Entropy driven separation of xylene isomers on graphitic carbon adsorbents

Separation of xylene isomers remains one of the most important and challenging applications of adsorption-based separations in petrochemical industry. Despite the sustainable success of zeolite-based separations a search for efficient adsorbents selective for xylenes, especially para-xylene, is constantly ongoing. In this work, a potentially scalable chromatographic separation of all three xylenes was achieved on graphitic carbon sorbents, including a self-packed sorbent based on an oligo-graphene. A curious feature of this separation is stronger retention of para-xylene than meta- and, in some conditions, even than ortho-xylene. Noticeably, separation selectivity between para- and meta-isomers does not depend on temperature. Apparently, lower entropy of para-xylene in solution due to its higher molecular symmetry leads to a lesser adsorption entropy loss, which makes its adsorption statistically more likely. The concept of using carbon adsorbents for entropy driven chromatography separations may be useful for the isolation of xylenes from their mixture and, possibly, for other positional isomers separation.