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Adsorption of n-alkanes in faujasite zeolites: molecular simulation study and experimental measurements

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Abstract

We report an application of a previously developed force field for adsorption of hydrocarbons in silicalite (Pascual, P., et al. in Phys. Chem. Chem. Phys. 5:3684–3693, 2003), to the case of the linear alkane-sodium faujasite systems. In order to extend this force field from siliceous to cationic zeolites, we propose to take into account the polarization part of the zeolite-molecule interaction energy. A first order polarization term is explicitly considered for this purpose, using standard molecular polarizabilities. Polarization appears to amount to 30–40% of the zeolite-alkane interaction energy, as a consequence of the strong electric field created by the sodium cation distribution and negatively charged framework. This approach is compared with experimental adsorption isotherms of ethane, propane, n-octane and n-decane in NaY from the literature and with original measurements of n-butane isotherms in NaY obtained by thermal gravimetry. Henry constants and heats of adsorption at zero coverage of n-alkanes (n=6–10) are also compared with experimental measurements. Although no specific parameter has been calibrated for extending the force field, the general agreement between simulation results and experiments is satisfactory. Cation redistribution upon alkane adsorption is not observed in these simulations.

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Abbreviations

a i :

Torsion parameters

A :

Parameter of Henry constant expression, mol/kg/Pa

B :

Parameter of Henry constant expression

E i :

Local electrical field, J/mol

ΔG :

Gibbs free energy, kJ/mol

ΔH 0 :

Heat of adsorption, kJ/mol

ΔS 0,local :

Entropy of adsorption at low coverage, kJ/mol/K

f i :

Fugacity of molecule i, Pa

k :

Ideal gas constant, J/mol/K

K H :

Henry constant, mol/kg/Pa

K′:

preexponential factor, mol/kg/Pa

N :

Number of adsorbed molecules

N i :

Number of adsorbed molecules i

p θ :

Standard pressure, bar

r ij :

Distance between two centres of force i and j, Å

T :

Temperature, K

U bend :

Bond-bending interaction, J/mol

\(\bar{U}_{\mathit{ext}\_\mathit{new}}\) :

Lennard Jones energy obtained with the United Atom model, J/mol

U s ext :

Intermolecular interactions in the adsorbed phase, J/mol

U intra :

Intramolecular interaction, J/mol

U LJ :

Lennard-Jones potential, J/mol

U pol :

Polarization energy, J/mol

U tors :

Torsion interaction, J/mol

V :

Unit volume, Å3

W new :

Rosenbluth factor

σ i :

Lennard-Jones parameter of the centre of force i, Å

ε i :

Lennard-Jones parameter of the centre of force i, K

σ ij :

Crossing Lennard-Jones parameter between the centre of force i and j, Å

ε ij :

Crossing Lennard-Jones parameter between the centre of force i and j, K

θ :

Bending angle, degree

φ :

Dihedral angle, degree

α p :

Polarizability tensor

\(\bar{\mu}_{i}\) :

Chemical potential

n T :

Number of adsorption sites

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Authors and Affiliations

  1. IFP, 1-4 avenue de Bois Préau, 92852, Rueil-Malmaison Cedex, France

    A. Wender, A. Barreau, C. Lefebvre & P. Ungerer

  2. Laboratoire de Chimie Physique, Bâtiment 349, UMR 8000 CNRS, Université de Paris-Sud, 91405, Orsay, France

    A. Di Lella & A. Boutin

  3. Ecole Nationale Supérieure de Chimie de Paris (ENSCP), 11 rue Pierre et Marie Curie, 75231, Paris Cedex 05, France

    A. H. Fuchs

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  1. A. Wender
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  2. A. Barreau
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  3. C. Lefebvre
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  4. A. Di Lella
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  5. A. Boutin
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  6. P. Ungerer
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  7. A. H. Fuchs
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Correspondence to A. Boutin.

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Wender, A., Barreau, A., Lefebvre, C. et al. Adsorption of n-alkanes in faujasite zeolites: molecular simulation study and experimental measurements. Adsorption 13, 439–451 (2007). https://doi.org/10.1007/s10450-007-9036-2

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  • DOI: https://doi.org/10.1007/s10450-007-9036-2

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