Sulfated zirconia as a robust superacid catalyst for multiproduct fatty acid esterification

Sulfated zirconia catalysts obtained by employing chlorosulfuric acid show significantly higher activity in the esterification of fatty acids with different alcohols compared with catalysts made using sulfuric acid. The superior performance results from higher sulfur content, larger pores and stronger acid sites. These catalysts are robust and do not leach out sulfonic groups. Catalyst performance depends strongly on the sulfation reagent and the calcination conditions of the intermediate zirconium hydroxide. A series of kinetic experiments was carried out with lauric acid and various alcohols (methanol, 2-ethylhexanol, propanols and butanols). The new catalysts are ca. five times faster when using primary alcohols independent of the alcohol chain length. When using secondary and tertiary alcohols the reaction rate drops considerably. This is explained by a linear free energy relationship of substituent reactivity. The kinetic investigation shows that chlorosulfated zirconia is suitable as a multiproduct catalyst for manufacturing fatty esters, by employing a catalytic reactive distillation process.