ALL-CRAFT Technology for Low-Pressure Storage of...

34th Annual Missouri Waste Management ConferenceLake Ozark, June 25-27, 2006 1/32

ALL-CRAFT Technology for Low-PressureStorage of Methane from Biomass

Peter PfeiferDepartment of Physics, University of Missouri

Columbia, MO 65211

http://all-craft.missouri.edu


Programmatic Overview


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)• Biodiesel (from soybeans, vegetable oils, …)• Hydrogen* (from NG, water & electricity)• Electricity (from coal/nuclear/hydroelectric/solar/wind power plants)

* ALL-CRAFT


How do alternative fuels work together?

Ready to go:NG from domestic (85%)& Canadian (~rest) fields

In progress:Renewable methanefrom landfills & biomass

Next-generation clean vehicles:NG internal combustion engine

Long-term goal:Hydrogen fuel-cell cars

NG, methane

In 10-20 years:Methane from deep-seamethane hydrate fields


Who we are—Partners

• MU (lead institution): Physics (Pfeifer, Project Leader), Chemistry (Atwood),Chemical Engineering (Suppes), Civil Engineering (Bowders), Office ofTechnology and Special Projects (Nixon), 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), St. Louis

• 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


• Develop low-pressure, high-capacity storage technologies for natural gas(NG), based on new adsorbent materials discovered at MU:— nanoporous carbon from waste corn cobs 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)

• Train students to become future leaders in alternative energy technologyand build outreach programs for alternative energy innovations

What we do

Funded by: – NSF Program “Partnerships for Innovation”– MU, MRI, Advanced Photon Source, DED/GAANN


Current natural-gas vehicles

• Low emission of hydrocarbons ( ozone, smog), NOx, particulatematter. NG stored as compressed natural gas (CNG) in steel orcomposite cylinders at 250 atm (3600 psi).

• Clean Cities Coalitions:

– Los Angeles: 1500 CNG buses– Kansas City: 200 CNG public utility vehicles– U.S.: 300,000 CNG vehicles– worldwide: 4 million CNG vehicles

/


Goal: Develop low-pressure (34 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:


Best flat-panel tank previously

Atlanta Gas Light Adsorbent ResearchGroup (AGLARG), 1997:

Adsorbent: monolithic activatedcarbon from peach pit

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

© A

GLA

RG

1997

© A

GLA

RG

1997©

AG

LA

RG

1997


Performance of AGLARG tank

• Target pressure for flat tank: 3.4 MPa (34 atm, 500 psi *); without adsorbent,pressure would have to be 15 MPa, much more than what a flat tank can bear

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

• Troublesomemaintenanceof consistentquality ofbriquettes;binder blockspores

• ALL-CRAFTtarget: >100 g/lAchieved!

© A

GLA

RG

1997

*) 500 psi:pressure in NGpipelines


• 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; use as renewable energy; reduce energy “crisis”

• Annual CH4 emission from landfills in U.S.:– Could power 4 million homes: $5 billion/yr– Greenhouse equivalent to emission from 100 million cars (2/3 of cars in U.S.)– If captured, equivalent to planting forest 2 x area of MO

Recovery ofmethane fromlandfills andbiomass


Current recovery of methane from landfills

• Electricity generation(large sites: STL, KC, Columbia, …)

• Direct heat(large/intermediate sites:STL, KC, Columbia, …)

Opportunity:During high-flow periods,store in stationary tanks

• Flare off (small sites)

• Not captured (abandoned sites)

Opportunity:Store in transportable tanks


Bucky Katt’s and Rob Wilco’sperspective


NGVAmerica in NYT & WSJ (2/8/06), in response to thePresident’s State of the Union Address

• 85% of NG is produced domestically; U.S. has huge amounts of NG

• 25% of NG is used to generate electricity; replaceable by other fuels, freeingNG for transportation

• Renewable NG in the form of biogas from landfills, sewage, farms, feedlots

• NG produces less air pollution and greenhouse gases than gasoline and diesel

• Even at today’s high prices, NG is cheaper than gasoline or diesel at the pump

• NGVs are the pathway to hydrogen transportation; much of the hydrogentechnology is based on NG technology

• Other countries are far ahead of us


ALL-CRAFT AccomplishmentsJanuary 2005 - June 2006


ALL-CRAFT tank


ALL-CRAFT tank, cont’d


ALL-CRAFT tank,cont’d


Carbon production & methane storage capacity

• Production of ~ 80 different carbons fromcorn cob, with variable activation procedures

• Search for maximum NG storage capacity

• Capacity in:– M/V: gram of NG per liter of carbon– V/V: NG, as volume of gas at 25 oC and

1 atm, per volume of carbon– M/M: gram of NG per kilogram of carbon

ALL-CRAFT,typical briquette(Sample B-21/k)

ALL-CRAFT,best performance(Sample B’-21/k)

AGLARG,bestperformance

ANG DOEtarget

M / V 73-95 g/liter 104-107 g/liter110% of AGLARG90% of DOE

98 g/liter 118 g/liter

V / V 112-145 liter/liter 159-163 liter/liter 150 liter/liter 180 liter/literM / M 170-220 g/kg 210-220 g/kg

130% of AGLARG170 g/kg N/A

Starting material & final product


Methane storage capacity, cont’d

Pressure-differencemeasurementof methaneuptake on 3.5”carbonbriquettes (MRItest fixture):

Gravimetricmeasurementof methaneuptake onsmall samples:

Methane uptake onB-21/k with differentinstruments, M / M

Gravimetric,Chem. Eng.

221 g/kg (± 2%)

Gravimetric,Physics

209 g/kg (± 2%)

Pressuredifference

198 g/kg (± 4%)

NG storage capacity (g/liter), at 34 atm (500 psi) and 25 oC

0

20

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180

Best ALL-CRAFTcarbon

Best AGLARGcarbon

DOE target CNG, at 250 atm(3600 psi)

90% ofDOEtarget

83% ofDOEtarget


How do we make carbon briquettes?

Die & piston150-ton press


Road test of ALL-CRAFT tank on a Ford F-150 bifuel pickup:MRI, Kansas City: June-Sept. 2006—stay tuned

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

© M

RI 2006

© M

RI 2005


ALL-CRAFT tank on Ford F-150


Application to methane recovery fromlandfills and biomass

Premium for cars: minimize volume of tank

Premium for landfills: minimize weight of tank


Renewable NG from landfills

• Collect & purify methane at landfill

• 40,000 lb carbon tank, with 17 wt%storage capacity (200 g methane/kg carbon), can store 6,800 lb of methane

• Ship full tank on tractor trailer to central processing facility; discharge methane

• Return empty tank to landfill

• Example: Columbia landfill Flow rate One tank full in

Operated as “drytomb,” 2005

250 cuft/min15,000 lb/day

0.45 days

Operated asbioreactor, 2020

980 cuft/min57,000 lb/day

0.12 days

Methane recovery in transportable tanks

• Tanks of interest at small or abandoned landfills


Other deployment

• Collect & purify methane at landfill

• During high-flow periods, store methane in 500 psi stationary tanks

• Discharge tanks during low-flow periods

Uniform methane delivery from landfill:

Fueling station for garbage trucks:

• Use methane from landfill to refuel CNG garbage trucks

• Store methane in 500 psi stationary tanks, designed as fueling station

• Of interest when there is no nearby NG station


Columbia landfill

Figure 1: Estimated Methane Collection Rates (Aquaterra March 2005 Report)

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2004 2006 2008 2010 2012 2014 2016 2018 2020 2022 2024 2026

Time (Year)

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"Dry Tomb"

"Bioreactor"


Columbia landfill, cont’d

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Oct-95 Jul-96 Mar-97 Nov-97 Jul-98 Mar-99 Dec-99 Aug-

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Time (Month-Year)

Meth

an

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CF

M)

"Phase 3" -Added 8 Gas Wells to the System

"Phase 2" - Added ? Gas Wells to the System

Methane flow rate vs. time


Columbia landfill, cont’d

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Percentage methane vs. time


Strategic and economic opportunities

National level

• NG fueled cars = next-generation clean vehicles/transportation1. Reduce smog, respiratory disease, cardio-vascular disease, …2. Reduce greenhouse gas emissions3. Reduce dependence on foreign oil now (not in 2040 as in H2 economy)4. Harness domestic NG fields (Alaska), deep-sea methane hydrate fields

(Oregon), renewable NG from landfills & biomass (Missouri, …)

• Recovery of NG from landfills1. Pollutant to energy, renewable energy2. Economic growth in rural areas

• Duplicate ALL-CRAFT success for hydrogen tanks

State level

• Produce NG/hydrogen tanks, from MO corn cob, for 10 million cars/year:$5 billion/yr

• Produce & operate NG tanks, from MO corn cob, for 2,500 landfills: $5 billion/yr• Produce NG tanks, from MO corn cob, for large-scale NG shipping: $3 billion/yr

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