The hydrogenolysis of glycerol to lower alcohols.

Abstract

Much work has been done towards the hydrogenolysis of glycerol to 1,2-PDO and 1,3-PDO using various heterogeneous systems including Rh, Ru, Pt, PtRu, copper systems and Raney Ni in batch systems. However, routes to lower alcohols, such as 1-propanol and ethanol have been less discussed. From an industry point of view, the production of lower alcohols, such as propanol and ethanol, is very interesting. Different ruthenium, palladium and platinum catalysts were employed to study the effect of the support on the catalytic performance in batch mode. These catalysts were evaluated for their production of lower alcohols, especially 1-propanol using concentrated glycerol solutions. Among the other solid acids tested in combination with Ru/C, Amberlyst DT gave the most promising results from a 1-PO point of view, achieving a 34.9 mol% glycerol conversion with a selectivity of 38 mol% selectivity to 1-propanol. Despite the low glycerol conversion (1.3 mol%), Pd/C gave a promising 1-PO selectivity (> 85 mol%). The use of supported Ni catalysts, an inexpensive system, towards the chemical transformation of glycerol to lower alcohols, has appeared less frequently in the literature. The activity of Ni supported catalysts on silica and alumina was studied for the transformation of glycerol to lower alcohols, primarily 1-propanol and ethanol in a fixed bed continuous flow reactor. Several characterisation techniques were performed on the fresh and used catalyst, such as BET, XRD, TPD, TPR, TGA and electron microscopy. The objective was also to continue the development of a more detailed mechanistic understanding of the formation of lower alcohols from glycerol. In an endeavour to understand the process better, the role of proposed intermediates, 1,2-propanediol, 1,3- propanediol, ethylene glycol and ethanol was investigated, as well as the influence of the hydrogen partial pressure. Under the reaction conditions employed, it was clear that the hydrogenolysis of C-C and C-O bonds of glycerol took place to a lesser extent when compared to dehydrogenation and dehydration which are seen as the dominating initial steps. Ethanol was produced in high selectivities with 1,2-propanediol as feed and 1-propanol was the main product obtained when 1,3-propanediol was used as feed.