Article
Thermal Behavior of Pyrophyllite Ore during Calcination for Thermal Activation for Aluminum Extraction by Acid Leaching
- Murat Erdemoğlu, Mustafa Birinci, Turan Uysal
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 89-99
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In the production of alumina (Al2O3) from clays by acid leaching, thermal activation by calcination is applied widely as a pre-treatment to improve the dissolution of aluminum. Previous studies have focused only on the thermal behavior of high-purity kaolinite and pyrophyllite, individually. However, thermal activation of complex clay ores containing several silicate minerals and their effect on aluminum extraction have not been studied. The purpose of the present study was to characterize the thermal behavior of a clay ore containing mainly pyrophyllite (Al2Si4O10(OH)2), kaolinite (Al2Si2O5(OH)4), muscovite (KAl2(AlSi3O10)(OH)2), quartz (SiO2), and kyanite (Al2SiO5) from the Pütürge clay deposits (Malatya, Turkey) for possible use in alumina (Al2O3) production by acid leaching. The ore and its calcination products obtained at various temperatures were characterized with respect to their mineral paragenesis, crystal structure, surface morphology, and thermal, calorimetric, and aluminum dissolution properties in order to understand the changes that occurred. Aluminum recovery in the leach solution increased in direct proportion to the dehydroxylation degree (Dtg) of the ore as the calcination temperature increased to 900°C. A maximum aluminum extraction of 90.57% was achieved by leaching of the product from calcination at 900°C. Aluminum extraction decreased sharply above that temperature, even though Dtg increased a little. By increasing the calcination temperature; the structures of pyrophyllite, kaolinite, and muscovite were destroyed by dehydroxylation, resulting in the exfoliation of the mineral layers, thus, a mixture of dehydroxylated phases formed. Depending mainly on the temperature range at which each of the dehydroxylated phases is durable, aluminum could be leached to some extent. The sharp decrease in the extraction of aluminum, iron, and potassium at higher temperatures was attributed to compaction of previously exfoliated layers of the minerals through re-crystallization to form mullite-like structures which seemed insensitive to acid attack during the leaching.
Original Paper
Comparative Modeling of Ions and Solvent Properties in Ca-Na Montmorillonite by Atomistic Simulations and Fluid Density Functional Theory
- Guomin Yang, Nikolaos I. Prasianakis, Sergey V. Churakov
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 100-114
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Molecular dynamics (MD) simulations provide an accurate description of the mineral–fluid interface from the perspective of the atomistic level taking into account all atom interactions. This simulation approach is computationally expensive if applied to large molecular systems. Classical Fluid Density Functional Theory (f-DFT) delivers structural and thermodynamic information at comparatively small computational costs. Numerous applications of f-DFT for electrolytes neglect an explicit consideration of solvent. In this work, an unrestricted three-component model (3CM) of f-DFT was applied, which incorporates Lennard-Jones (LJ) attractions for the description of the short-range interactions of fluid–fluid and fluid–wall rather than the hard sphere repulsions, named DFT/LJ-3CM. The DFT/LJ-3CM model considers ions as charged LJ particles and treats solvent molecules as neutral LJ particles. To validate the performance of the DFT/LJ-3CM, the f-DFT calculations were compared with atomistic simulations for montmorillonite (Mnt) with various hydrated states in electrolyte solutions. This benchmarking was used to assess critically the advantages and limitations of the f-DFT model. The calibrated DFT/LJ-3CM model for Na and Ca Mnt was applied to calculate cation selectivity for the ion exchange equilibrium with effective ion radius and swelling behavior of Mnt. The predictions of the DFT/LJ-3CM model were found to be in good agreement with the atomistic simulations and experimental data under a wide range of conditions. At the same time, the DFT calculations were 3–4 orders of magnitude faster than conventional MD simulations. Thus, the DFT/LJ-3CM model can be a computationally effective alternative to atomistic simulation in providing structural and thermodynamic properties of fluid–clay mineral interfaces. The DFT/LJ-3CM model provides a robust approach, which can be used for upscaling in reactive transport simulators and modeling ion migration taking place under more complex thermo-chemo-hydro-mechanical conditions.
Article
The Formation of Clay Minerals in the Mudflats of Bolivian Salars
- Jennifer L. Bentz, Ronald C. Peterson
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 115-134
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Understanding clay-mineral assemblages forming in saline lakes aids in reconstructing paleoenvironments on Earth and other terrestrial planets; this is because authigenic phyllosilicates are sensitive to the prevailing geochemical conditions present during formation. In most geochemical models, evaporative concentration favors sepiolite with increasing silica and Mg2+ concentrations without considering the role of the biogenic removal of silica from solution by diatoms. In the present study, phyllosilicates occurring in the mudflats of Bolivian salars were investigated to aid in understanding the geochemical factors that control mineral assemblages forming in (SO42–)- and (Cl–)-rich environments in relation to dissolved silica. From transects across the mudflats, the physical, chemical, and mineralogical characteristics of the bulk sediment and the <2 μm fraction of each sedimentary layer were analyzed. From these analyses, three types of sediments were identified: (1) regolith sediments dominated by Al-dioctahedral smectite, illite, and chlorite; (2) detritus-rich mudflat sediments with Mg-trioctahedral smectite and Al-dioctahedral smectite along with illite and chlorite; and (3) authigenic mudflat sediments dominated by poorly formed Mg-trioctahedral smectite, kerolite, and biogenic silica. The absence of sepiolite-palygorskite in the salars is the result of excessively high Mg:Si ratios within the waters. In the surface water Mg becomes enriched relative to Si as diatoms remove dissolved Si from solution through biologically mediated uptake. The geochemical conditions present within the salars that act to preserve the diatom frustules and prevent their dissolution include: neutral–slightly alkaline pH solutions, cold temperatures, shallow water, and high salinity. Under these conditions the formation of sepiolite is restricted by the small amount of dissolved silica, despite the silica-rich environment. The formation of Mg-smectite and kerolite is favored under these conditions.
Original Paper
Clay Minerals as the Key to the Sequestration of Carbon in Soils
- Gordon Jock Churchman, Mandeep Singh, Amanda Schapel, Binoy Sarkar, Nanthi Bolan
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- 01 January 2024, pp. 135-143
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Results from earlier laboratory and field experiments were interrogated for the possibilities of sequestration, or long-term accumulation, of carbon from excess greenhouse gases in the atmosphere. In the laboratory study, samples of three (top) soils dominated by kaolinite and illite (together), smectite, and allophane were examined for the adsorption and desorption of dissolved organic carbon (DOC). Adsorption and desorption of DOC were carried out on clay fractions extracted physically and after first native organic matter and then iron oxides were removed chemically. Labeled organic material was added to the soils to assess the priming effect of organic carbon (OC). In the field, changes in OC were measured in sandy soils that had been amended by additions of clay for between 3 and 17 years, both through incorporation of exogenous clay and delving of in situ clay. The laboratory experiments demonstrated that a portion of DOC was held strongly in all soils. The amount of DOC adsorbed depended on clay mineral types, including Fe oxides. Much adsorbed DOC was lost by desorption in water and a substantial amount of native OC was lost on priming with new OC. Addition of clay to soils led to increased OC. Therefore, addition of clay to soil may enhance net sequestration of C. Organic carbon close to mineral surfaces or within microaggregates is held most strongly. Carbon sequestration may occur in subsoils with unsaturated mineral surfaces. However, incorporation of carbon into macroaggregates from enhanced plant growth might be most effective in removing excess carbon from the atmosphere, albeit over the short-term.
Article
Hydrothermal Interaction of Wyoming Bentonite and Opalinus Clay
- Kirsten Sauer, Florie Caporuscio, Marlena Rock, Michael Cheshire, Carlos Jové-Colón
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- 01 January 2024, pp. 144-160
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Most investigations into clay-mineral stability and new mineral formation within engineered barrier system (EBS) materials for geologic repositories of nuclear waste have focused on temperatures <100°C. In response to the United States Department of Energy’s interest in disposing of waste packages with higher thermal loads, higher temperature (200–300°C) and pressure (~150 bar), long-term (6-week to 6-month), hydrothermal experiments were conducted to evaluate the interaction of Opalinus Clay (wall rock) and Wyoming bentonite (clay buffer) with synthetic Opalinus Clay groundwater. Experiments were conducted in autoclaves using a flexible gold reaction cell with water:rock ratios between 6:1 and 9:1. Run products were characterized in terms of mineralogy and geochemistry. Montmorillonite remained stable at 200 and 300°C; traces of illite-smectite interstratified minerals were observed. Clay minerals in Opalinus Clay experienced significant changes at 300°C, including the formation of illite, illite-smectite, and chlorite-smectite. Montmorillonite illitization within the Wyoming bentonite EBS material was likely limited by the bulk chemistry of the system (i.e. low potassium) and newly formed illite was likely limited to the Opalinus Clay fragments, nucleating on pre-existing illite in the clay rock. Zeolite minerals with compositions between analcime and wairakite formed at 300°C along edges of Opalinus Clay fragments and within the bentonite matrix, but not at 200°C. Aqueous fluids remained undersaturated with respect to quartz in Opalinus Clay ± Wyoming bentonite 300°C experiments, and dissolution and re-precipitation of phases such as kaolinite, calcite, and smectite likely contributed to zeolite formation. These results can be applied to understanding zeolite formation, clay-mineral phase stability, and silica saturation within EBS materials of a high-temperature repository.
Analysis of the Mineral Compositions of Swell-Shrink Clays From Guangxi Province, China
- ZHAOTIAN ZENG, HAIBO LU, YANLIN ZHAO, YINGHONG QIN
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 161-174
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Swell-shrink clays are widely distributed in the Guangxi province of southern China in the form of expansive soils and lateritic clays. They have high particle dispersion, poor permeability, and significant swell-shrink properties. In recent decades, a series of problems closely related to the physical-mechanical properties of the swell-shrink clays have been encountered in various engineering projects. Mineral composition is a critical factor affecting the physical-mechanical properties of these clays. However, determining accurately their mineral compositions is difficult because the analytical methods available are expensive, time consuming, and have a high possibility of errors. Therefore, identifying a method suitable for quantitatively analyzing the mineral composition of the swell-shrink clays is necessary. In the current study several swell-shrink clays, including two expansive soils and four lateritic clays, from the Guangxi region were investigated. Qualitative analytical methods such as differential thermal analysis (DTA) and X-ray diffraction (XRD) were conducted to identify the mineral composition of the soils. The results indicated that the expansive soils were composed mainly of quartz (Qz), montmorillonite (Mnt), illite (Ilt), and kaolinite (Kln). The Baise specimen also contained a certain amount of calcite (Cal), while the lateritic clays primarily contained Kln and goethite (Gth) as well as lesser amounts of Qz and gibbsite (Gbs). On the basis of the aforementioned results, rough quantitative analyses of the mineral compositions were conducted using X-ray fluorescence (XRF) and the Bogue method. The results indicated that the lateritic clay samples from Wuming, Guilin, and Liuzhou contained 70–80% Kln, while the Laibin lateritic clay was 50% Kln. The lateritic clays contained ~10% Gth. The expansive soils were 30–40%, 25–30%, and 10–15% of Ilt, Qz, and Mnt, respectively. Finally, the relationships between the mineral compositions, zeta potentials, and free swelling ratios are discussed briefly. This investigation indicated that the zeta potential was mainly related to the type and content of clay minerals in the soil when neutral water was used as the free solution (pH = 7). The correlation between the swelling index and the zeta potential of the expansive soils was greater than that of the lateritic clays, which indicated that the swelling properties of expansive soils were more affected by the clay mineral composition than those of the lateritic clays. The results provide a systematic method for the qualitative and quantitative analysis of the mineral composition of swell-shrink clays and primary data for studying how mineral composition affects the physical properties of swell-shrink clays in the study area.
Original Paper
Optical Theory-Based Simulation of Attenuated Total Reflection Infrared Spectra of Montmorillonite Films
- Brian Grégoire, Baptiste Dazas, Maud Leloup, Fabien Hubert, Emmanuel Tertre, Eric Ferrage, Sabine Petit
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- Published online by Cambridge University Press:
- 01 January 2024, pp. 175-187
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Infrared analyses of clay mineral samples are usually performed by transmission techniques. While transmission measurements are easy and inexpensive, the sample preparation plays a critical role in the quality of the data. Alternatively, attenuated total reflection (ATR) provides a powerful and often simpler analysis method. However, the ATR spectra reveal significant differences when compared to transmission spectra sometimes leading to confusion in the interpretations. Indeed, optical effects play a prominent role in the ATR spectral profile and their identification is mandatory for obtaining quantitative information regarding molecular/particle orientation or film thickness. The objective of the present study was to perform exact spectral simulations of montmorillonite films by making use of optical theory, including the determination of the anisotropic optical constants from the experimental reflectance spectra by Kramers-Kronig (KK) transformation. This methodology was used: (1) to choose the appropriate optical conditions for advanced and reliable characterization of clay minerals; (2) to extract quantitative information such as the estimation of the film thickness; and (3) to discriminate optical phenomena (optical interferences) from chemical/structural features of the sample.