AIChE Journal, Vol.62, No.4, 1162-1173, 2016
Kinetic modeling of Pt/C catalyzed aqueous phase glycerol conversion with in situ formed hydrogen
Detailed kinetic modeling of Pt/C catalyzed conversion of glycerol to lactic acid, glycols, and alcohols with in situ formed hydrogen is reported. Experimental concentration-time profiles were obtained in a batch slurry reactor at different glycerol concentrations, nitrogen partial pressures, and NaOH concentrations in a temperature range of 130-160 degrees C. Six different kinetic models were evaluated to describe the competing dehydrogenation, hydrogenolysis, dehydration, and CC cleavage reactions, and discriminated to fit the experimental data. It is found that a dual-similar-site mechanism involving alkali promoted dehydrogenation, on two adjacent Pt sites to affect CC and CO cleavage best describes the experimental data. The dehydrogenation reaction proceeds with a significantly lower activation barrier (E-a=53 kJ/mol) compared with the noncatalytic hydrothermal conversion (E-a=128 kJ/mol). The activation energy for glycerol hydrogenolysis on Pt/C catalyst without adding hydrogen is estimated to be 64 kJ/mol. (c) 2015 American Institute of Chemical Engineers AIChE J, 62: 1162-1173, 2016