Prof. Victor Teixeira da Silva, Federal University of Rio de Janeiro, Brazil Dibanet Networking event (FP7 project) 31 October 2013 CERTH, Thessaloniki, Greece Further info and videos: http://www.dibanet.org/networking_day_greece.php

1. 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

2. Residual Biomass Transformations
Residual Biomass
Hemicellulose, Cellulose
Pentoses Hexoses
(Xylose) (Glucose, Fructose, Mannose)
H+ - H2O H+ - H2 O
Furfural 5-Hydroxymethylfurfural (HMF)
H2O, H+
Levulinic acid

3. Levulinic acid as a platform molecule
Corma, Iborra and Velty, Chem. Rev. 2007, 107, 2411-2502

4. Levulinic acid as a platform molecule
• Food industry (flavors)
• Solvents
• Plasticizers
• Diesel Miscible Biofuel

5. Levulinic acid as a platform molecule
• Food industry (flavors)
• Solvents
• Plasticizers
• Diesel Miscible Biofuel
www.dibanet.org

6. Ethyl levulinate synthesis
T = 343 K
t=5h
2.5 wt.% of catalyst
EtOH/LvAc = 5/1
2411
747
1867
2181
2414
2360
1167
892
584
429
342
D.R. Fernandes et al. Applied Catalysis A: General 425– 426 (2012) 199– 204

7. Sulfated stania

8. Catalyst synthesis
Solubilization
leading 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.

9. Catalyst synthesis
Arata, App. Catal. A 1996, 146, 3-32.
Matsuhashi, Miyazaki, Kawamura, Nakamura, Arata, Chem. Mater. 2001, 13, 3038-3042.

10. Catalyst characterization - XRD

11. Catalyst characterization - Raman

12. Catalyst characterization – N2
physisorption
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

13. Characterization – SEM

14. 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

15. Catalyst characterization – NH3 TPD
4.4 μmol m-2
6.0 μmol m-2
6.9 μmol m-2
m/z = 15 signal / A. U.
8.4 μmol m-2
7.2 μmol m-2
7.3 μmol m-2
Temperature / oC

16. Modification of the sulfur incorporation

17. Characterization – N2 physisorption

18. Characterization – XRD

19. Characterization – XRD

20. Catalytic activity T = 343 K
t=5h
2.5 wt.% of catalyst
EtOH/LvAc = 5/1

21. Catalytic activity T = 343 K
t=5h
2.5 wt.% of catalyst
EtOH/LvAc = 5/1

22. Catalytic activity T = 343 K
t=5h
2.5 wt.% of catalyst
EtOH/LvAc = 5/1

23. Reusability – Amberlyst 15

24. Reusability – GIA-5%

25. Reusability – GIA-5%

26. Reusability – GIA-5%

27. Conclusions
• For sulfated solid oxide catalyts there is a correlation between the
total acidity and activity;

28. 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;

29. 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.

30. 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.

31. 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.

32. Acknowledgments
Thanks for your
attention!
ευχαριστώ!

33. Back-up slides