Clay catalysed rapid valorization of glycerol towards cyclic acetals and ketals

Abstract

Biodiesel production usually results in a huge amount of glycerol, raising a critical need to transform it into high value products. The present study highlights that solvent-free, conventional thermal activation, and non-conventional microwave/ultrasonic activation in the liquid phase are able to selectively transform glycerol into cyclic acetals and ketals using an optimised acid activated clay catalyst. Several parameters for the acid activation of bentonite clay were optimized under mild reaction conditions with a high concentration of clay (6%) and varying the acid concentration in the range of 6 to 15 N. The acid-activated clay samples were characterized by XRD, FT-IR, BET, and XRF analysis. The active sites of the catalyst were examined by volumetric titration and confirmed by pyridine adsorbed FT-IR and advanced NH₃-TPD analyses. The activation performed at relatively mild conditions, i.e.; 6 N H₂SO₄ and 6% w/v clay, reproducibly resulted in an improved surface area (180 m² g⁻¹) and surface acidity (23 mg KOH g⁻¹), with superior quantitative Brönsted and Lewis acidic sites. Moreover, the eco-friendly process involving a catalyst, microwave, or ultra-sonication were successfully utilized to achieve a commercially valuable hyacinth fragrance, in addition to furan-based fuel additive precursors exhibiting a high conversion of glycerol and excellent selectivity within much less activation time (2 min).