Selectivity enhancement in the catalytic heterogeneous hydrogenation of limonene in supercritical carbon dioxide by an ionic liquid

Ionic liquids as coated catalysts or additives tremendously alter the selectivity pattern of the heterogeneous solid catalyst in the selective hydrogenation of limonene. The conventional monometallic ruthenium over alumina catalyst combined with an ionic liquid enables the one-pot synthesis of the intermediate p-menthene through limonene hydrogenation in supercritical carbon dioxide. Among eight screened imidazolium ILs, [C10mim]NTf2 was employed as additive, or as the coating agent of ruthenium catalyst in the reaction under supercritical conditions. ating of the heterogeneous catalyst allows the selective production of p-menthene and increases the conversion level of limonene (>99%) compared to the conversion of limonene in the reaction carried out in the presence of an ionic liquid as an additive. Results of the catalyst recycling indicate that there is no depletion of catalyst reactivity even after four successive cycles of operation under the studied reaction conditions. Further hydrogenation of p-menthene is strongly inhibited by employing an ionic liquid. The solubility of limonene or p-menthene in an ionic liquid governs the selective hydrogenation of limonene towards p-menthene.