Reaction enthalpies for the hydrogenation of alkyl levulinates and levulinic acid on Ru/C– influence of experimental conditions and alkyl chain length

The development of process flow diagrams requires knowledge of reaction enthalpy for pinch analysis and thermal risk assessment. Such information is missing for some biomass processes, such as the production of γ-valerolactone (GVL) from the hydrogenation of levulinic acid or alkyl levulinate. To fill this gap, this manuscript describes a detailed calorimetric study on the hydrogenation of levulinic acid (LA), methyl levulinate (ML), ethyl levulinate (EL), propyl levulinate (PrL), butyl levulinate (BL) and pentyl levulinate (PeL) over Ru/C. This reaction system occurs through a two-step pathway with a domino hydrogenation/cyclization sequence. The cyclization step (lactonization) was found to be endothermic and was evaluated by a Tian-Calvet C80 micro-calorimeter, whereas the hydrogenation step was found to be exothermic and was tracked by a RC1 Mettler Toledo High-Pressure calorimeter. It was verified that reaction enthalpy is independent of reaction temperature (in the operating conditions used in this work), levulinate concentration and solvent (levulinate, corresponding alcohol or GVL). It was also found that reaction enthalpy for both steps did not depend linearly on alkyl chain length.