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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Programmatic Overview

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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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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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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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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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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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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.

© A

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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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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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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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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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Methane storage capacity, cont.’d

© A

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

0

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60

80

100

120

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160

180

Best ALL-CRAFT

carbon

Best AGLARG

carbon

ANG industry

target

CNG, at 250 atm

(3600 psi)

91% ofindustry target

83% ofindustry target

Meth

an

e C

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g/k

g)

Pressure (psia)

AGLARG sample

Methane adsorption isotherm

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0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0

Pressure (MPa)

Me

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Ca

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g/k

g)

ALL-CRAFT Sample B-21/k

Methane adsorption isotherm

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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

volu

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cm3/g

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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)

0

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25

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35

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CH4 adsorptionisotherm (300 K)for B-18

Adso

rbed

CH

4 (

g/k

g)

Pressure (MPa)

1.0E-06

1.0E-05

1.0E-04

1.0E-03

1.0E-02

1.0E-01

1.0E+00

1 10 100 1000 10000

Differential pore volumedistribution, from N2

desorption isotherm, for B-18

Pore radius r (Å)

dV

/dr

(cm

3/Å

/g)

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 width range (nm)

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Pore-size distribution fromCH4 isotherm, for B-18 Consistent with

distribution from N2

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Case Study B-18, cont.’d

Small-angle x-ray scattering (Advanced Photon Source, ArgonneNational Laboratory) gives spatial arrangement of pores

1.E-02

1.E+00

1.E+02

1.E+04

1.E+06

1.E+08

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1.E-04 1.E-03 1.E-02 1.E-01 1.E+00

Exper. Calc. Calc., PSD only

Scattered wave vector (Å–1)

Sca

ttere

d in

tensi

ty (

cm–1)

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

dr

dr

r 30

+ BqDs 6

2.3-dimensionalfractal surface

dV/dr ~ r –1.7 fromN2 adsorption

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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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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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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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• 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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Other developments

Methane storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC:

1

2

1

2

1: 17 g/kg; 17 g/liter

2: 22 g/kg; 24 g/liter

Voids hostingmethane

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Other developments, cont.’d

Hydrogen storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC :

1

2

1: 0.2 mass%2: 0.2 mass%

3

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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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

RI 2006

© M

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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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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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