Ferenc Lónyi

1. Studies of the Catalytic Conversions of Bio-Oils Obtained by Pyrolytic Decomposition of Non-Edible Biomaterials Ferenc Lónyi Institute of Materials and Environmental Chemistry Research Centre for Natural Sciences Hungarian Academy of Sciences

2. Biomass conversion Product Biomass Conversion - Diversity - Seasonal and disseminated occurrence • Near to the location • of biomass generation • Using the best conversion • technology (economy and product requirement) • - Locally used energy (heat or electric) • Transportable energy • Intermediates and chemicals Liquid fuel - biodiesel - ”green” diesel - FT fuel - lower alcohols Produces - vegetable oil - algae oil - energy plants Biological - aerobic and anaerobic fermentation - enzymatic hydrolysis Chemical (catalytic) -transesterification of oils - hydrorefining of oils - processing the products of other conversions, e.g. gasification of pyrolysis oil to H2/CO mixture Pipeline gas - bio-methane • Wastes • - lignocellulosic • - communal • - industrial • animal • by-products • Thermal • - combustion • - gasification • Pyrolysis • (CO2 negative) Electric energy - fuel cell - Gas turbine/generator - Gas engine/generator

3. Pyrolysis Char (~35 wt%) Pyrolysis gas (~65 wt%) Biomass (e.g. Meat and Bone Meal) ~85 %-a condensable Pyrolysis (~450 – 500 0C) Pyrolysis oil • Not suitable as fuel: • relatively low energy density • - chemical instability • corrosivity • immiscible with conventional fuels • environmentally hazardous • emission (e.g. NOx) Reforming is needed!

4. Composition of pyrolysis oils Pyrolysis oil of plant origin (e.g. from agricultural and forestry residues) Pyrolysis oil of animal origin* (e.g. from meat and bone meal (MBM)) C, wt%: 60 H, wt% 7 O, wt% 32 N, wt% 1 ----------------------------------------- Density (kg/dm3): 1.12 Heating value (MJ/kg) 21.3 (Zhang et al., Bioresource Technology 96 (2005) 545 C, wt%: 74 H, wt% 12 O, wt% 5 N, wt% 9 ----------------------------------------- Density (kg/dm3): 0.97 Heating value (MJ/kg) 36.5 • Reforming: • - Catalytic steam reforming to H2/COmixture • Catalytic cracking and decarboxylation • Catalytic esterification • Reforming: • - Catalytic steam reforming to H2/COmixture • Hydrotreating (heteroatom removal) * • ~20 million tons of animal by-products in the EU 27 countries • environmentally dangerous waste (microbiological re- and trans-contamination) • incineration is not favored (fly ash, emission of furans, dioxins and NOx) → pyrolysis

5. Catalytic steam reforming of pyrolysis oils CxHyNvOz + xH2O → xCO + (y/2+x-z)H2 + (v/2)N2 [1] CO + H2O CO2 + H2 [2] [1] highly endotherm [2] slightly exotherm Products: H2,CO,CO2,N2, (CH4)

6. Catalytic steam reforming of pyrolysis oil obtained from MBM

7. Catalytic hydrotreating of pyrolysis oils CxHyNvOz + nH2 → CxH2x+2 + zH2O + vNH3 (heteroatom removal via HDO and HDN) Unattractive process for pyrolysis oils of plant origin: - high H2 demand due to the high oxygen content (>30 wt%) - useless H2O is formed as by-product Feasible process for pyrolysis oils of animal origin: - relatively low H2 demand - valuable NH3 is formed as by-product Pyrolysis oil from MBM Hydrocarbon fuel + H2 + NH3(+H2O) catalyst N-compounds: aliphatic nitriles, amines and amides

8. Catalytic hydrodenitrogenation (HDN) of propyl-amine model compound (preliminary experiment) Ni2P/silicagel, WHSV= 1 h-1, p= 30 bar Conversion Ammonia Conversion, Yield, mol% Propane Ammonia Selectivity, mol% Propane Temperature, oC

9. Thank you for your kind attention !