Surface Speciation of Brucite Dissolution in Aqueous Mineral Carbonation: Insights from Density-Functional Theory Simulations.

Aqueous mineral carbonation of brucite is an important mineralization route for carbon capture and sequestration. Prerequisite to mineral carbonation are the simultaneous CO2 absorption and brucite dissolution which imply, in the first place, the formation and release in the liquid phase of CO32-, HCO3-, Mg2+, MgOH+, and MgHCO3+ ions. To gain insights on the nature of adsorption sites and resulting surface complexes, the affinity of water and of dissolved species for pristine and partially dissolved brucite (001) cleaved surfaces in aqueous mineral carbonation has been investigated using density-functional theory (DFT) simulations. The species' affinity for uptake by the brucite (001) surface is predicted to obey the trend: Mg2+ > MgHCO3+ > MgOH+ > HCO3- > CO32-, whereas the surface acid/base behavior controls affinity following the order: dehydroxylated (001) surface > deprotonated (001) surface > neutral and protonated (001) surfaces. Covalent bonds have been predicted for the following (charge-determining) ion-(001) brucite surface sites: CO32- ≡ dehydroxylated site, HCO3- ≡ dehydroxylated site, MgOH+ ≡ dehydroxylated/deprotonated sites, MgHCO3+ ≡ dehydroxylated/(de)protonated sites, and Mg2+ ≡ neutral/(de)protonated/dehydroxylated sites. Congruent dissolution of (001) brucite surface leads to a diverse population of coordination-deficient Mg and O centers which are more active to form covalently bonded surface complexes with aqueous CO32-, HCO3-, Mg2+, MgOH+, MgHCO3+ as compared to the undissolved surface. However, although affinity of the altered surfaces for dissolved ions increases conspicuously, the same affinity trend is predicted for the dissolving surfaces as compared to the pristine (001) brucite surface.

Atmospheric Carbon Mineralization in an Industrial-Scale Chrysotile Mining Waste Pile.

Magnesium-rich minerals that are abundant in ultramafic mining waste have the potential to be used as a safe and permanent sequestration solution for carbon dioxide (CO2). Our understanding of thermo-hydro-chemical regimes that govern this reaction at an industrial scale, however, has remained an important challenge to its widespread implementation. Through a year-long monitoring experiment performed at a 110 Mt chrysotile waste pile, we have documented the existence of two distinct thermo-hydro-chemical regimes that control the ingress of CO2 and the subsequent mineral carbonation of the waste. The experimental results are supported by a coupled free-air/porous media numerical flow and transport model that provides insights into optimization strategies to increase the efficiency of mineral sequestration at an industrial scale. Although functioning passively under less-than-optimal conditions compared to laboratory-scale experiments, the 110 Mt Thetford Mines pile is nevertheless estimated to be sequestering up to 100 tonnes of CO2 per year, with a potential total carbon capture capacity under optimal conditions of 3 Mt. Annually, more than 100 Mt of ultramafic mine waste suitable for mineral carbonation is generated by the global mining industry. Our results show that this waste material could become a safe and permanent carbon sink for diffuse sources of CO2.

Tuning mass transport in magnetic nanoparticle-filled viscoelastic hydrogels using low-frequency rotating magnetic fields.

This study investigates the response of magnetic nanoparticles (MNPs), dispersed in a viscoelastic hydrogel, to an external rotating magnetic field (RMF) for the purpose of developing a new class of magneto-responsive materials with tunable mass transport properties. Ferrogels were prepared by chemical cross-linking and polymerization of acrylamide in colloidal dispersions of thermally blocked MNPs of cobalt ferrite. Magnetization measurements of ferrogels in a swollen state revealed a transitional state from ferromagnetism to superparamagnetism through the shrinkage of hysteresis loops and the reduction of remanent magnetization. A quantitative analysis of magnetization data indicated the existence of hydrodynamically free MNPs, susceptible to Brownian relaxation along with the blocked ones. It was found through rheological analysis that inclusion of MNPs within the polymer matrix significantly alters the ferrogel's elasticity. At low chemical crosslinking ratios, MNPs improve elasticity through the formation of physical crosslinks ensued by reduction in the fraction of the free MNPs. As the crosslinking ratio was increased, the polymer network showed a tendency toward blockage of more MNPs. Effective diffusion coefficients in both particle-free hydrogels and ferrogels were obtained by measuring the release kinetics of a model compound in the absence and presence of an external low-frequency RMF. Experimental results showed that conversion of magnetic energy to kinetic energy by rotational movement of the free MNPs in a RMF escalates mass transport provided that hydrodynamically free MNPs are available within the ferrogels. The effectiveness of excitation by a RMF showed correlation with the density of free MNPs. Release experiments at constant RMF intensity and various frequencies revealed augmentation of effective diffusivities as the frequency was increased from 10 to 75 Hz.

Modeling of Shear Flows over Superhydrophobic Surfaces: From Newtonian to Non-Newtonian Fluids.

The design and use of superhydrophobic surfaces have gained special attentions due to their superior performances and advantages in many flow systems, e.g., in achieving specific goals including drag reduction and flow/droplet handling and manipulation. In this work, we conduct a brief review of shear flows over superhydrophobic surfaces, covering the classic and recent studies/trends for both Newtonian and non-Newtonian fluids. The aim is to mainly review the relevant mathematical and numerical modeling approaches developed during the past 20 years. Considering the wide ranges of applications of superhydrophobic surfaces in Newtonian fluid flows, we attempt to show how the developed studies for the Newtonian shear flows over superhydrophobic surfaces have been evolved, through highlighting the major breakthroughs. Despite the fact that, in many practical applications, flows over superhydrophobic surfaces may show complex non-Newtonian rheology, interactions between the non-Newtonian rheology and superhydrophobicity have not yet been well understood. Therefore, in this Review, we also highlight emerging recent studies addressing the shear flows of shear-thinning and yield stress fluids in superhydrophobic channels. We focus on reviewing the models developed to handle the intricate interaction between the formed liquid/air interface on superhydrophobic surfaces and the overlying flow. Such an intricate interaction will be more complex when the overlying flow shows nonlinear non-Newtonian rheology. We conclude that, although our understanding on the Newtonian shear flows over superhydrophobic surfaces has been well expanded via analyzing various aspects of such flows, the non-Newtonian counterpart is in its early stages. This could be associated with either the early applications mainly concerning Newtonian fluids or new complexities added to an already complex problem by the nonlinear non-Newtonian rheology. Finally, we discuss the possible directions for development of models that can address complex non-Newtonian shear flows over superhydrophobic surfaces.

Insight into the Binding Mechanisms of Quartz-Selective Peptides: Toward Greener Flotation Processes.

Mining practices, chiefly froth flotation, are being critically reassessed to replace their use of biohazardous chemical reagents in favor of biofriendly alternatives as a path toward green processes. In this regard, this study aimed at evaluating the interactions of peptides, as potential floatation collectors, with quartz using phage display and molecular dynamics (MD) simulations. Quartz-selective peptide sequences were initially identified by phage display at pH = 9 and further modeled by a robust simulation scheme combining classical MD, replica exchange MD, and steered MD calculations. Our residue-specific analyses of the peptides revealed that positively charged arginine and lysine residues were favorably attracted by the quartz surface at basic pH. The negatively charged residues at pH 9 (i.e., aspartic acid and glutamic acid) further showed affinity toward the quartz surface through electrostatic interactions with the positively charged surface-bound Na+ ions. The best-binding heptapeptide combinations, however, contained both positively and negatively charged residues in their composition. The flexibility of peptide chains was also shown to directly affect the adsorption behavior of the peptide. While attractive intrapeptide interactions were dominated by a weak peptide-quartz binding, the repulsive self-interactions in the peptides improved the binding propensity to the quartz surface. Our results showed that MD simulations are fully capable of revealing mechanistic details of peptide adsorption to inorganic surfaces and are an invaluable tool to accelerate the rational design of peptide sequences for mineral processing applications.

Emerging Trends of Computational Chemistry and Molecular Modeling in Froth Flotation: A Review.

Froth flotation is the most versatile process in mineral beneficiation, extensively used to concentrate a wide range of minerals. This process comprises mixtures of more or less liberated minerals, water, air, and various chemical reagents, involving a series of intermingled multiphase physical and chemical phenomena in the aqueous environment. Today's main challenge facing the froth flotation process is to gain atomic-level insights into the properties of its inherent phenomena governing the process performance. While it is often challenging to determine these phenomena via trial-and-error experimentations, molecular modeling approaches not only elicit a deeper understanding of froth flotation but can also assist experimental studies in saving time and budget. Thanks to the rapid development of computer science and advances in high-performance computing (HPC) infrastructures, theoretical/computational chemistry has now matured enough to successfully and gainfully apply to tackle the challenges of complex systems. In mineral processing, however, advanced applications of computational chemistry are increasingly gaining ground and demonstrating merit in addressing these challenges. Accordingly, this contribution aims to encourage mineral scientists, especially those interested in rational reagent design, to become familiarized with the necessary concepts of molecular modeling and to apply similar strategies when studying and tailoring properties at the molecular level. This review also strives to deliver the state-of-the-art integration and application of molecular modeling in froth flotation studies to assist either active researchers in this field to disclose new directions for future research or newcomers to the field to initiate innovative works.

CO2 capture in alkanolamine-RTIL blends via carbamate crystallization: route to efficient regeneration.

One of the major drawbacks of aqueous alkanolamine based CO(2) capture processes is the requirement of significantly higher energy of regeneration. This weakness can be overcome by separating the CO(2)-captured product to regenerate the corresponding amine, thus avoiding the consumption of redundant energy. Replacing aqueous phase with more stable and practically nonvolatile imidazolium based room-temperature ionic liquid (RTIL) provided a viable approach for carbamate to crystallize out as supernatant solid. In the present study, regeneration capabilities of solid carbamates have been investigated. Diethanolamine (DEA) carbamate as well as 2-amino-2-methyl-1-propanol (AMP) carbamate were obtained in crystalline form by bubbling CO(2) in alkanolamine-RTIL mixtures. Hydrophobic RTIL, 1-hexyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([hmim][Tf(2)N]), was used as aqueous phase substituent. Thermal behavior of the carbamates was observed by differential scanning calorimetry and thermogravimetric analysis, while the possible regeneration mechanism has been proposed through (13)C NMR and FTIR analyses. The results showed that decomposition of DEA-carbamate commenced at lower temperature (∼55 °C), compared to that of AMP-carbamate (∼75 °C); thus promising easy regeneration. The separation of carbamate as solid phase can offer two-way advantage by letting less volume to regenerate as well as by narrowing the gap between CO(2) capture and amine regeneration temperatures.

Carbon sequestration kinetic and storage capacity of ultramafic mining waste.

Mineral carbonation of ultramafic rocks provides an environmentally safe and permanent solution for CO(2) sequestration. In order to assess the carbonation potential of ultramafic waste material produced by industrial processing, we designed a laboratory-scale method, using a modified eudiometer, to measure continuous CO(2) consumption in samples at atmospheric pressure and near ambient temperature. The eudiometer allows monitoring the CO(2) partial pressure during mineral carbonation reactions. The maximum amount of carbonation and the reaction rate of different samples were measured in a range of experimental conditions: humidity from dry to submerged, temperatures of 21 and 33 °C, and the proportion of CO(2) in the air from 4.4 to 33.6 mol %. The most reactive samples contained ca. 8 wt % CO(2) after carbonation. The modal proportion of brucite in the mining residue is the main parameter determining maximum storage capacity of CO(2). The reaction rate depends primarily on the proportion of CO(2) in the gas mixture and secondarily on parameters controlling the diffusion of CO(2) in the sample, such as relative saturation of water in pore space. Nesquehonite was the dominant carbonate for reactions at 21 °C, whereas dypingite was most common at 33 °C.

Determination of free cyanide and zinc cyanide complex by capillary electrophoresis.

A capillary electrophoretic (CE) protocol was developed for the separation and quantification of free cyanide and zinc cyanide complex, two key species in gold cyanidation of zinc-bearing sulfidic ores. Several common carrier electrolytes were implemented in an indirect UV detection method. The effect of electric field strength, injection volume, concentration of electro-osmotic flow (EOF) modifier and UV-absorbing agent in background electrolyte (BGE) was examined while peak height, peak area and noise were considered for optimization. The best results were obtained using a BGE that contained 35 mM sodium chromate, 12 mM free cyanide and 0.45 mM hexamethonium bromide at pH 10.5. Free cyanide concentration was compared to that measured with the conventional silver nitrate titration method in solutions containing free cyanides and weak cyano-complexes. The developed CE protocol proved very robust in capturing the concentration of free cyanides (4% error) unlike the titration method which exhibited substantial sensitivity to the interfering weak cyano-complexes (38% error).

Reaction-Diffusion Model for Gasification of a Shrinking Single Carbon-Anode Particle.

The present work focuses on the gasification of a single carbon-anode particle with CO2, using a detailed reaction-transport model based on the reaction intrinsic kinetics and transport of gaseous species. The model includes the mass conservation equations for the gas components and solid carbon particles, resulting in a set of nonlinear partial differential equations, being solved using numerical techniques. The model may predict the gas generation rate, the gas compositions, and the carbon consumption rate during the gasification of a carbon particle. Five kinetic models were compared to describe the gasification behavior of carbon particles. It was found that the random pore model (RPM) provided the best description of the reactivity of anode particles. The model also predicted the particle shrinkage during the gasification process. The model was validated using experimental results obtained with different particle size ranges, being gasified with CO2 at 1233 K. The experiments were performed in a thermogravimetric analyzer (TGA). Good agreement between the model results and the experimental data showed that this approach could quantify with success the gasification kinetics and the gas distribution within the anode particle. In addition, the Langmuir-Hinshelwood (L-H) model is used in order to capture the inhibition effect of carbon monoxide on the gasification reaction. The effectiveness factor and Thiele modulus simulated for various particle sizes helped assess the evolution of the relative dominance of diffusion and chemical reactions during the gasification process.

Insights into the Solubility of Carbon Dioxide in Grafted Mesoporous Silica for the Catalytic Synthesis of Cyclic Carbonates by Nanoconfinement.

Gas solubility can go beyond classical bulk-liquid Henry's law saturation under the nanoconfinement of a liquid phase. This concept establishes the foundation of the current study for developing a novel catalytic system for transformation of carbon dioxide to cyclic carbonates at mild conditions with major emphasis on application for CO2 capture and utilization. A series of mesoporous silica-based supports of various pore sizes and shapes grafted with a quaternary ammonium salt is synthesized and characterized. CO2 sorption in styrene oxide, either in bulk or nanoconfined state, as well as catalytic reactivity for CO2 transformation into styrene carbonate, are experimentally evaluated. The family of mesoporous catalysts with aligned cylindrical pores (MCM-41 and SBA-15) with pore sizes ranging from 3.5 to 9 nm exhibit enhanced sorption of CO2 in nanoconfined styrene oxide with maximum sorption capacity taking place in MCM-41 with the smallest pore size. The catalysts with interconnected cylindrical pores (KIT-6) with pore sizes ranging from 4.5 to 8.7 nm showed CO2 solubilities almost equal to the bulk solubility of styrene oxide. Monte Carlo simulations revealed that the oversolubility in styrene oxide confined complex is directly related to the density of adsorbed solvent in the nanopore, which is less than its bulk density. Catalytic reactivities correlate with CO2 sorption enhancement, showing higher turnover frequencies for catalysts having higher CO2 sorption capacity. The turnover frequency is increased by a factor of 7.5 for grafted MCM-41 with the smallest pore size with nanoconfined styrene oxide in comparison to the homogeneous reaction implemented in bulk.

Capillary electrophoretic analysis of sulfur and cyanicides speciation during cyanidation of gold complex sulfidic ores.

A capillary electrophoretic protocol for the separation and quantification of the most important species potentially liberated during the cyanidation of gold sulfide-rich ores was accomplished in this study. The separation of 11 ions: S2O3(2-), Cu(CN)3(2-), Fe(CN)6(4-), Fe(CN)6(3-), SCN(-), Au(CN)2(-), Ag(CN)2(-), SO4(2-), OCN(-), SO3(2-), and HS(-) was achieved using an indirect UV detection method. The robustness of the analytical protocol was tested by analyzing ions speciation during the cyanidation of two gold sulfide-rich ores. The 1-h cyanidation of the two ores released up to six complexes into solution: S2O3(2-), Cu(CN)3(2-), SCN(-), Fe(CN)6(4-), OCN(-), and SO4(2-). The mineralogy of the ore was found to influence directly the nature and the amount of the dissolved species. Conserving the cyanidation solution for 72 h after sampling resulted in 96% total sulfur recovery. These results allow us to conclude that the analytical protocol developed in this study can become very useful for the optimization of precious-metals cyanidation plants.

Optimal design of radioactive particle tracking experiments for flow mapping in opaque multiphase reactors.

In the past decade, radioactive particle tracking techniques have emerged in the field of chemical engineering and have become increasingly popular for non-invasive flow mapping of the hydrodynamics in multiphase reactors. Based on gamma-ray sensitization of an array of scintillation detectors, the Computer Automated Radioactive Particle Tracking (CARPT) technique measures flow fields by monitoring the actual motion path of a single discrete radioactive flow follower which has the physical properties of the phase whose motion is being followed. A limitation to the accuracy of CARPT lies in the error associated with the reconstruction of the tracer particle position which affects the space-resolution capability of the technique. It is of interest, therefore, to minimize this error by choosing wisely the best hardware and an optimal configuration of CARPT detectors' array. Such choices are currently based on experience, without firm scientific basis. In this paper, through theoretical modeling and simulation, we describe how the accuracy of a radioactive particle tracking setup may be assessed a priori. Through an example of a proposed implementation of CARPT on a gas-solids riser, we demonstrate how this knowledge can be used for choosing the hardware required for the experiment. Finally, we show how the optimal arrangement of detectors can be effected for maximum accuracy for a given amount of monetary investment for the experiment.

Allothermal steam gasification of biomass in cyclic multi-compartment bubbling fluidized-bed gasifier/combustor - new reactor concept.

A new reactor concept of allothermal cyclic multi-compartment fluidized bed steam biomass gasification is proposed and analyzed numerically. The concept combines space and time delocalization to approach an ideal allothermal gasifier. Thermochemical conversion of biomass in periodic time and space sequences of steam biomass gasification and char/biomass combustion is simulated in which the exothermic combustion compartments provide heat into an array of interspersed endothermic steam gasification compartments. This should enhance unit heat integration and thermal efficiency and procure N(2)-free biosyngas with recourse neither to oxygen addition in steam gasification nor contact between flue and syngas. The dynamic, one-dimensional, multi-component, non-isothermal model developed for this concept accounts for detailed solid and gas flow dynamics whereupon gasification/combustion reaction kinetics, thermal effects and freeboard-zone reactions were tied. Simulations suggest that allothermal operation could be achieved with switch periods in the range of a minute supporting practical feasibility for portable small-scale gasification units.

Hydrosulfide oxidation pathways in oxic solutions containing iron(III) chelates.

The role of dissolved oxygen (DO2) on the oxidation of hydrosulfide ions (HS-; C(HS-)0 = 50-150 micromol/L) into polysulfides (S(n)2-; n = 2-9), colloidal sulfur, and oxysulfur species with iron(III) trans-1,2-diaminocyclohexanetetraacetate (iron(III)-cdta; C(Fe(III)0 = 50-300 micromol/L) complexes in alkaline solutions (pH 9-10.2) was investigated at 25 +/- 1 degree C. At higher pH, oxygen was seen to slow down the hydrosulfide conversion rate. For instance, the HS- half-life was 24.8 min in a DO2-saturated iron(III)-cdta solution compared to 11.3 min in the corresponding anoxic solution (pH 10.2, C(HS-)0 = 80 micromol/L, C(Fe(III))0 = 200 micromol/L). In anoxia, HS- oligomerizes into chain-like polysulfides which behave as autocatalysts on the HS- conversion rates. The presence of DO2 disrupts the HS- oligomerization process by generating thiosulfate precursors from polysulfides, a pathway that impedes the HS- uptake. At lower alkaline pH where the hydroxide-free Fe(3+)cdta(4-) is the prevailing iron(III)-cdta species, the "iron(II)-cdta + DO2" oxidative reaction becomes crucial. Oxidative regeneration of iron(III) as Fe(3+)cdta(4-) (being more reactive than Fe(3+)OH(-)cdta(4-)) offsets to some extent the restrictive role of oxygen on the accumulation of polysulfides. Thiosulfate and sulfate were the main end-products for the current experimental conditions to the detriment of colloidal sulfur, which did not form in DO2-saturated solutions.

Capillary electrophoretic separation of inorganic sulfur-sulfide, polysulfides, and sulfur-oxygen species.

A CE protocol was developed for the identification and separation of inorganic polysulfides simultaneously with other inorganic sulfur-bearing species coexisting in aqueous hydrosulfide/sulfur solutions. The electrophoretic separation of thiosulfate, sulfate, hydrosulfide, sulfite, tetrathionate, and polysulfides was achieved at pH values between 8.2 and 12.2. The peaks attributed to the polysulfide species were strongly sensitive to pH. CE analysis of hydrosulfide/sulfur solutions at different pH values permitted possible identification of two forms of polysulfides: S4(2-) and S3(2-). Upon exposure to air at ambient temperature, thiosulfate was the main oxidation product of hydrosulfide/sulfur solutions mainly in the first 60 min, when hydrosulfide was rapidly consumed. Analysis of the oxidation reaction products provided retrospectively tentative evidence that the peaks separated and identified as tri- and tetrasulfide may be ascribed to polysulfides.