Bifunctional Co3O4/ZSM-5 Mesoporous Catalysts for Biodiesel Production via Esterification of Unsaturated Omega-9 Oleic Acid

In the present work, two sets of the Co/ZSM-5 mesoporous catalysts with different acidity and Co loadings varying from 1 to 5 and 10 wt% were prepared using mesoporous ZSM-5-A (Si/Al = 50) and ZSM-5-B (Si/Al = 150) as support. X-ray diffraction (XRD) analysis showed that the Co3O4 phase was formed in the surface of catalysts and the reducibility of Co3O4 nanoparticles on the ZSM-5-B was greater in comparison with that on the ZSM-5-A solid. In situ FTIR of pyridine adsorption characterization confirmed that all of the Co/ZSM-5 catalysts contained both Lewis (L) and Bronsted (B) acid sites, with a relatively balanced B/L ratio ranging from 0.61 to 1.94. Therefore, the Si/Al molar ratio in ZSM-5 affected both the surface acidity and the cobalt oxide reducibility. In the esterification of unsaturated omega-9 oleic acid with methanol, under the optimal reaction conditions (temperature 160 degrees C, catalyst concentration 2 g/L, methanol/oleic acid molar ratio 30, and reaction time 180 min), the biodiesel selectivity reached 95.1% over the most active 10 wt% Co/ZSM-5-B catalyst. The higher esterification activity of the Co/ZSM-5-B catalysts can be correlated with the greater amount of B and L acid sites, the balanced B/L ratio, and the higher reducibility of Co3O4 nanoparticles. The oleic acid esterification reaction followed the bifunctional mechanism of combining metal function (dispersed Co3O4 with a greater reducibility) with the acidity function (both B and L acid sites with a relative balanced B/L ratio) on the catalysts, which may help in providing a deep understanding of the esterification pathways and benefiting the design of novel bifunctional catalysts for biofuel production.

Automated summary

In this study, Co/ZSM-5 mesoporous catalysts with different acidity and Co loadings were prepared using mesoporous ZSM-5 as support. The results showed that the Si/Al ratio in ZSM-5 affected the surface acidity and cobalt oxide reducibility. Under optimal reaction conditions, the 10 wt% Co/ZSM-5 catalyst exhibited high biodiesel selectivity. This can be attributed to the presence of acid sites, a balanced B/L ratio, and the high reducibility of Co3O4 nanoparticles.