshwater and seawater. Batch flocculation experiments were performed to determine the size of the flocculated aggregates over time by using focused beam reflectance measurements. Sedimentation tests were performed to analyze the settling rate of the solid-liquid interface and the turbidity of the supernatant. Subsequently, a model that relates the hindered settling rate to the aggregate size was used to determine the mass fractal dimension (Df). Flocculation kinetics revealed that greater amounts of kaolin generated larger aggregates because of its lamellar morphology. The maximum size was between 10 and 20 s of flocculation under all conditions. However, the presence of kaolin reduced the settling rate. The fractal dimension decreased with the increase in the kaolin content, resulting in the formation of irregular and porous aggregates. By contrast, factors such as the flocculation time, water quality, and quartz size had limited influences on the fractal dimension. Seawater produced a clearer supernatant because of its higher ionic strength and precoagulation of particles. Notably, the harmful effect of clays in seawater was reduced.

Compressive Yield Stress of Flocculated Kaolin Suspensions in Seawater.

The mining industry has resorted to using seawater while trying to find a solution to the water shortage, which is severe in some regions. Today, the industry looks to tailings dams to recover more water and, thus, increase recirculation. The migration of interstitial water due to the consolidation of particle networks can give rise to large water mirrors in different dam areas. These pools can contain enough water to be recovered and recirculated if the external stress caused by the weight of the pulp exceeds the compressive yield stress. The density and rheological properties of the discarded pulps determine the feasibility of water expulsion during tailings consolidation. As these conditions are largely established in the thickening stage, it is necessary to revisit operations, looking at the dam as a water source. Thus, a thorough understanding of the compressive properties that determine the level of consolidation of typical pulps and their relationships to aggregate properties, such as size and fractal dimension, is crucial. Here, the effect of two types of water, industrial water and synthetic seawater, on kaolin flocculation, sedimentation rate, yield stress, and compressive yield stress were studied. In addition, the relationship of these properties with the flocculant dose and the resulting aggregate size and fractal dimension was examined. One promising finding to practitioners was that salt and small doses of high molecular weight flocculant improved the consolidation of kaolin slurries under compression. These conditions generated low compressive yield stress compared to fresh water and water with low salt content, favoring the consolidation of the pulps and the release of water.

Understanding the Behavior of Sodium Polyacrylate in Suspensions of Silica and Monovalent Salts.

This study investigated the interaction of monovalent cations with different sizes on quartz surfaces and the rheological impact that this causes in concentrated suspensions when subjected to the action of a rheological modifier, in this case, sodium polyacrylate (NaPA). Yield stress was determined using a rheometer with a vane-in-cup configuration to establish the relationship between shear stress and strain. Experiments were carried out in LiCl, NaCl, KCl, and CsCl solutions. The results show that the yield stress increases following the order Li < Na < K < Cs in the absence of PAA. However, the addition of NaPA significantly reduced the yield stress in all cases. This reduction was more noticeable in the LiCl and NaCl solutions than in the KCl and CsCl solutions, suggesting a more pronounced effect of PA in maker salts. We conducted molecular dynamics simulations to understand how PA interacts with dissolved salts on the quartz surface. Our results showed that Li had the highest adsorption, followed by Na, K, and Cs. As the salt concentration increased, so did the adsorption. We validated these simulation results with rheological experiments, which helped us understand the observed differences. The molecular interactions indicate that, in the lithium system, cationic bridges and the synergy between hydrogen bridges and hydrophobic bridges predominate mainly. This tendency decreases as the type of cation is changed due to the decrease in the electrical density of the cation in the following order: Li < Na < K < Cs. This reduces bridging with the quartz surface and, therefore, directly impacts the system's rheological properties.

Reducing Magnesium within Seawater Used in Mineral Processing to Improve Water Recovery and Rheological Properties When Dewatering Clay-Based Tailings.

In areas where access to water for mineral processing is limited, the direct use of seawater in processing has been considered as an alternative to the expense of its desalination. However, efficient flotation of copper sulfides from non-valuable phases is best achieved at a pH > 10.5, and raising the pH of seawater leads to magnesium precipitates that adversely affect subsequent tailings dewatering. Seawater pre-treatment with lime can precipitate the majority of magnesium present, with these solids then being removed by filtration. To understand how such treatment may aid tailings dewatering, treated seawater (TSw) was mixed with raw seawater (Rsw) at different ratios, analyzing the impact on the flocculated settling rate, aggregate size as measured by focused beam reflectance measurement (FBRM), and vane yield stress for two synthetic clay-based tailings. A higher proportion of Tsw (10 mg/L Mg2+) led to larger aggregates and higher settling rates at a fixed dosage, with FBRM suggesting that higher calcium concentrations in Tsw may also favor fines coagulation. The yield stress of concentrated suspensions formed after flocculation decreased with higher proportions of Tsw, a consequence of lower flocculant demand and the reduced presence of precipitates; while the latter is a minor phase by mass, their high impact on rheology reflects a small particle size. Reducing magnesium concentrations in seawater in advance of use in processing offers advantages in the water return from thickening and subsequent underflow transport. However, this may not require complete removal, with blending Tsw and Rsw an option to obtain acceptable industrial performance.

Flocculation of Clay-Based Tailings: Differences of Kaolin and Sodium Montmorillonite in Salt Medium.

Complex gangues and low-quality waters are a concern for the mining industries, particularly in water shortage areas, where the closure of hydric circuits and reduction in water use are essential to maintain the economic and environmental sustainability of mineral processing. This study analyzes the phenomena involved in the water recovery stage, such as sedimentation of clay-based tailings flocculated with anionic polyelectrolyte in industrial water and seawater. Flocculation-sedimentation batch tests were performed to ascertain the aggregate size distribution, the hindered settling rate, and the structure of flocs expressed through their fractal dimension and density. The aggregates' properties were characterized by the Focused Beam Reflectance Measurement (FBRM) and Particle Vision Microscope (PVM) techniques. The impact of the type of water depends on the type of clay that constitutes the suspension. For quartz/kaolin, the highest performance was obtained in industrial water, with bigger aggregates and faster settling rates. However, the tailings composed of quartz/Na-montmorillonite reversed this trend. The type of water impacted the efficiency of primary-particle aggregation. The trials in industrial water generated a portion of non-flocculated particles, which was observed through a bimodal distribution in the unweighted chord-length distribution. This behavior was not observed in seawater, where a perceptible fraction of non-flocculated particles was not found. The additional cationic bonds that offer seawater favor finer primary-particle agglomeration for all tailings types.

Froth Flotation of Chalcopyrite/Pyrite Ore: A Critical Review.

In the present work an intense bibliographic search is developed, with updated information on the microscopic fundamentals that govern the behavior of flotation operations of chalcopyrite, the main copper mineral in nature. In particular, the effect caused by the presence of pyrite, a non-valuable mineral, but challenging for the operation due to its ability to capture a portion of collector and float, decreasing the quality of the concentrate, is addressed. This manuscript discusses the main chemical and physical mechanisms involved in the phenomena of reagent adsorption on the mineral surface, the impact of pH and type of alkalizing agent, and the effect of pyrite depressants, some already used in the industry and others under investigation. Modern collector reagents are also described, for which, although not yet implemented on an industrial scale, promising results have been obtained in the laboratory, including better copper recovery and selectivity, and even some green reagents present biodegradable properties that generate a better environmental perspective for mineral processing.

A Molecular Dynamics Simulation of Polymers' Interactions with Kaolinite (010) Surfaces in Saline Solutions.

The search for polymers that meet the demands of the water recovery process in mining is a contingent challenge. Both the presence of clays and saline waters can impair water recovery from tailings when conventional flocculants are used. In this work, the adsorption of polyacrylamide (PAM), hydrolyzed polyacrylamide (HPAM), poly(2-acrylamido-2-methyl-1-propane sulfonic acid) (PAMPS), polyacrylic acid (PAA), polyethylene oxide (PEO), and guar gum (GUAR) on a kaolinite surface (010) was investigated using classical molecular dynamics. The results show that the presence of sodium chloride modifies the affinities of the polymers with kaolinite (010). At low salt concentrations, the PAM and GUAR polymers generally show higher adsorption due to the formation of hydrogen bridges. However, the highest adsorptions occur in salt solutions in the presence of HPAM by cationic bridging with sodium ions as a mediator. This high affinity of HPAM is not efficient for flocculation because it re-disperses the particles, but it is promising for the design of new additives produced by grafting HPAM groups onto advanced polymers.

Study of Molybdenite Floatability: Effect of Clays and Seawater.

Current challenges in froth flotation are the presence of complex gangues and the use of low-quality waters, such as seawater. In this scenario, the recovery of molybdenum minerals is difficult, mainly due to the hydrophobic faces' physicochemical changes. In the present study, the natural floatability of pure molybdenite was analyzed by using microflotation assays, and hydrophobicity was measured by performing contact-angle measurements. The impact of two clays, kaolin (non-swelling) and Na-montmorillonite (swelling), was studied. The behavior in freshwater and seawater at pH 8 was compared, considering the current condition of the Cu/Mo mining industries, which use seawater in their operations. The presence of clays lowered the natural floatability of molybdenite precisely because they adhere to the surface and reduce its contact angle. However, the intensity with which they cause this phenomenon depends on the type of water and clay. Kaolin strongly adheres to the valuable mineral in both freshwater and seawater. For its part, Na-montmorillonite does it with greater intensity in a saline medium, but in freshwater, a high concentration of phyllosilicate is required to reduce the hydrophobicity of molybdenite. The clays' adherence was validated by scanning electron microscopy (SEM) analysis.

Estimating the Shear Resistance of Flocculated Kaolin Aggregates: Effect of Flocculation Time, Flocculant Dose, and Water Quality.

The resistance of kaolin aggregates to shearing in water clarification and recovery operations is a critical input in designing thickener feed wells. A recently formulated but already available criterion is used to determine the shear strength of flocculated kaolin aggregates. The flocculant is a high molecular weight anionic polyelectrolyte. The resistance of the aggregates is evaluated as a function of flocculation time, flocculant dosage, and water quality. The determination is based on a standardized experimental method. First, the time evolution of the average size of kaolin flocs is measured when aggregates are exposed to incremental shear rates from a predetermined base value. Then, the results are fitted to a pseudo-first-order model that allows deriving a characteristic value of the shear rate of rupture associated with the upper limit of the strength of the aggregates. In seawater, at a given dose of flocculant, the strength of the aggregates increases with time up to a maximum; however, at longer times, the resistance decreases until it settles at a stable value corresponding to stable aggregates in size and structure. A higher flocculant dosage leads to stronger aggregates due to more bridges between particles and polymers, leading to a more intricate and resistant particle network. In industrial water with very low salt content, the resistance of the kaolin aggregates is higher than in seawater for the same dose of flocculant. The salt weakens the resistance of the aggregates and works against the efficiency of the flocculant. The study should be of practical interest to concentration plants that use seawater in their operations.

Molecular Dynamics Study of the Conformation, Ion Adsorption, Diffusion, and Water Structure of Soluble Polymers in Saline Solutions.

Polymers have interesting physicochemical characteristics such as charge density, functionalities, and molecular weight. Such attributes are of great importance for use in industrial purposes. Understanding how these characteristics are affected is still complex, but with the help of molecular dynamics (MD) and quantum calculations (QM), it is possible to understand the behavior of polymers at the molecular level with great consistency. This study was applied to polymers derived from polyacrylamide (PAM) due to its great use in various industries. The polymers studied include hydrolyzed polyacrylamide (HPAM), poly (2-acrylamido-2-methylpropanesulfonate) (PAMPS), polyacrylic acid (PAA), polyethylene oxide polymer (PEO), and guar gum polysaccharide (GUAR). Each one has different attributes, which help in understanding the effects on the polymer and the medium in which it is applied along a broad spectrum. The results include the conformation, diffusion, ion condensation, the structure of the water around the polymer, and interatomic polymer interactions. Such characteristics are important to selecting a polymer depending on the environment in which it is found and its purpose. The effect caused by salinity is particular to each polymer, where polymers with an explicit charge or polyelectrolytes are more susceptible to changes due to salinity, increasing their coiling and reducing their mobility in solution. This naturally reduces its ability to form polymeric bridges due to having a polymer with a smaller gyration radius. In contrast, neutral polymers are less affected in their structure, making them favorable in media with high ionic charges.

Lime/Sodium Carbonate Treated Seawater to Improve Flocculation and Sedimentation of Clay-Based Tailings.

Seawater treated with lime and sodium carbonate in different proportions to reduce magnesium and calcium contents is used in flocculation and sedimentation tests of artificial quartz and kaolin tailings. Solid complexes were separated from water by vacuum filtration, and factors such as lime/sodium carbonate ratio, kaolin content, flocculation time, and flocculant dose are evaluated. The growth of the aggregates was captured in situ by a focused beam reflectance measurement (FBRM) probe. Solid magnesium and calcium complexes are formed in raw seawater at pH 11, impairing the performance of flocculant polymers based on polyacrylamides. The results show that the settling rate improved when the treatment's lime/sodium carbonate ratio increased. That is, when a greater removal of magnesium is prioritized over calcium. The amount of magnesium required to be removed depends on the mineralogy of the system: more clay will require more significant removal of magnesium. These results respond to the structural changes of the flocs, achieving that the more magnesium is removed, the greater the size and density of the aggregates. In contrast, calcium removal does not significantly influence flocculant performance. The study suggests the necessary conditions for each type of tailing to maximize water recovery, contributing to the effective closure of the water cycle in processes that use seawater with magnesium control.

Long-term persistence of the floating bull kelp Durvillaea antarctica from the South-East Pacific: Potential contribution to local and transoceanic connectivity.

Current knowledge about the performance of floating seaweeds as dispersal vectors comes mostly from mid latitudes (30°-40°), but phylogeographic studies suggest that long-distance dispersal (LDD) is more common at high latitudes (50°-60°). To test this hypothesis, long-term field experiments with floating southern bull kelp Durvillaea antarctica were conducted along a latitudinal gradient (30°S, 37°S and 54°S) in austral winter and summer. Floating time exceeded 200d in winter at the high latitudes but in summer it dropped to 90d, being still higher than at low latitudes (<45d). Biomass variations were due to loss of buoyant fronds. Reproductive activity diminished during long floating times. Physiological changes included mainly a reduction in photosynthetic (Fv/Fm and pigments) rather than in defence variables (phlorotannins and antioxidant activity). The observed long floating persistence and long-term acclimation responses at 54°S support the hypothesis of LDD by kelp rafts at high latitudes.

Population balance modelling of particle flocculation with attention to aggregate restructuring and permeability.

A population balance model based on a detailed literature review is used to describe coagulation and flocculation kinetics as well as the time evolution of aggregate size distribution in a turbulent shear flow simultaneously with the breakage and restructuring of aggregates. The fractal nature and permeability of the aggregates and their evolution with time are also part of the model. Restructuring is absent in coagulation with soluble salts, but is present in flocculation caused by large polyelectrolyte molecules; in the latter, aggregates never reach a steady-state size, but a size that decreases gradually through particle and polymer rearrangement. The model is tested against available experimental data for monodisperse polystyrene particles coagulated with hydrated aluminium sulphate at different shear rates, and precipitated calcium carbonate flocculated with a cationic polyelectrolyte of very high molecular weight at different flocculant dosages. The numerical solution of the model requires adjusting three parameters, i.e, maximum collision efficiency (αmax), critical force needed for the breakage of the aggregates (B) and rate of aggregate restructuring (γ), which are obtained from minimising the difference between experimental data and model predictions. The model studied for the two very different systems shows excellent agreement with experimental flocculation kinetics and a reasonably good fit for aggregate size distributions. The model is most sensitive to the fragmentation rate through parameter B, somewhat less to the collision efficiency through parameter αmax and little to γ. When the aggregates undergo restructuring, properties such as permeability, breakage rate and collision rate change considerably over time. When the aggregates are permeable, the collision frequency is significantly smaller than when they are impervious.

Nanoscale adhesive forces between silica surfaces in aqueous solutions.

Nanoscale adhesive forces between a colloidal silica probe and a flat silica substrate were measured with an atomic force microscope (AFM) in a range of aqueous NaCl, CaCl2, and AlCl3 solutions, with concentrations ranging from 10(-)(6) to 10(-)(2) M at pH ∼5.1. Notably, the measured force curves reveal large pull-off forces in water which increase in electrolyte solutions, with jump-off-contact occurring as a gradual detachment of the probe from the flat substrate rather than as a sharp discontinuous jump. The measured force curves also show that the number and size of the steps increase with concentration and notably with electrolyte valence. For the higher concentration and valence the steps become jumps. We propose that these nanoscale adhesive forces between mineral surfaces in aqueous solutions may arise from newly born cavities or persistent subnanometer bubbles. Formation of cavities or nanobubbles cannot be observed directly in our experiments; however, we cannot disregard them as responsible for the discontinuities in the measured force data. A simple model based on several cavities bridging the two surfaces we show that is able to capture all the features in the measured force curves. The silica surfaces used are clean but not intentionally hydroxylated, as contact angle measurements show, and as such may be responsible for the cavities.