Solid Acid Catalysts for Biomass Transformations
A.S. Rocha, D. R. Fernandes, T. Firmino, E. F. Mai, B. L. Oliveira, and V. Teixeira da Silva
Thessaloniki, 31st October 2012
Residual Biomass Transformations
Residual Biomass
Hemicellulose, Cellulose
Pentoses(Xylose)
Hexoses(Glucose, Fructose, Mannose)
Furfural 5-Hydroxymethylfurfural (HMF)
Levulinic acid
H+ - H2O H+ - H2O
H2O, H+
Levulinic acid as a platform molecule
Corma, Iborra and Velty, Chem. Rev. 2007, 107, 2411-2502
• Food industry (flavors)• Solvents• Plasticizers• Diesel Miscible Biofuel
Levulinic acid as a platform molecule
• Food industry (flavors)• Solvents• Plasticizers• Diesel Miscible Biofuel
www.dibanet.org
Levulinic acid as a platform molecule
Ethyl levulinate synthesis
23601167
892584429342
2411747
186721812414
D.R. Fernandes et al. Applied Catalysis A: General 425– 426 (2012) 199– 204
T = 343 Kt = 5 h
2.5 wt.% of catalystEtOH/LvAc = 5/1
Sulfated stania
Catalyst synthesis
Solubilizationleading to a low yield of the dried gel
Arata, App. Catal. A 1996, 146, 3-32.Matsuhashi, Miyazaki, Kawamura, Nakamura, Arata, Chem. Mater. 2001, 13, 3038-3042.
Catalyst synthesis
Arata, App. Catal. A 1996, 146, 3-32.Matsuhashi, Miyazaki, Kawamura, Nakamura, Arata, Chem. Mater. 2001, 13, 3038-3042.
Catalyst characterization - XRD
Catalyst characterization - Raman
Catalyst characterization – N2physisorption
Sample Sg / m2 g-1
SnO2 40
SO4-2/ SnO2 (1M) 108
SO4-2/ SnO2 (2M) 120
SO4-2/ SnO2 (3M) 130
SO4-2/ SnO2 (4M) 140
SO4-2/ SnO2 (5M) 148
Characterization – SEM
Catalyst characterization - XRF
Sample %SO3 % SnO2 % Cl
SnO2 0.004 99.902 0.094
SO4/SnO2 (1M) 4.503 95.478 0.019
SO4/SnO2 (2M) 5.046 94.921 0.033
SO4/SnO2 (3M) 5.309 94.659 0.032
SO4/SnO2 (4M) 5.280 94.660 0.059
SO4/SnO2 (5M) 5.025 94.926 0.046
Catalyst characterization – NH3 TPD
Temperature / oC
m/z
= 1
5 si
gnal
/ A
. U.
4.4 μmol m-2
6.0μmol m-2
6.9μmol m-2
8.4μmol m-2
7.2μmol m-2
7.3μmol m-2
Modification of the sulfur incorporation
Characterization – N2 physisorption
Characterization – XRD
Characterization – XRD
Catalytic activity T = 343 Kt = 5 h
2.5 wt.% of catalystEtOH/LvAc = 5/1
Catalytic activity T = 343 Kt = 5 h
2.5 wt.% of catalystEtOH/LvAc = 5/1
Catalytic activity T = 343 Kt = 5 h
2.5 wt.% of catalystEtOH/LvAc = 5/1
Reusability – Amberlyst 15
Reusability – GIA-5%
Reusability – GIA-5%
Reusability – GIA-5%
Conclusions
• For sulfated solid oxide catalyts there is a correlation between the total acidity and activity;
Conclusions
• For sulfated solid oxide catalyts there is a correlation between the total acidity and activity;
• For zeolites the pore structure seems to play a more important role than the total acidity;
Conclusions
• For sulfated solid oxide catalyts there is a correlation between the total acidity and activity;
• For zeolites the pore structure seems to play a more important role than the total acidity;
• Sulfated stania presents a good activity in levulinic acid esterification but undergoes deactivation. Changing the washing procedure it ispossible to reuse the catalyst.
Conclusions
• For sulfated solid oxide catalyts there is a correlation between the total acidity and activity;
• For zeolites the pore structure seems to play a more important role than the total acidity
• Sulfated stania presents a good activity in levulinic acid esterification but undergoes deactivation. Changing the washing procedure it is possible to reuse the catalyst.
• Amberlyst-15, a commercial available resin is active and stable in the liquid phase levulinic acid esterification with ethanol.
Acknowledgments
This work was performed within the DIBANET Network, a project within the European Community’s Seventh Framework Programme (FP7/2007-2013) under grant agreement no: 227248-2.
Acknowledgments
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