Esterification of Levulinic Acid with Different Alcohols Using Mesoporous Stannosilicates As the Catalyst.

Abstract

The mesoporous stannosilicates SnMCM-41-25 and SnMCM-41-80, synthesized, respectively, at 25 and 80 °C and exhibiting a well-ordered hexagonal structure, were applied for the first time as heterogeneous catalysts in the esterification of levulinic acid (LA) with different alcohols. The nonhydrothermal method was effective to obtain materials with a high degree of ordering, high acidity, and promising catalytic activity in this esterification. The SnMCM-41-80 led to conversions of 71.0 and 83.6% in 120 and 180 min, respectively, while the respective values for the material without Sn were 33.2 and 40.1% under the same conditions (MeOH:LA molar ratio of 5:1, 1 wt % catalyst, 3 h, 120 °C). In addition, concerning the use of different alcohols, the reaction rate constants (k ap) were related to the effects of substituents by Taft equation. In general, the polar and steric effects follow the Taft relation, and the length of the chain exerted less influence on the decrease in conversion in comparison to the presence of branches. These results indicate that it is possible to incorporate Sn into the structure of MCM41, thus, making the modified materials more active in the esterification investigated.