The selective continuous flow synthesis of lower alcohols from polyols-a mechanistic interpretation of the results

In an endeavour to understand the hydrogenolysis pathway of glycerol to lower alcohols over Ni on Al₂O₃ and SiO₂ catalysts, the role of the intermediates (1,2-propanediol (1,2-PDO), 1,3-propanediol (1,3-PDO), ethylene glycol (EG) and ethanol) was investigated. Under the reaction conditions employed in this study, it was clear that the hydrogenolysis of the C-C and C-O bonds of glycerol takes place to a lesser extent as compared to dehydrogenation and dehydration which are seen as the dominating initial steps. Ethanol was produced in high selectivities (~67%) with 1,2-propanediol as feed and 1-propanol (1-PO, ~80%) was the main product obtained when 1,3-propanediol was used as feed. Ethylene glycol gave methanol and methane as products, whereas ethanol gave methane and CO₂ as major products.