KC Press Conference—2/16/07 1/18

Clean Vehicles: From Agricultural Waste toHigh-Tech Storage Tanks

Peter PfeiferDepartment of PhysicsUniversity of MissouriColumbia, MO 65211

http://all-craft.missouri.edu

Your next carmight well run onclean natural gasand be ready forhydrogen when it

comes along

KC Press Conference—2/16/07 2/18

• Develop low-pressure, high-capacity storage technologies for natural gas(NG, methane, CH4) and hydrogen (H2), based on new adsorbent materialsdiscovered at MU:— nanoporous carbon from waste corncob in Missouri (“sponge for NG”)— calixarene (“crystalline vacuum pump”)

• Demonstrate low-pressure, flat-panel NG tank for— next-generation clean vehicles (NG internal combustion engines)— hydrogen fuel cell cars (no hydrogen infrastructure needed)— collection of NG from landfills (“pollutant to renewable energy”)— large-scale shipping of NG from Alaska and deep-sea methane hydrate

fields (reduction of dependence on foreign oil)

• Develop low-pressure, flat-panel H2 tank for hydrogen fuel cell car

ALL-CRAFT 2004-present: Objectives

Funded by: – NSF Program “Partnerships for Innovation”– MU, MRI, Advanced Photon Source, DED/GAANN– Total: $1.1 million (2004-present)

KC Press Conference—2/16/07 3/18

Partners

• MU (lead institution): Physics (Pfeifer, Principal Project Leader; Wexler),Chemistry (Atwood & Hawthorne), Chemical Engineering (Suppes), CivilEngineering (Bowders), Office of Research (Coleman)

• Lincoln University, Jefferson City

• Midwest Research Institute (MRI), Kansas City

• DBHORNE, LLC, Atlanta

• Renewable Alternatives, LLC, Columbia

• Missouri Biotechnology Association (MOBIO), Jefferson City

• Clean Vehicle Education Foundation, Washington, DC

• Missouri Dept. of Natural Resources (Energy Center), Jefferson City

• City of Columbia (Municipal Landfill), Columbia

• Kansas City Office of Environmental Quality/Central Fleet, Kansas City

KC Press Conference—2/16/07 4/18

Low-tech waste material high-tech product

Van der Waalsattraction innanopores forcesNG into liquid-likedense fluid (170 g/lat 35 atm)

1.4 nm

Press coverage 2002

KC Press Conference—2/16/07 6/18

Why alternative fuels?

• Reduce dependence on foreign oil• Harness domestic renewable energy sources• Create new opportunities for domestic agriculture• Create clean air in cities• Reduce transportation costs by improving energy efficiency• Reduce greenhouse gas emissions

What are alternative fuels?

Developsustainabletransportationin U.S.

• Ethanol (from corn, wood, …)• Natural gas*‡ (NG; from domestic gas fields, deep-sea methane hydrate

fields, landfills, biomass); 85% of NG used in U.S. is domestic• Biodiesel (from soybeans, vegetable oils, …)• Hydrogen* (from NG, water & electricity, coal, …)• Electricity (from coal/nuclear/hydroelectric/solar/wind power plants)

* ALL-CRAFT ‡At pump: ~$1.25 less than equivalent gallon of gasoline

KC Press Conference—2/16/07 7/18

Current natural-gas vehicles

• Low emission of hydrocarbons ( ozone, smog), CO, NOx, particulatematter. Up to 40% reduction of CO2. NG stored as compressed naturalgas (CNG) in steel or composite cylinders at 250 atm (3600 psi).

• Clean Cities Coalitions:

– Los Angeles: 1500 CNG buses– Kansas City: 200 CNG public utility vehicles– U.S.: 130,000 CNG vehicles– worldwide: over 5 million CNG vehicles

/

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Goal: Develop low-pressure (35 atm, 500 psi), “flat-panel” tank, like gasolinetank. Store NG in nanoporous carbon; pores adsorb NG like a sponge: ANG tank

Why are we not already driving NG-fueled cars?

• High-pressure cylindrical/sphericaltanks take up passenger or trunkspace.

CNG cylinders in transit bus:

• Only NG passenger car in U.S.: Honda Civic GX; CNG tank in trunk:

KC Press Conference—2/16/07 9/18

Best flat-panel tank previously

Atlanta Gas Light Adsorbent ResearchGroup (AGLARG), 1997:

Adsorbent: monolithic activated carbon(“briquettes”) from peach pit;troublesome maintenance of consistentquality of briquettes; binder blocks pores

ALL-CRAFT: Monolithic carbon, withsuperior performance, from corncob.Missouri corn can supply raw materialfor NG tanks of all cars in the U.S.

© A

GLA

RG

1997

4 tanks in bed ofNG Dodge Dakota

© A

GLA

RG

1997

KC Press Conference—2/16/07 10/18

• Landfills: largest human-made source of methane (CH4) in U.S.Landfill gas (LFG): ~ 50% CH4, ~ 50% CO2

• CH4: 20 times more potent greenhouse gas than CO2

Capture CH4 at landfill: “pollutant to renewable energy”If no power plant: recover CH4 in 60,000 pound ANG tanks

• Annual CH4 emission from landfills in U.S.:– Could power 4 million homes: $5 billion/yr– Greenhouse equivalent to emission from 90 million cars (~1/2 of cars in U.S.)– If captured, equivalent to planting forest 2 x area of MO

Recovery ofbiomethanefrom landfillsand farms

KC Press Conference—2/16/07 11/18

Performance of ALL-CRAFT tank

• Target pressure for flat tank: 35 bar (35 atm, 500 psig *); without adsorbent,pressure would have to be 150 bar, much more than what a flat tank can bear

• DOE target capacity: 118 g/l (volume CH4 at 25 oC & 1 bar, per volume tank: 180)

• AGLARG tank:98 g/l

• ALL-CRAFTtarget: >100 g/lachieved!DOE targetachieved!

© A

LL-C

RA

FT

2007

*) 500 psi:pressure in NGpipelines

DOE target; best ALL-CRAFT carbon

AGLARG capacity

Adsorbent Filled Tank (ANG)

Empty Tank (CNG)

KC Press Conference—2/16/07 12/18

Carbon production and NG storage capacity

Produced over 100 different carbons from corncob(variable formulations) & searched for maximumstorage capacity

NG storage capacity (volume for volume), at 500 psi and 25 oC

0

50

100

150

200

250

Best ALL-CRAFT

carbon (180 V/V)

Best AGLARG

carbon (142 V/V)

DOE target

(180 V/V)

CNG, at 3000 psi

(208 V/V)

100% ofDOEtarget 79% of

DOEtarget

KC Press Conference—2/16/07 13/18

Research & development in the lab

CH4 uptake on briquettes (MRI test fixture)

CH4 uptake on small samples X-ray analysis at Advanced Photon Source

150-ton pressto makebriquettes

KC Press Conference—2/16/07 14/18

Bindingenergy:17 kJ/mol

Why are nanopores important?

In narrow pores, van derWaals potentials overlap;create deep energy well:Max. CH4 capacity in poresof width 1.1 nm.Molecules are held in tight-packed configurations.

KC Press Conference—2/16/07 15/18

ALL-CRAFT ANG tank on Ford F-150: MRI, Kansas CityOffice of Environmental Quality—October 2006 to present

Ford F-150 pickup for road test inKansas City (MRI, 4/06 - 9/06)

© M

RI 2006

© M

RI 2005

6 Al tubesholding300 carbonbriquettes

© M

RI 2006

KC Press Conference—2/16/07 16/18

ALL-CRAFT tank on Ford F-150

KC Press Conference—2/16/07 17/18

Natural gas vehicles over time

First NG vehicle 1910 (USA) with balloon tank on trailer NG vehicle~1930(France)with balloontank on roof

Current NG vehicle withhigh-pressure tank in trunk

Future NG vehicle with low-pressuretank under floor

From agricultural waste to high-tech storage tanks