1. Recent progress in the thermocatalytic processing of biomass into advanced biofuels David Serrano Rey Juan Carlos University, IMDEA Energy Institute Biofuels2015, Valencia, August 2015

2. World biofuels production (Mtoe) 2014 figures (BP statistical review of world energy, 2015): Global growth in primary energy consumption: 0.9% Biofuels production growth: 7.4%

3. Negative effects on the food market and prices. Deforestation and land use changes. Environmental impact: uncertain reduction of CO 2 emissions, water consumption. Limits in the proportion they can be incorporated into conventional engines. Production costs: 2-3 times higher than those of petroleum fuels (high cost of both the raw biomass and the conversion process). Hindrances for the commercial deployment of first generation biofuels

4. BP Energy Outlook 2035 (2015): Transport sector sector

5. First generation biofuels

6. Second generation biofuels

7. Biofuels from microorganisms Third generation biofuels Genetic engineering for biofuels production F. Sarkeyeva et al., Photosynth.. Res. 125 (2015) 329-340. Microalgae Macroalgae Oleaginous yeasts Cyanobacteria

8. Production from non-food related raw materials: Lignocellulose, residues, microorganisms. Properties close to those of conventional fossil fuels: low oxygen content, high heat value, preferred as liquids. Deep transformation of the raw biomass resources: integration into biorefineries. Co-production of biofuels and bio-chemicals. Advanced biofuels

9. Horizon 2020 objective: 10% renewable share in the transport sector, with a 5% limit in the contribution of first generation biofuels. “European Biofuels Technology Platform (EBTP)” and “European Industrial Bioenergy Initiative (EIBI): to promote the industry involvement. Minimum of GHG reduction for the new biofuels production facilities: 60%. Effects of land use change must be taken into account. Advanced biofuels must be promoted. EU initiatives for biofuels development

10. Uncertainty in the estimation of lignocellulose resources

11. Potential of lignocellulosic biomass resources in Europe By 2030 about 1/3 of the energy consumed in transport could be covered by the European bioenergy sector. A. Sanna, Bionerg. Res. 7 (2014) 36-47.

12. Plants for advanced biofuel production Transgenic woody plants for biofuel production Genetic modification of forest trees is being investigated to improve their properties: - Fast growing trees. - Higher cellulose content (for bioethanol production) - Improved properties to be grown more widely: insect and herbicide resistance, salt and frost tolerance, etc. Hazards: transfer of the synthetic genes to other plant species, risk for human health. W. Tang et al., J. For. Res. 25(2) (2014) 225-236.

13. Transgenic woody plants for biofuel production Genetic modification of forest trees is being investigated to improve their properties: - Fast growing trees. - Higher cellulose content (for bioethanol production) - Improved properties: insect and herbicide resistance, salt and frost tolerance, etc. Hazards: transfer of the synthetic genes to other plant species, risks for human health. W. Tang et al., J. For. Res. 25(2) (2014) 225-236.

14. Biomass conversion routes into liquid biofuels

15. Lignocellulose conversion routes into biofuels A. Sanna, Bionerg. Res. 7 (2014) 36-47.

16. Main modifications of the biomass components: Oxygen removal Increase of the hydrogen content Improvement of the heat value Depolymerization followed by C- C bonds formation Lignocellusose conversion into advanced biofuels

17. Hydrothermal treatment of biomass (200 – 370ºC, 100 – 200 atm) in aqueous media. Production of a hydrophobic bio-oil: great part of the oxygen is removed by dehydration and decarboxylation reactions. Use of both homogeneous and heterogeneous catalysts. High operation and plant investment costs. Convenient treatment for biomass with high water content, like microalgae. Liquefaction

18. Microalgae liquefaction High bio-oil yield compared to microalgae oil extraction or pyrolysis. No limit in the raw water content. Bio-oil is separated by solvent extraction and evaporation. Enhanced yield if using supercritical conditions. W. Chen et al., Bioresour. Technol. 184 (2015) 314-327.

19. Aqueous phase reforming Moderate reaction conditions. Sequential combination of catalytic steps: interest in multifunctional catalysts. The deoxygenation takes place without external hydrogen supply (in situ production from CO + H 2 O). The lignin fraction is not converted and must be earlier removed by a previous hydrolytic treatment of the lignocellulose.

20. Gasification + Fischer Tropsch Adaptation of the technology initially developed for coal: partial oxidation, leading to syngas (CO and H 2 ). Reaction conditions: T > 800 ºC, using oxygen, air, steam or mixtures as gasifying agent. Use of catalysts in the FT step: mainly Co and Fe containing catalysts. The gaseous stream must be subjected to exhaustive cleaning before the FT step to remove particulates, tars, alkali, nitrogen and sulphur. Novel catalysts have been proposed to reduce tars and coke formation.

21. Gasification + Fischer Tropsch (BTL) Corrosion and fouling of heat exchangers. High complexity and costs (both operation and investment). Scale economy: plants of higher capacity, co-processing.

22. Fixed carbon, volatile material, ash H 2, CO, CO 2, H 2 O, CH 4, C 2 H 2, C 2 H 4 Oxygenated organics, hydrocarbons, water, tars Lignocellolose Biomass Lignin + Cellulose + Hemicellulose Pyrolysis Gas (10-35 %) Bio-oil (10-75 %) Char (10-35 %) Thermal treatment in inert atmosphere. Main parameters: Temperature-time Heating rate Reactor type Biomass pre-treatment Pyrolysis

23. Commercial process of biomass pyrolysis (Joensuu, Finland) Capacity: 50.000 t/y of bio-oil Compared to gasification and liquefaction, pyrolysis is the cheapest technology requiring the lowest capital investment. The produced bio-oil can be competitive even with petroleum-derived fuels provided that biomass is available.

24. Organic compounds in Bio-oils Acids Alcohols Ketones Aldehydes Phenols Guaiacols Syringols Sugars Furans Misc. oxygenates Lignocellulose pyrolysis: bio-oil composition Catalytic bio-oil upgrading

25. Organic compounds in Bio-oils Acids Alcohols Ketones Aldehydes Phenols Guaiacols Syringols Sugars Furans Misc. oxygenates Bio-oil upgrading Catalytic pyrolysis Deoxygenation C-C bond forming reactions

26. Future perspectives and challenges Thermocatalytic processes will play a relevant role in the commercial deployment of advanced biofuels, but this will still require to successfully face a number of challenges. More accurate estimation of the potential of lígnocelllusic resources. Genetic engineering is a powerful tool for improving biofuels-producing microorganisms and woody plants. Liquefaction: new catalysts for conversion of high-water content biomasses. Gasification: co-processing with other materials to reduce costs. Pyrolysis: Improvement of bio-oil properties by catalytic upgrading.

27. Thanks for your kind attention