Glycerol, as a plentiful residual co-product in the biodiesel manufacturing, and CO2, a non-toxic and abundant C1 resource, have attracted much interest in the field of sustainable chemistry. Thus, the conversion of glycerol and CO2, two inexpensive and renewable resources, into high value-added glycerol carbonate is an attractive project. In the present work, Ce1-xZrxO2 solid solutions which show redox and acid-base properties as well as thermal stabilities, were investigated as catalysts in the synthesis of glycerol carbonate from glycerol and CO2 in the presence of 2-cyanopyridine. The effects of Zr/Ce ratio in Ce1-xZrxO2 and the possible reaction mechanism in the carbonylation of glycerol with CO2 to glycerol carbonate were also studied. Ce-Zr mixed oxides were prepared by hydrothermal method, and the catalysts were denoted as Ce1-xZrxO2, where x represents the molar fraction of Zr (0, 0.01, 0.02, 0.05, 0.1, 0.2). The physicochemical properties of Ce1-xZrxO2 catalysts were characterized by ICP, XRD, BET, TEM, NH3/CO2-TPD, H2-TPR and XPS, and the activation route of CO2 and glycerol were measured by DRIFTS and FT-IR. The catalytic reactions were conducted in a high-pressure agitated autoclave. Results showed that Ce1-xZrxO2 solid solutions exhibited enhanced catalytic performance towards the formation of glycerol carbonate with respect to pure CeO2. The different activities of Ce1-xZrxO2 were in associated with the BET surface area, oxygen storage capacity and the amount of acid-base sites. Furthermore, glycerol and CO2 could be activated on CeO2-based catalysts, and a plausible mechanism was proposed for the synthesis of glycerol carbonate from glycerol and CO2 in the presence of 2-cyanopyridine in DMF solvent over CeO2-based catalysts.

Effect of physicochemical properties of Ce1-xZrxO2 solid solutions on carbonylation of glycerol with CO2 into glycerol carbonate

255th National Meeting (2018)

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