Solid Acid Catalysts for Biomass Transformations

A.S. Rocha, D. R. Fernandes, and V. Teixeira da Silva

T.

Firmino,

E.

F.

Mai,

B.

L.

Oliveira,

Thessaloniki, 31st October 2012

Residual Biomass Transformations

Residual Biomass

Hemicellulose, Cellulose Pentoses (Xylose)

H+ - H2O

Hexoses (Glucose, Fructose, Mannose)

H+ - H2O

Furfural

5-Hydroxymethylfurfural (HMF)
H2O, H+

Levulinic acid

Levulinic acid as a platform molecule

Corma, Iborra and Velty, Chem. Rev. 2007, 107, 2411-2502

Levulinic acid as a platform molecule

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

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

Sulfated stania

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.

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 N2 physisorption

Sample

Sg / m2 g-1

SnO2
SO4-2/ SnO2 (1M)

40
108

SO4-2/ SnO2 (2M) SO4-2/ SnO2 (3M)

SO4-2/ SnO2 (4M) SO4-2/ SnO2 (5M)

120 130
140 148

Characterization SEM

Catalyst characterization - XRF

Sample

%SO3

% SnO2

% Cl

SnO2
SO4/SnO2 (1M) SO4/SnO2 (2M) SO4/SnO2 (3M) SO4/SnO2 (4M)

0.004
4.503 5.046 5.309 5.280

99.902
95.478 94.921 94.659 94.660

0.094
0.019 0.033 0.032 0.059

SO4/SnO2 (5M)

5.025

94.926

0.046

Catalyst characterization NH3 TPD

4.4 mol m-2 6.0 mol m-2

m/z = 15 signal / A. U.

6.9 mol m-2 8.4 mol m-2 7.2 mol m-2 7.3 mol m-2

Temperature / oC

Modification of the sulfur incorporation

Characterization N2 physisorption

Characterization XRD

Characterization XRD

Catalytic activity

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

Catalytic activity

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

Catalytic activity

T = 343 K t=5h 2.5 wt.% of catalyst EtOH/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 is possible 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 Communitys Seventh Framework Programme (FP7/2007-2013) under grant agreement no: 227248-2.

Acknowledgments

Thanks for your attention! !

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