ber jun10

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Hydrocarbons from Biomass Synthesis Gas - Biomass-to-Liquid BTL Conversion Georg Schaub Engler-Bunte-Institut Berlin, Juni 2010

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n CO + 2n H2 -(CH2)n- + n H2O feedstock biomass synthetic hydrocarbons synthesis gas production synthesis product upgrade CH1.6O0.7 + O2 / H2O CO + 2 H2 (+ CO2) overall: CH1.6O0.7 + a O2 b -(CH2)- + c CO2 + d H2O + heat BTL Conversion Overall Process and Chemical Reactions C5-20 alternatives: Fischer-Tropsch / HP Methanol / MTG HP : Hydroprocessing MTG : Methanol-to-Gasoline

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Synthetic Hydrocarbon Fuels Present Context BTL Gas-to-Liquid GTL commercial plants Qatar in operation / start-up 1.5 (+6.5) Mt/yr - improved reactor technologies (Fischer-Tropsch) - process optimization Biomass-to-Liquid BTL - demonstration plant Freiberg start-up 15 kt/yr - R&D gasification / pyrolysis / synthesis New projects, design studies GTL, CTL, BTL

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Synthetic Fuels – Fossil and Renewable hydrocarbons natural gas petroleum fractions coal biomass CO + H2 (CO2) synthesis gas CH3OH DME CH4 H2 world production (present) 9 Mt/a 38 Mt/a 1 Mt/a 45 Mt/a 1 Mt/a 1 partial oxidation steam reforming gasification 1 2 3 2 synthesis 3 product upgrade 1 syngas production world demand automotive fuels : ca. 2 Gt/a

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BTL Conversion Incentives and Challenge Incentive - lignocellulose feedstocks (whole plants, residues) - high-quality products - compatible, low pollutant - improved engine technology Challenge - solid feedstock processing low energy density, decentral high-T, endothermic - process complexity - economics

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Context and BTL process Integration aspects gasification - synthesis Future and development Hydrocarbons from Biomass Synthesis Gas - Biomass-to-Liquid BTL Conversion

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BTL Conversion Integration Aspects - Example FTS high T 700-1400 °C endothermic low T 220-250 °C exothermic decentral - central feedstock biomass synthetic hydrocarbons synthesis gas production Fischer-Tropsch Synthesis hydro processing C5-20 petroleum refinery product upgrading

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BTL Conversion Biomass Gasification CH1,6O0,7 + O2/H2O CO + H2 (+ CO2) endothermic tar conversion O2-feed moving bed fluidized bed entrained flow effect O2 : temperature temperature tar yield syngas yield

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Synthesis of Hydrocarbon Fuels n CO + 2n H2 -(CH2)n- + n H2O -(CH2)n- (+ H2 ) -(CH2)m- "polymerisation" ∆RH < 0 Co, Fe cat, 10-60 bar, 200-250 °C gas-liquid-solid hydroprocessing Methanol / MTG CO + 2 H2 CH3OH n CH3OH -(CH2)n- + n H2O CuO-ZnO/Al2O3 50-150 bar, 250-300 °C zeolite ZSM-5 10-20 bar, 350-400 °C Fischer-Tropsch

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BTL Conversion Chemical Reactions – Heat Effects biomass stoichiometry Biomass + O2/H2O CO + 2 H2 CO + 2 H2 -(CH2)- + H2O heat effects energy CO+H2 -CH2-

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BTL Conversion FT Diesel synthetic hydrocarbons Fischer-Tropsch Synthesis hydro processing petro Diesel : C10-C20 alkane (n + i) naphthenes aromatics poly-Ar < 10 % m/m TS 200-350 °C sulfur < 10 ppm alkane (n) var ratio n/i var aromatics ~ 0 sulfur ~ 0 Fuel Product Quality - Example FTS Diesel CO/H2

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BTL Conversion Product Yield and Efficiency Published Process Studies - Example FTS feed flow dry t/h 80 – 18/900 GW 0.37 – 0.1/5 product flow -(CH2)- 1) t/h 10 – 139 η carbon 2) % 23 – 41 η chem energy 3) % 29 – 51 source : Tijmensen et al. 2002 Dimmig et al. 2003 Dena 2006 Leible et al. 2007 1) liquid fuels C5-20 2) HHV of C5-20 / HHV of biomass feed 3) mC in C5-20 / mC in biomass feed

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BTL Conversion Hydrocarbon Product Yields - Example FTS natural gas 1) 100 CH4 68-80 -(CH2)- 53-63 biomass 2) 100 CH1.6O0.7 24-40 -(CH2)- 30-50 coal 3) 100 CH0.8O0.1 28-40 -(CH2)- 35-50 petroleum 4) 100 CH1.8 86-94 -(CH2)- 86-94 HHV (%) 1) Audus et al. 2001, Sie et al. 1991, 2) Tijmensen et al. 2002, 3) Hoogendorn 1976, from: Jüntgen et al., in: Elliott (Ed.) 1980, 4) reference, own estimate

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Liquid Hydrocarbon Fuels Correlation Investment – Feedstock / Process (schematic, orientation) energy requirement (% of HHV feedstock) "degree of upgrading" spec investment 0 10 20 30 40 50 60 conv oil refining bitumen tar sand BTL* CTL * investment Σ syngas production : 60-70 %

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Fischer-Tropsch Synthesis Status and Development source : webpages Sasol, Shell etc. 03/2005 – 08/2009 biomass ?

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BTL Conversion Conclusion and Outlook - process technology is/will be available - critical : complexity, efficiency, investment compared to conventional petroleum refining less critical : low-quality petroleum feedstocks aromatic crudes, tar sand, (coal) - gasification / synthesis in biorefineries residues from pulp and paper fuels, chemicals compared to

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Hydrocarbons from Biomass Synthesis Gas - Biomass-to-Liquid BTL Conversion Georg Schaub Engler-Bunte-Institut Berlin, Juni 2010