Synthetic fuels and chemical from biomass by the bioliq-process Nicolaus Dahmen Institute for Catalysis Research and Technology KIT University of the State of Baden-Wuerttemberg and National Research Center of the Helmholtz Association www.kit.edu
Opening statements Biomass is the only renewable carbon resource and has to be used primarily for chemistry including carbon based fuels bioliq explores the possible use of biomass in large scale conversion processes Syngas is a useful switch between chemical & energy as well as between fossil fuels and biomass In any case there is polygeneration: heat and power are important by-products enabling high CO 2 reduction potentials 2 21.10.2013
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. 3 21.10.2013
Potential feedstocks Agriculture Forestry Straw, hay,. Energy crops 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 Omnivores required allowing for broad feed stock and fuel properties range fitted to industrial production size and standards 4 21.10.2013
De-central / 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 3 5 21.10.2013
Effect of energy densification by fast pyrolysis 250 km Transport costs /t (waf) 100 50 30 km Truck Tractor Straw BioSyncrude Truck Rail Rail 0 0 100 200 300 400 500 Transport distance / km Source: Leible et al., ITAS 6 21.10.2013
Technology scheme biosyncrude O 2 (Steam) Gas cleaning and conditioning Biomass 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 7 21.10.2013
Pilot plant targets Demonstration Reliable m&e balances Representative products Practicability and operation Cost estimates Scale-up... Research & Development Feed and fuel flexibility Metrology/diagnostics Process control and understanding Optimization and spin-offs.. As small as possible, as large as necessary 8 21.10.2013
State of the project Stage 1 Stage 2 Stage 3 Stage 4 Process Fast pyrolysis High pressure entrained flow gasification Gas cieaning and Synthesis I Synthesis II Product BioSyncrude Synthesis gas Dimethylether Gasoline Capacity 2 MW (500 kg/h) 5 MW (1 t/h) 150 kg/h < 100 l/h Realization 2005-2008 2008-2013 2009-2011 State In operation In operation Performance test successful, start of operation 2014 Partners Lurgi, MAT Lurgi MUT, CAC 9 21.10.2013
The bioliq pilot plant at KIT October 2012 10 21.10.2013
Fast pyrolysis Twin screw mixer reactor for mechanical fluidization Heat transfer by sand, recycled by a heat carrier loop Reaction temperature 500 C, gas retention time ~3 sec Current feed material: wheat straw R&D fuel flexibility process (component) optimization towards long term operation modeling, simulation online monitoring of slurry properties alternative product utilization Pyrolysis oils, char, slurries, pastes.. 11 21.10.2013
Pyrolysis pilot plant scheme In cooperation with: 12 21.10.2013
Pilot test campaigns 14 Test campaigns since 2009 Operation time of heat carrier loop > 1000 h Product distribution in agreement with PDU findings Heat carrier 10:1 Water Aqueous condensate 85-90% energy conservation! Straw (waf) Pyrolysis gas Tar condensate Solids Ash Abrasives Char for internal combustion 13 21.10.2013
Controlled thermal aging of bio-oil Stability of the pyrolysis oil according to composition after solvent fractionation mass fraction (wt%) 100 80 60 40 20 0 14 21.10.2013 13,2 13,9 5,9 6,7 33,5 33,3 6,1 5,5 23,3 21,3 17,6 18,4 22.07.2011 07;00 22.07.2011 07:00:00 + 3 months Data on an ash free basis sa m ple Water DDS DDIS Extractives DS DIS Controlled Thermal Aging in the tar loop keeping bio-oil under controlled conditions Optimization of tar quench temperature in regard to viscosity (water and volatiles) and heat transfer properties
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 Distribution sum Original char Particle diameter / m 15 21.10.2013
R&D on BioSyncrudes Wasser M Flow properties of slurries Varying heating values Equipment testing (Pumping, stirring, heating.) New metrology devices Materials selection and testing Vergaser M Meßstutzen Wasser Slurry 16 21.10.2013
High pressure entrained flow gasification Suitable for feeds rich of ash Gasification with oxygen Temp. >1200 C, up to 80 bar Tar free, low methane syngas Proof at the 3-5 MW th gasifier of Future Energy (today Siemens FGT) Fuel Oxygen Cooling screen Syngas Slag 17 21.10.2013
High pressure entrained flow gasification Dip tube quench, free quench for hot gas abstraction later 18 21.10.2013
Test Run / Load Natural gas Slurry feed Q screen 20 21.10.2013
Earlier gasification test campaigns 80 70 Cold gas efficiency / % 60 50 40 30 20 10 0 Typical syngas composition Component Vol.% H 2 20 25 CO 25 37 CO 2 12-18 CH 4 0-1 H 2 O 25-30 5 10 15 20 25 30 O 2 0 BioSyncrude heating value (MJ/kg) N 2 4 15 Pilot gasifier in Freiberg, Germany 21 21.10.2013
R&D on gasification Fuel conditioning Atomization of slurries (PAT) Synthesis gas quality Chemical quenching Slag behavior and re-use Inline diagnostics Scale-up considerations Hot gas abstraction.. Knowledge based simulation tool for design and scale-up of technical EFG for a wide range of feedstock Test rig REGA Optical access to the reaction chamber EBI-VBT, ITC Test rig PAT 22 21.10.2013
High temperature 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 later max. 1000 Nm 3 /h synthesis gas (45 m³/h at 80 bar, 500-800 C) Successfully verified in bench scale Raw syngas Ceramic particle filter Fixed bed sorption Syngas Catalytic reactor Entrained flow adsorbens Potential of savings in energy, operation and construction efforts Raw syngas Catalytic ceramic filter Syngas 23 21.10.2013
HT-HP gas cleaning Commissioning November 2013 24 21.10.2013
DME and fuel synthesis DME synthesis optimal for CO/H 2 ratios around 1:1 One step DME synthesis Innovative isothermal reactor Temp. of 250 C, pressure 60 bar Two Stage Synthesis Methanol Synthesis Direct Synthesis DtG-synthesis Zeolithe catalyzed dehydratization, oligomerization and isomerization Temp. 350-450 C, pressure 25 bar Recycling of unconverted gas Gasoline stabilization Source: Ogawa et al., J. Nat. Gas Chem. 2003,12, 219-227 Selective synthesis of value added fuel components and chemicals 25 21.10.2013
Synthesis plant scheme Cycle gas Flare DMEreactor WGSreactor CO2-Absorber Gasoline reactor Distillation Air Gasoline Syngas CO 2 -Absorber Separator Heavy fraction Process water CO 2 Desorber 26 21.10.2013
Commissioning July 2013 Production of first 100 l gasoline, but 28 21.10.2013
R&D activities on syngas chemistry Methanol route: high product variability Actual focus on gasoline Methanol based kerosene and diesel Oxygenates (fuel components and chemicals) EtOH + higher alcohols 275 250 225 200 175 150 125 100 75 50 25 0 Ottokraftstoff (DIN EN 228) MLV1-14 MKL01-11 Syngas-To-Alcohols (STA) Dimethylether-To-Olefins (DTO) -25-50 0 10 20 30 40 50 60 70 80 90 100 Syngas MeOH DME Olefins Fuels Syngas-To-DME (STD) DME-To-Gasoline (DTG) Catalyst preparation Catalyst characterization Screening in lab scale Process development units Reactor design 29 21.10.2013
Systems analysis Crucial for biomass logistics and value chain assessment Technology assessment Process variants Sensitivity analysis Biomass potential and supply Integrated model for regional scenarios Optimization of site number, capacity, and location Extension to EU scene Definition of reasonable base case Variation of transportation, investment and energy costs Cost estimates (1 1.8 /ltr.) Sustainable supply, ILUC, acceptance. ITAS, IIP Source: Diss. F. Trippe, 2012 straw plus wood Source: Diss. F. Schwaderer, 2012 30 21.10.2013
The world wide demand on personal vehicles will not exceed 1 Million cars. only because there are not enough chauffeurs Gottlieb Daimler 1901 Thanks for your attention! 31 21.10.2013