Heterogeneous catalysis for valorisation of vegetable oils via metathesis reactions: Ethenolysis of methyl oleate

NIERES PABLO D.; ZELIN JUAN; APESTEGUÍA CARLOS R.; TRASARTI ANDRES F.

Catalysis Science & Technology

Royal Society of Chemestry

Año: 2016 vol. 6 p. 6561 - 6568

The cross-metathesis of methyl oleate (MO) with ethylene was studied on second-generation Hoveyda-Grubbs complex supported on silica (HG/SiO2). The reaction was carried out in a batch slurry reactor at 313-353 K and 2.5-7.5 bar of C2H4(5%)/N2, using toluene as solvent. The MO ethenolysis products were methyl 9-decenoate and 1-decene. Competitive MO self-metathesis reaction formed 9-octadecene and methyl 9-octadecen-1,18-dioate. The yield (YE) and selectivity (SE) to ethenolysis products at P_(C_2 H_4 )= 0.125 bar (total pressure = 2.5 bar) were 52% and 69%, respectively. Both parameters increased with P_(C_2 H_4 ), essentially because the reaction equilibrium was shifted to higher methyl oleate conversions. Thus, at P_(C_2 H_4 )= 0.250 bar, the YE and SE values were 63% and 77%, respectively. Nevertheless, catalyst deactivation was observed for ethylene pressures higher than 0.125 bar, thereby suggesting that the presence of ethylene may suppress the metathesis cycle on HG/SiO2 catalysts. The yield to ethenolysis products decreased when the temperature was increased, reflecting mainly the MO equilibrium conversion diminution.