Comparative Fast Pyrolysis of Agricultural Residues for Use in Biorefineries Institute for Wood Technology and Wood Biology, amburg e ECI Bioenergy-II: Fuels and Chemicals from Renewable Resources Rio de Janeiro, Brazil, March 8-13, 2009 Dietrich Meier, Jens Markgraf utline! Background! Bio crude oil (BC) properties & applications! BC technologies! Experimental results! utlook 1
From Lignocelluloses to Energy & Chemicals Chemolysis (alkali, acids, steam, solvents, enzymes) LC Energy & Chemicals Thermolysis (pyrolysis, gasification) Biorefinery Concepts! General Use of lignocelluloses (LC): wood, residues (e.g. straw, bagasse) no competion with food restricted accessibility of biopolymers => pretreatment =>conversion! Classic approach limited feedstock selectivity (conditioning) (pretreatment necessary with pressure processes, e.g. organosolv, steam) separation & cleaning Use only after conversion or modification (degradation to monomers, functionalisation, polymerisation)! Thermochemical approach broad selection of raw LC materials (e.g. straw, bark, DDGS, shells, etc.) simple thermal treatment by fast-pyrolysis at atmospheric pressure decentral conversion - central refining (separation & cleaning) Direct or indirect use after modificationen 2
The Approach LC Materials omogenization thermo-chemical conversion by fast-pyrolysis into Bio-il + Coke Generation of Energy & Chemicals Fast Pyrolysis Principle! Fast chemical degradation due to rapid heating in the absence of oxygen! Process characteristics: Temperature 500 C Pressure 1 bar Particle size < 5 mm t vapours < 2 s! The main product is a liquid: Bio- il or Bio Crude il (BC; approx. 70 wt.%) Prins, W., 2007 3
C3 C3 C2 C C C3 Products of Fast Pyrolysis from Py-GC/MS C C TIC: [BSB1]AVICELL.D Cellulose (Avicell) C2 C4 C2 C 2 C C C C C C C C 3C C C 3C C C C 3C C 3C C C 3C 3C C C 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 C 2 Lignin C3 C2 C C3 C3 S S G C2 C3 C3 C C2 C C S C3 C3 C3 S C C2 G C C3 C min. C C C 3C R 2 S C 3 R 1 R 2 G C 3 R 1 syringyl guaiacyl 3C C C3 C3 G G C3 C3 C3 C3 S S C3 C C C 0 5.00 10.00 15.00 20.00 25.00 30.00 35.00 40.00 45.00 50.00 55.00 60.00 65.00 70.00 RT (min) BC Properties 1 MJ Feedstock 1 MJ Product Prins, W., 2007 4
verall Composition of Fast Pyrolysis Liquids Reactor Designs for Fast Pyrolysis circulating fluidized bed fixed bed oil hot cyclone sand loop biofuel sand bed from char combustor excess gas char hot cyclone pneumatical fluidisation biofuel recycle gas recycle gas recycle gas rotating cone char twin char combustor twin screw hot cyclone condenser biofuel sand loop oil excess gas oil, gas sand loop char combustion gas heater in sand loop mechanical fluidisation condenser hot cyclone biofuel oil char ablation cold biofuel vacuum biofuel vapour hot disc see also vortex reactor rotating hot disc, cylinder, blade direct contact gas molten salt vacuum tank char oil 5
Utilization Pathways for Pyrolysis Liquids Bio-il thermal chemical gasifier boiler gas turbine, diesel engine fractions components syngas heat power liquid smoke, adhesives, fertilizer aldehydes phenols, levoglucosan transp. fuel Productivity of Biofuels (yields/ha) Biofuel 2nd Generation whole plants BTL-fuel 3.101 L diesel equivalent Biofuel 1st Generation cereals vegetable oil Ethanol 1.653 L diesel equivalent Biodiesel 1.183 L diesel equivalent veg. oil 1.254 L diesel equivalent source: VW 6
The FZK BioLiq-Concept regional 50 MW (th) Fast pyrolysis plants Conditioning milling, drying Fast pyrolysis 1 bar, ~500 C, t some s il/coke-slurry Slurry transport by train from 20 to 40 pyrolysis plants Wärmeträgerkreislauf to a central gasification plant Entrained flow gasifier ~1300 C, >60 - bar, t 2-3 s teerfreies Rohsyngas Gas cleaning Gas conditioning Synthesis gas BC + Char Gasification => FZK-BILIQ => Me 7
BT-Pilot Plant in Bülkau 1 opper 2 Dryer 3 Pyrolyser 4 Condensation 5 CP plant 1 2 5 4 3 Conceptual Pyrolysis Process BIMASS Char separation Cool & collect Gas Drying < 10 % Grinding < 3 mm Pyrolysis BI-IL Coke 8
BIMASS Process Modifications Char separation Cool & collect Gas Drying < 10 % Grinding < 3 mm Pyrolysis BI-IL Pretreat Whole biomass - Remove ash - Add catalyst Separate bio-polymers into cellulose and lignin - Pulping - Biorefineries Pyrolyse Vary parameters - Temperature - Time - Pressure - Atmosphere Add catalysts Coke Upgrade Physically - Staged condens. Chemically - React, derivatize - De-oxygenate - Gasify to syngas Laboratory Fluidized Bed Reactor 9
Laboratory Fluidized Bed Reactor Yields of Products Based on Dry Feedstock 10
Distribution of Main Chemical Groups in Bio-ils Ash Content vs. Reaction Water 11
Compilation of Pyrolysis Behavior and Phase Separation Material Feeding Behaviour in il Phases LFBU Beech wood +++ ++ single Rape silage -- ++ single Sudan grass silage +++ +++ single Wheat straw + +++ multiple Wheat ++ -- multiple groats Barley silage + +++ multiple at silage - + multiple Corn whole + --- multiple plant Corn silage ++ +++ multiple Whole plant ++ ++ multiple silage emp/flax press cakes ++ -- multiple N-modified BC 450 g/m 2 N-modified BC 0 April ctober Conventional fertilizer N-BC 12
The Potential Role of Fast Pyrolysis! Part of a ethanol-based bio-refinery based on residue pyrolysis for fuel and/or chemicals! Incorporation into a gasification and chemicals/fuel synthesis plant! Stand-alone facilities with distributed production and centralized processing and refining! Part of a petroleum refinery with distributed production and centralized processing Zero-waste Concept Koks Shells Grains DDG Straw Bark Wood Silage Mineral fertilizer Ash Energy Fertilizer Smoke aroma Ceramics C 2 -Sequestration Soil improver Coke Bio- il Furfural Phenols org. Acids Methanol Levoglucosan -acetaldehyde 13
14