Activity Comparison of Different Solid Acid Catalysts in Etherification of Glycerol with tert-Butyl Alcohol in Flow and Batch Reactors

Abstract

In the presented work, etherification of glycerol with TBA was investigated in a continuous flow and also in a batch reactor using nine different commercial solid acid catalysts, namely Amberlyst-15, Amberlyst-36, Amberlyst-35, Amberlyst-16, Relite EXC8D, Lewatit K2629, H-Beta, H-Mordenite and Nafion SAC-13. Results proved the advantages of flow reactor to achieve quite high glycerol conversion values in very short residence times, due to efficient contact of reactants with the solid catalyst, which was caused by higher catalyst to reactant ratio within the reactor. Results of batch reactor experiments obtained in the temperature range of 80–200 °C proved the importance of operating temperature on the catalytic performance of these materials. Amberlyst-15, which has the highest Brønsted acidity, gave the highest glycerol conversion at 90–100 °C. However, this material is unstable at temperatures higher than 110 °C. Performances of Amberlyst-36 and Relite EXC8D were the best in the range of 110–150 °C, which started to become unstable at 150 °C. Although the catalytic performance of Nafion-SAC-13 was not as good as Amberlyst type resins at temperatures up to 150 °C, its thermal stability was higher and could be used up to 200 °C. Although Brønsted acidity was the most important property of these materials in the etherification reaction of glycerol, results also proved the importance of diffusion resistance on the observed conversion values, which limited the penetration of glycerol to the active acid sites, especially in the catalysts with smaller pore diameters and at lower temperatures. Increased significance of swelling at higher temperatures, especially with Amberlyst-36 which had lower cross-linking in its structure and less rigidity, contributed to the penetration of the reactants to the active sites. Water produced during the etherification reaction was also shown to cause deactivation of the catalysts by reversible adsorption on the acid sites.