A DFT Study for Catalytic Deoxygenation of Methyl Butyrate on a Lewis Acid Site of ZSM-5 Zeolite

The catalytic deoxygenation mechanism of fatty acid esters on a Lewis acid site of ZSM-5 zeolite was elucidated via density functional theory (DFT) by using a methyl butyrate (MB) as the model compound for fatty acid esters. The configurations of the initial reactant, transition states, and products together with the activation barrier of each elementary reaction were determined. The activation barrier of different initial cracking reactions decreases in the order of alpha-C-C > beta-C-C > alpha-C-O > beta-C-O. The best reaction path for catalytic deoxygenation of methyl butyrate over Lewis acid site is CH3CH2CH2C(OCH3)=OMIDLINE HORIZONTAL ELLIPSISLewis -> CH3CH2MIDLINE HORIZONTAL ELLIPSISLewisMIDLINE HORIZONTAL ELLIPSISC(=CH2)OCH3 -> CH2=CH2 + CH3COOCH3 + Lewis. The oxygen of methyl butyrate is mainly removed as CO2, methyl acetate, formaldehyde, and butyraldehyde, while ethylene, propylene, and butane are the main hydrocarbon products. In addition, the group generated by cracking of methyl butyrate form a bond with the Lewis acid site, promoting the transformation between a Lewis acid and a Bronsted acid. The corresponding intermediates have a high single point energy, but the poor stability leads to further deoxygenation and cracking reactions. This work provides a theoretical basis for the modification in the number of Bronsted acid and Lewis acid sites in the ZSM-5 zeolite.