Glycerol Oxidation in the Liquid Phase over a Gold-Supported Catalyst: Kinetic Analysis and Modelling
Abstract
:1. Introduction
2. Results
2.1. Influence of the Reaction Conditions
2.1.1. Reaction Temperature
2.1.2. NaOH/Glycerol Ratio
2.1.3. Species Initial Concentration
2.2. Kinetic Model
3. Discussion
4. Materials and Methods
5. Conclusions
Acknowledgments
Author Contributions
Conflicts of Interest
References
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T (°C) | NaOH/GLY (mol/mol) | C0GLY (mol/L) | C0PRODUCTS (mol/L) | XGLY (%) a | Initial Reaction Rate b | SGLYCERIC (%) a | SGLYCOLIC (%) a |
---|---|---|---|---|---|---|---|
Without catalyst | |||||||
40 | 4 | 0.3 | - | 0 | 0 | - | - |
60 | 4 | 0.3 | - | 3.6 | 4.9 × 10−4 | 33.3 | 29.5 |
80 | 4 | 0.3 | - | 18.5 | 4.3 × 10−3 | 24.9 | 40.1 |
100 | 4 | 0.3 | - | 68.0 | 1.7 × 10−2 | 17.2 | 49.9 |
60 | 0 | 0.3 | - | 0 | 0 | - | - |
60 | 1 | 0.3 | - | 1.6 | 2.0 × 10−4 | 48.7 | 13.9 |
60 | 2 | 0.3 | - | 1.8 | 3.4 × 10−4 | 51.0 | 19.2 |
Au-based catalyst (GLY/Au ratio 3500 mol/mol) | |||||||
40 | 4 | 0.3 | - | 69.8 | 0.019 | 52.3 | 31.3 |
60 | 4 | 0.3 | - | 89.8 | 0.057 | 55.6 | 24.7 |
80 | 4 | 0.3 | - | 99.6 | 0.058 | 56.4 | 15.0 |
100 | 4 | 0.3 | - | 100 | 0.210 | 21.4 | 14.7 |
60 | 0 | 0.3 | - | 0 | 0 | - | - |
60 | 2 | 0.3 | - | 94.0 | 0.104 | 59.1 | 25.3 |
60 | 6 | 0.3 | - | 87.1 | 0.030 | 69.9 | 18.3 |
40 | 4 | 0.1 | - | 55.0 | 0.017 | 56.0 | 29.5 |
40 | 4 | 0.5 | - | 95.8 | 0.033 | 53.4 | 28.5 |
60 | 4 | 0.1 | - | 99.9 | 0.132 | 54.1 | 22.2 |
60 | 4 | 0.1 | 0.1 Glyceric acid | 88.6 | 0.024 | 10.1 | 12.8 |
60 | 4 | 0.1 | 0.1 Tartronic acid | 94.6 | 0.082 | 62.3 | 11.3 |
60 | 4 | 0.3 | 0.1 Glycolic acid | 87.4 | 0.052 | 61.2 | 20.4 |
60 | 4 | 0.1 | 0.1 Formic acid | 100 | 0.140 | 42.1 | 23.7 |
r2 = 0.9729 | ||
---|---|---|
Parameter a | Estimate ± σ/1%σ| | t-Test b/Meaningful? |
−9.65 ± 0.11/1.14% | 87.64 > 1.96/YES | |
35.58 ± 0.51/1.43% | 69.72 > 1.96/YES | |
−7.31 ± 0.05/0.69% | 146.2 > 1.96/YES | |
27.35 ± 0.34/1.24% | 80.44 > 1.96/YES | |
−9.74 ± 0.10/0.98% | 97.40 > 1.96/YES | |
30.13 ± 0.20/0.67% | 150.65 > 1.96/YES | |
5.87 ± 0.13/2.14% | 45.15 > 1.96/YES | |
−1.99 ± 0.27/13.65% | 7.37 > 1.96/YES | |
3.60 ± 0.13/3.57% | 27.69 > 1.96/YES | |
3.26 ± 0.48/14.82% | 6.79 > 1.96/YES | |
5.09 ± 0.13/2.46% | 39.15 > 1.96/YES | |
−10.38 ± 0.30/2.93% | 34.6 > 1.96/YES | |
2.69 ± 0.18/6.83% | 14.94 > 1.96/YES | |
−0.91 ± 0.59/64.49% | 1.54 > 1.96/NO | |
2.95 ± 0.13/4.43% | 22.69 > 1.96/YES | |
−19.56 ± 0.22/1.14% | 88.91 > 1.96/YES | |
4.99 ± 0.08/1.62% | 62.37 > 1.96/YES | |
−12.34 ± 0.45/3.63% | 27.42 > 1.96/YES | |
3.86 ± 0.07/1.77% | 55.14 > 1.96/YES | |
−3.14 ± 0.19/6.10% | 16.53 > 1.96/YES |
Reaction | kj (60 °C) | Activation Energy | |||
Without catalyst | r1 | 6.51 × 10−5 | L/(mol·min) | 99 | kJ/mol |
r3 | 6.69 × 10−4 | 76 | |||
r4 | 5.89 × 10−5 | 83 | |||
Au-based catalyst | r1,cat | 0.39 | mol/(L·g·min) | 57 | kJ/mol |
r2,cat | 5.25 × 10−3 | 52 | |||
r3,cat | 0.18 | 34 | |||
r5,cat | 2.11 × 10−3 | 40 | |||
Adsorption Terms | Kj (60 °C) | Adsorption Enthalpy | |||
Glycerol | 19.11 | L/mol | −54 | kJ/mol | |
Glyceric acid | 146.94 | −34 | |||
OH− | 47.46 | −9 |
Catalyst | (kJ/mol) a | Reference |
---|---|---|
Au/Al2O3 | 57 | This work |
Au/C | 50 b | [20] |
Pt-Bi/C | 67 | [3] |
Catalyst | Metal Loading (wt %) | Main Au Particle Diameter 1 (nm) | Theoretical Dispersion (%) |
---|---|---|---|
Au/Al2O3 | 0.98 | 4.7 ± 2.6 | 30 |
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Díaz, J.A.; Skrzyńska, E.; Girardon, J.-S.; Capron, M.; Dumeignil, F.; Fongarland, P. Glycerol Oxidation in the Liquid Phase over a Gold-Supported Catalyst: Kinetic Analysis and Modelling. ChemEngineering 2017, 1, 7. https://doi.org/10.3390/chemengineering1010007
Díaz JA, Skrzyńska E, Girardon J-S, Capron M, Dumeignil F, Fongarland P. Glycerol Oxidation in the Liquid Phase over a Gold-Supported Catalyst: Kinetic Analysis and Modelling. ChemEngineering. 2017; 1(1):7. https://doi.org/10.3390/chemengineering1010007
Chicago/Turabian StyleDíaz, José Antonio, Elżbieta Skrzyńska, Jean-Sébastien Girardon, Mickaël Capron, Franck Dumeignil, and Pascal Fongarland. 2017. "Glycerol Oxidation in the Liquid Phase over a Gold-Supported Catalyst: Kinetic Analysis and Modelling" ChemEngineering 1, no. 1: 7. https://doi.org/10.3390/chemengineering1010007