Understanding of the Key Factors Determining the Activity and Selectivity of CuZn Catalysts in Hydrogenolysis of Alkyl Esters to Alcohols
Abstract
:1. Introduction
2. Results
2.1. Physico-Chemical Characterization
2.1.1. Chemical Analysis
2.1.2. XRD Study
2.1.3. Catalyst Surface Area
2.1.4. TPD of Adsorbed CO2 and NH3
2.1.5. Specific Copper Surface Area
2.2. Catalysis
2.2.1. The Hydrogenolysis of Methyl Hexanoate (MeHe) in Presence of CuZn-R Catalysts Varied in Cu/Zn Ratio
2.2.2. The Hydrogenolysis of Hexyl Hexanoate in Presence of CuZn-R Catalysts with Different Cu/Zn Ratio
2.2.3. The Stability of CuZn Catalysts in Repeating Reaction Cycles
2.2.4. The Hydrogenolysis of Methyl Esters with the Different Length of Carbon Chain
3. Materials and Methods
3.1. Preparation of Catalysts
3.2. Catalyst Characterization
3.3. Catalyst Testing
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Sample | As-Prepared Samples | Calcined Samples | Spent Catalysts | |||||
---|---|---|---|---|---|---|---|---|
Targeted Cu/Zn Ratio | CuO by XRF, wt.% | ZnO by XRF, wt.% | Cu/Zn Ratio by XRF | BET Surface Area, m2·g−1 | Pore Volume, cm3·g−1 | BET Surface Area, m2·g−1 | Pore Volume, cm3·g−1 | |
0.5CuZn 1CuZn 3CuZn 6CuZn | 0.5 1 3 6 | 35.2 51.4 75.8 85.9 | 64.8 48.6 24.2 14.1 | 0.54 1.05 3.12 6.08 | 59 61 64 60 | 0.23 0.26 0.26 0.25 | 53 46 34 16 | 0.22 0.19 0.15 0.04 |
Sample | Number of Acid Sites, mmol·g−1 | Number of Basic Sites, mmol·g−1 |
---|---|---|
0.5CuZn-C 1CuZn-C 3CuZn-C 6CuZn-C | 0.135 0.136 0.168 0.151 | 0.176 0.187 0.237 0.190 |
Sample | CuO Content (wt.%) by XRF | Consumed H2 (mmol·g−1) | CuO Content (wt.%) Calculated from Adsorbed H2 | SCu, m2·gcat−1 | SCu, m2·gCu−1 | Cu Dispersion, % |
---|---|---|---|---|---|---|
0.5CuZn-C 1CuZn-C 3CuZn-C 6CuZn-C | 35.2 51.4 75.8 85.9 | 4.62 7.03 10.10 11.42 | 36.8 55.9 80.4 90.9 | 14.0 15.1 15.1 11.9 | 50 37 25 17 | 3.65 2.73 1.85 1.29 |
Catalyst | MeHe Hydrogenolysis | HeHe Hydrogenolysis | TOFMeHe/ TOFHeHe | ||
---|---|---|---|---|---|
Initial Reaction Rate, rini (nMeHe·gcat−1·min−1) | TOF × 10−2 (s−1) | Initial Reaction Rate, rini (nHeHe·gcat−1·min−1) | TOF × 10−2 (s−1) | ||
0.5CuZn-R 1CuZn-R 3CuZn-R 6CuZn-R | 1.83 2.49 3.23 2.70 | 2.0 2.5 3.3 3.5 | 1.99 2.70 2.49 1.49 | 2.2 2.5 2.8 1.9 | 0.9 0.9 1.3 1.8 |
Sample | ZnO Content in Catalysts, g | HeHe Yield (%) after 40 min | Formation Rate, mmolHeHe·gcat−1·min−1 | Corrected Formation Rate, mmolHeHe·gZnO−1·min−1 |
---|---|---|---|---|
ZnO 0.5CuZn-R 1CuZn-R 3CuZn-R 6CuZn-R | 0.75 0.97 0.72 0.36 0.20 | 4.45 1.40 1.46 1.89 3.61 | 0.82 0.13 0.13 0.17 0.33 | 0.82 0.20 0.28 0.73 2.43 |
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Kikhtyanin, O.; Aubrecht, J.; Pospelova, V.; Kubička, D. Understanding of the Key Factors Determining the Activity and Selectivity of CuZn Catalysts in Hydrogenolysis of Alkyl Esters to Alcohols. Catalysts 2021, 11, 1417. https://doi.org/10.3390/catal11111417
Kikhtyanin O, Aubrecht J, Pospelova V, Kubička D. Understanding of the Key Factors Determining the Activity and Selectivity of CuZn Catalysts in Hydrogenolysis of Alkyl Esters to Alcohols. Catalysts. 2021; 11(11):1417. https://doi.org/10.3390/catal11111417
Chicago/Turabian StyleKikhtyanin, Oleg, Jaroslav Aubrecht, Violetta Pospelova, and David Kubička. 2021. "Understanding of the Key Factors Determining the Activity and Selectivity of CuZn Catalysts in Hydrogenolysis of Alkyl Esters to Alcohols" Catalysts 11, no. 11: 1417. https://doi.org/10.3390/catal11111417