Applied Catalysis B: Environmental, Vol.163, 258-266, 2015
One-pot tandem processing of glycerol stream to 1,2-propanediol with methanol reforming as hydrogen donor reaction
1,2-propanediol is formed efficiently using bio-glycerol feedstock via hydro-deoxygenation reaction with H-2 formed in-situ by a novel reaction cycle. The new catalytic route presented here includes the reformation of methanol, remained unreacted after transesterification, for the production of the active H-2 which is consumed in the tandem reaction of glycerol hydrogenolysis. The overall process proceeds in liquid phase over Pt or Cu based catalysts at 220-250 degrees C and 3.5 MPa initial N-2 pressure for 1 and 4 h reaction time. The test over Pt/SiO2 catalyst resulted in 1,2-propanediol yield of 21.4%. The yield to the desired product in the presence of Al2O3 supported Pt is further limited due to the high extent of the over-hydrogenolysis reactions to propanols, which are promoted by the catalyst acidity. Cu:Zn:Al catalysts showed promising performance in the combined reaction cycle. The Cu bulk catalyst (with 49 wt% Cu) synthesized by the oxalate gel co-precipitation route exhibits similar to 35% yield to 1,2-propanediol at the standard reaction conditions. Further increase to 1,2-propanediol yield (up to similar to 45%) was achieved by tuning the reaction conditions. Experiments with labeled (CH3OH)-C-13 shed light into the H-2 formation origin and proved that similar to 70% of the total H-2 is indeed produced from the reformation of methanol. (C) 2014 Elsevier B.V. All rights reserved.
Keywords:Copper catalyst;Platinum catalyst;Glycerol hydrogenolysis;Methanol reforming;1,2-propanediol