Esterification of Levulinic Acid Using ZrO₂-Supported Phosphotungstic Acid Catalyst for Ethyl Levulinate Production

Ethyl levulinate (EL) is a versatile bio-based chemical with various applications such as fragrance and flavoring agents and also fuel blending component. EL can be produced through catalytic esterification of levulinic acid (LA) with ethanol. Herein, a series of zirconia (ZrO₂)-supported phosphotungstic acid (HPW) (HPW/Zr) catalyst, 15-HPW/Zr, 20-HPW/Zr, and 25-HPW/Zr, were prepared, characterized, and tested for EL production. The physicochemical properties of catalysts were characterized using Fourier-transformed infrared (FTIR) spectroscopy, x-ray diffraction (XRD), field emission scanning electron microscope (FESEM), N₂ physisorption, and ammonia temperature-programmed desorption (NH₃-TPD). The effect of reaction parameters: reaction time, temperature, catalyst loading, and molar ratio of LA to ethanol was inspected on LA conversion and EL yield. The catalyst with high surface area and high acidity seemed suitable for EL production. Among the catalysts tested, 20-HPW/Zr exhibited the highest EL yield of 97.3% at the following conditions: 150 °C, 3 h, 1.0 g of 20-HPW/Zr and 1:17 M ratio of LA to ethanol. The 20-HPW/Zr could be reused for at least four times with insignificant decrease in the EL yield. This study demonstrates the potential of ZrO₂-supported HPW for bio-based alkyl levulinate production at mild process conditions.