The directly synthesis of glycerol carbonate from glycerol and CO2 is a very attractive subject because of the high atom utilization of 87%. Furthermore, this reaction could convert the primary greenhouse gas CO2 and the by-product glycerol of biodiesel into high value-added chemicals. However, this reaction is limited by thermodynamics. In order to break the thermodynamic limit, the water formed in the reaction of glycerol with CO2 needs to be removed by the hydrolysis of acetonitrile  (CH3CN). The hydrolysis product (acetic acid) from CH3CN could also react with glycerol to form monoacetin. Based on our research results, Cu-based catalysts were highly active for the carbonylation of glycerol with CO2 in the presence of CH3CN. This work investigated the effect of supports on the catalytic performance of Cu-based catalysts and the catalytic mechanism.        Supported Cu catalysts (Cu/CaO, Cu/MgO, Cu/La2O3, Cu/Al2O3, Cu/ZrO2, Cu/Mg-Al-Zr, Cu/CNTs, Cu/MCM-41 and Cu/HZSM-5) were prepared by impregnation method. The properties of Cu-based catalysts were characterized by XRD, BET, TEM, NH3/CO2-TPD, H2-TPR, XPS and N2O chemisorptions. The catalytic performance of Cu-based catalysts was evaluated in a high-pressure autoclave. The characterization results showed that these Cu-based catalysts exhibited different Cu particle sizes and acid-base properties. The reaction routes were divided into three steps: the carbonylation of glycerol with CO2, the hydrolysis of CH3CN and the esterification of glycerol with acetic acid. The carbonylation of glycerol with CO2 might be a structure sensitive reaction, and the conversion rate of glycerol decreased with the increase of Cu particle size. Cu species played the decisive role in this reaction. The base catalysts tended to favor the formation of glycerol carbonate, and the acid catalysts accelerated the esterification of glycerol with acetic acid.Acknowledgement:  National Nature Science Foundation of China (Grant No: 21033004).

Studies on the reaction of CO<sub>2</sub> and glycerol to glycerol carbonate catalyzed by Cu-based catalysts

247th National Meeting (2014)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.

Studies on the reaction of CO2 and glycerol to glycerol carbonate catalyzed by Cu-based catalysts

Studies on the reaction of CO₂ and glycerol to glycerol carbonate catalyzed by Cu-based catalysts