Synthesis and characterization of zirconia based solid acid catalysts for biodiesel production

Abstract

Biodiesel is a promising renewable alternative fuel to fossil energy. For the biodiesel production from low-cost feedstock, a pretreatment step is essential, which is the esterification of free fatty acids (e.g. oleic acid) in the feedstock in order to avoid soap formation and minimize catalyst deactivation. Sulfuric acid modified zirconia (H2SO4-ZrO2) is known as an effective heterogeneous catalyst for esterification. However, due to rapid 〖SO〗_4^(2-) leaching, its reusability is low and its practical use is thus largely hindered.

Zirconia supported on silica (ZrO2-SiO2) serves as a kind of non-sulfated zirconia catalyst against the leaching of the active species. Moreover, the silica support offers a large surface area and excellent thermal stability, which can accommodate a number of active zirconia species. Furthermore, there are Zr-O-Si bondings at the contact area between ZrO2 and SiO2, which might result in the formation of a new strong acid species and induce an increase of the zirconia acidity accordingly. Herein, two types of ZrO2-SiO2 catalysts were prepared, by using the reverse microemulsion method and sol-gel-hydrothermal method, denoted as ZrO2-SiO2-ME and ZrO2-SiO2-SG, respectively. The as synthesized ZrO2-SiO2 were characterized by TEM, SEM, EDX, XRD, BET and IR. ZrO2-SiO2-ME demonstrated a good dispersion of ZrO2 nanoparticles, encapsulating in the monodispersed SiO2 host matrix, while ZrO2-SiO2-SG possessed the SiO2 support with a mesoporous structure, with an average pore size of ~7 nm and a surface area of 418 m2/g. The catalysts both exhibited excellent catalytic activity and stable performance in the esterification of oleic acid.

Besides non-sulfated zirconia, sulfated zirconia catalysts other than traditional H2SO4-ZrO2 were also developed as solid acid catalysts for biodiesel production. Two sulfur-containing strong acids, chlorosulfonic acid (HClSO3) and (NH4)2SO4, were employed to acidify ZrO2, and two sulfated zirconia catalysts were prepared accordingly, namely HClSO3-ZrO2 and S-ZrO2. They were characterized by SEM, EDX, XRD, BET, IR, TGA and NH3-TPD. Comparing with H2SO4-ZrO2, HClSO3-ZrO2 and S-ZrO2 contained higher sulfur content and more acid sites. More importantly, both HClSO3-ZrO2 and S-ZrO2 demonstrated high catalytic activity and excellent durability in the esterification of oleic acid.

It is known that consecutive esterification and transesterification reactions are suitable for direct biodiesel production and acetylation of glycerol enables the conversion of this biodiesel byproduct to a biofuel additive. Therefore, all the above mentioned catalysts were examined to compare their catalytic abilities in these reactions. Among the four catalysts, HClSO3-ZrO2 exhibited the highest catalytic activity in both reactions under optimal conditions.

The thesis work here described the preparation and characterization of four types of ZrO2-based solid acid catalysts. Their catalytic activities were thoroughly investigated upon the several essential steps in biodiesel production. In addition, the synthesis condition-activity relation was studied and the synthesis and reaction conditions were delicately tuned.