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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