Glycerol Hydrogenolysis to Produce 1,2-Propanediol in Absence of Molecular Hydrogen Using a Pd Promoted Cu/MgO/Al2O3 Catalyst
Abstract
:1. Introduction
2. Results and Discussion
2.1. Catalyst Screening
2.2. Catalyst Characterization
2.2.1. Temperature Programmed Reduction
2.2.2. X-ray Diffraction
2.2.3. Transmission Electron Microscopy
2.3. Kinetic Analysis
2.4. The Promoting Effect of Pd on Cu/MgO/Al2O3 Catalysts
2.4.1. Effect of Pd Loadings on the Cu/MgO/Al2O3 Catalysts for the Glycerol Hydrogenolysis with In Situ Hydrogen Produced from Methanol Steam Reforming
2.4.2. The Promoting Effect of Pd on Acetol Hydrogenation with Molecular Hydrogen
2.5. Factorial Design Analyses
2.5.1. Effects of Factors on 1,2-PD Selectivity
2.5.2. Effects of Factors on Glycerol Conversion
3. Materials and Methods
3.1. Catalyst Preparation
3.2. Catalyst Characterization
3.3. Catalyst Activity Test
3.4. Fractional Factorial Design and Analyses
- Ei—Effect of single factor i
- Ri—Response at factor i level (+/−)
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Conflicts of Interest
Appendix A. Factorial Design Analysis
Exp# | Glycerol Conversion % | Selectivities % | ||||
---|---|---|---|---|---|---|
1,2-PD | Acetol | EG | Propanol | Others | ||
17 | 96.2 | 81.7 | 0.7 | 8.5 | 0.7 | 8.3 |
18 | 95.3 | 80.7 | 1.1 | 8.1 | 1.2 | 8.9 |
19 | 98.2 | 82.1 | 0.6 | 9.3 | 0.2 | 7.8 |
20 | 98.8 | 81.5 | 0.5 | 8.3 | 0.2 | 9.5 |
mean | 97.1 | 81.5 | 0.7 | 8.6 | 0.6 | 8.6 |
SD a | 1.7 | 0.6 | 0.3 | 0.5 | 0.5 | 0.7 |
CoV b | 0.02 | 0.01 | 0.4 | 0.1 | 0.8 | 0.1 |
Factors | DF | Effect | SS | MS | f-Value a | p-Value b |
---|---|---|---|---|---|---|
A | 1 | −8.9 | 315.95 | 315.95 | 4.48 | 0.058 |
B | 1 | 12. 9 | 664.35 | 664.35 | 9.42 | 0.011 |
C | 1 | −27.9 | 3122.02 | 3122.02 | 44.27 | 0.000 |
D | 1 | 8.1 | 261.63 | 261.63 | 3.71 | 0.080 |
E | 1 | −1.7 | 11.06 | 11.06 | 0.16 | 0.700 |
F | 1 | 7.0 | 193.91 | 193.91 | 2.75 | 0.126 |
G | 1 | 5.6 | 127.13 | 127.13 | 1.8 | 0.206 |
Curvature | 1 | |||||
Error | 11 | 775.78 | 70.53 | |||
Total | 19 | 6110.83 |
Factors | DF | Effect | SS | MS | f-Value a | p-Value b |
---|---|---|---|---|---|---|
A | 1 | 21.0 | 1761.90 | 1761.90 | 25.11 | 0.000 |
B | 1 | 8.6 | 296.70 | 296.70 | 4.23 | 0.000 |
C | 1 | −1.1 | 4.73 | 4.73 | 0.07 | 0.064 |
D | 1 | 9.0 | 326.71 | 326.71 | 4.66 | 0.800 |
E | 1 | 5.9 | 141.02 | 141.02 | 2.01 | 0.054 |
F | 1 | −6.6 | 172.27 | 172.27 | 2.46 | 0.184 |
G | 1 | −3.4 | 45.90 | 45.90 | 0.65 | 0.145 |
Curvature | 1 | |||||
Error | 11 | 771.79 | 70.16 | |||
Total | 19 | 3870.04 |
Appendix B. Calculation of Kinetic Parameters for Glycerol Hydrogenolysis to 1,2-PD and Glycerol C–C Cleavage to EG with Molecular Hydrogen
(a) | |
---|---|
Reaction | Rate expression |
Glycerol dehydration | |
Glycerol C-C cleavage | |
(b) | |
Compound | Rate expression |
Glycerol | |
1,2-PD | |
EG |
Temperature °C | Conversion, % | Selectivity, % | Rate Constant, s−1 | ||||
---|---|---|---|---|---|---|---|
Glycerol | 1,2-PD | Acetol | EG | Others | k1 | k2 | |
180 | 42.9 | 90.0 | 0.0 | 9.3 | 0.7 | 9.72 × 10−6 | 1.32 × 10−6 |
200 | 83.9 | 89.6 | 0.5 | 9.0 | 0.8 | 3.61 × 10−5 | 4.34 × 10−6 |
220 | 100.0 | 86.1 | 0.5 | 9.2 | 3.5 | 9.26 × 10−5 | 1.38 × 10−5 |
Acetol Conversion (%) | 1,-2PD Selectivity (%) | Others Selectivity (%) | k0’ (s-1 gcat−1) | |
---|---|---|---|---|
2% Pd-200 °C | 100.0 | 95.3 | 4.7 | 9.854 × 10−4 |
2% Pd-180 °C | 100.0 | 97.4 | 2.6 | 3.974 × 10−4 |
2% Pd-160 °C | 100.0 | 98.7 | 1.3 | 3.168 × 10−4 |
Pre-Exponential Factor | Activation Energy kJ/mol | |
---|---|---|
Glycerol dehydration | 1.10 × 107 | 104.85 |
Glycerol C–C cleavage | 5.8 × 106 | 108.97 |
Acetol Hydrogenation | 0.092 | 18.81 |
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Entry | Catalysts | Conversion | Selectivity | ||||
---|---|---|---|---|---|---|---|
% | % | ||||||
Glycerol | 1,2-PD | Acetol | EG | Propanol | Others | ||
1 | Cu/ZnO/ZrO2 | 75.2 | 57.3 | 13.7 | 3.7 | 0.7 | 24.6 |
2 | Cu/ZrO2/Al2O3 | 59.1 | 52.9 | 20.6 | 5.2 | 0.8 | 20.5 |
3 | Cu/La2O3/Al2O3 | 29.7 | 58.0 | 30.0 | 6.1 | 0.0 | 6.1 |
4 | Cu/ZnO/Al2O3 2 | 87.1 | 70.7 | 6.0 | 3.3 | 0.8 | 19.2 |
5 | 5Ni/Cu/ZnO/Al2O3 2 | 70.0 | 85.5 | 5.0 | 5.0 | 0.9 | 3.7 |
6 | Cu/MgO/Al2O3 | 95.6 ± 3.2 | 79.5 ± 1.19 | 1.0 ± 0.72 | 8.1 ± 0.93 | 0.8 | 10.6 ± 1.72 |
7 | 1Pd/Cu/ZnO/Al2O3 3 | 94.9 | 74.3 | 4.1 | 3.9 | 0.8 | 16.8 |
8 | 1Pd/Cu/MgO/Al2O3 | 97.2 ± 3.2 | 83.4 ± 1.25 | 0.0 | 9.5 ± 1.09 | 0.7 | 6.4 ± 1.04 |
9 | 2Pd/ZnO 3 | 83.0 | 49.7 | 11.6 | 2.9 | 0.0 | 35.8 |
10 | 5Ni/ZnO/Al2O3 2 | 4.8 | 0.0 | 47.9 | 0.0 | 0.0 | 52.1 |
11 | ZnO/MgO/Al2O3 4 | 2.9 | 59.2 | N/A | 29.2 | N/A | N/A |
12 | Cu/MgO | 80.6 | 62.3 | 2.7 | 7.1 | 1.1 | 26.7 |
(a) | |
---|---|
Reaction | Rate Expression |
Glycerol dehydration | |
Acetol hydrogenation | |
Glycerol C–C cleavage | |
(x): molar concentration of each compound (mol L−1) ri: rate of the reaction (mol L−1 s−1 gcat−1) ki: rate constant of each reaction (s−1 gcat−1) | |
(b) | |
Compound | Rate Expression |
Glycerol | |
Acetol | |
1,2-PD | |
EG | |
(i): molar concentration of each compound per g of catalyst (mol L−1) ri: rate of the reaction (mol L−1 s−1 gcat−1) w: weight of catalyst (g) |
Catalyst | k1 (s−1 gcat−1) | k2 (s−1 gcat−1) | k3 (s−1 gcat−1) |
---|---|---|---|
1Pd/Cu/MgO/Al2O3 | 6.850 × 10−5 | 2.752 × 10−3 | 7.707 × 10−6 |
Cu/MgO/Al2O3 | 3.843 × 10−5 | 4.897 × 10−4 | 4.203 × 10−6 |
Catalysts | Conversion | Selectivity | ||||
---|---|---|---|---|---|---|
% | % | |||||
Glycerol | 1,2-PD | Acetol | EG | Propanol | Others | |
Cu/MgO/Al2O3 | 97.4 | 54.9 | 2.0 | 4.5 | 2.1 | 36.4 |
1Pd/Cu/MgO/Al2O3 | 100.0 | 66.8 | 0.7 | 5.5 | 0.7 | 26.3 |
2Pd/Cu/MgO/Al2O3 | 100.0 | 73.2 | 0.4 | 6.6 | 1.4 | 18.4 |
3Pd/Cu/MgO/Al2O3 | 100.0 | 73.6 | 0.4 | 6.6 | 1.2 | 18.2 |
2Pd/Cu/MgO/Al2O3 2 | 100.0 | 85.3 | 0.7 | 7.8 | 0.3 | 5.9 |
Catalysts | Acetol Conversion (%) | 1,2-PD Selectivity (%) | Others Selectivity (%) | k2 (s−1 gcat−1) |
---|---|---|---|---|
Cu/MgO/Al2O3 | 86.8 | 68.6 | 31.5 | 2.262 × 10−4 |
2Pd/Cu/MgO/Al2O3 | 100.0 | 95.3 | 4.7 | 9.854 × 10−4 |
Conditions | Code | −1 | 0 | +1 |
---|---|---|---|---|
Temperature (°C) | A | 200 | 220 | 240 |
Catalyst loading (wt%) | B | 3 | 5 | 7 |
Glycerol feed concentration (wt%) | C | 20 | 30 | 40 |
Pd loading (wt%) | D | 0 | 1 | 2 |
Stirring Speed (RPM) | E | 400 | 500 | 600 |
Nitrogen Pressure (bar) | F | 15 | 25 | 35 |
Water/Methanol (molar) | G | 1 | 1.2 | 1.4 |
Exp | A | B | C | D | E = ABC | F = BCD | G = ACD |
---|---|---|---|---|---|---|---|
1 | −1 | −1 | −1 | −1 | −1 | −1 | −1 |
2 | 1 | −1 | −1 | −1 | 1 | −1 | 1 |
3 | −1 | 1 | −1 | −1 | 1 | 1 | −1 |
4 | 1 | 1 | −1 | −1 | −1 | 1 | 1 |
5 | −1 | −1 | 1 | −1 | 1 | 1 | 1 |
6 | 1 | −1 | 1 | −1 | −1 | 1 | −1 |
7 | −1 | 1 | 1 | −1 | −1 | −1 | 1 |
8 | 1 | 1 | 1 | −1 | 1 | −1 | −1 |
9 | −1 | −1 | −1 | 1 | −1 | 1 | 1 |
10 | 1 | −1 | −1 | 1 | 1 | 1 | −1 |
11 | −1 | 1 | −1 | 1 | 1 | −1 | 1 |
12 | 1 | 1 | −1 | 1 | −1 | −1 | −1 |
13 | −1 | −1 | 1 | 1 | 1 | −1 | −1 |
14 | 1 | −1 | 1 | 1 | −1 | −1 | 1 |
15 | −1 | 1 | 1 | 1 | −1 | 1 | −1 |
16 | 1 | 1 | 1 | 1 | 1 | 1 | 1 |
17 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
18 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
19 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
20 | 0 | 0 | 0 | 0 | 0 | 0 | 0 |
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Liu, Y.; Wu, M.; Rempel, G.L.; Ng, F.T.T. Glycerol Hydrogenolysis to Produce 1,2-Propanediol in Absence of Molecular Hydrogen Using a Pd Promoted Cu/MgO/Al2O3 Catalyst. Catalysts 2021, 11, 1299. https://doi.org/10.3390/catal11111299
Liu Y, Wu M, Rempel GL, Ng FTT. Glycerol Hydrogenolysis to Produce 1,2-Propanediol in Absence of Molecular Hydrogen Using a Pd Promoted Cu/MgO/Al2O3 Catalyst. Catalysts. 2021; 11(11):1299. https://doi.org/10.3390/catal11111299
Chicago/Turabian StyleLiu, Yuanqing, Michael Wu, Garry L. Rempel, and Flora T.T. Ng. 2021. "Glycerol Hydrogenolysis to Produce 1,2-Propanediol in Absence of Molecular Hydrogen Using a Pd Promoted Cu/MgO/Al2O3 Catalyst" Catalysts 11, no. 11: 1299. https://doi.org/10.3390/catal11111299