Synthesis and characterization of solid metal oxide nanaostructures for biodiesel production

Abstract

Solid basic metal oxides have been extensively studied for biodiesel production via transesterification, researches are now focused on attaining high catalytic activity and durability towards one-step alkali transesterification, as well as high stability towards high free fatty acids (FFAs) and water content in oils for simultaneous esterification and transesterification, to enable their commercialization in industry.

This work encompasses the design and characterization of three mixed metal oxide systems, with a detailed evaluation of their potential application in catalyzing transesterification of camelina oil to yield biodiesel.

Na0.1Ca0.9TiO3 nanorods were synthesized via a simple alkaline hydrothermal pathway with ethanol as a co-solvent. Owing to their high basic strength of 11<H_<15, 92.7% biodiesel conversion was reached at mild reaction conditions. However, the catalyst showed poor recycle performance, probably attributed to the leaching of active species during transesterification, as revealed by X-ray photoelectron spectroscopy (XPS).

A new class of mesoporous Zn/MgO catalyst was synthesized by a simple alkaline hydrothermal method. Zn/MgO calcinated at 600 ℃ exhibited 88.7% biodiesel conversion at 120 ℃ with 3% w/w catalyst, 24:1 methanol to oil molar ratio for 8 h. The catalyst could be reused for five runs without significant loss of activity (≥84.0% biodiesel conversion). The excellent catalyst performance is possibly attributed to its high surface area and large mesopores. The higher surface basic sites density as compared to mesoporous MgO, as indicated by higher total basicity determined from benzoic titration and an increased lattice O2- percentage as revealed from XPS, attributing to its superior catalytic activity.

A series of nano-sized MgO-ZnO catalysts with precise stoichiometry were successfully prepared by a simple EDTA complexing approach. Mg0.5Zn0.5 calcinated at 600 ℃ gave a maximum biodiesel conversion of 89.3% at 120 ℃ with 3% w/w catalyst, 24:1 methanol to oil molar ratio for 8 h. Its superior catalytic performance to MgO is mainly associated with the high basic sites density as determined from benzoic titration and XPS. The biodiesel conversion retained over 83.0% for five runs. The enhanced catalyst activity and stability might be contributed by the incorporation of Zn2+ for Mg2+ in MgO lattice and a high homogeneous distribution of MgO particles on ZnO, with the formation of Mg-O-Zn bond as evidenced by Fourier transform infrared spectroscope (FTIR) and XPS. The catalyst also demonstrated high tolerance to FFAs (10% w/w) and water (2% w/w) content, which make it desirable for direct conversion of oils with high FFAs level to biodiesel in a single-step process.

Lastly, a Zn/La2O3 catalyst was synthesized by a simple hydrothermal pathway. It exhibits a higher basic strength than La2O3, as evidenced by the slightly lower O1s binding energy determined by XPS, leading to a higher catalytic activity. The enhanced catalytic activity and stability is likely contributed by the incorporation of Zn2+ for La3+ in the lattice. Using 1% w/w Zn/La2O3 as catalyst, the highest biodiesel conversion of 92.7% was obtained at 120 ℃ for 16 h with 36:1 methanol to oil molar ratio. The effective catalyst displayed a biodiesel conversion greater than 84.0% for four runs.