The epoxidation of FAME provides access to a broad range of large-scale industrial syntheses of chemicals and intermediates such as plasticizers and stabilizers in PVC, intermediates in the production of polyurethane polyols or components for lubricants, paints, cosmetics or pharmaceuticals. To avoid the use of organic peroxycarbonic acids as epoxidizing agents in industrial-scale epoxidation of unsaturated fatty acid compounds, hydrogen peroxide would be economically and environmentally largely preferred. Earlier, our group has shown that the epoxidation of FAME can be accomplished over conventional titanium silicalite-1 (TS-1) with aqueous H₂O₂ at mild temperatures (< 80°C) with an epoxide selectivity up to 80% [1]. However, the conversion of fatty acid methyl esters over TS-1 is limited by mass-transfer within the catalyst particles, largely due to the size of its micropores with respect to the bulky FAME molecules.

This presentation will highlight how TS-1-based catalysts can be rationally designed towards improved conversion of FAME with aqueous H₂O₂. First, the enhancement of accessibility of active sites with respect to diffusion improvements by a hierarchical pores system will be shown, including studies with PFG NMR to follow diffusion processes [2,3]. Especially, the introduction of a secondary, intracrystalline “auxiliary” system of larger, mainly meso- and macropores, results in improved catalytic activity for the epoxidation of FAME. Secondly, the combination of TS-1 with activated carbon as a hydrophobic catalyst component for enhanced sorption of the FAME reactant on the catalyst is demonstrated to further enhances the epoxidation activity of the composite catalysts [4, 5].

References:

1.	N. Wilde, C. Worch, W. Suprun, R. Gläser, Microporous Mesoporous Mater. 164, 182-189 (2012).
2.	M. Dvoyashkin, N. Wilde, J. Haase, R. Gläser, RSC Advances 8, 38941–44 (2018).
3.	A.O. Hernández, M. Goepel, D. Poppitz, R. Gläser, Mater. Chem. Phys. 335, 130462 (2025).
4.	P.C. With, N. Wilde, A. Modrow, S. Fichtner, B. Böhringer und R. Gläser, Chem. Eng. Technol. 38, 1671-1676 (2015).
5.	A.O. Hernández, M. Goepel, D. Poppitz, M. Dvoyashkin, R. Gläser, RSC Advances 15, 7111-7120 (2025).