Bleaching Earths as Powerful Additives for Ru-Catalyzed Self-Metathesis of Non-Refined Methyl Oleate at Pilot Scale

5 years ago

Bleaching Earths as Powerful Additives for Ru-Catalyzed Self-Metathesis of Non-Refined Methyl Oleate at Pilot Scale

Idriss Curbet, Guillaume Chollet, Olivier Baslé, Christophe Crévisy, Marc Mauduit, Frédéric Caijo, Sophie Sambou, Fabien Tripoteau, Yann Raoul, Jessica Allard

A practical and cost-effective ruthenium-catalyzed self-metathesis of non-refined methyl oleate (85 %) derived from very high oleic sunflower oils was demonstrated at pilot scale using a robust and kg-scale commercially available SIPr-M71 pre-catalyst. The simple addition of 1 wt % bleaching earths (Tonsil 110FF) to a thermally pretreated oil could efficiently prevent catalyst deactivation. Remarkably, without the need for filtration, the catalytic system was able to achieve a turnover number (TON) of more than 744 000 at a catalyst loading of only 1 ppm. At large scale (up to 200 kg), the equilibrium of the self-metathesis reaction was reached within 1 hour at 50 °C under neat conditions at a very low 5 ppm catalyst loading to produce the expected primary metathesis products (PMP), that is, 9-octadecene and dimethyl-9-octadecenoate, with a productive TON of 94900. An efficient and cost-effective pretreatment was proposed to mediate the Ru-catalyzed self-metathesis of non-refined methyl oleate ((Z)-1; 85 %) derived from very high oleic sunflower oils. The use of bleaching earths (Tonsil 110FF, 1 wt %) combined with a thermic pretreatment enabled metathesis under neat conditions with a catalytic loading as low as 0.0001 mol % (1 ppm) and impressive turnover number (TON) of 744 000. The robust catalytic process has proven to be efficient at pilot scale (200 kg) with a remarkable productive TON (94 900) for expected primary metathesis products 9-octadecene (2) and dimethyl-9-octadecenoate (3).

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201703049