Abstract
The present work aimed to investigate the law of the conversion of glycerol with diethyl carbonate (DEC) over the highly efficient Ce–NiO catalyst prepared by co-precipitation method. The thermodynamic and kinetics parameters of this reaction for glycerol carbonate synthesis were studied. The reaction equilibrium constants were investigated experimentally in the temperature region of 338–358 K, and the standard molar properties (at 298 K) were obtained (△H0= 115.71 kJ mol−1, △G0= 13.523 kJ mol−1, △S0= 0.343 kJ mol−1). Effects of various experimental conditions including stirring speed, reaction temperature, catalyst amount, reactant mole ratio on the reaction kinetics were also studied. Different order kinetic equations were used to simulate law of the transesterification process. The result shows a three-order equation of glycerol (two orders) and DEC (one order) was more appropriate to interpret the law of glycerol transesterification with diethyl carbonate. The activation energy of this reaction was obtained with 87.90 kJ mol−1. Finally, the microstructure and physicochemical properties of the Ce–NiO samples were studied by XRD, SEM, TEM, and CO2-TPD.
Graphical abstract
One-pot catalytic conversion of glycerol into glycerol carbonate over Ce–NiO catalyst.
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Reproduced with permission (Wu et al. 2017). Copyright 2017, ELSEVIER Publications
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Abbreviations
- \(\alpha\) :
-
Reaction order of glycerol
- \(\beta\) :
-
Reaction order of diethyl carbonate
- \(c_{{{\text{A}}_{0} }}\) :
-
Initial concentration of glycerol (mol L−1)
- \(c_{{{\text{B}}_{ 0} }}\) :
-
Initial concentration of diethyl carbonate (mol L−1)
- \(c_{\text{A}}\) :
-
Concentration of glycerol after time t (mol L−1)
- \(c_{\text{B}}\) :
-
Concentration of diethyl carbonate after time t (mol L−1)
- \(c_{\text{C}}\) :
-
Concentration of glycerol carbonate after time t (mol L−1)
- \(c_{\text{D}}\) :
-
Concentration of ethanol after time t (mol L−1)
- \(\theta\) :
-
Mole ratio of \(c_{{{\text{A}}_{0} }}\) to \(c_{{{\text{B}}_{0} }}\)
- \(k\) :
-
Rate constant
- \(t\) :
-
Reaction time (h)
- K C :
-
Equilibrium constant
- x G :
-
Equilibrium conversion of glycerol (%)
- \(x\) :
-
Conversion of glycerol (%)
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Acknowledgements
This work was financially supported by National Natural Science Foundation of china (nos. 21276050, 21676054, 21406034), Natural Science foundation of Jiangsu (no. BK20161415), Fundamental Research Funds for the central Universities (nos. 2242018K40041, 3207045414, 3207045101, 3207045426), Key Laboratory Open Fund of Jiangsu Province (JSBEM201409).
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Zhang, J., Wu, Y., Song, X. et al. Thermodynamic and kinetic studies for synthesis of glycerol carbonate from glycerol and diethyl carbonate over Ce–NiO catalyst. Chem. Pap. 72, 2909–2919 (2018). https://doi.org/10.1007/s11696-018-0518-3
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DOI: https://doi.org/10.1007/s11696-018-0518-3