ALL-CRAFT—Alliance for Collaborative Research in Alternative

Transcription

Progress Report
July 2005-Present
Advisory Panel Meeting
Midwest Research Institute, February 27, 2006
http://all-craft.missouri.edu
Advisory Panel Meeting — February 27, 2006
Copyright © 2006 — ALL-CRAFT. All rights reserved.
ALL-CRAFT—Alliance for Collaborative Research
in Alternative Fuel Technology
NSF Program “Partnerships for Innovation”
1/25
Programmatic Overview
2/25
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
Develop
sustainable
transportation
in U.S.
•
•
•
•
•
•
What are alternative fuels?
• 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
3/25
How do alternative fuels work together?
Long-term goal:
Hydrogen fuel-cell cars
Next-generation clean vehicles:
NG internal combustion engine
NG, methane
Ready to go:
NG from domestic (85%)
& Canadian (~rest) fields
In progress:
Renewable methane
from landfills & biomass
In 10-20 years:
Methane from deep-sea
methane hydrate fields
4/25
• 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 energy
technology, through research internships at MU and partner institutions
• Build outreach programs, statewide and at national level, for alternative
energy innovations and transition to a sustainable environment/economy
5/25
ALL-CRAFT Objectives
• MU (lead institution): Physics (Pfeifer, Project Leader), Chemistry (Atwood),
Chemical Engineering (Suppes), Civil Engineering (Bowders), Office of
Technology 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
6/25
ALL-CRAFT Partners
Current natural-gas vehicles
/ ozone, smog), NOx, particulate
• Low emission of hydrocarbons (
matter. NG stored as compressed natural gas (CNG) in steel or
composite 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
7/25
Why are we not already driving NG-fueled cars?
CNG cylinders in transit bus:
© AGLARG 1997
© AGLARG 1997
• ALL-CRAFT: Develop low-pressure, “flat-panel” tank, comparable to gasoline
tank, and safe (pressure: 34 atm, 500 psi). Store NG in nanoporous carbon
(pores adsorb NG like a sponge; ANG tank), made from corn cob:
Missouri
corn can
supply raw
material for
all cars in
the U.S.
8/25
• High-pressure cylindrical/spherical
tanks take up passenger or trunk
space.
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 of
all cars in U.S.)
– If captured, equivalent
to planting 300,000 km2
forest (2 x area of MO)
9/25
• 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, freeing
NG for transportation
• Renewable NG in the form of biogas from landfills, sewage, farms, feedlots
NGVAmerica, Feb. 8, 2006 (NYT, WSJ), in response to the
President’s State of the Union Address, Jan. 31, 2006
• 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 hydrogen
technology is based on NG technology
• Other countries are far ahead of us
10/25
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, Sean
Crockett, Monty Kemiki, Serean Spellerberg
• Chemistry: Jerry Atwood, Praveen Thallapally
• Civil & Environmental Engineering: John Bowders, Joshua Bergsten
ALL-CRAFT Accomplishments
Highlights July 2005 - February 2006
11/25
Carbon production & methane storage capacity
• 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)
M / V 73-95 g/liter
V / V 112-145 liter/liter
M / M 170-220 g/kg
ALL-CRAFT,
best performance
(Sample B’-21/k)
104-107 g/liter
159-163 liter/liter
210-220 g/kg
AGLARG,
best
performance
98 g/liter
150 liter/liter
170 g/kg
ANG
industry
target
118 g/liter
180 liter/liter
N/A
• Production of ~ 80 different carbons from
corn cob, with variable activation procedures
12/25
Methane storage capacity, cont.’d
NG storage capacity (g/liter), at 34 atm (500 psi) and 25 oC
180
140
120
91% of
industry
target
83% of
industry
target
100
80
60
40
160
140
120
100
80
ALL-CRAFT Sample B-21/k
Methane adsorption isotherm
60
40
20
20
0
0.0
0
Best AGLARG
carbon
ANG industry
target
CNG, at 250 atm
(3600 psi)
0.5
1.0
1.5
2.0
2.5
3.0
3.5
Pressure (MPa)
Methane Capacity (g/kg)
© AGLARG 1997
Best ALL-CRAFT
carbon
AGLARG sample
Methane adsorption isotherm
Pressure (psia)
160
Methane Capacity (g/kg)
180
13/25
4.0
Methane storage capacity, cont.’d
Methane uptake on
B-21/k with different
instruments, M / M
221 g/kg (± 2%)
209 g/kg (± 2%)
198 g/kg (± 4%)
0.6
0.5
0.4
0.3
Pore-size distribution
of B-21/k from
methane isotherm
0.2
0.1
0.0
Pressuredifference
measurement
of methane
uptake on 3.5”
carbon
briquettes (MRI
test fixture):
Gravimetric,
Chem. Eng.
Gravimetric,
Physics
Pressure
difference
Pore volume (cm3/g)
Gravimetric
measurement
of methane
uptake on
small samples:
0.4 - 0.6 - 1.0 - 1.5 - 2.0 - 4.0 - 6.0 - 10 - 15 - 20 - >50
0.6 1.0 1.5 2.0 4.0 6.0 10.0 15 20 50
Pore width range (nm)
14/25
What does the pore space look like? — Case Study B-18
dV/dr (cm3/Å/g)
1.0E+00
1.0E-01
1.0E-02
1.0E-03
N2 adsorption/desorption
isotherm (77 K) for B-18.
Surface area: 605 m2/g
1.0E-04
Differential pore volume
distribution, from N2
desorption isotherm, for B-18
Vol. in r < 10 Å: 0.13 cm3/g
Vol. in r = 10-20 Å: 0.15 cm3/g
Vol. in r = 20-1400 Å: 0.10 cm3/g
Power law: dV/dr ~ r –1.7
1.0E-05
Pore radius r (Å)
1.0E-06
Pressure (MPa)
0.0
0.5
1.0
Pore volume (cm3/g)
35
30
25
20
15
10
5
0
Adsorbed
CH4 (g/kg)
1
CH4 adsorption
isotherm (300 K)
for B-18
1.5
2.0
10
100
1000
10000
0.2
0.1
Pore-size distribution from
CH4 isotherm, for B-18
Consistent with
distribution from N2
0.1
0.0
2.5
0.4 - 0.6 - 1.0 - 1.5 - 2.0 - 4.0 - 6.0 - 10 - 15 - 20 0.6 1.0 1.5 2.0 4.0 6.0 10.0 15
20
50
Pore-size distribution from adsorption isotherms
(N2: standard; CH4: not widely used)
>50
Pore width range (nm)
15/25
Case Study B-18, cont.’d
1.E+10
Scattered intensity (cm–1)
Experimental data
Experimental and
calculated intensity
1.E+08
1.E+06
1.E+04
1.E+02
1.E+00
1.E-04
dV/dr ~ r –1.7 from
N2 adsorption
2.3-dimensional
fractal surface
1.E-03
1.E-02
Scattered wave vector
1.E-01
1.E+00
(Å–1)
1.E-02
Exper.
Calculated intensity: surface fractal at large
length scales (Ds = 2.3); pore-size distribution
from N2 adsorption at small scales:
I calc (q) = A
Calc.
Calc., PSD only
FormFactor(r , q)
0
dV dr
+ BqDs 6
3
dr r
Small-angle x-ray scattering (Advanced Photon Source, Argonne
National Laboratory) gives spatial arrangement of pores
16/25
Case Study B-18, cont.’d
Schematic model of pore space of B-18,
from scattering data
Model consistent with scanning
electron micrographs
Uncorrelated pores,
radii r = 7-1400 Å
(independent
scatterers),
nonfractal power law
dV/dr ~ r –1.7
Snapshots of simulation
of oxidative removal of
carbon by a chemical
agent (gray). Resulting
pore space is similar to
Sample B-18
Fractal surface,
Ds = 2.3
17/25
N2 ads./des. Isotherm for S-33/k
Micropore volume: 1.1 cm3/g
Superb candidate for H2 storage
Differential porevolume distribution,
from N2 isotherm, of
S-33/k
Most pores of width
< 10Å
Expected pore-space
structure: nearly spacefilling pore fractal, similar
to results of Pfeifer et al.,
Phys. Rev. Lett. 88,
15502 (2002):
Candidate for high-capacity H2 storage: S-33/k
18/25
Sample S-30
Sample B’-21/k’
N2 ads./des. Isotherm for S-30
Pure binder
N2 ads./des. Isotherm for B’-21/k’
Highest-density carbon
Pore-size distribution of other samples
19/25
Prediction of storage capacity and heat release
= 2.8 x 10–20 J
• McEnaney et al. (GCMC,
1997): Max. CH4 capacity in
pores of width 1.1 nm
• Nicholson (1998): Van der
Waals potential of CH4 in slit
pore of width 1.1 nm
• Energy lost by adsorption ~
2 x energy lost by condens.
(latent heat at 109 K)
Compression vi vf (isobaric) from :
=
• Energy loss more than
enough to compress CH4
into dense fluid;
remaining energy heat
T c P (P,v) dv P(v f v i )
vi
v P
vf
20/25
Other developments
1
1: 17 g/kg; 17 g/liter
2
2: 22 g/kg; 24 g/liter
2
1
Voids hosting
methane
Methane storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC:
21/25
Methane storage capacity of
p-tert-butyl-calix[4]arene (TBC4),
carbon nanotubes (CNT), and
isoreticular metal-organic frameworks
(IRMOF-1), at ~1 atm and 25 oC :
Hydrogen storage capacity of p-tert-R-calix[4]arenes, at ~34 atm and 25 oC :
1: 0.2 mass%
2: 0.2 mass%
3: 0.1 mass%
1
2
3
Other developments, cont.’d
22/25
© MRI 2006
© MRI 2005
Ford F-150 pickup for road test in
Kansas City (MRI, 4/06 - 9/06)
Road test of carbon-based ALL-CRAFT ANG tank—
Midwest Research Institute
23/25
Renewable NG from landfills
Methane recovery in transportable tanks
• 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
Operated as “dry 250 cuft/min
tomb,” 2005
15,000 lb/day
Operated as
980 cuft/min
bioreactor, 2020 57,000 lb/day
One tank full in
0.45 days
0.12 days
• Tanks of interest at small or abandoned landfills
• Collect & purify methane at landfill
24/25
Strategic and economic opportunities
• NG fueled cars = next-generation clean vehicles/transportation
1. Reduce smog, respiratory disease, cardio-vascular disease, …
2. Reduce greenhouse gas emissions
3. 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 landfills
1. Pollutant to energy
2. Economic growth in rural areas
• Duplicate ALL-CRAFT success for hydrogen tanks
State level
National 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
25/25

ALL-CRAFT—Alliance for Collaborative Research in Alternative

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