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HYDROGEN STORAGE ON CARBONIZED CHICKEN
FEATHER FIBERS
Erman Şenöz, Richard P. WoolDepartment of Chemical Engineering
University of Delaware
13th Annual Green Chemistry & Engineering Conference, June 23, 2009
OUTLINE
IntroductionStorage Problem OverviewStructure of Chicken Feather Fibers (CFF)
Experimental ResultsThermal Analysis (DSC and TGA with Mass Spec.)Hydrogen Storage Results
ConclusionsAcknowledgements
Hydrogen Facts
Energy density ~3 times larger than gasoline1
Fuel cells are at least 2 times more efficient than combustion engines2
Gasoline density: 0.75 kg/LH2 density at STD: 8.98x10-5 kg/L 8000 times lighterH2 density at 350 bars: 0.025 kg/L 30 times lighterLiquid H2: 0.07 kg/L 11 times lighter
If a material fulfills the DOE H2 storage targets for 300 miles range:
~75 kg/vehicle is required
$5.5 million/vehicle is required for SWCNT$22, 000/vehicle is required for MWCNT
1 Louis Schlapbach, MRS Bull., 20022 Jesse L. C. Rowsell and Omar M. Yaghi, Angew. Chem. Int. 2005,44, 4670-46793 UDaily Archive April 9, 2007
Hydrogen Powered UD Bus3
OBJECTIVESTo find the best process to obtain H2 storage material from waste materials, chicken feather fibers (CFF)
To fulfill Department of Energy’s (DOE) 2010 H2storage targets which are
Gravimetric Capacity= 6 wt% H2 (light)Volumetric Capacity= 45 g H2/l (compact)System Storage Cost= $4 /kWh (cheap to store)System Cost= $666 (cheap)
for future H2 powered technologies.
BackgroundPhysisorption
(∆Hads= ~4 kJ/mol)GraphiteCarbon NanofibersCarbon NanotubesMetal Organic Frameworks (MOF)Activated Carbon
Chemisorption(∆Hads = ~50-100 kJ/mol)
Metal HydridesComplex Hydrides
Status of hydrogen storage vs. system targets as of 20081
1 Annual Progress Report, DOE Hydrogen Program, 2008
Chicken Feather Fiber (CFF) Properties
Bio-renewableAgricultural wasteVery cheap!6 µm diameter1
Above 92% Keratin2
Hollow tubes1
Low density SEM image of CFF, X1000 magnification
1 Hong, Chang K and Richard P. Wool “Development of a Bio-based Composite Material from Soybean Oil and Keratin Fibers” 20052 Farner, Donald S. et al. Avian Biology. vol 6. Academic Press, New York: 1982.
α-helix KeratinStructure
0 2 4 6 8 1 0 1 2 1 4 1 6 1 8 2 0 2 2 2 4 2 6 2 8 3 0 3 2
0
5 0
1 0 0
1 5 0
2 0 0
2 5 0
3 0 0
3 5 0
4 0 0
4 5 0
Tem
pera
ture
(0 C)
T im e (h )
XPS ANALYSIS OF PYROLYSIS OF CFF
215 0C
400-450 0C
Specific Surface Area =
100-450 m2/g
Pore Volume = 0.06 - 0.2 cm3/g
Pore Size=< 1 nm
Carbonized Chicken Feather Fiber (CCFF)
Crosslinking
40 60 80 100 120 140 160 180 200 220 240 260
Temperature (0C)
Endotherm
With isotherm at 215 0C
With isotherm at 185 0C
2 hrs isothermal heat treatment at 215 215 00CC
2 hrs isothermal heat treatment at 185 185 00CC
MELTING PEAK !
NO MELTING !
Thermal Analysis of CFF (TGA and DSC)
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 01 0
2 0
3 0
4 0
5 0
6 0
7 0
8 0
9 0
1 0 0
Wei
ght (
%)
T e m p e ra tu re ( 0 C )
- 0 .6
0 .0
0 .6
Heat Flow
(W/g)
Melting transition is at ~230 0C
Thermal Analysis of CFF (TGA and DSC)
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0-1 0
-8
-6
-4
-2
0
Deg
rada
tion
Rat
e (%
/s)
T e m p e ra tu re ( 0 C )
- 0 .6
- 0 .3
0 .0
0 .3
0 .6
Heat Flow
(W/s)
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0
1 E -3
0 .0 1
0 .1
1
1 0
Elec
tron
Cur
rent
(nA)
T e m p e r a tu r e ( 0 C )
3 4 2 2 1 8 8 9 7 6 6 7 6 6 6 5 6 4 6 0 5 8 5 5 5 1 5 0 4 8 4 4 1 0 6 1 0 3 9 4 9 1
Thermal Analysis (TGA+Mass Spec.)
Thermal Analysis (TGA+Mass Spec.)
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 00 .0 0
0 .0 5
0 .1 0
0 .1 5
0 .2 0
Ele
ctro
n C
urre
nt (n
A)
T e m p e ra tu re ( 0 C )
3 4 (S H 2+ )
7 6 (C S2
+ )
6 4 (S O 2+ , S 2
+ )
4 8 (C H 3S H + ,S O + )
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0
T e m p e ra tu re ( 0 C )
1 8 (H 2O + )-S-S-
-S-S--S-S-
-S-S-
-S-S-
-S-S-
Methionine Cysteine
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 00 .0 0
0 .0 5
0 .1 0
0 .1 5
0 .2 0
Ele
ctro
n C
urre
nt (n
A)
T e m p e ra tu re ( 0 C )
3 4 (S H 2+ )
7 6 (C S2
+ )
6 4 (S O 2+ , S 2
+ )
4 8 (C H 3S H + ,S O + )
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0
T e m p e ra tu re ( 0 C )
1 8 (H 2O + ) --NH-C-----
-NH-C---
-----NH-C------
-----NH-C------
=O
=O=O=O
Thermal Analysis (TGA+Mass Spec.)Glutamic Acid ArginineAspartic
acidLysine
---NH-C---=O
Thermal Analysis (TGA+Mass Spec.)
0 50 100 150 200 250 300 350 400 450 500 550 600
1E-3
0.01
Elec
tron
Cur
rent
(nA)
Temperature (0C)
66 65 51 91 106 0 1 00 20 0 3 00 40 0 50 0 60 0
1E -3
0 .01
Elec
tron
Cur
rent
(nA)
T e m pe ra tu re (0C )
89 76 66 50 10 3
89103
103766650
0 1 0 0 2 0 0 3 0 0 4 0 0 5 0 0 6 0 0
1 E -3
0 .0 1E
lect
ron
Cur
rent
(nA
)
T e m p e ra tu re ( 0C )
6 7 5 5
Hydrogen Uptake Capacities
5 10 15 20 25 30 35 40 45 500.0
0.3
0.6
0.9
1.2
1.5
350 0C 400 0C 420 0C 450 0C
Hyd
roge
n U
ptak
e (w
t%)
Pressure (bar)
Hydrogen storage capacities of CCFF heated up to 350, 400, 420, 450 0C for 2 hrs
0.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
Maximum Heating Temperature (0C)
450420400
Hyd
roge
n S
tora
ge C
apac
ity (w
t%)
350
Hydrogen Uptake Capacities
0 10 20 30 40 500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
1 hr 1.5 hr 2 hrH
ydro
gen
Upt
ake
(wt%
)
Pressure (bar)
5 10 15 20 25 30 35 40 45 500.0
0.2
0.4
0.6
0.8
1.0
1.2
1.4
1.6
2 hr 1.5 hr 1 hr
Hyd
roge
n U
ptak
e (w
t%)
Pressure (bar)
1.0 1.5 2.00.0
0.5
1.0
1.5
Hyd
rgoe
n St
orag
e C
apac
ity (w
t%)
Heating time at 450 0C (hr)
Hydrogen storage capacities of CCFF heated up to 450 0C for 1, 1.5 and 2 hrs
performed at 77K
Hydrogen storage capacities of CCFF heated up to 400 0C for 1, 1.5 and 2 hrs
performed at 77K
1.0 1.5 2.00.0
0.5
1.0
1.5
Hyd
roge
n St
orag
e C
apac
ity (w
t%)
Heating time at 400 0C (hr)
ConclusionsCFF structure can be retained even at high temperatures by crosslinking during heat treatment. Sulfur and Amide crosslinks play an important role.
Above 260 0C systematic aromatization and cyclization reactions take place accompanying the degradation.
Optimized heating time and temperature values were determined:400 0C for 1.5-2 hrs or 450 0C for 1hr
Pore size distribution is quite suitable for H2 storage.
Seeking other applications for the CCFF? Gas separation and purificationMechanical properties of non-porous CCFF samplesSeparation of pyrolysis products
ACKNOWLEDGEMENTS
This project was supported by the National Research Initiative of the USDA Cooperative State Research, Education and Extension Service, grant number 2005-35504-16137.
Anne Dillon - National Renewable Energy Laboratory
The Wool Research Group
The Lobo Group
George Whitmyre - Colburn Lab Manager
Steve Sauerbrunn - METTLER TOLEDO
How to reach 300 miles range?
Required adsorbent mass and CCFF tank volume to build a car with 300 miles range
0 1 2 3 4 5 6 7 8 9
0200
400600800
1000
12001400
Vo
lum
e of
Sto
rage
Ta
nk w
ith C
CFF
(lite
rs)
wt% H2 Storage
101 liter
0 1 2 3 4 5 6 7 8 90
200
400
600
800
1000
75.6 kgMas
s of
Ads
orbe
nt
M
ater
ial (
kg) Hydrogen’s extreme
low density requires huge tanks!
Relatively high wt% H2 storage values has to be achieved!
Material has to be as cheap as possible!
DOE Target
Thermal Analysis (TGA+Mass Spec.)89103
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0
1 E -3
0 .0 1
Elec
tron
Cur
rent
(nA
)
T e m p e ra tu re ( 0C )
8 9 7 6 6 6 5 0 1 0 3
103766650
Thermal Analysis (TGA+Mass Spec.)
6755
0 5 0 1 0 0 1 5 0 2 0 0 2 5 0 3 0 0 3 5 0 4 0 0 4 5 0 5 0 0 5 5 0 6 0 0
1 E -3
0 .0 1
Ele
ctro
n C
urre
nt (n
A)
T e m p e ra tu re ( 0 C )
6 7 5 5