Biodiesel Production by Methanolysis of Rapeseed Oil—Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO)
Abstract
:1. Introduction
2. Results and Discussion
2.1. Transesterification of Vegetable Oil with Methanol Reaction
2.2. Specific Surface Area Measurements of the Catalytic Materials—Brunauer–Emmett–Teller
2.3. Phase Composition Studies of Catalysts
2.4. Basic Properties of the Synthesized Catalyst Systems
2.5. Morphology of the Investigated Catalysts
2.6. Sorption Properties of Investigated Catalysts in Relation to Methanol
3. Materials and Methods
3.1. Preparation of the Catalytic Materials
3.2. Characterization of the Catalytic Material
3.3. Catalytic Activity Measurements in Transesterification of the Vegetable Oil with Methanol
4. Conclusions
Author Contributions
Funding
Data Availability Statement
Acknowledgments
Conflicts of Interest
References
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Catalyst | Reaction Temperature [°C] | Reaction Time [h] | Molar Ratio Methanol/Oil | Calcination Temperature [°C] | Catalyst Weight [g] | Triglycerides Conversion [%] | FAME Yield [%] |
---|---|---|---|---|---|---|---|
BEA (Si/Al = 25) | 180 | 2 | 9:1 | 500 | 0.5 | 33.9 | 3.0 |
220 | 68.7 | 30.0 | |||||
BEA (Si/Al = 300) | 180 | 2 | 9:1 | 500 | 0.5 | 17.5 | 3.1 |
220 | 52.5 | 25.0 | |||||
10% MgO/BEA (Si/Al = 25) | 180 | 2 | 9:1 | 500 | 0.5 | 66.8 | 46.0 |
220 | 69.5 | 55.7 | |||||
10% MgO/BEA (Si/Al = 300) | 180 | 2 | 9:1 | 500 | 0.5 | 63.0 | 29.0 |
220 | 59.7 | 74.4 | |||||
10% CaO/BEA (Si/Al = 25) | 180 | 2 | 9:1 | 500 | 0.5 | 90.4 | 78.2 |
220 | 90.2 | 92.6 | |||||
10% CaO/BEA (Si/Al = 300) | 180 | 2 | 9:1 | 500 | 0.5 | 84.2 | 64.0 |
220 | 90.5 | 94.6 | |||||
10% SrO/BEA (Si/Al = 25) | 180 | 2 | 9:1 | 600 | 0.5 | 80.0 | 74.8 |
220 | 74.4 | 89.6 | |||||
10% SrO/BEA (Si/Al = 300) | 180 | 2 | 9:1 | 600 | 0.5 | 71.4 | 65.4 |
220 | 87.8 | 98.5 |
Catalyst | BET Surface Area (m2/g) | t-Plot Micropore Area (m2/g) | t-Plot External Surface Area (m2/g) | Pore Volume (cm3/g) | t-Plot Micropore Volume (cm3/g) | Average Pore Size (nm) |
---|---|---|---|---|---|---|
10% MgO/BEA (Si/Al = 25) | 305 | 191 | 113 | 0.576 | 0.098 | 9.85 |
10% MgO/BEA (Si/Al = 300) | 314 | 253 | 62 | 0.083 | 0.130 | 3.28 |
10% CaO/BEA (Si/Al = 25) | 346 | 227 | 119 | 0.557 | 0.117 | 8.99 |
10% CaO/BEA (Si/Al = 300) | 326 | 262 | 64 | 0.091 | 0.135 | 3.23 |
10% SrO/BEA (Si/Al = 25) | 401 | 249 | 152 | 0.681 | 0.129 | 8.27 |
10% SrO/BEA (Si/Al = 300) | 404 | 289 | 115 | 0.114 | 0.149 | 2.45 |
Catalyst | Average Size of Oxide Crystallites [nm] |
---|---|
10% MgO/BEA (Si/Al = 25) | MgO = 12 |
10% MgO/BEA (Si/Al = 300) | MgO = 9 |
10% CaO/BEA (Si/Al = 25) | CaO = 16 |
10% CaO/BEA (Si/Al = 300) | CaO = 14 |
10% SrO/BEA (Si/Al = 25) | SrO = 9 |
10% SrO/BEA (Si/Al = 300) | SrO = 13 |
Catalytic Systems | Weak Centers [mmol/g] 100–300 °C | Medium Centers [mmol/g] 300–450 ° C | Strong Centers [mmol/g] 450–600 ° C | Total Basicity [mmol/g] 100–600 ° C |
---|---|---|---|---|
10% MgO/BEA (Si/Al = 25) | 0.10 | 0.28 | 0.64 | 1.03 |
10% MgO/BEA (Si/Al = 300) | 0.55 | 0.49 | 0.61 | 1.65 |
10% CaO/BEA (Si/Al = 25) | 0.24 | 0.41 | 0.58 | 1.22 |
10% CaO/BEA (Si/Al = 300) | 0.57 | 0.69 | 0.67 | 1.93 |
10% SrO/BEA (Si/Al = 25) | 0.15 | 0.38 | 0.57 | 1.10 |
10% SrO/BEA (Si/Al = 300) | 0.21 | 0.37 | 0.40 | 0.99 |
Mobile Phase Gradient | Flow Rate [mL∙min−1] | ||
---|---|---|---|
Time [min] | Solvent A (%) | Solvent B (%) | |
0 | 100 | 0 | 0.9 |
20 | 100 | 0 | 0.9 |
45 | 0 | 100 | 0.9 |
70 | 0 | 100 | 0.9 |
75 | 100 | 0 | 0.9 |
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Szkudlarek, Ł.; Chałupka-Śpiewak, K.; Maniukiewicz, W.; Nowosielska, M.; Szynkowska-Jóźwik, M.I.; Mierczyński, P. Biodiesel Production by Methanolysis of Rapeseed Oil—Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO). Int. J. Mol. Sci. 2024, 25, 3570. https://doi.org/10.3390/ijms25073570
Szkudlarek Ł, Chałupka-Śpiewak K, Maniukiewicz W, Nowosielska M, Szynkowska-Jóźwik MI, Mierczyński P. Biodiesel Production by Methanolysis of Rapeseed Oil—Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO). International Journal of Molecular Sciences. 2024; 25(7):3570. https://doi.org/10.3390/ijms25073570
Chicago/Turabian StyleSzkudlarek, Łukasz, Karolina Chałupka-Śpiewak, Waldemar Maniukiewicz, Magdalena Nowosielska, Małgorzata Iwona Szynkowska-Jóźwik, and Paweł Mierczyński. 2024. "Biodiesel Production by Methanolysis of Rapeseed Oil—Influence of SiO2/Al2O3 Ratio in BEA Zeolite Structure on Physicochemical and Catalytic Properties of Zeolite Systems with Alkaline Earth Oxides (MgO, CaO, SrO)" International Journal of Molecular Sciences 25, no. 7: 3570. https://doi.org/10.3390/ijms25073570