The Carbonate-catalyzed Transesterification of Sunflower Oil for Biodiesel Production: in situ Monitoring and Density Functional Theory Calculations

Abstract

Biodiesel has emerged as a promising alternative fuel to replace dwindling fossil-based resources, particularly in view of its added environmental merit of  reducing additional air pollution. Its specific attraction stems from the similarity of its physical properties to fossil fuel-derived diesel. Although the  production of biodiesel is a relatively straightforward process, reaction progress monitoring and product analysis require costly specialist equipment,  such as gas chromatography and mass spectrometry. In this study, we investigate the use of pH in monitoring the progress of carbonate-catalyzed  transesterification reactions. Specifically, we focus on potassium and sodium carbonates and sunflower oil. Our results are consistent with the results  obtained by other studies using different methods of monitoring. To test the generality of the method, pH measurements were also used to monitor the  progress of the potassium carbonate transesterification reaction in the presence of added water, glycerol and gamma-valerolactone (GVL). The obtained  results are as expected, with a limited amount of water increasing the transesterification rate; glycerol slowing the reaction slightly in accord with Le  Chatellier’s principles; and GVL increasing the rate due to co-solvent effects. Atomic-level insights into the adsorption mechanism of methanol and water  on the (001) surfaces of Na₂CO₃ and K₂CO₃ catalysts are provided by first-principles DFT calculations, which explain the increase in transesterification    reaction rate upon the addition of water.