1. Biofuels in Brazil “van’t Hoff Institute for Molecular Sciences” Amsterdam, 2007 Prof. Donato Aranda Federal Univ. Rio de Janeiro

2. Energy Mix

3.  1925: First experiments with ethanol/gasoline blends  1975: Ethanol program started after the 1st oil crisis  1989: Leaded Gasoline forbiden.  1993: E-20 to E-25 mandatory in all the country (33,000 gas stations)  2003: Flex Fuel engines  2006: 80% of new vehicles are Flex (2.5 million/year)  615 million ton of CO 2 avoided emissions, so far Ethanol Program in Brazil

4. Sugar Cane Output/Input Energy ~ 8.2* Ethanol production in 2006: 16 billion liters *Goldenberg, J.L.C Renewable Energies, Island Press, 1993

5. Ethanol Plants 313 Ethanol Plants 1 million employees 60,000 agric. producers 5 million ha (0.6 % of Br. area) 89 New plants are being contructed

6. Source: Brazilian Agricultural Ministry Physical Productivity

7. Source: F.O.Licht (in “New trends to the ethanol supply chain in Brazil”, Simoes, R.B., Master Thesis, Universiteit Van Tilburg, Holanda, Jul-2006) Wheat Corn Sugar Beet Sugar Cane (Brazil) Ethanol Energetic Balance Output/Input Energy

8. Sugar Cane Energy 1 mton of Sugar Cane: 1.7 10 3 kcal ~ 1.2 barrel of petroleum Sugar cane bagasse is producing ~ 2,500 MW Breakthrough: ethanol from bagasse and other residual biomass

9. Sugar Cane Energy

10. Basic Biomass Composition Cellulose (40-60%) Cellulose (40-60%) Hemicellulose (20-40%) Hemicellulose (20-40%) Lignin (10-25%) Lignin (10-25%) Hemicellulose convertion to ethanol: Brazilian Patent: Petrobras/UFRJ n o PI0505299-8 (11/2005)

11. Lignin Coniferilic Alcohol Cumaric Alcohol Sinapilic Alcohol

12. Flash Pyrolysis

13. PYROLYSIS OIL ~ 30% Oxygen pH ~ 2 Collaboration with Brem, C. and Brammer, J.G, Twente University Twente University

14. Ethanol/Biodiesel Integration Barralcool (Mato Grosso State) Produces: 100,000 mt/year of Ethanol 50,000 mt/year of Biodiesel

15. Biodiesel Program  B2 mandatory at Jan/2008 (850,000 ton/year)  B5 mandatory at Jan/2010 (2013, originaly) Now:  10 biodiesel plants working (500,000 ton/year)  4,000 gas stations providing B2  Some transportation companies using B30 (More than 2,000 buses)  Projects: More than 100 new biodiesel plants LOW FEDERAL TAXES FOR SOCIAL PROJECTS AND POOR REGIONS

17. Soybean,Tallow,Cotton Palm Castor Sunflower Jatropha Jatropha Canola Babassu Peanut

18. Soybean Biodiesel (Output/input energy ~ 3)* * NREL (USA) http://www.nrel.gov/docs/legosti/fy98/24089.pdf

19. Jatropha curcas Biodiesel Output/Input Energy ~ 5- 6* *Ref: Ouedraogo, 1991

20. Palm Oil Biodiesel

21. Output/Input Energy ~ 8* *Ref: Lor, E.E.S. et al, World Bioenergy http://www.svebio.se/attachments/33/295.pdf

22. Palm -Production Costs US$ 240/ton of oil 5,000 – 8,000 Liters/ha

23. 1 st Biodiesel Plant – Heterogeneous Catalyst/Residual Feedstock (Crude Palm Fatty Acids) Patent:D. A. G. Aranda et al; PI0301103-8, 2003. D. A. G. Aranda et al, WO2004096962, 2004.

24. AGROPALMA: BIODIESEL FROM RESIDUES

25. Esterification Catalysts Esterification Catalysts  Heterogeneous Catalyst  Reusable  Zero Soap  Easy to remove  No neutralization step Nobic Acid (CBMM)

26. HOMO methanol LUMO protonated acid E= -0,264 eV E= -0,230 eV

27. HOMO and LUMO from Alcohols and Glycerides

28. Hydrolysis H 3 C-CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH 2 H 3 C-CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH H 3 C-CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 - CH 2 -COCH 2 O O O H 2 O + Lypases Hydrolysis Industrial Process: 99% conversion: 3 plants in Brazil (Non-catalytic process)

29. Hydroesterification Esterification of Fatty Acids (AGROPALMA ) Industrial Hydrolysis Why don’t integrate these process ??? +

30. TriglycerideFatty Acid FA FA +FA WaterGlycerol Hydroesterification + 3G H2OH2O G 3 FA A A H2OH2O + Fatty Acid Alcohol Biodiesel Water (No acidity restriction in feedstock) Much better with Catalytic Distillation !!

31. Custos Operacionais: Hidroesterificação vs Transesterificação (50,000 mton/year) TransesterificationHydrolysis + Esterification Chemicals (¢/L)41 Energy (¢/L)12 Oper.Costs (¢/L)53 If biodiesel plant is integrated with an ethanol plant, operating costs will be less than 2 ¢/L. No acidity limits in the feedstocks

32. My team:  Postdocs: Luciana Camacho and Ricardo Valdez  Ph D students: Neyda Om, Yordanka Reyes, Gisel Chenard, Immacolata Manco, Rosana Amorim, Marcia Castoldi, Marcelo Tondello, Rafael Monteiro, Elisa Cruz, Anderson Kurunczi  M Sc students: Ana Encarnação, Rafael João, Jussara Gonçalves, Layla Rocha, Luana Rocha, Leonardi Almeida, Carla Pereira, Margarida Castello, Marlon Almeida

33. Thank you ! www.greentec-ufrj.com “ God causes all things to work together for good to those who love Him” ( Rm 8,28)

34. Biodiesel plant 100,000 t/year, oil costs: US$ 250/t and Biodiesel sold at US$ 0.60/L (No incentive scenario) Gross Margin: 30.8% Gross Margin: 24.1 % Gross Margin: 33.3 % a) Regular Transesterification b) Hydroesterification c) Hydroesterification integrated with Ethanol plant