Adsorption of Bitumen Model Compounds on Kaolinite in Liquid and Supercritical Carbon Dioxide Solvents: A Study by Periodic Density Functional Theory and Molecular Theory of Solvation

Lage, Mateus R.; Stoyanov, Stanislav R.; Carneiro, José Walkimar de M.; Dąbroś, Tadeusz; Kovalenko, Andriy

doi:10.1021/ef502202q

Cited by 11 publications

(9 citation statements)

References 89 publications

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“…Theoretical calculations make a useful contribution to efforts to elucidate the fundamental mechanisms behind the interactions between an organic molecule and a surface. − Techniques such as density functional theory (DFT) are often used because they allow accurate adsorption energy and geometry to be determined without the need of developing accurate force fields, as are needed for classical molecular dynamics simulations. On the other hand, with DFT, the size of the model system is slightly limited compared to classical force field studies.…”

Section: Introductionmentioning

confidence: 99%

Calculation of Entropy of Adsorption for Small Molecules on Mineral Surfaces

2018

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We performed density functional theory calculations for small organic molecules adsorbed on calcite, quartz, and kaolinite mineral surfaces and calculated the entropy change as a result of adsorption. Our results demonstrate that the entropy contribution to the free energy is mainly independent of the mechanism of binding, but it is affected by surface coverage, molecule size, character, and degrees of freedom. Compared with experimental results for weakly bonded molecules, density functional theory calculations predict a higher loss of entropy as a result of adsorption, which can be used as the upper limit for estimating the entropy contribution for adsorption to a mineral surface. The study has demonstrated a linear relationship between the entropy of the adsorbed molecule and the gas phase entropy, which can be used to estimate the entropy contribution to the free energy of adsorption on minerals without explicit density functional theory calculations, which is an important step forward in predicting the behavior of contaminants and other organic compounds in porous media such as soils, aquifers, and oil reservoirs.

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Section: Introductionmentioning

confidence: 99%

Calculation of Entropy of Adsorption for Small Molecules on Mineral Surfaces

2018

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“…Rezaei Gomari et al 2006), and kaolinite (Lage et al 2015;Lebedeva and Fogden 2011;Murgich and Rodrí-guez 1998;Tabrizy et al 2011a, b), to ease the conception of the phenomena. Nevertheless, those researches pinpoint to the complexity of wetting behavior existent in different types of minerals.…”

Section: Introductionmentioning

confidence: 99%

A molecular dynamics investigation into the adsorption behavior inside {001} kaolinite and {1014} calcite nano-scale channels: the case with confined hydrocarbon liquid, acid gases, and water

Fazelabdolabadi¹,

Alizadeh-Mojarad

2017

Appl Nanosci

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A set of molecular dynamics simulations was conducted, as the first comparative study of the adsorption behavior of liquid hydrocarbon/acid gases/water molecules over f10 14g calcite surface and {001} octahedral kaolinite surface in nanoconfined slit. According to atomic z-density profiles, hydrocarbon molecules have higher tendency towards the f10 14g calcite surface than the {001} octahedral kaolinite surface. In addition, water molecules form stronger adsorption layer over calcite surface than kaolinite. In contrast, acid gas molecules have higher tendency towards kaolinite surface than calcite. This behavior was spotted within nanometer-sized slit pores. The results also point to reduction in self-diffusion coefficient of molecules with strong adsorption over mineral surfaces in nano-confined environment.

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“…In the inclined and perpendicular orientations, the aromatic amine group was oriented close to the surface. Thus, three input files were generated for each heterocycle and used as inputs for the geometry optimization of systems I and II, as in our recent study …”

Section: Experimental and Computational Models And Methodsmentioning

confidence: 99%

“…An important method for solvation modeling in complex molecular nanosystems is the three-dimensional reference interaction site model theory of solvation with the Kovalenko and Hirata closure relation (3D-RISM-KH). − The 3D-RISM-KH molecular theory of solvation has been employed to study the multilayer adsorption of indole on kaolinite in toluene and heptane solvents and the molecular recognition interaction between heterocycles and kaolinite in toluene, as well as the effect of acrylate and styrene additives on the stacking of kaolinite nanoplatelets in aqueous solutions . The optimal temperature and pressure conditions for the desorption of bitumen components from kaolinite in liquid and supercritical CO 2 solvent have been explored using the 3D-RISM-KH approach . The effects of trace amounts of water and temperature on asphaltene aggregation in organic media have been elucidated. , The solvation structure and thermodynamics of ionic liquids and electrolyte solutions, gelation, self-assembly of supramolecular rosette nanotubes, cellulose aggregation in hydrothermal treatment conditions, and the hierarchy of supramolecular interactions in plant cell walls have also been investigated. , …”

Section: Introductionmentioning

confidence: 99%

“…46 The optimal temperature and pressure conditions for the desorption of bitumen components from kaolinite in liquid and supercritical CO 2 solvent have been explored using the 3D-RISM-KH approach. 47 The effects of trace amounts of water and temperature on asphaltene aggregation in organic media have been elucidated. 48,49 The solvation structure and thermodynamics of ionic liquids 50 and electrolyte solutions, 42 gelation, 51 self-assembly of supramolecular rosette nanotubes, 52 cellulose aggregation in hydrothermal treatment conditions, 53 and the hierarchy of supramolecular interactions in plant cell walls have also been investigated.…”

Section: Introductionmentioning

confidence: 99%

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Computational and Experimental Investigations of the Role of Water and Alcohols in the Desorption of Heterocyclic Aromatic Compounds from Kaolinite in Toluene

et al. 2018

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Nonaqueous extraction is an attractive alternative to the currently employed warm water process for extraction of bitumen from oil sands, as it could use less energy and water. Hydroxylated cosolvents, such as alcohols, that compete for the adsorptive clay surfaces and help release bitumen components could help improve bitumen recovery. The water naturally present in oil sand also affects oil−mineral interactions. Electronic structure methods and the statistical-mechanical 3D-RISM-KH molecular theory of solvation as well as experimental desorption measurements are employed to study the effects of water and aliphatic alcohol cosolvents in toluene solvent on the desorption of fused pyridinic heterocycles (ArN) from kaolinite. The geometries of phenanthridine and acridine (representative of pyridinic heterocycles of petroleum asphaltenes) adsorbed on the kaolinite clay surface are optimized in periodic boundary conditions using density functional theory. The 3D-RISM-KH method is employed to calculate the solvation free energy and potential of mean force for adsorption of the heterocycles on kaolinite in pure and alcohol-containing toluene. The potentials of mean force show that the adsorption of the fused pyridines on kaolinite is stronger in pure toluene than in toluene mixed with aliphatic alcohol. Analysis of the mechanism of desorption of phenanthridine and acridine from kaolinite in toluene containing alcohol reveals that the alcohol stabilizes both the pyridinic moiety and kaolinite platelet by hydrogen bonding, thus disrupting the ArN•••HO−Al(kaolinite) hydrogen bond. A mechanism for retention of toluene on kaolinite is also highlighted. Experimental studies of the desorption of fused pyridines from an ArN−kaolinite aggregate show that in water-saturated toluene the rate of desorption of the phenanthridine from kaolinite is twice as high as that in dry toluene. The experimental and computational results show that water and aliphatic alcohols in toluene help desorb pyridinic heterocycles from kaolinite, a clay mineral abundant in the oil sands. The presented insights are valuable for understanding the molecule-clay interactions in solution and relevant to improving the nonaqueous extraction of bitumen from oil sand.

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Adsorption of Bitumen Model Compounds on Kaolinite in Liquid and Supercritical Carbon Dioxide Solvents: A Study by Periodic Density Functional Theory and Molecular Theory of Solvation

Cited by 11 publications

References 89 publications

Calculation of Entropy of Adsorption for Small Molecules on Mineral Surfaces

Calculation of Entropy of Adsorption for Small Molecules on Mineral Surfaces

A molecular dynamics investigation into the adsorption behavior inside {001} kaolinite and {1014} calcite nano-scale channels: the case with confined hydrocarbon liquid, acid gases, and water

Computational and Experimental Investigations of the Role of Water and Alcohols in the Desorption of Heterocyclic Aromatic Compounds from Kaolinite in Toluene

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