(730f) Glycerol Transfer-Hydrogenation of Levulinic Acid Using Ru and Ir Carbene Organometallics Immobilized on Active Hydrotalcites

Authors: 
Heltzel, J., George Washington University
Voutchkova-Kostal, A., George Washington University
Finn, M., George Washington University
Wang, K., George Washington University
Sandefur, E., George Washington University
The mechanism and kinetics of levulinic acid (LA) hydrogenation to gamma-valerolactone (GVL) have been extensively studied over the last decade. Despite improvements in selectivity and the use of alternative hydrogen sources such as formic acid and secondary alcohols, economic production of GVL remains hindered by slow reaction rates and the high cost of current hydrogen sources. The use of glycerol, a waste byproduct in biodiesel synthesis, as a hydrogen donor could alleviate the economic challenges associated with GVL production. Herein we tested hydrogenation/deoxygenation of LA under dilute aqueous to neat conditions using Ru and Ir N-heterocyclic carbene (NHC) organometallic catalysts while also varying pH with potassium hydroxide. A total of 7 Ru and Ir homogeneous catalysts were screened for activity, the most active catalysts were then immobilized onto tunable hydrotalcites (HT). A 3:1 ratio of Mg:Al HT was used as a basis for all HT catalytic reactions while substitutions of Al with Fe, Ni, and Co were tested for improved catalytic activity. Products were identified using LCMS, HPLC, NMR, GCMS, and FTIR. The products formed and reaction rates were pH-dependent; acidic conditions favored ketal formation between LA and glycerol whereas alkaline conditions with an Ir(I) complex favored GVL and lactic acid formation at a turnover frequency (TOF) above 66,000 h-1 at 150ËšC for GVL. The Ir(I) catalyst achieved unprecedented reaction rates with glycerol, therefore, a comparison to reaction rates achieved with formic acid was demonstrated and showed negligible differences in rates and selectivity. Upon immobilizing the NHC catalysts on HT, the non-active Ru and Ir catalysts achieved activity over 10,000 h-1. Under the same conditions the immobilized Ir(I)HT rate was reduced to 15,000 h-1 for GVL. The increase in activity from the other Ru and Ir(III) complexes tested are believed to be a result of the HT Lewis acid sites.