Molecular simulation of hydrocarbons adsorption in aluminophosphates / Simulação molecular da adsorção de hidrocarbonetos em aluminofosfatos

AUTOR(ES)
DATA DE PUBLICAÇÃO

2006

RESUMO

Molecular simulation techniques were used to study the ortho-selectivity causes of C8 isomers in aluminophosphate molecular sieves structures. Approximated and optimized force fields of the AA type were applied in the grand canonical ensemble with biased and conventional Monte Carlo algorithms (GCMC). We simulated pure-components isotherms, adsorption heats at low loading and made a detailed structural analysis to define adsorption sites and molecular positionings in the AlPO4-5, AlPO4-8, AlPO4-11 and VPI-5 pores. We obtained quantitative agreement between experimental and simulated isotherms for the system xylenes / AlPO4-5 and a qualitative agreement for the system xylenes/AlPO4-11. The structural analysis of the adsorbed phases was performed considering the dimensional variations inside the aluminophosphates pores that are composed of two regions: a wide region (fences) and a narrow region that corresponds to the 12-ring oxygen windows areas. The ortho-selectivity experimentally evidenced was caused by the strong interaction xylene-sieve and the channels modulation. These two factors determine the molecules positioning inside the pores. For ortho-xylene this micro-environment provokes a face-to-face positioning in the wide regions, while para-xylene was positioned almost parallel to the c-axis in the windows. This positioning difference originates the ortho-selectivity phenomenon for the AlPO4-5, AlPO4-8, and VPI-5 sieves. In the o-xylene simulations, AlPO4-8 presents a fraction of the face-to-face positioning and thus shows a lighter adsorption capacity for o-xylene (14%). In VPI-5 we can not find any fraction of face-to-face position, so it did not present preferential adsorption for none of the xylenes. In AlPO4-11 the ortho-selectivity comes from the o-xylene molecule smaller length in the c-axis direction. A strong interaction between the xylenes methyl radicals and the wide region oxygen atoms, was identified based in the structural analysis. We proposed that this interaction causes deformations and/or structural changes in the AlPO4-11 sieve. In the second part of this study the behavior of cyclic, linear and branched molecules was analyzed with relation to the positioning and adsorption sites. We used the same molecular simulation techniques. Benzene, cyclohexane, o-xylene, butane, n-pentane, n-hexane, 2-methylbutane and 2,4-dimethylbutane were studied in AlPO4-5 with different force field models. We applied AA, UA and AUA force fields in the grand canonical ensemble with the conventional GCMC algorithm. The structural analysis of the cyclic molecules showed that benzene was face-to-face and c-axis parallel positioned. As opposed to other previous studies, cyclohexane did not present any particular order, the molecules positioning in a chaotic way along the pores of AlPO4-5. The benzene and cyclohexane molecules were much more sensible to the kind of force field than o-xylene. This sensibility can be related to the critical geometric condition denominated levitation effect. The n -hexane molecules adsorb preferably in the window region and butane in the wide region. They are positioned respectively, parallel and horizontally to the c-axis plane. The branched molecules are positioned horizontally in the pore wide region. The n-pentane presented a complex behavior in relation to positioning and adsorption sites. This complex behavior can also be related to the levitation effect. In all tested models a strong interaction between the methyl groups of the molecules extremities and the wide region oxygens influenced the positioning and the adsorption sites

ASSUNTO(S)

adsorption peneiras moleculares metodo de monte carlo hidrocarbonetos monte carlo simulação (computadores) simulation molecular sieves adsorção hydrocarbons

ACESSO AO ARTIGO

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