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We  have developed a novel concept for separating alkane mixtures, in the 5–7 carbon atom range, into three  separate fractions consisting of linear, mono-methyl and di-methyl alkanes by adsorption on silicalite. We make  use of the fact that with increased degree of branching, the “ packing efficiency” within the silicalite matrix  is significantly lower. This configurational entropy effect comes into play when the loading exceeds 4 molecules  per unit cell, when all the intersection sites are occupied, and results in the following hierarchy of sorption  strengths: linear alkanesmono-methyl alkanesdi-methyl alkanes. To demonstrate the feasibility of the  entropy-based separation concept we carried out configurational-bias monte carlo simulations for a variety  of binary, ternary and quaternary mixtures of alkanes, n-pentane (n-C5), 2-methylbutane (2MB), n-hexane  (n-C6), 2-methylpentane (2MP), 3-methylpentane (3MP), 2,2-dimethylbutane (22DMB), n-heptane (n-C7), 2-methylhexane (2MH), 2,2-dimethylpentane (22DMP). The entropy-driven separation concept has been verified, in part,  by comparison with the experimental  sorption  data of Santilli (J. Catal.,  1986, 99, 335) for the mixture n-C6–3MP–22DMB.

physical chemistry chemical physics/pccp. physical chemistry chemical physics

Separation of linear, mono-methyl and di-methyl alkanes in the 5–7 carbon atom range by exploiting configurational entropy effects during sorption on silicalite-1