Synthetic fuels and chemical from biomass by the bioliq-process

Transcription

1 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

2 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

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 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

5 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

6 Effect of energy densification by fast pyrolysis 250 km Transport costs /t (waf) km Truck Tractor Straw BioSyncrude Truck Rail Rail Transport distance / km Source: Leible et al., ITAS

7 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

8 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

9 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 State In operation In operation Performance test successful, start of operation 2014 Partners Lurgi, MAT Lurgi MUT, CAC

10 The bioliq pilot plant at KIT October

11 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

12 Pyrolysis pilot plant scheme In cooperation with:

13 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

14 Controlled thermal aging of bio-oil Stability of the pyrolysis oil according to composition after solvent fractionation mass fraction (wt%) ,2 13,9 5,9 6,7 33,5 33,3 6,1 5,5 23,3 21,3 17,6 18, ; :00: 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

15 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

16 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

17 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

18 High pressure entrained flow gasification Dip tube quench, free quench for hot gas abstraction later

19 Test Run / Load Natural gas Slurry feed Q screen

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

21 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 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 Nm 3 /h synthesis gas (45 m³/h at 80 bar, 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 HT-HP gas cleaning Commissioning November

24 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 C, pressure 25 bar Recycling of unconverted gas Gasoline stabilization Source: Ogawa et al., J. Nat. Gas Chem. 2003,12, Selective synthesis of value added fuel components and chemicals

25 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 Commissioning July 2013 Production of first 100 l gasoline, but

27 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 Ottokraftstoff (DIN EN 228) MLV1-14 MKL01-11 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 units Reactor design

28 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,

29 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!