Status Update November 21, 2008 Thomas Horgan

Outline Residential Scale Methanol Fuel Synthesis Advanced Research Topics Biomass Fuel Synthesis by Ionic Liquids Syngas by Catalytic Gasification Next Steps Other Topics

Residential Liquid Fuel Synthesis Classic Methanol Production (Wood Alcohol) DigesterPressing Sawdust H2SO4 Boiler Steam Sawdust H2O Fermen- tation Yeast Steam partially condense to Turpentine (0.3 kg/Tonne) Liquor 100 Proof methanol 57.1% by Vol 73 liter/tonne dry wood 150C, 7.5 Atm, 1h3 to 5 days

Residential Liquid Fuel Synthesis Industrial Methanol Production Compressor Methanol Convertor Syngas Recycle Loop Cooling/ Distillation Syngas (H2, CO (CO2, N2)) Purge Gas DesulphSMR GasifierCleaning Natural Gas Coal or Biomass Steam methanol Steam O2, Air 2H2 + CO  CH3OH 50 Atm, 270C Copper Oxide Catalyst  H = -92 kJ/mol

Residential Liquid Fuel Synthesis Small Scale Syngas Based MeOH System Assume Capacity: 200 lbs wood per day (1 cord ~ 4,000 lbs), 10 GPD MeOH Downdraft Gasifier Outside dimensions (w/ hopper): 4ft h x 1.5ft d Syngas production rate: ~ 35 ft 3 /lb of 15% wood Max Capacity: ~700 lbs wood/day ft 3 /h Outlet Temp: 50/75C after cyclone/filter Acceptable for MeOH synthesis? $2300 Assembled $1400 Not Assm

Residential Liquid Fuel Synthesis Small Scale Syngas Based MeOH System Compressor/Raise Temp MeOH Converter CO2+CO+5H2  2CH3OH+H2O+Heat Cu-Zn, 50 Atm, 270C Issues with Heat Removal 25% per pass efficiency (multi pass) Adiabatic vs Isothermal Reactors Needs to be cooled, flashed Residential scale reactor options?

Residential Liquid Fuel Synthesis Small Scale Syngas Based MeOH System Distillation Crude Methanol contains dissolved CO, CO2, H2, N2 and volatile organics (acetone, ethers, esters) May be acceptable for some engines/turbines ? Distilled for chemical grade Need to deal with off gasses

Residential Liquid Fuel Synthesis Small Scale Syngas Based MeOH System Methanol Gas Generator MeOH acceptable gasoline substitute poor cold starts, better efficiency/heat removal Lower volumetric heating value Seal wear Pramac S7500 Deluxe Electric Start Generator With Honda Gx390 Engine, 6.1 kW $2,000, Home Depot 31 x 22 x 25 inches, 200 lbs 8 gal tank, 10 hrs on gasoline 5 hrs on methanol

Residential Liquid Fuel Synthesis Community Power Corp - Littleton, Co Community Power Corp - Littleton, Co Small/Medium Scale Wood Generators Commercial 25kW, 75kW and 100 kW systems available $225 to $400k. Custom 5kW system ~ $150k 2 lbs of woodchips per kWh Footprint for 25kW system: 8’ x 8’ x 20’ Small/Medium Scale Prototype FT System (Farm) Fully Operational. Press release in two weeks 50 gal transportation diesel per ton woodchips Gasifier Footprint: 8’ x 8’ x 40’ FT Module Footprint: 8’ x 8’ x 20’

Biomass Fuel Synthesis By Ionic Liquids Dissolution of biomass: Potential first step to many new, low energy, homogeneous conversion routes Dimitris Argyropoulos, NC State Four patent applications Has one letter of intent (hedging). Company specifically interested in catalytic cracking Actively seeking investment partner (wants to develop, not publish) $150k for 4 years, $200k for 3 years

Biomass Fuel Synthesis By Ionic Liquids Ionic Liquids Air and moisture stable salts – electrically conductive, low vapor pressure, liquid at room temp Composed of 100% ions - large organic cat ions (~10 18 ), small inorganic anions (much less) Applications: Stable solvents, acid scavenging, cellulose processing, petrochemical synthesis, transport medium, many others Dissolve wood & other organics (0.2 to 2mm, < 150C, < 30min) Safety: Low vapor pressure and highly recyclable. Some are combustible. Many are toxic if released to the environment.

Biomass Fuel Synthesis By Ionic Liquids Argyropoulos Patents Low Energy Pyrolysis of Wood – WO 2008/ A1 IL Pyrolysis: Wood dissolved in IL, 190/200C (20 min), 10% more tar, 12% less char, 10% higher/more selective yield of distillates than Fast Pyrolysis Fast Pyrolysis: Pretreated w/ organic solvents, 425/500C (2s), tar, char, liquids (200+ intermediates) Low Energy Glucose from Wood for BioEthanol– US 2008/ IL dissolved wood is easily hydrolyzed by enzymes to release Glucose for production of bioethanol Polymers and Composites from Dissolved Wood – US 2008/ IL dissolved wood can be blended with co-polymers, polymers and functional additives to form eco-friendly (degradable) composites

Biomass Fuel Synthesis By Ionic Liquids Potential for Transportation Fuel Synthesis IL Pyrolysis produces a much narrower range of hydrocarbons with higher potential for catalytic cracking to trans fuels Sludge dissolution and homogenous processing to fuels Catalytic Gasification of Dissolved Wood (Syngas) Other undiscovered routes to aliphatics/aromatics Petrochina – Gasoline by alkylation of C4 olefins with iso-butane in ionic liquids

Syngas By Catalytic Gasification Syngas Methods Noncatalytic Supercritical: (450/600C, 4000/6000 PSIG) Hi Cap Cost, Limited Biomass testing Low Temp Catalytic (225/265C, 400/800 PSIG, Pt or Ni) Simple organics, not tried on biomass Fuel Gas Methods Catalytic Hydrothermal (350C, 3000PSIG, Ru or Ni) Good carbon conversion, biomass & sludge Supercritical Carbon Catalyzed (600C, 3700PSIG) Good carbon conversion, coke, ash, plugging

Syngas By Catalytic Gasification PNNL Project Concepts Low Energy Catalytic Biomass Syngas Gasification Investigate routes with lower temps and pressures. Preprocessing. Low Energy Catalytic Sludge Syngas Gasification Investigate routes with lower temps and pressures. Preprocessing. Catalytic Fuel Gas Gasification w/ Reforming Steam vs. Autothermal, Modeling for feasibility (efficiency/cost) Direct Fischer Tropsch Synthesis to Trans Fuels Design and control studies to narrow product range

Next Steps Note: Recommend work w/ Argyropoulos on Ionic Liquids, not Elliot (change memo) Plant visits and tours PNNL – discuss catalytic syngas gasification work. See labs, processes, etc. NREL – discuss lab capabilities/collaboration opportunities? Community Power Corp – 10 minutes from NREL. We’re invited. NC State – More detailed understanding of practical use of ionic liquids Residential Scale Methanol Synthesizer Develop detailed drawings, BOM, etc (model in Aspen?) Source other gasifiers Understand issues with crude methanol/distillation Source or design small scale MeOH converter Others…

Other Topics

Economics & Energy Analysis Energy

Economics & Energy Analysis Economics

Huber Process Professor George Huber – Umass, Amherst Has developed catalytic pyrolysis process for ‘Green Gasoline’ As of last , has already licensed technology (unclear) Have not connected by phone Green Gasoline Process Converts powdered cellulose at 600C, over zeolite catalyst to aromatic mix Not really a gasoline (actual gasoline is less than 25% aromatics) Useful as a blend Not yet tested on actual cellulose/biomass

Methanol to Gasoline (Mobil Process) Process Flow Sheet 320C Alumina 400/420C Light HC, CO2, H2

Gasification Technologies Updraft Gasifier Advantages Simple, low cost process Able to handle biomass with a high moisture and high inorganic content (e.g.,municipal solid waste) Proven technology Disadvantages Syngas contains 10-20% tar by weight, requiring extensive syngas cleanupbefore engine, turbine or synthesis applications Downdraft Gasifier Advantages Up to 99.9% of the tar formed is consumed, requiring minimal or no tar cleanup Minerals remain with the char/ash, reducing the need for a cyclone Proven, simple and low cost process Disadvantages Requires feed drying to a low moisture content (<20%) Syngas exiting the reactor is at high temperature, requiring a secondary heat recovery system 4-7% of the carbon remains unconverted

Gasification Technologies Bubbling Fluidized bed Advantages Yields a uniform product gas Exhibits a nearly uniform temperature distribution throughout the reactor Able to accept a wide range of fuel particle sizes, including fines Provides high rates of heat transfer between inert material, fuel and gas High conversion possible with low tar and unconverted carbon Disadvantages Large bubble size may result in gas bypass through the bed Circulating Fluidized bed Advantages Suitable for rapid reactions High heat transport rates possible due to high heat capacity of bed material High conversion rates possible with low tar and unconverted carbon Disadvantages Temperature gradients occur in direction of solid flow Size of fuel particles determine minimum transport velocity; high velocities may result in equipment erosion Heat exchange less efficient than bubbling fluidized-bed