Mineral Surfaces Research Articles

Environmentally friendly production of petroleum systems with high CO2 content

Natural gas hydrates represents a huge source of energy. At the same time substantial leakages of natural gas from hydrates contributes significantly to climate changes. One of the most important reasons for these natural gas fluxes is leakage of seawater in to the hydrates from seafloor, through fracture systems. Hydrate dissociates if surrounding seawater is less than hydrate stability limit. Another interesting aspect of natural gas hydrates is the potential for safe CO2 storage. These different aspects of hydrates in natural sediments put demands on thermodynamic models. In addition to accurate description of pressure temperature hydrate stability there also a need to describe hydrate dissociation in concentration gradients towards surrounding water or surrounding gas as two examples. In this work we present new experimental data and an extensive thermodynamic model for hydrate. In contrast to conventional thermodynamic models for hydrate the model is consistent since all thermodynamic properties are derived from the Gibbs free energy. In this work we examine mixtures of CH4, C2H6, N2, CO2 from the China Sea and some synthetic mixtures, using this model. Maximum CO2 content in these mixtures are 60 mol% and the rest is dominated by CH4. Agreement between experimental data and model calculations are generally good and average deviations are below 5.5% for all the systems and conditions examined. Another aspect of the model is the ability for incorporation of effects of mineral surfaces. Specifically it is illustrated that adsorption of water on rust dominates liquid water drop out from gas as compared to water dew-point. Production of natural gas with such high CO2 content requires a strategy for CO2 separation and storage. It is proposed that the CH4 is separated from the C2H6, CO2 and N2 and cracked to H2 and CO2 using steam. Thermodynamic analysis indicates a significant potential for safe CO2 storage in natural gas hydrate and H2 as the only export product.

A zero-carbon emission approach for the reduction of refractory iron ores: Mineral phase, magnetic property and surface transformation in hydrogen system

In this study, a feasible strategy, named hydrogen mineral phase transformation (HMPT) technology, is proposed and employed to achieve efficient and clean recovery of Hainan Shilu refractory iron ore (HSRIO). The influences of HMPT roasting temperature, roasting time, and H2 concentration on the separation index of HSRIO are investigated. Under the optimal experimental conditions, the iron concentrate grade increases from 62.5% to 67.9%, and the iron recovery increases from 65.0% to 94.7% compared with the original beneficiation process. In addition, the evolution of mineral phases, magnetic properties, and mineral microstructures is analyzed using XRD, VSM, SEM, and high-temperature hot-stage microscopy. It is revealed that the transformation of hematite to magnetite occurs during the HMPT process, with the newly formed magnetite exhibiting a loose and porous reticulation structure. This study is of guiding significance for the development of Hainan Shilu refractory iron ore with high efficiency and zero-carbon emission.

The influence of NaCl on xanthate adsorption on chalcopyrite surface and chalcopyrite flotation

Due to freshwater scarcity, mineral flotation plants have been using alternative water resources including seawater together with water recycling, resulting in the accumulation of salts in process water. However, how salts affect the adsorption of xanthates on the surfaces of sulphide minerals and subsequent sulphide mineral flotation is unclear. To address the knowledge gap, this study investigated how NaCl affected the adsorption of potassium amyl xanthate (PAX) on chalcopyrite surface and chalcopyrite flotation. Cyclic voltammetry (CV) tests identified that NaCl increased the oxidation of PAX and its adsorption on chalcopyrite surface due to elevated ionic strength and electrical conductivity of water, facilitating charge transfer among PAX, chalcopyrite surface and oxygen. NaCl also increased chalcopyrite surface oxidation to produce more CuS, facilitating the formation of copper-xanthate complexes. Flotation tests identified that the increased adsorption of PAX by NaCl was only translated into improved true flotation of chalcopyrite at a low PAX concentration such as 50 ppm in NaCl solutions with low and medium concentrations (0.1 and 0.7 M, respectively). At a high PAX concentration such as 150 ppm, the coexistence of high concentrations of PAX and NaCl led to strong froth destabilisation, resulting in a dramatic reduction in water recovery and true flotation recovery of chalcopyrite. The findings from this study will be able to guide the flotation plants to maximise mineral flotation by choosing collector dosage based on the ionic strength of process water.

Cerium(III)-induced structural transformation of hexagonal birnessite: Effect of mineral phase transition on arsenite transport and valence changes

The widespread mining and application of rare earth elements (REEs) have led to their continuous accumulation in the environment, with increasing concentrations in soil. The interaction between the most abundant REEs, cerium (Ce), and the prevalent hexagonal birnessite (HB) in the environment is worth attention. HB is one of the most effective metal oxides for the oxidation of arsenite [As(III)] and subsequent adsorption, and thus for arsenic (As) immobilization. Therefore, in this study, we investigated the effect of the presence of Ce(III) ion on the HB formation process and the influence of generating minerals on the oxidation and removal of As(III). Research has found that the interfacial reactions of REEs in manganese (Mn) minerals not only affect their cycling but also alter the properties of the Mn minerals, thereby affecting the environmental fate of As. The results indicated that the presence of Ce ions affected the structure of HB during mineral synthesis and reduced the crystallinity of the conversion products. Their substitution for Mn(IV) in the lattice increased the specific surface area of minerals, reduced particle size, and produced more hydroxyl groups that were conducive to the immobilization of As(III). Meanwhile, Ce(III) was oxidized to Ce(IV) during the formation of Ce-bearing hexagonal birnessite (Ce-HB), and CeO2 nanoparticles were formed on the mineral surface and the removal rate of As(III) by Ce-HB was greatly improved. When the As concentration was lower than 6 mg·L−1, the removal effect of Ce-HB could reach the drinking water standard. However, the oxidation rate decreased due to the decrease in the proportion of Mn(IV). This study fundamentally reveals the behavior of HB coexisting with Ce in the migration and transformation of As(III) in the environment.

Interfacial properties of CO2 and liquid sulfur in high-sulfur gas fields: Molecular simulations on carbonate mineral surfaces

As the global energy landscape transforms, the development of high-sulfur natural gas has become increasingly critical. However, sulfur deposition during these gas field developments significantly affects operational efficiency. This study employed molecular dynamics simulation to explore the effectiveness of CO2 in alleviating sulfur deposition on carbonate rock reservoirs. Specifically, it examined the interfacial tension between liquid sulfur and CO2, the wettability of sulfur on carbonate rock mineral surfaces, and the kinetics of CO2 displacing liquid sulfur. Results show that as CO2 pressure increases from 10 MPa to 60 MPa, the interfacial tension between liquid sulfur and CO2 decreases by 84 %, from 35.54 mN/m to 5.53 mN/m. The contact angles of sulfur droplets on calcite and dolomite surfaces stabilize at 41.82° ± 2.10° and 44.33° ± 3.27°, respectively, indicating greater sulfur spread on calcite surfaces. With higher CO2 pressures, sulfur deposition on mineral surfaces and interfacial tension both decrease significantly, while the wetting angle of liquid sulfur increases, particularly on dolomite. At 60 MPa CO2 pressure, the adsorption energy of dolomite for liquid sulfur drops from 364.56 kcal/mol to 25.46 kcal/mol, a 93 % reduction, suggesting CO2′s dual role in displacing sulfur and promoting its desorption from mineral surfaces. Furthermore, the efficiency of sulfur deposition alleviation in carbonate rock slit structures improves and stabilizes at around 40 MPa CO2 pressure. This study presents a potential environmentally friendly approach for efficiently developing high-sulfur gas fields, and its findings provide practical insights for optimizing CO2 injection strategies to mitigate sulfur deposition.

Nanoconfinement effect on the miscible behaviors of CO2/shale oil/surfactant systems in nanopores: Implications for CO2 sequestration and enhanced oil recovery

Currently, CO2 flooding is the most promising carbon capture, utilization, and storage (CCUS) technology in the energy industry. Understanding the nanoconfinement effect on the CO2-oil miscible process is crucial for accurately determining the minimum miscibility pressure (MMP) of CO2/oil in shale reservoirs. In this study, we conducted molecular dynamics (MD) simulations to investigate the effects of pore size, surfactants, and pore type on the MMP of nanoconfined CO2/shale oil/surfactant systems. Validations against experimental data show a deviation of 2.98 % in the CO2 MMP. The MMPs under nanoconfinement are found to be significantly lower than those in bulk phase conditions (up to 22.94 %). The simulation results reveal that decreasing pore size can enhance the miscibility of CO2 and oil by increasing the CO2 adsorption ratio, improving CO2-surfactant interactions, and inhibiting the tendency of CO2 molecules to self-aggregate. The enhancement of CO2-oil miscibility caused by surfactants is ranked by CFP > SF > SDS according to the mixing degrees (Dmix) and the spatial distribution of CO2 around surfactant molecules. In addition, pore type exhibits various abilities in influencing the MMP, owing to their different mineral surface properties and ability to influence CO2-surfactant interactions. Nanopores with stronger hydrophobicity and a denser CO2 distribution around surfactant molecules have lower MMPs. The results show that the order of MMP in terms of pore types is Quartz < Kaolinite < I/M clay. This study elaborates the micro-mechanisms of surfactant-assisted CO2-oil miscibility under nanoconfinement, offering valuable insights for effectively designing CO2 miscible flooding in shale oil reservoir development.

An integrated experimental-modeling approach to identify key processes for carbon mineralization in fractured mafic and ultramafic rocks.

Controlling atmospheric warming requires immediate reduction of carbon dioxide (CO2) emissions, as well as the active removal and sequestration of CO2 from current point sources. One promising proposed strategy to reduce atmospheric CO2 levels is geologic carbon sequestration (GCS), where CO2 is injected into the subsurface and reacts with the formation to precipitate carbonate minerals. Rapid mineralization has recently been reported for field tests in mafic and ultramafic rocks. However, unlike saline aquifers and depleted oil and gas reservoirs historically considered for GCS, these formations can have extremely low porosities and permeabilities, limiting storage volumes and reactive mineral surfaces to the preexisting fracture network. As a result, coupling between geochemical interactions and the fracture network evolution is a critical component of long-term, sustainable carbon storage. In this paper, we summarize recent advances in integrating experimental and modeling approaches to determine the first-order processes for carbon mineralization in a fractured mafic/ultramafic rock system. We observe the critical role of fracture aperture, flow, and surface characteristics in controlling the quantity, identity, and morphology of secondary precipitates and present where the influence of these factors can be reflected in newly developed thermo-hydro-mechanical-chemical models. Our findings provide a roadmap for future work on carbon mineralization, as we present the most important system components and key challenges that we are overcoming to enable GCS in mafic and ultramafic rocks.

Comparison between Co(II) and Ni(II) cycling at goethite-water interfaces: Interplay with Fe(II)-catalyzed recrystallization

Cobalt (Co) and nickel (Ni) are critical metals for modern renewable energy technologies as well as essential micronutrients for terrestrial plant health and marine primary production. Both metals are commonly surface-adsorbed onto and/or structurally-incorporated into iron (oxyhydr)oxide minerals, such as goethite (α-FeOOH), that are ubiquitously present in soils and sediments at the Earth’s surface. In sub- and anoxic environments, aqueous ferrous iron (Fe(II)) generated from dissimilatory Fe(III) reduction can induce the recrystallization of goethite and subsequently influences the speciation and mobilization of associated metals, e.g., Co(III) being reduced to Co(II). While it is generally considered that divalent Co and Ni behave similarly at goethite-water interfaces, there lacks a direct comparison of their cycling through goethite in response to Fe(II)-catalyzed recrystallization. Here, under circumneutral anoxic conditions with and without addition of aqueous Fe(II), we performed batch reaction experiments on Co(II)-substituted goethite and Co(II) and Ni(II) sorption experiments on pure goethite. The redox state and coordination environment of Co associated with goethite were determined using high energy resolution fluorescence detected X-ray absorption spectroscopy at the Co K-edge, and the distribution of solid-bound Co and Ni in goethite following sorption was revealed by sequential dissolution. Our results show that substitution of Co(II) for Fe(III) in goethite has less negative feedback on Fe(II)-catalyzed recrystallization than Ni(II), which may be related to their differing structural distortions as evidenced by EXAFS. In the absence of Fe(II), aqueous Co(II) is more favourably adsorbed onto and incorporated deeper into goethite than Ni(II), suggesting that Co(II) is more structurally compatible with goethite. The presence of Fe(II) markedly enhances the structural incorporation of both Co(II) and Ni(II) as a result of goethite recrystallization, which in turn can be inhibited by the accumulation of metals at the mineral surface. Furthermore, structurally-incorporated Co(II) is more difficult to be released back into solution (i.e. sum of aqueous and extract fractions) than Ni(II) during Fe(II)-catalyzed goethite recrystallization. Overall, our work highlights the significant differences between Co(II) and Ni(II) in their cycling at goethite-water interfaces and intricate interplay with Fe(II)-catalyzed recrystallization. This improves our understanding of their mobilization and distribution in anoxic goethite-rich systems and can provide useful insights for their enrichment and extraction from natural and artificial laterites generated from the enhanced weathering of ultramafic mine tailings.

Water Vapor Adsorption-Desorption Hysteresis Due to Clustering of Water on Nonporous Surfaces.

Water vapor is continuously adsorbed onto and desorbed from all kinds of surfaces depending on changes in relative humidity. Adsorption-desorption hysteresis of water that occurs on various nonporous surfaces and extends down to low relative humidities has been reported for decades, but remains unexplained. Here we show experimentally that such hysteresis is a common phenomenon on metal oxide and mineral surfaces and can be divided into two distinct categories based on the wettability of the adsorbent surface. Type I hysteresis occurs on more hydrophobic surfaces and is associated with adsorption isotherms that behave rather linearly as water saturation is approached, whereas type II hysteresis occurs on more hydrophilic surfaces and is associated with adsorption isotherms that curve steeply upward close to saturation. Our model calculations strongly indicate that adsorption in both types occurs cluster-wise, and the type I hysteresis is caused by contact angle hysteresis, while type II hysteresis is associated with film formation close to saturation. The understanding of water vapor adsorption and desorption mechanisms may be key for explaining and quantifying physical and chemical interfacial phenomena in atmospheric and industrial environments.

A study on the mechanisms and influencing factors of interfacial physicochemical interactions between asphalt and mineral aggregates based on multiscale evaluation methods

The elucidation of interfacial physicochemical mechanisms between asphalt and mineral aggregates is vital for comprehending the interface formation in asphalt mixtures and enhancing their performance. To this end, multiscale evaluation methods were used to investigate the mechanisms and influencing factors of interfacial physicochemical interactions between asphalt and mineral aggregates (IPIAMA). Initially, the dynamic shear rheometer (DSR) was used to measure the complex shear modulus (G*) of various asphalt mastics. Subsequently, the interface film thickness was calculated using G* in conjunction with the Hashin and Mori-Tanaka (MT) micromechanical models. This indicator facilitated quantitative assessments and the analysis of influencing factors. The results indicated that the MT model underestimated the interface film thickness by approximately 0.08–0.29 % compared to the Hashin model, a discrepancy attributable to assumptions regarding aggregate particle interlocking. Moreover, the interface film thickness systematically varied with factors such as aggregate content, type of aggregate, and type of asphalt, ranging from 0.24 to 0.53 μm. To further elucidate the IPIAMA mechanisms behind these variations, the fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), x-ray photoelectron spectroscopy (XPS), and the ultraviolet test (UV) testing were conducted. FTIR tests demonstrated that the primary components of mineral aggregates—dolomite, calcite, and quartz—contributed to the physical adsorption increments on asphalt functional groups by 0.0185, 0.0509, and 0.004, respectively. SEM images revealed that dolomite and calcite possessed more surface fissures and pores than quartz. XPS tests showed that calcium carbonate and magnesium carbonate chemically reacted with asphalt, resulting in electron shifts of 0.9 eV and 1.1 eV, respectively, while silicon oxide only exhibited electron shifts when combined with a silane coupling agent-modified asphalt. UV tests demonstrated that lighter asphalt fractions were preferentially absorbed into the pores and micro-cracks of mineral aggregates. Consequently, the complex IPIAMA involved physical adsorption, chemical reactions, and selective absorption, strongly correlating with factors such as mineral composition, surface morphology, and asphalt type.

Abiotic transformation of chlorinated organics at the active surface of iron-bearing minerals in soils and sediments

Abiotic transformation of chlorinated organics at the active surface of iron-bearing minerals in soils and sediments

Application of waste gypsum as novel selective depressant in the flotation separation of apatite from dolomite

The accumulation of gypsum slag not only causes resource wastage, but also poses serious environmental hazards, therefore, utilizing the resources of the main components in gypsum slag is an imperative task. In this study, gypsum was used as an inorganic depressant for the flotation separation of apatite from dolomite through the selective adsorption of gypsum on the surface of dolomite. Micro-flotation experiments showed that sodium oleate exhibited a good ability to collect apatite and dolomite, but poor ability to collect gypsum. At pH 9.5, when 3.75 g/L gypsum was added to the slurry, the recovery of dolomite decreased from 76.77 % to 18.34 %, whereas that of apatite was 86.45 %. Atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to elucidate the adsorption characteristics of gypsum on the apatite and dolomite surfaces. The results showed that gypsum was selectively adsorbed on the raised particles on the dolomite surface and combined with the active sites of Ca and Mg metal ions. However, the adsorption of gypsum on the surface of apatite was weak and had little effect on the flotation performance. Density functional theory calculations showed that the O in gypsum reacted easily with Ca and Mg metal ions on the mineral surface. The adsorption energies of gypsum at the Ca and Mg sites on the dolomite surface were −81.97 and −86.18 kJ/mol, respectively, whereas the adsorption energy on the apatite surface was only −34.20 kJ/mol. Gypsum is the main component of gypsum slag, and this study provides a potential recycling method for gypsum slag resources.

Tailor-made polymer tracers reveal the role of clay minerals on colloidal transport in carbonate media

HypothesisHost rock weathering and incipient pedogenesis result in the exposition of minerals, e.g., clay minerals in sedimentary limestones. Once exposed, these minerals provide the surfaces for fluid–solid interactions that control the fate of dissolved or suspended compounds such as organic matter and colloids. However, the functional and compositional diversity of organic matter and colloids limits the assessment of reactivity and availability of clay mineral interfaces. Such assessment demands a mobile compound with strong affinity to clay surfaces that is alien to the subsurface. ExperimentWe approached this challenge by using poly(ethylene glycol) (PEG) as interfacial tracer in limestone weathering experiments. FindingsPEG adsorption and transport was dependent on the availability of clay mineral surfaces and carbonate dissolution dynamics. In addition, PEG adsorption featured adsorption–desorption hysteresis which retained PEG mass on clay mineral surfaces. This resulted in different PEG transport for experiments conducted consecutively in the same porous medium. As such, PEG transport was reconstructed with a continuum-scale model parametrized by a Langmuir-type isotherm including hysteresis. Thus, we quantified the influence of exposed clay mineral surfaces on the transport of organic colloids in carbonate media. This renders PEG a suitable model colloid tracer for the assessment of clay surface exposition in porous media.

Dependence of Simulated Fault Gouge Frictional Behavior on Mineral Surface Chemistry Quantified by Cation Exchange Capacity

AbstractThe slip behavior of crustal faults is known to be controlled by the composition of the fault gouge, but the exact mechanisms, especially considering the role of water‐rock interactions, are still under investigation. Here, we use a geochemical approach measuring the cation exchange capacity (CEC) of several phyllosilicate minerals and non‐clays, using CEC as a proxy for the ability to bind water to the mineral surfaces and/or develop electrostatic forces between particles. Laboratory shearing experiments show that low CEC materials (&lt;3 mEq/100 g) tend to exhibit high friction, low cohesion, and velocity‐weakening frictional behavior. Phyllosilicate minerals exhibit CEC values up to 78 mEq/100 g and correspondingly lower friction coefficients, higher cohesion, and a tendency for velocity‐strengthening friction. Zeolite behavior is atypical, exhibiting a high CEC value typical of phyllosilicates but the strength and frictional characteristics of a non‐clay with low CEC. This suggests that the structure of the mineral is important for non‐phyllosilicates. For phyllosilicates, our results can be explained by water bound to mineral surfaces, creating bridges of hydrogen or van der Waals bonds between particles. The enhanced particle bonding for high CEC materials is consistent with high cohesion under zero effective stress conditions, and lowered friction by trapping bound water between the mineral surfaces under normal load. Bound water may explain the tendency for velocity‐strengthening friction in high CEC materials by hindering a Dieterich‐type time‐dependent frictional strengthening mechanism.

Hydrocarbons, Hydrogen, and Organic Acids Generation by Ball Milling and Batch Incubation of Sedimentary Rocks

Pulverized rock samples are widely used in laboratory experiments, e.g., to assess microbial or abiotic processes in batch incubation tests. However, it is unclear if ball-milled samples accurately reflect in-situ conditions and if observed processes are affected by by-products artificially generated during the sample preparation procedure. As such, this study examined the effects of dry ball milling on the release of gases, which include C1-C4 hydrocarbons, carbon dioxide (CO2), hydrogen (H2), and low molecular weight organic acids (LMWOAs) from different sedimentary rocks. The experiments involved pulverization using a gas-tight zirconium oxide planetary ball mill followed by wet and dry batch incubation and thermal desorption up to 200 o C. During milling, all sedimentary rocks, except a low organic carbon sandstone sample, yielded methane (CH4), ethane (C2H6), propane (C3H8), butane (C4H10), H2, CO2, and unsaturated hydrocarbons, e.g., ethene (C2H4). Sandstones only yielded H2, CH4, and CO2. Stable carbon isotope signatures of these products are similar to thermogenic gases. The gases were also detected in subsequent wet incubation experiments (after gases from milling had been removed). Additionally, formate, acetate, and citrate, were detected in all samples except for sandstone. Pyruvate, malate, and succinate were also detected in some samples. Thermal desorption products of powdered limestone, shale, and pyrite concretion samples included organic acids, such as acetate and formate, which were higher in milled samples than in crushed particles (∼1 mm). The original geological thermal maturity of the studied sedimentary rock samples was low (below “oil window”) and, thus, considerably below “gas window”, suggesting that most of the detected gases were generated during ball milling. H2 generated during ball milling may be derived from the reduction of water from fluid inclusion or phyllosilicates, involving the formation of reactive mineral surfaces or radicals. Notably, the concentrations of gaseous hydrocarbons derived from milling are relatively high and comparable to “wet” gases. At the same time, these data indicate that substantial amounts of gases and LWMOAs might be artificially generated during laboratory batch experiments with milled samples. Hence, ball milled rock samples must be used with caution if assessing (bio-)geochemical processes for natural environments.

Enhancement of copper mobilization using acidic AlCl3 − rich lixiviant

Copper (Cu) extraction from low-grade ores is limited by the formation of secondary minerals that can passivate the surfaces of Cu-sulphide minerals in these ores. Hence, a novel approach utilizing AlCl3 as a lixiviant was developed to modify coupled dissolution-reprecipitation processes at the mineral interface. The formation of Al-rich phases instead of Fe-hydroxysulphates enhanced Cu extraction through combined ferric-iron and proton-promoted dissolution. AlCl3 accelerated chalcopyrite and bornite dissolution by forming soluble intermediate Cu-phases (e.g., covellite) at consistently high Eh (550–650 mV) and acidity due to the Lewis acid property of AlCl3. X-ray diffraction analysis revealed that Na-bearing jarosite [(K0.61Na0.41)Fe3(SO4)2(OH)] and sideronatrite [Na2Fe(SO4)2(OH)(H2O)] formation in lixiviants without AlCl3 decreased Fe3+(aq) availability for Cu-sulphide minerals dissolution. In contrast, significant amounts of AlSO4+(aq) formed in the AlCl3-rich lixiviant at pH 1–3, which reduced the sulphate activity and decreased the saturation state of the Fe-hydroxysulphates. Further, AlCl3 promoted the formation of amorphous, porous Al-rich phases, facilitating quick Fe diffusion through the passivating layer and improving Cu recovery compared to lixiviants containing CaCl2, NaCl, or acid-only.

Influence of Ca2+ substitution on the surface hydration characteristics of kaolinite: Combination of simulations and experiments

To investigate the changes in kaolinite surface hydration characteristics after Ca2+ substitution, water molecule adsorption onto the surface of Ca2+-substituted kaolinite was studied using density functional theory. Changes in the hydration film on the surface of kaolinite (001) and the mineral surface hydrophilicity after Ca2+ substitution were studied using molecular dynamics methods. Several Ca2+-substituted kaolinite samples were hydrothermally synthesized, and their hydration characteristics were analyzed using contact-angle and microcantilever humidity-test methods. The energy of a water molecule adsorbed on a Ca2+-substituted kaolinite surface is > 5 % lower than on pure kaolinite, and microscopic interactions between water molecules and the kaolinite surface are enhanced. Further, water molecules are more likely to be adsorbed onto the (001) surface than the (001¯) surface of kaolinite. After Ca2+ substitution, the hydration film on the kaolinite (001) surface becomes denser and the hydrophilicity of the mineral surface is enhanced. Using X-ray diffraction, Fourier-transform infrared spectroscopy, and X-ray photoelectron spectroscopy to characterize the synthesized samples, we confirmed successful Ca2+ substitution within the kaolinite structure. Hydration-test results showed that the surface hydrophilicity of kaolinite is enhanced after Ca2+ substitution and increases with increasing Ca2+ substitution. The experimental results thus verified the simulations.

New Insights into the Depressive Mechanism of Sodium Silicate on Bastnaesite, Parisite, and Fluorite: Experimental and DFT Study

The surface properties of bastnaesite and parisite are similar to their associated gangue mineral, fluorite, which makes the flotation separation of these two rare earth minerals from fluorite one of the industry’s most significant challenges. This study systematically investigates the inhibitory effects and mechanisms of sodium silicate (SS) on bastnaesite, parisite, and fluorite in an octyl hydroxamic acid (OHA) collector system through flotation experiments, various modern analytical methods, and DFT simulations. The flotation test results indicate that the inhibition effects of SS on the three minerals are in the order: fluorite &gt; parisite &gt; bastnaesite. Detection and analysis results indicate that SS forms hydrophilic complexes with Ca atoms on the surfaces of fluorite and parisite, enhancing surface hydrophilicity and inhibiting OHA adsorption, but its impact on bastnaesite is relatively minor. DFT simulation results show that OHA forms covalent bonds with metal ions on mineral surfaces, favoring five-membered hydroxamic-(O-O)-Ce/Ca complexes, and reacts more strongly with Ce atoms than Ca atoms. SS primarily forms covalent bonds with metal atoms on mineral surfaces via the SiO(OH)3− component, and OHA and SS compete for adsorption on the mineral surfaces. OHA has a stronger affinity for bastnaesite, whereas SS shows the highest affinity for fluorite, followed by parisite, and the weakest affinity for bastnaesite.

Application of novel ionic liquids in flotation separation of quartz and magnesite and its mechanism

Application of a novel ionic liquid as flotation reagent in the flotation separation of quartz and magnesite has been investigated. The flotation behavior and surface properties of quartz and magnesite flotation with dodecyl trimethyl ammonium-diethylphosphonic acid (N12111-DEPA) as flotation reagent were studied by microbubble flotation experiments, contact angle, fourier transforming infrared spectra (FT-IR), and X ray photoelectron spectroscopy (XPS) spectrometer analysis. The micro-flotation of single mineral results demonstrated that N12111-DEPA exhibited a good collection selectivity for quartz. Under the optimum flotation conditions of pulp pH 7.0 and 15 mg/L N12111-DEPA, the grade and recovery of MgO in concentrate were 41.21 % and 97.45 %, respectively. The analysis of contact angle shown that N12111-DEPA increased the surface hydrophobicity of quartz and decreases the surface hydrophobicity of magnesite, thus increasing the difference of floatability between the two minerals. The analysis of FT-IR and XPS confirmed that the cations of N12111-DEPA are mainly adsorbed on quartz surface through electrostatic affinity, while the anions of N12111-DEPA are mainly adsorbed on magnesite surface through chelation with exposed magnesium sites on mineral surface. This demonstrated that N12111-DEPA had a good application potential in reverse flotation separation of magnesite and quartz.

Leaching process assisted by cetyltrimethylammonium chloride for weathered crust elution-deposited rare earth ores: Leaching behavior, kinetic analysis and interfacial regulation

Magnesium salts are commonly employed as ammonium-free leaching agents in the extraction of weathered crust elution-deposited rare earth ores (WCE-REO). Nonetheless, these salts frequently face technical challenges, including relatively low leaching rates and inadequate permeability in the in-situ leaching process. In this study, cetyltrimethylammonium chloride (CTAC) was used as a novel leaching aid agent to improve the rare earth leaching process. The effects of CTAC and pH on the rare earth leaching behavior and permeability was investigated. The leaching kinetic model was established and the regulation mechanism by which CTAC interacts with clay mineral surfaces was revealed for rare earth leaching process enhanced by CTAC. The results indicate that the appropriate amount of CTAC can increase the permeation velocity by 1.16×10−4 cm·s−1. Moreover, the rare earth leaching rate increased from 83.75 % to 95.65 %, accompanied by a reduction in leaching equilibrium time under optimal conditions. However, a higher concentration of CTAC results in a lower permeation velocity due to the increasing viscosity and the hydrophilicity. The relatively low pH will affect permeability of composite leaching agent in the ore pillar, diminishing its beneficial impact on rare earth leaching. The kinetic equation, fitted by the shrinking core model, suggests that the leaching adheres to an internal diffusion control mechanism, underscoring mass transfer as the pivotal limiting factor in rare earth leaching. CTAC reduces surface tension and viscosity, facilitating the permeation of the leaching solution into the rare earth ore. Furthermore, CTAC can be adsorbed on the surface of rare earth mineral particles, increasing the contact angle of clay minerals, elevating the Zeta potential, and diminishing the thickness of the diffusion layer, thus promoting mass transfer during leaching. The results of atomic force microscopy (AFM) analysis shows that the appropriate amount of CTAC adsorbed on rare earth ores can decreases the thickness of the hydration film on the particles’ surface, further improving the mass transfer efficiency during the leaching process. The findings of this study offer new insights into the green and efficient extraction of rare earth resources from both theoretical and technical perspectives.