Heterogenization of a Tungstosilicic Acid Catalyst for Esterification of Bio-Oil Model Compound

Based on a prior demonstration of the high activity of a homogeneous tungstosilicic acid catalyst for the esterification of acetic acid as bio-oil model compound, a further study has been undertaken in an attempt to heterogenize the catalyst. Tungsten oxide was supported on amorphous silica (W/A150) using incipient wetness impregnation and incorporated into the structure of structured silica (W-KIT-5) via a one-step hydrothermal synthesis. The catalysts were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), physisorption (BET), and temperature-programmed desorption of ammonia (NH3-TPD). Both series were evaluated for the esterification of acetic acid with ethanol and compared with the homogeneous 12-tungstosilicic acid catalyst. The result of XRD analysis suggests the average crystallite size of the W oxide nanoparticles on both supports to be less than 2 nm, while XPS analysis revealed that all W existed in the W 6+ oxidation state. From the BET and NH3-TPD analyses, it was shown that the KIT-5 series had higher surface area and acidity than the W/A150 catalyst. The 10% W-KIT-5 was shown to be the best heterogeneous catalyst with the highest activity and acid conversion of about 20% and 93% of the homogeneous catalyst. Significant leaching of tungsten from both the supports occurred and will have to be solved in the future.