Glycolic acid is an important chemical that has uses as a cleaning agent as well as a chemical intermediate. At present glycolic acid is manufactured from either chloroacetic acid or from formaldehyde hydrocyanation, both routes being nongreen and using nonsustainable resources. We investigate the possibility of producing glycolate from the oxidation of glycerol, a sustainable raw material. We show that by using 1 % wt Au/carbon catalysts prepared using a sol-immobilization method glycolate yields of ca. 60 % can be achieved, using hydrogen peroxide as oxidant in an autoclave reactor. We describe and discuss the reaction mechanism and consider the reaction conditions that maximize the formation of glycolate.
To study the mechanism of acrylonitrile formation, the ammoxidation of [3-13C]propene was studied in the presence of a bismuth molybdate catalyst on a silica support. The reaction was carried out at 723 K with a conversion of about 40 vol % of the propene to acrylonitrile and a small amount of acetonitrile. The 13C distribution among the reaction products was examined quantitatively with a high-resolution mass spectrometer. Half of the I3C in the acrylonitrile was found to be in the CN-group and the other half in the C2H3-group. This result points to a symmetrical intermediate, such as an allylic species, in the ammoxidation reaction. A similar intermediate was observed in the catalytic oxidation of propene to acrolein. The total 13C content in the acetonitrile amounted to only half that of the acrylonitrile, which indicates carbon-carbon bond fissure of the allylic intermediate in the mechanism of acetonitrile formation. Ammoxidation of propene does not seem to involve acrolein as an intermediate. As a matter of fact, the addition of ammonia to a mixture of propene + oxygen + helium completely suppresses acrolein formation at 623 K.
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