Javier Fermoso 1, Héctor Hernando 1, Ángel Peral 2, Prabhas Jana 1, Thangaraju M. Sankaranarayanan 1, Patricia Pizarro 1,2, Juan M. Coronado 1, David P. Serrano 1,2 1 Thermochemical Processes Unit, IMDEA Energy Institute, 28935, Móstoles, Madrid, Spain 2 Chemical and Environmental Engineering Group, ESCET, Rey Juan Carlos University, 28933, Móstoles, Madrid, Spain. International Congress and Expo on Biofuels & Bioenergy Rey Juan Carlos University (Madrid-Spain)

CxHyOzCxHyOz BIOMASS CO CO 2 H 2 C 1 -C 3 GAS (10-30 wt.%) CHAR (10-35 wt.%) BIO-OIL (10-75 wt.%) Cellulose Hemicellulose Lignin Reaction Conditions: Temperature Heating rate Vapors residence time … (≈ 500 ºC) ( K/s) (≈ 1-2 sg) PYROLYSIS “Fast-Pyrolysis” Pyrolysis : reaction and products

Bio-oil properties:  High water content (≈ 25 wt.%)  High oxygen content (≈ 50 wt.%)  Low HHV (≈ 17 MJ/kg)  High acidity (pH = 2.5)  Low stability … ACIDS PHENOLS FURANS ALDEHYDES ALCOHOLS KETONES SUGARS BIOMASS CATALYTIC PYROLYSIS (I) CATALYTIC HDO (III) INTERMEDIATE DEOXYGENATION (II) BIO-OIL UPGRADED BIO-OIL

Objective: Objective: Study of the in-situ upgrading of fast-pyrolysis bio-oil from eucalyptus woodchips using metal oxide/h-ZSM-5 catalysts: Nanostructured materials with high accessibility Mild acid properties: avoid excessive coking Oxygen removal: decarboxylation BIOMASS CATALYTIC HDO (III) INTERMEDIATE DEOXYGENATION (II) BIO-OIL UPGRADED BIO-OIL CATALYTIC PYROLYSIS (I) o h-ZSM-5 o 10%MgO/h-ZSM-5 o 10%ZnO/h-ZSM-5 o 1%Pd/h-ZSM-5

Synthesis and characterization of catalysts S ILANIZATION OF ZEOLITIC UNITS TEOS (silica source) TPAOH (Structure directing agent) AIP (Aluminium source) h-ZSM-5 PHAPTMS (Silanization agent) 2 STEPS W ET I MPREGNATION (10 WT % M E O X ) S YNTHESIS OF SUPPORT M ETAL INCORPORATION Support Ethanol + M(NO 3 ) 2, M=Mg, Zn C ALCINATION 450 º C, 6 H, AIR C ALCINATION 450 º C, 6 H, AIR C HARACTERIZATION TECHNIQUES XRD: Crystallinity Ar (87K) physisorption: Textural properties TEM: Morphology & pore structure ICP-OES: chemical compositionNH 3 -TPD: acidity measurements

Experimental fast-pyrolysis lab-scale setup Furnace 1 Furnace 2 Non-catalytic zone N 2 /GAS (H 2, CO, CO 2, C 1 -C 3 ) MFC 1 N Nml/min BIO-OIL condensation system Reactor BIO-OIL ≈ 0-4ºC N2N2 N Nml/min MFC 2 Thermocouples (non-catalytic and catalytic zones) CATALYST BED CHAR Biomass tank purge valve Biomass tank Biomass feeding valve N 2 /Air

Reaction conditions: Temperature: 500ºC Pressure: 1 atm N 2 flow rate: 100 Nml/min Biomass fed: ≈ 5 gr Catalyst bed: 1 gr Eucalyptus woodchips (0.5-1 mm) Biomass: Eucalyptus woodchips (EU) Experimental conditions for pyrolysis tests Fast-pyrolysis - Non-catalytic Catalytic(h-ZSM-5) h-ZSM-5 10%MgO/h-ZSM-5 10%ZnO/h-ZSM-5 1%Pd/h-ZSM-5 SampleH2OH2O Proximate Analysis (db, wt.%)Ultimate Analysis (daf, wt.%) HHV (MJ/kg) Volatile matter Ash Fixed Carbon CHNO EU db: dry basis daf: dry, ash free basis

Catalysts characterization Catalysts physico-chemical properties Ar (87K) adsorption-desorptionNL-DFT pore size distribution MFI micropores Secondary porosity CatalystSi/Al MeO/Pd loading (wt.%) S BET (m 2 /g) S MESO+EXT (m 2 /g) S MICRO (m 2 /g) Total acidity (mmol NH3 /g) Total basicity (mmol CO2 /g) h-ZSM ,3600,018 10%MgO/h-ZSM-5-8, ,6600,219 10%ZnO/h-ZSM-5-9, ,7040,030 NH 3 -TPD NH 3 desorbed x 10 3 (a.u.)

Catalysts characterization XRD analysis MgO/h-ZSM-5 ZnO/h-ZSM-5 h-ZSM nm 50 nm 500 nm TEM analysis Metal oxides not detected in the XRD patterns neither in TEM micrographs High dispersion into the support leading to very small particles Partial ion exchange of protons of the support by Mg 2+ and Zn 2+ cations?

Catalysts characterization Ar (87K) adsorption-desorption TEM analysis CatalystSi/Al MeO/Pd loading (wt.%) S BET (m 2 /g) S MESO+EXT (m 2 /g) S MICRO (m 2 /g) Total acidity (mmol NH3 /g) Total basicity (mmol CO2 /g) h-ZSM ,3600,018 1%Pd/h-ZSM-5-1, Pd/h-ZSM nm

Mass yield of fast-pyrolysis products (Bio-oil*: bio-oil in water free basis) Gas (from 12 to wt.%) Decarboxylation (- CO 2 ) Decarbonylation (- CO) Cracking 3 wt.% Dehydration (- H 2 O) Bio-oil * : Non-catalytic 42 wt% > wt% Catalytic Activity tests

Deoxygenation selectivity Pd promotes decarbonylation Removal of Brönsted sites beneficial for reducing decarbonylation ZnO promotes water was shift reaction Activity tests

Bio-oil phases distribution Activity tests

Van Krevelen diagram NON-CATALYTIC EU CRUDE OIL HHV (MJ/kg) Activity tests

Quantity vs quality… Dehydration (- H 2 O) Decarboxylation (- CO 2 ) Decarbonylation (- CO) HHV (MJ/kg bio-oil* ) ENERGY YIELD: - COKE (4-6%) - Hydrocarbons (2.5-4 %) Activity tests

Bio-oil composition Activity tests

o The use of zeolitic catalysts reduces the bio-oil yield (in a water free basis) due to the oxygen removal as the bio-oil undergoes extensive deoxygenation over the catalyst, which in turn implies an improvement of its quality as fuel. o Using the zeolitic catalysts, large amounts of both oxygenated aromatic compounds and aromatic hydrocarbons are produced due to the extensive conversion of sugar derivatives and furans. o Very high dispersions have been achieved by wet impregnation of MgO, ZnO and Pd over h- ZSM-5 zeolite. o The incorporation of Mg and Zn phases causes strong changes in both the surface area and the acid-base properties of the zeolite, suppressing in a great extension the Brönsted acidity. o Pd/h-ZSM-5 exhibits the poorest performance by promoting the decarbonylation of pyrolysis vapours. o MgO moderates the formation of aromatic hydrocarbons in favor of oxygenated aromatics due to the reduction caused by these metals in the concentration of strong zeolitic acid sites.

The authors gratefully acknowledge the financial support from the European Union Seventh Framework Programme (FP7/ ) under grant agreement n° Thermochemical Processes Unit David Serrano Juan M. Coronado Prabhas Jana T. M. Sankaranarayanan Inés Moreno Javier Fermoso Antonio Berenguer Héctor Hernando Sergio Jiménez Technicians: Laura García Marís Eugenia Ana Mª Fernández Fernando Pico URJC Ángel Peral María Linares Special Thanks to:

Javier Fermoso 1, Héctor Hernando 1, Ángel Peral 2, Prabhas Jana 1, Thangaraju M. Sankaranarayanan 1, Patricia Pizarro 1,2, Juan M. Coronado 1, David P. Serrano 1,2 1 Thermochemical Processes Unit, IMDEA Energy Institute, 28935, Móstoles, Madrid, Spain 2 Chemical and Environmental Engineering Group, ESCET, Rey Juan Carlos University, 28933, Móstoles, Madrid, Spain. International Congress and Expo on Biofuels & Bioenergy