The MxOy-MCr2O4 (M-Cr-O; M = Mg, Fe, Co, Ni, Cu and Zn) mixed oxides obtained from their respective M-(II)-Cr-III) hydrotalcite precursors have been examined for vapour phase dehydrocyclization of bio-glycerol and 1,2-propanediamine. The physico-chemical properties of the calcined M-Cr-O are characterized by various adsorption and spectroscopic methods. The high 2,6-dimethylpyrazine rate of Cu-Cr-O is rationalized by a combined effect of copper species in close proximity to the CuCr2O4. The kinetic studies demonstrated that glycerol undergoes dehydration to hydroxyacetone (75%) on acidic sites and dehydrogenation to produce dihydroxyacetone on basic sites (25%) at low GHSV. However, a reverse trend has been observed at higher GHSV. Fe2O3-Cr2O3 is found to be active for 2,6-dimethylpiperazine and copper in the vicinity of CuCr2O4 is highly selective for 2,6-DMP formation. (C) 2014 Elsevier B.V. All rights reserved.