Catalytic hydrogenolysis of ethanol organosolv lignin
Journal article, 2009
The production of ethanol based on lignocellulosic materials will bring about the coproduction of significant amounts of under-utilized lignin. This study examines the potential of conventional heterogeneous and novel homogeneous catalysts for the selective cleavage of the aryl-O-aryl and aryl-O-aliphatic linkages of ethanol organosolv lignin to convert it from a low grade fuel to potential fuel precursors or other value added chemicals. The development of hydrogenolysis conditions that effectively increase the solubility of lignin were initially examined with Ru(Cl)(2)(PPh3)(3) and demonstrated the ability to decrease the molecular weight and enhance the solubility of the lignin polymer. Later studies examined several heterogeneous and homogeneous hydrogenation catalysts at optimized reaction conditions resulting in 96.4% solubility with Ru(Cl)(2)(PPh3)(3), increase in H/C ratio with Raney-Ni, Pt/C and extensive monomer formation with NaBH4/I-2. The changes in molecular structure of lignin were followed by size exclusion chromatography, qualitative and quantitative NMR spectroscopy and elemental analysis. These studies demonstrated that aryl-O-aryl and aryl-O-aliphatic linkages could be cleaved and the hydrogenated lignin had a decrease in oxygen functionality and the formation of products with lower oxygen content.
size exclusion chromatography
P-31 NMR spectroscopy