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Robert C. Brown Iowa State University and Jennifer Holmgren UOP
• Rapid thermal decomposition of organic compounds in the absence of oxygen to produce liquids, char, and gas
– – – – – – Dry feedstock: <10% Small particles: <3 mm Short residence times: 0.5 - 2 s Moderate temperatures (400-500 oC) Rapid quenching at the end of the process Typical yields
Oil: 60 - 70% Char: 12 -15% Gas: 13 - 25%
Pyrolysis liquid (bio-oil) from flash pyrolysis is a low viscosity, dark-brown fluid with up to 15 to 20% water
Source: Piskorz, J., et al. In Pyrolysis Oils from Biomass, Soltes, E. J., Milne, T. A., Eds., ACS Symposium Series 376, 1988.
White Spruce 7.0 1000 500 0.65 11.6 7.8 12.2 66.5 3.3 6.5 10.1 0.35 1.24 2.0 11.0 34.5 20.6 11.4
Moisture content, wt% Particle size, µm (max) Temperature Apparent residence time Product Yields, wt %, m.f. Water Gas Bio-char Bio-oil Bio-oil composition, wt %, m.f. Saccharides Anhydrosugars Aldehydes Furans Ketones Alcohols Carboxylic acids Water-Soluble – Total Above Pyrolytic Lignin Unaccounted fraction
3.3 590 497 0.48 12.2 10.8 7.7 65.7 2.4 6.8 14.0 -1.4 1.2 8.5 34.3 16.2 15.2
Multiple reaction pathways for pyrolysis of cellulose
Depolymerization Fast Alkali-catalyzed dehydration Hydroxyacetaldehyde Slow Char + water Levoglucosan
Fast Pyrolysis • Advantages – Operates at atmospheric pressure and modest temperatures (450 C) – Yields of bio-oil can exceed 70 wt-% • Disadvantages – High oxygen and water content of pyrolysis liquids makes them inferior to conventional hydrocarbon fuels – Phase-separation and polymerization of the liquids and corrosion of containers make storage of these liquids difficult .
Several Kinds of Fast Pyrolysis Reactors • • • • • • Bubbling fluidized bed Circulating fluidized beds/transport reactor Rotating cone pyrolyzer Ablative pyrolyzer Vacuum pyrolysis Auger reactor .
Char.Bubbling Fluidized Bed Gas. and Oil Vapors and Aerosol • Heat supplied externally to bed • Good mass & heat transfer • Requires small biomass particles (2-3 mm) Freeboard Biomass Fluid bed Feeder Distributor plate Fluidizing gas Heat .
Circulating Fluidized Bed/Transport Reactor • Hot sand circulated between combustor and pyrolyzer • Heat supplied from burning char • High throughputs but more char attrition Pyrolyzer Gas and Oil Vapors and Aerosol Combustor Flue Gas Biomass Sand & char Distributor plate Air Fluidizing gas Feeder Hot Sand .
Rotating Cone Pyrolyzer • Sand and biomass brought into contact within rotating cone • Compact design and does not need carrier gas • Requires very small biomass particles and is hard to scale-up Biomass Hot Sand Vapors and Aerosol Rotation .
Ablative Pyrolyzer • High pressure of particle on hot reactor wall achieved by centrifugal or mechanical motion • Can use large particles and does not require carrier gas • Complex and does not scale well Spinning Disk Pressure Applied to Wood Bio-oil Liquid Released from Wood .
Vacuum Pyrolysis • Biomass moved by gravity and rotating scrappers through multiple hearth pyrolyzer with temperature increasing from 200 C to 400 C • Can use larger particles and employs little carrier gas Char • Expensive vacuum pump and difficult to scale-up Scrapper Driver Biomass Multiple hearth Condensers Vacuum pump vacuum pyrolysis reactor .
Auger Reactor • Hot sand and biomass mixed by auger • Suitable for small scale • Requires hot sand heating and circulation system Biomass Hot sand Vapors & aerosol to condenser Char & sand Auger driver Auger reactor .
Relative Merits of Various Reactors Property Status Biooil wt% 75 75 65 65 75 65 60 Complexity Medium High High High High Low High Feed size Small Medium Small V small Large Small Large Inert gas need High High High Low Low Low Low Specific size Medium Large Large Small Small Medium Large Scale up Easy Easy Easy Hard Hard Easy Hard Fluid bed CFB Entrained Rotating cone Ablative Auger Vacuum Demo Pilot None Pilot Lab Lab Demo The darker the cell color.uk .co. Lab: 1 – 20 kg h-1 Pilot: 20 – 200 kg h-1 Demo: 200 – 2000 kg h-1 Adapted from PYNE IEA Bioenergy http://www. the less desirable the process.pyne.
co.pyne.Which will dominate? TECHNOLOGY STRENGTH Strong MARKET ATTRACTIVENESS Average Weak Ablative High Cyclonic Rotating cone Entrained flow Fluid bed Circulating fluid bed and transport reactor Auger Adapted from PYNE IEA Bioenergy http://www.uk Low .
gas.Fast Pyrolysis System Lignocellulosic feedstock Mill Flue gas Vapor. char products Pyrolysis reactor Motor Feeder Combustor Pyrolysis gases Cyclone Quencher Hopper Char Bio-oil Bio-oil storage Fluidizing gas Air .
0 3.C.0 2.000 pbpd $3. ACS Meeting.0 4.Scale 0 $8.000 Small gasification (multiple units 110. D..0 .000 $5.0 Biomass Input (million US tons/yr) Adapted from: Bridgwater.000 $1.000 pbpd $0 0.000 Capital Cost (million 2005 US dollars) $7.000 US ton/yr) + small FT multiple units Small pyrolysis (multiple units 110.0 1.000 US ton/yr) + large FT Large gasification + large FT Diesel Output (million US gallons/yr) 50 100 150 200 250 $400.000 $6. Washington.000 $2.000 $4. 2005 5.000 $100.
Suitable Feedstocks • Wide variety of feedstocks can be used • Fibrous biomass usually employed • Wood higher yielding than herbaceous biomass .
Storage & Transportation • Distributed preprocessing allows transport and storage as liquid • High acidity requires storage in stainless steel or plastic • Stability problems need to be solved .
Post Processing to Motor Fuels • • • • Direct application of bio-oil Hydrocracking of bio-oil Gasification of bio-oil Fermentation of Bio-oil .
Bio-Oil Burned in Diesel Engines • Bio-oil used as directly as diesel fuel substitute • Only suitable for stationary power applications Bio-oil vapor Cyclone Bio-Oil Recovery Bio-Oil Bio-Oil Storage Stationary Diesel Engine Fibrous biomass Pyrolyzer Char .
and water) and char • Bio-oil catalytically converted into hydrocarbon fuel (green diesel) Green diesel Cyclone Bio-oil vapor Hydrogen Hydrocracker Char Pyrolyzer Bio-Oil Recovery Phase Separation Lignin Steam Reformer Fibrous biomass Carbohydrate derived aqueous phase . carbohydrate derivatives.Bio-Oil Hydrocracking • Directly converts biomass into liquid bio-oil (lignin.
Bio-Oil Gasification • Bio-oil and char slurried together to recover 90% of the original biomass energy • Slurry transported to central processing site where it is gasified in an entrained flow gasifier to syngas • Syngas is catalytic processed into green diesel (F-T liquids) Bio-oil vapor Entrained Flow Gasifier Bio-Oil Recovery Bio-Oil Slurry Preparation Pump Fischer Tropsch Reactor Green Diesel Cyclone Fibrous biomass Pyrolyzer Char Slag .
Bio-Oil Fermentation Fiber Distillation Ethanol Hot water extraction Pentose Fermenter Fiber byproduct Cyclone Bio-oil vapor Bio-Oil Recovery Phase Separation Water Char Pyrolyzer Detoxification Fermenter Anhydrosugar & other carbohydrate Lignin .
Energy Efficiency • Conversion to 75 wt-% bio-oil translates to energy efficiency of 70% • If carbon used for energy source (process heat or slurried with liquid) then efficiency approaches 94% Source: http://www.ensyn.htm .com/info/23102000.
Co-Products • Gas (CO. light hydrocarbons) – Can be used to heat pyrolysis reactor • Char: Several potential applications – Process heat – Activated carbon – Soil amendment . H2.
7 8.57 2.96 67.2 10.88 15.4 68.6 13. 2001) No Pretreatment Products (Wt% maf) Char Water Organics Gases Organics (Wt %) Cellobiosan Levoglucosan Hydroxy-acetaldehyde Formic acid Acetic acid Acetol Formaldehyde Pyrolytic lignin trace 2.97 23.26 trace trace 17.44 Acid Hydrolysis Acid Wash Acid Wash with catalyst .63 16.02 13.6 67.8 2.55 17.75 11.93 0.61 3.73 0.69 5.40 4.2 9.5 7.Potential Co-Products from Bio-Oil Products of pyrolysis for several different pretreatments of cornstover (Brown et al.70 20.40 4.51 trace 1.12 3.74 4.53 2.9 7.2 10.73 Trace 1.75 33.57 59.10 3.08 15.89 3.1 22.97 Trace 1.40 trace 0.34 20.
Quality Assurance • Bio-oil quality issues: – Moisture content – Particulate content – Sulfur and nitrogen content – Stability .
Equipment Maintenance • Potential problems with pyrolysis equipment – Bed agglomeration – Clogging of condensers – ESP performance • Catalytic reactors – Poisoning by sulfur and chlorine – Coking .
bio-oil) account for all mass of biomass feedstock .Waste Streams • Main products (gas. char.
Technical Barriers • Preparing dry. finely divided biomass particles • Maintaining high bio-oil yields • Improving bio-oil stability • Determining optimal scale of facility .
MJ/km Source: CONCAWE / EU CAR / EU Comm’n. FC DME from NG GTL from NG FAME Conventional EtOH Hydrogen from bio.Alternative Fuels: Targets WTW Energy /GHG Emissions Clusters 400 GHG. CO2 Equivalent. gm/km 350 300 250 200 Gasoline & Diesel 150 100 50 400 600 800 Energy. DME from gas – close. ICE Alternative fuels may need to target: – < 100 gm CO2/km WTW – GTL. but not there yet Several other alternatives in study (not shown for simplicity) Engine manufacturers developing more efficient advanced ICE’s in addition to hybrids and FC’s – Variable DI gasoline – “Part Homogeneous” diesel combustion – “Combined Combustion” systems – Improve fuel efficiency Gasoline & Diesel in Advanced ICE’s Set Tough Targets! . Dec 2003 0 0 200 1000 Green Diesel Hydrogen from coal.
Biorenewables and Petroleum Feeds: Relative Availability Global 50 Liquid Transport Fuels Diesel Available Oil/Grease Cellulosic Waste US 14 12 10 Liquid Transport Fuels Gasoline Diesel Available Oil/Grease Cellulosic Waste 40 MBPD MBPD 30 20 8 6 4 10 0 2 Current Potential 0 Current Potential Available Cellulosic Biomass Could Make a Significant Impact in Fuels Pool UOP 4434A-09 .
Py Oil Portfolio Solid Cellulosic Biomass Gasoline Pyrolysis Oil/ Lignin Hydrogen/ Power Generation Diesel .
Lignin Molecular Structure .
Treating Technologies Hydrotreating • Hydrotreating is the key process to meet quality specifications for refinery fuel products • Removes sulfur. cetane. and metals using hydrogen • Hydrogen addition also improves the quality of distillate fuels (poly aromatics. olefins. smoke point) • Treating feedstocks for other processing units . nitrogen.
higher value. low sulfur products • High pressure is used to add hydrogen and produce premium distillate products • Naphtha products normally are low octane and are upgraded in a reformer • Product volume is 10-20% higher than the feedstock .Conversion Technologies Hydrocracking • Hydrocracking upgrades heavy feeds including gas oils and cycle oils into lighter.
Hydrocracking Catalyst Portfolio HC-215 New Generation Current Generation Flexible Max Naphtha Distillates Selectivity HC-115 DHC-8 Max Diesel DHC-32 HC-150 DHC-39 DHC-41 DHC-41 HC-43 HC-33 HC-170 HC-29 HC-190 Distillates HC-26 HC-24 HC-34 Activity Distillate Selectivity Decreases with Increasing Activity .
YE for Hydrocracking Pyrolysis Oil Feed Pyrolysis Oil H2 Products Lt ends Gasoline Diesel Water.250 100 4-5 15 1. CO2 Wt% bpd 2.010 30 250 8 51-52 .
4 T 64T/D 1.2 million/year .303 52.500 25.800 12.250 21.010 250 $ 4.520 12.680 19.Gasoline Production from Py Oil ($40/bbl crude) Feed Pyrolysis Oil H2 Products Lt Hydrocarbons Gasoline Diesel Utilities Net $/D 40.843 bpd 2.000 -4.
0 $20.0 $0.9 $24.00 $ 1.0 $5. $MM $28.Hydroprocessing costs: Effect of Scale HDT Capital Cost vs Capacity Unit size (bpd) 30000 27500 25000 22500 20000 17500 15000 12500 10000 7500 5000 2500 Cost.96 $ 1.08 $ 1.4 $25.6 $9.9 $12.0 $15.0 $30.0 $25.9 $27. BPD .1 $14.3 $22.9 $19.68 $ 1.49 $ 1.19 $ 1.60 Capital Cost.1 $17.04 $ 1.27 $ 1.0 0 5000 10000 15000 20000 25000 30000 35000 Capacity.0 $10.37 $ 1.97 $ 2.7 $20.9 $6.5 Cost/ 1000 bpd $MM $ 0.13 $ 1. $MM (2006) $35.
000 bpd HC unit (typical refinery size) 30000 459.3 174072 65% 267803 734 bbl/day M gal/year tonnes/yr tonnes/yr tonne/day plant pyrolysis oil processed pyrolysis oil processed Conv. to biooil biomass 30. to biooil biomass .Size of Hydroprocessing Units 2000 bpd HC units Dynamotive’s Planned 200 tpd Plant Dynamotive's 200 tonne/day facility (planned production) 200 tonne/day biomass processed 200000 kg/day % conversion biomass to pyrolysis 65% oil 130000 kg/day biooil 1.2 kg/liter density of pyrolysis oil 108333 liter/day 28622 gal/day 681 bbl/day Hydroprocessing unit 2500 38.9 2088866 65% 3213640 8804 bbl/day M gal/year tonnes/yr tonnes/yr tonne/day plant pyrolysis oil processed pyrolysis oil processed Conv.
6 6519 425271 Million dry tons logging residue available (Billion ton annual study) % water of biomass for pyrolysis unit Million tons of logging residue feed % conversion to pyrolysis oil million tons of pyrolysis oil M gallons of pyrolysis oil from logging residue bbl/day ~14 30.000 bpd hydroprocessing units – Estimated cost: $405 MM ~170 2500 bpd hydroprocessing units – Estimated cost: $1105 MM .Example: Potential from logging residues 41 10% 46 65% 29.
BTL Key Decision: What are we planning to transport? . Centralized Refining P Gasifier P Biomass Gasification Reforming Natural Gas DME Methanol Integrated into traditional natural gas conversion process or refinery P P Synthesis Gas H2 P P GTL.Distributed Pyrolysis Plants.
centralized Catalyst and process invention/development/commercialization .Technical Barriers Securing a consistent py Oil feedstock Logistics Balance of distributed vs.
grease and pyrolysis oil could be feasible feedstocks for conventional petroleum refineries – Other feedstocks and processing options also look promising – Increased volumes of biobased feedstocks required • Consistent source of pyrolysis oil or other lignocellulosic biomass Biorenewable processing options identified are not limited to refinery integration – Stand alone units possible • Biorefineries.Summary Vegetable oils. Biofeedstock source • Portable H2 UOP 4434A-36 .
Acknowledgements DOE. Project DE-FG36-05GO15085 Contributors MTU – David Shonnard NREL – Stefan Czernik – Richard Bain Contributors PNNL – Doug Elliott – Don Stevens UOP – Tom Kalnes – Terry Marker – Dave Mackowiak – Mike McCall – John Petri Project Manager: Rich Marinangeli .
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