ALL-CRAFT—Alliance for Collaborative Research in...
Transcript of ALL-CRAFT—Alliance for Collaborative Research in...
Advisory Panel Meeting — February 27, 2006 1/25
ALL-CRAFT—Alliance for Collaborative Research
in Alternative Fuel Technology
NSF Program “Partnerships for Innovation”
http://all-craft.missouri.edu
Progress Report
July 2005-Present
Advisory Panel Meeting
Midwest Research Institute, February 27, 2006
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Advisory Panel Meeting — February 27, 2006 2/25
Programmatic Overview
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Advisory Panel Meeting — February 27, 2006 3/25
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 Co
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Advisory Panel Meeting — February 27, 2006 4/25
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
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Advisory Panel Meeting — February 27, 2006 5/25
ALL-CRAFT Objectives
• 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 undergraduates to become future leaders in alternative energytechnology, through research internships at MU and partner institutions
• Build outreach programs, statewide and at national level, for alternativeenergy innovations and transition to a sustainable environment/economy
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Advisory Panel Meeting — February 27, 2006 6/25
ALL-CRAFT 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, 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
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Advisory Panel Meeting — February 27, 2006 7/25
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: 150 CNG public utility vehicles– U.S.: 300,000 CNG vehicles– worldwide: 4 million CNG vehicles
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Advisory Panel Meeting — February 27, 2006 8/25
Why are we not already driving NG-fueled cars?
• High-pressure cylindrical/sphericaltanks take up passenger or trunkspace.
CNG cylinders in transit bus:
• ALL-CRAFT: Develop low-pressure, “flat-panel” tank, comparable to gasolinetank, and safe (pressure: 34 atm, 500 psi). Store NG in nanoporous carbon(pores adsorb NG like a sponge; ANG tank), made from corn cob:
Missouricorn cansupply rawmaterial forall cars inthe U.S.
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Advisory Panel Meeting — February 27, 2006 9/25
Storage of NG from landfills
• Landfills are largest human-made source of methane (CH4, NG) in U.S.Landfill gas: ~ 50% CH4, ~ 50% CO2, < 1% non-CH4 organic compounds
• CH4: 20 times more potent greenhouse gas than CO2
Capture CH4 at landfill; use as renewable energy source; at small landfills,store in mobile ANG tanks and process elsewhere
• Annual CH4 emission from landfills in U.S.:– 60 million tons of carbon
equivalent– Powers 4 million homes– Greenhouse equivalent to annual emission from
100 million cars (2/3 ofall cars in U.S.)
– If captured, equivalentto planting 300,000 km2
forest (2 x area of MO)
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Advisory Panel Meeting — February 27, 2006 10/25
NGVAmerica, Feb. 8, 2006 (NYT, WSJ), in response to thePresident’s State of the Union Address, Jan. 31, 2006
• 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 Co
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Advisory Panel Meeting — February 27, 2006 11/25
ALL-CRAFT AccomplishmentsHighlights July 2005 - February 2006
ALL-CRAFT team at University of Missouri:
• Physics: Peter Pfeifer, Jacob Burress, Lacy Hardcastle, Robert Schott,Demetrius Taylor, Mikael Wood
• Chemical Engineering: Galen Suppes, Parag Shah, Mona-Lisa Banks, SeanCrockett, Monty Kemiki, Serean Spellerberg
• Chemistry: Jerry Atwood, Praveen Thallapally
• Civil & Environmental Engineering: John Bowders, Joshua Bergsten
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Advisory Panel Meeting — February 27, 2006 12/25
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
ANGindustrytarget
M / V 73-95 g/liter 104-107 g/liter 98 g/liter 118 g/liter
V / V 112-145 liter/liter 159-163 liter/liter 150 liter/liter 180 liter/liter
M / M 170-220 g/kg 210-220 g/kg 170 g/kg N/A
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Advisory Panel Meeting — February 27, 2006 13/25
Methane storage capacity, cont.’d
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NG storage capacity (g/liter), at 34 atm (500 psi) and 25 oC
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Best ALL-CRAFT
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CNG, at 250 atm
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91% ofindustry target
83% ofindustry target
Meth
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Pressure (psia)
AGLARG sample
Methane adsorption isotherm
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ALL-CRAFT Sample B-21/k
Methane adsorption isotherm
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Advisory Panel Meeting — February 27, 2006 14/25
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%)
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Pore-size distributionof B-21/k frommethane isotherm
Pore width range (nm) P
ore
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cm3/g
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Advisory Panel Meeting — February 27, 2006 15/25
What does the pore space look like? — Case Study B-18
N2 adsorption/desorptionisotherm (77 K) for B-18.Surface area: 605 m2/g
Pore-size distribution from adsorption isotherms(N2: standard; CH4: not widely used)
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CH4 adsorptionisotherm (300 K)for B-18
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Differential pore volumedistribution, from N2
desorption isotherm, for B-18
Pore radius r (Å)
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Vol. in r < 10 Å: 0.13 cm3/gVol. in r = 10-20 Å: 0.15 cm3/gVol. in r = 20-1400 Å: 0.10 cm3/gPower law: dV/dr ~ r –1.7
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Pore-size distribution fromCH4 isotherm, for B-18 Consistent with
distribution from N2
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Advisory Panel Meeting — February 27, 2006 16/25
Case Study B-18, cont.’d
Small-angle x-ray scattering (Advanced Photon Source, ArgonneNational Laboratory) gives spatial arrangement of pores
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Exper. Calc. Calc., PSD only
Scattered wave vector (Å–1)
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Experimental data
Experimental andcalculated intensity
Calculated intensity: surface fractal at largelength scales (Ds = 2.3); pore-size distributionfrom N2 adsorption at small scales:
I calc(q) = A FormFactor(r , q)dV
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r 30
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2.3-dimensionalfractal surface
dV/dr ~ r –1.7 fromN2 adsorption
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Advisory Panel Meeting — February 27, 2006 17/25
Case Study B-18, cont.’d
Schematic model of pore space of B-18,from scattering data
Snapshots of simulationof oxidative removal ofcarbon by a chemicalagent (gray). Resultingpore space is similar toSample B-18
Fractal surface,Ds = 2.3
Model consistent with scanningelectron micrographs
Uncorrelated pores,radii r = 7-1400 Å(independentscatterers),nonfractal power lawdV/dr ~ r –1.7
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Advisory Panel Meeting — February 27, 2006 18/25
Candidate for high-capacity H2 storage: S-33/k
N2 ads./des. Isotherm for S-33/kSurface area: 2540 m2/gMicropore volume: 1.1 cm3/gSuperb candidate for H2 storage
Differential pore-volume distribution,from N2 isotherm, ofS-33/k
Most pores of width< 10Å
Expected pore-spacestructure: nearly space-filling pore fractal, similarto results of Pfeifer et al.,Phys. Rev. Lett. 88,15502 (2002):
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Advisory Panel Meeting — February 27, 2006 19/25
Pore-size distribution of other samples
N2 ads./des. Isotherm for S-30Surface area: 783 m2/gMicropore volume: 0.31 cm3/gPure binder
N2 ads./des. Isotherm for B’-21/k’Surface area: 1890 m2/gMicropore volume: 0.76 cm3/gHighest-density carbon
Sample S-30
Sample B’-21/k’
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Advisory Panel Meeting — February 27, 2006 20/25
• McEnaney et al. (GCMC,1997): Max. CH4 capacity inpores of width 1.1 nm
• Nicholson (1998): Van derWaals potential of CH4 in slitpore of width 1.1 nm
• Energy lost by adsorption ~2 x energy lost by condens.(latent heat at 109 K)
• Energy loss more thanenough to compress CH4
into dense fluid;remaining energy heat
Prediction of storage capacity and heat release
= 2.8 x 10–20 J
Compression vi vf (isobaric) from :
= vi
vf
cP (P,v)T
v
P
dv P(vf v i )
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Advisory Panel Meeting — February 27, 2006 21/25
Other developments
Methane storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC:
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1: 17 g/kg; 17 g/liter
2: 22 g/kg; 24 g/liter
Voids hostingmethane
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Advisory Panel Meeting — February 27, 2006 22/25
Other developments, cont.’d
Hydrogen storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC :
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1: 0.2 mass%2: 0.2 mass%
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3: 0.1 mass%
Methane storage capacity ofp-tert-butyl-calix[4]arene (TBC4),carbon nanotubes (CNT), andisoreticular metal-organic frameworks(IRMOF-1), at ~1 atm and 25 oC :
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Advisory Panel Meeting — February 27, 2006 23/25
Road test of carbon-based ALL-CRAFT ANG tank—Midwest Research Institute
Ford F-150 pickup for road test inKansas City (MRI, 4/06 - 9/06)
© M
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© M
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Advisory Panel Meeting — February 27, 2006 24/25
Renewable NG from landfills
• Collect & purify methane at landfill
• 40,000 lb carbon tank, with 17 wt% storage capacity, 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
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Advisory Panel Meeting — February 27, 2006 25/25
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 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 C
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