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Studies of the Catalytic Conversions of Bio-Oils Obtained by Pyrolytic Decomposition of NonEdible Biomaterials Ferenc Lónyi Institute of Materials and Environmental Chemistry Research Centre for Natural Sciences Hungarian Academy of Sciences Biomass conversion Biomass - Diversity - Seasonal and disseminated occurrence Produces - vegetable oil - algae oil - energy plants Wastes - lignocellulosic - communal - industrial - animal by-products Conversion Product - 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 Biological - aerobic and anaerobic fermentation - enzymatic hydrolysis Thermal - combustion - gasification - Pyrolysis (CO2 negative) Chemical (catalytic) - transesterification of oils - hydrorefining of oils - processing the products of other conversions, e.g. gasification of pyrolysis oil to H2/CO mixture Liquid fuel - biodiesel - ”green” diesel - FT fuel - lower alcohols Pipeline gas - bio-methane Electric energy - fuel cell - Gas turbine/generator - Gas engine/generator Pyrolysis Char (~35 wt%) Pyrolysis gas (~65 wt%) Biomass (e.g. Meat and Bone Meal) Pyrolysis (~450 – 500 0C) ~85 %-a condensable Pyrolysis oil Reforming is needed ! Not suitable as fuel: - relatively low energy density - chemical instability - corrosivity - immiscible with conventional fuels - environmentally hazardous emission (e.g. NOx) Composition of pyrolysis oils Pyrolysis oil of plant origin Pyrolysis oil of animal origin * (e.g. from agricultural and forestry residues) (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 C, wt%: 74 H, wt% 12 O, wt% 5 N, wt% 9 ----------------------------------------Density (kg/dm3): 0.97 Heating value (MJ/kg) 36.5 (Zhang et al., Bioresource Technology 96 (2005) 545 Reforming: - Catalytic steam reforming to H2/CO mixture - Catalytic cracking and decarboxylation - Catalytic esterification * Reforming: - Catalytic steam reforming to H2/CO mixture - 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 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) Catalytic steam reforming of pyrolysis oil obtained from MBM TOS d, XC.e, T a, WHSV b, c S/C Catalyst 0 wt% h h-1 C 97.9 7 5 8 (0.8) 750 Ni/K/ >99 35 5 γ-Al2O3 f 750 4 (0.4) M-1 f M-2 f M-2 g a H2 N2 CO CH4 CO2 Product distribution [%] 55-60 10-15 5-10 3-5 15-20 750 750 700 700 700 700 700 700 18 (0.8) 9 (0.4) 9 (0.4) 9 (0.8) 4.5 (0.4) 9 (0.8) 4.5 (0.4) 4.5 (0.4) 5 5 5 5 5 5 5 3 13 19 24 11 16 12 18 23 94.0 >99 >99 >99 >99 >99 >99 >99 Reaction temperature (the dolomite guard bed was kept always at 800°C). Weight hourly space velocity based on the weight of the Ni-catalyst, not including the weight of the cordierite support (the values in parenthesis are the WHSV for the dolomite guard bed). c Steam to carbon molar ratio of the feed. d Time on stream. e Carbon conversion. f Catalyst was pre-reduced in H at 500°C. 2 g The catalyst was used without pre-reduction. b 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 catalyst N-compounds: aliphatic nitriles, amines and amides + NH3 (+H2O) Catalytic hydrodenitrogenation (HDN) of propyl-amine model compound (preliminary experiment) Konverzió, Hozam, mol% Yield, mol% Conversion, 100 Ni2P/silicagel, WHSV= 1 1h h-1-1,, p= 30bar bar Ni2P/Szilikagél, WHSV= p= 30 Conversion Konverzió 80 Ammónia Ammonia 60 Propán Propane DPA 40 20 TPA Szelektivitás, mol% mol% Selectivity, 100 0 80 Ammónia Ammonia 60 Propán Propane 40 DPA 20 TPA 0 200 250 300 Hõmérséklet,o°C Temperature, C 350 400