Status UpdateNovember 21, 2008

Thomas Horgan

OutlineResidential Scale Methanol Fuel Synthesis

Advanced Research TopicsBiomass Fuel Synthesis by Ionic LiquidsSyngas by Catalytic Gasification

Next Steps

Other Topics

Residential Liquid Fuel SynthesisClassic Methanol Production (Wood Alcohol)

Digester PressingSawdust

H2SO4

Boiler

Steam

Sawdust

H2O

Fermen-tation

Yeast

Steam partially condense to Turpentine (0.3 kg/Tonne)

Liquor

100 Proof methanol57.1% by Vol73 liter/tonne dry wood

150C, 7.5 Atm, 1h

3 to 5 days

Residential Liquid Fuel SynthesisIndustrial Methanol Production

Compressor

Methanol

Convertor

Syngas Recycle Loop

Cooling/Distillatio

n

Syngas (H2, CO (CO2, N2))

PurgeGas

Desulph SMR

Gasifier Cleaning

Natural Gas

Coal or Biomass

Steam

methanol

SteamO2, Air

2H2 + CO CH3OH 50 Atm, 270CCopper Oxide CatalystH = -92 kJ/mol

Residential Liquid Fuel SynthesisSmall 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 ft3/lb of 15% wood Max Capacity: ~700 lbs wood/day - 1000 ft3/h Outlet Temp: 50/75C after cyclone/filter Acceptable for MeOH synthesis? $2300

Assembled $1400 Not Assm http://www.allpowerlabs.org

Residential Liquid Fuel SynthesisSmall Scale Syngas Based MeOH System

Compressor/Raise TempMeOH Converter

CO2+CO+5H22CH3OH+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 SynthesisSmall 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 SynthesisSmall 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 SynthesisCommunity Power Corp - Littleton, CoCommunity 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 LiquidsDissolution of biomass: Potential first step to

many new, low energy, homogeneous conversion routes

Dimitris Argyropoulos, NC StateFour patent applicationsHas one letter of intent (hedging) . Company specifically interested

in catalytic crackingActively seeking investment partner (wants to develop, not publish)

$150k for 4 years, $200k for 3 years

Biomass Fuel Synthesis By Ionic LiquidsIonic Liquids

Air and moisture stable salts – electrically conductive, low vapor pressure, liquid at room temp

Composed of 100% ions - large organic cat ions (~1018), 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 LiquidsArgyropoulos Patents

Low Energy Pyrolysis of Wood – WO 2008/098036 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 2008/053139 IL dissolved wood is easily hydrolyzed by enzymes to release Glucose

for production of bioethanol

Polymers and Composites from Dissolved Wood – US 2008/053151

IL dissolved wood can be blended with co-polymers, polymers and functional additives to form eco-friendly (degradable) composites

Biomass Fuel Synthesis By Ionic LiquidsPotential 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 fuelsCatalytic 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 GasificationSyngas 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 MethodsCatalytic 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 GasificationPNNL 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 StepsNote: 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 AnalysisEconomics

Huber ProcessProfessor George Huber – Umass, Amherst

Has developed catalytic pyrolysis process for ‘Green Gasoline’ As of last e-mail, 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

320CAlumina

400/420C

Light HC, CO2, H2

Gasification TechnologiesUpdraft 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 TechnologiesBubbling 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