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