Effect of La-Fe/Si-MCM-41 catalysts and CaO additive on catalytic cracking of soybean oil for biofuel with low aromatics

Abstract

La-Fe modified Si-MCM-41 (La-Fe/Si-MCM-41) catalysts were prepared by the wet impregnation method and used in catalytic cracking of soybean oil (CCS) for biofuel production. The catalysts were characterized by BET, XRD, XPS, Py-FTIR and CO2-TPD. The results showed that the aromatics content increased with the increase in B/L value, while the content of oxygenated compounds decreased, indicating that Brönsted acid sites were the major active sites for deoxygenation and aromatization reactions. Compared with Si-MCM-41, the Brönsted acidity of LFM-6 sharply decreased from 22.49 to 5.86 μmol g−1. Accordingly, the aromatics content was reduced from 37.51 wt.% to 14.52 wt.% which was lower than the limitation (15 wt.%) according to the global environmental legislation. However, for the LFM-6 catalyst, the excessive loss of Brönsted acid sites and sharp decrease in BET surface area and pore volume led to the decrease in deoxygenation. As a result, the fatty acids content increased from 2.71 wt.% to 16.67 wt.% and the acid value reached 35.20 mgKOH g−1. When the La-Fe loading increased to 15 wt.%, part of fatty acids were converted into ketones by the active sites on Fe2O3/La2O3 and strong Lewis acid sites on catalysts. Besides, the new weak Lewis acid and basic sites on Fe2O3/La2O3 exhibited the synergistic effect on promoting the generation of alkenes. The CaO/LFM-6 composite catalysts prepared by the mechanical mixing of LFM-6 and CaO were used in CCS to reduce the acid value of biofuel. LFM-6-C-3 was proved to be an effective catalyst for CCS to produce biofuel with low aromatics (12.31 wt.%) and fatty acids (2.76 wt.%) content.