The bioliq BTL process for synthetic biofuels and chemicals production

Transcription

1 The bioliq BTL process for synthetic biofuels and chemicals production Eckhard Dinjus Institute for Catalysis Research and Technology KIT University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association

2 Motivation Use of biomass as the only renewable carbon source for production of fuels and chemicals prior to heat and power generation Large scale production of energy related products 1500 noch offen Geo- / ozeanische Energie Sola renergie 1000 N eue Biomasse Windenergie 500 Wa sserkra ft Trad. Biomasse Kernkra ft Erdga s Erdöl Kohle Source: Deutsche Shell AG

3 Chemical pathways to synthetic products Gases CH 3 -(CH 2 ) n -CH 3 LPG C 6 H 9 O 4 Fischer- Tropschsynthesis Refining Naphta Cerosene Diesel. Biomass Syngas H 2 + CO Hydrogen Methane (SNG) Propylene Direct use (Fuel cell, PME production, Methanolsynthesis CH 3 OH Dimethylether DME Ethylene Gasoline Acrylic acid Oxygenates

4 BTL-projects in Europe Process Type Capacity Pressure KIT bioliq, D Fast pyrolysis + high pressure entrained flow gasification + hot gas celaning + DME and DtG gasoline synthesis 5 MW th (2 MW th ) 80 bar Choren Carbo-V, D (IP now owned by Linde) CGT pressurized entrained flow gasification, FT-synthesis, SunFuel, plant mothballed! 45 MW th 4 bar TBM, D Allothermal fluidized bed, SNG 10 MW th atm. Biodies, F BioTfueL, F Güssing, A BioDME, S Planned for Choren-gasification + Rectisol + GTL.F1-Synthese 45 MW th 4 bar Torrefaction + Uhde Prentflo-gasification, FTsynthesis 15 MW th n.b. Staged fluidized bed, electricity, SNG (1 MW) and FT-synthesis 8 MW th atm. Black liquor entrained flow gasification, DME/methanol-synthesis 5 t/d DME 29 bar Neste Oil, FI Circulated fluidzed bed, FT-Synthese 12 MW th atm. Värmlands Methanol HTW-gasifier, methanol+heat 111 MW th n.b

5 Potential feedstocks Agriculture Straw, hay,. Energy crops Forestry Residues (brash, tops, stumps) Thinnings Short rotation plantation Trackside vegetation clearance Streets, railway tracks Power transmission lines Organic residues Recovered waste wood Organic waste fractions

6 Decentral-centralized concept Energy densification of biomass in regional distributed plants by bioliqsyncrude production Economic conversion in large scale to syngas and further refining into fuels & chemicals Energy density: 2 GJ/m 3 25 GJ/m 3 36 GJ/m

7 Biomass bioliq process scheme biosyncrude O 2 (Steam) Gas cleaning and conditioning Pre-treatment High pressure entrained flow gasification Filter Sorption Catalyst CO 2 and water separation Syngas Slag Synfuel Fast pyrolysis biosyncrude De-central Fuel synthesis Centralized DME synthesis

8 Bioliq pilot plant Designed for 1000 h/a operation 500 kg/h biomass input (50 L/h synfuel output) Mass and energy balances Cost estimates Scale-up considerations

9 State of construction Stage 1 Stage 2 Stage 3 Stage 4 Process Fast pyrolysis + BioSyncrude production HP Entrained flow gasification Gas cleaning + Synthesis I Synthesis II Product BioSyncrude Synthesis gas DME Gasoline Capacity 2 MW (500 kg/h) 5 MW (1 t/h) 150 kg/h 50 l/h Realization Partner Lurgi + MAT Mischanlagentechnik Lurgi MUT Advanced Heating Chemieanlagenbau Chemnitz

10 Total View of the pilot plant Mechanical completion: Nov

11 Fast pyrolysis pilot plant Biomass preparation Fast pyrolysis Pyrolysis product recovery Feed stock storage Biosyncrude preparation

12 Fast pyrolysis Twin screw mixer reactor Heat carrier loop with sand Reaction temperature 500 C Gas retention time ~3 sec Gaseous, liquid and solid products Hot sand Biomass Silo Cycone Filter Char Condensate Biosyncrude 85-90% energy conservation! Air Cyclone Quench Flare Water Aqueous condensate Cutting Air M Reactor Condenser I Condenser II Straw (waf) Pyrolysis gas Tar condensate Sand Burner M Char cooling Ash Solids Abrasives Char Tar condensate Aqueous condensate Char for internal combustion

13 Energieinhalt der Produkte [MJ/kg] Koks Gas Kondensat Δh R Energy balance of fast pyrolysis Hartholz (wf) Weichholz (wf) Weizenstroh (wf) Weizenkleie (wf) Heating up to 500 C and reaction enthalpy: 0,54 0,83 MJ/kg approx. Energy content of pyrolysis gas Fast pyrolysis PDU (10 kg/h, 500 C)

14 Pyrolysis product distribution wt. % Ash Char Condensate Gas Water Beech wood Wheat straw Rice straw Hay Wheat clay Bagasse Gas composition: CO 2 50 %, CO %, CH %, C %

15 Product composition of pyrolysis oil and char Particle size d 90 ( m) Char 150 Complex mixture Aqueous. of Org. cond. organic acids, aldehydes, Cond. ketones, furfurales, phenols, pyrolytic lignin Ash COOH Water (wt.%) 4,7 6,4 49,7 0,1 Ash (wt.%) 1,8 0 OH <0,05 Elemental analysis COOH COOH C (%) 84,4 58,6 24,3 2,6 CHO H (%) 2,7 6,2 OH 3,8 0,2 O (%) 6 28,4 21,9 N (%) 0,4 0,3 O O 0,3 0,3 O S (%) 0,07 <0,05 CH CHO 2 OH <0,05 1,0 OH OH O OH CHO OH CHO

16 Use of pyrolysis products Separation of valuable components Produce BioSyncrude from pyrolysis oil and char for gasification and synthesis gas generation Use of char for mono- and co-combustion for heat and electrical power production Upgrade of pyrolysis oils for Fuel production Refinery crude Pyrolysis oil Stabilization H 2, catalyst C, 20 MPa, min. Stable fragments soluble in water Hydrodexoygenation H 2, catalyst >250 C, 20 MPa min.-hour Non-polar fragments insoluble in water > 1.0 g cm -3 Hydrocracking H 2, catalyst >250 C, 35 MPa hour Non-polar fragments insoluble in water < 1.0 g cm -3 Methanation Methanation C x H y C x H y Mild hydro-treating of pyrolysis oils according to Venderbosch, Prins

17 Distribution sum BioSyncrude preparation Free flowing suspension High particle content up to 40wt.% Stable for storage and transport Easy to produce by colloidal mixing Heating value up to 25 MJ/kg Colloidal mixed char Original char Particle diameter / m

18 Transport costs /t (waf) Effect of energy densification by fast pyrolysis KIT: Leible et al. 250 km 100 Rail 30 km Straw 50 Truck Tractor BioSyncrude Truck Rail Transport distance / km

19 High pressure entrained flow gasification Suitable for feeds rich of ash Gasification with oxygen Temp. >1200 C, up to 80 bar Proof at the 3-5 MW th gasifier of Future Energy (today Siemens FGT) Tar free synthesis gas No syngas compression Cooling screen detail solid slag gasifier reaction chamber liquid slag refractory ramming mix water pipe > 1500 C boiler feedwater

20 High pressure entrained flow gasification

21 Pilot gasifier

22 Cold gas efficiency / % Gasification test campaigns Typical syngas composition Komponent Vol.% H CO CO CH H 2 O O 2 0 BioSyncrude heating value (MJ/kg) N Pilot gasifier in Freiberg, Germany

23 Liquid feed Gas Gas Burner development Two-fluid nozzle T. Kolb, ITC ATMO (1 bar) PAT (up to 20 bar) Spray at 16 bar

24 High pressure hot gas cleaning Hot gas filter for particle removal Dry sorption for separation of sour gases and alkali salts Catalytic decomposition of organic and nitrogen containing compounds CO 2 -separation (optional) 1000 Nm 3 /h synthesis gas (45 Bm³/h at 80 bar, 800 C) Successfully verified in bench scale Raw syngas Ceramic particle filter Fixed bed sorption Syngas Catalytic reactor Energy savings up to 10 % Potential for process integration Entrained flow adsorbens Raw syngas Syngas Catalytic ceramic filter

25 Distillation DME and fuel synthesis DME-synthesis One step DME synthesis Innovative isothermal reactor Temp. of 250 C, pressure 60 bar Lower investment costs Direct use of CO-rich syngas DtG-synthesis Zeolithe catalyzed Dehydratization, oligomerization and isomerization Temp C, pressure 25 bar Recycling of unconverted gas Gasoline stabilization high selectivity towards one product methanol route useful for oxygenates Syngas DMEreactor WGSreactor CO2-Absorber CO2 Desorber CO2-Absorber Cycle gas Gasoline reactor Separator Process water Heavy fraction Flare Air Gasoline

26 Synthesis pilot plant

27 Temperatur / C R&D on syngas chemistry EtOH + higher alcohols Syngas-To-Alcohols (STA) Dimethylether-To-Olefins (DTO) Syngas MeOH DME Olefins Fuels Syngas-To-DME (STD) DME-To-Gasoline (DTG) Catalyst preparation Catalyst characterization Screening in lab scale Process development unit MOSYS Ottokraftstoff (DIN EN 228) MLV1-14 MKL01-11 Simulated distillation curves of products without up-grading compared to gasoline Verdampfte Menge / Gew.%

28 Process efficiency To produce 1 t of synthetic biofuel 7 to of air dried biomass are required Around 45% of the energy initially contained in the biomass remain in the fuel Residual heat can be used for electrical power production Both can be used to make the process nearly energy autarkic Therefore, the process provides a high CO 2 reduction potential

29 Process implementation Operation of the pilot plant reliable cost estimate, practical experience Construction and operation of a demo plant Complementary R&D in lab and bench scale Optimisation, process alternatives, new applications Verification of potential feed stock range and availability Different types of biomass Alternative use of biosyncrude for: Co-combustion (Power plant) Mono-combustion (CHP) Upgrading to refinery compatible fuel Development of new products, e.g. oxygenates Oxygen is contained in biomass for free! Biomass much better fits to chemicals than to fuels capacities Business models in cooperation with industry and other partners

30 Stone era did not end because a lack of stones, and the oil era will not end up because oil is running out Sheich Zaki Yamani, 1974 former minister from Saudi Arab