Effective synthesis of limonene over mild alkali-modified 13X catalysts in α-pinene isomerization

Abstract

The mild alkali-treated 13X was employed in the liquid phase isomerization reaction of α-pinene to increase the yield of limonene. A maximum α-pinene conversion of 100% and limonene yield of 59.1% could be achieved. Crystallinity could be well retained, and the amounts of medium-strong acid sites and the distribution of Brønsted and Lewis acid sites could be changed after the mild alkali treatment for 13X zeolite. Samples with higher micropore specific surface area were easier to obtain higher yields of limonene due to shape-selectivity. A proper amount of the medium-strong acid and the synergistic effect of Brønsted and Lewis acid sites were beneficial to enhance the catalytic activity and the yield of monocyclic product limonene. The main reason for catalyst deactivation could be the decrease in the active sites due to soft coke deposition. For the regeneration process, the conversions of α-pinene were between 95% and 99% during the first seven cycles and the conversion dropped to 90.6% after the eighth cycle, which demonstrated that the ethanol flushing and calcination could be an effective regeneration method for the 13X catalyst used in the α-pinene isomerization reaction.