Fuel Cells for Transportation:

Fuel Processing Technology

Patrick B. Davis, JoAnn Milliken, William Cleary and Donna L. Ho

Office of Transportation Technologies
Office of Advanced Automotive Technologies
U.S. Department of Energy
SECA Workshop
February 14-15, 2001
Atlanta, Georgia

Fuel Options for PEM Transportation Systems

HYDROGEN
HYDROGEN
FUEL
FUEL
CELL
CELL
FUEL
FUEL
PROCESSOR
PROCESSOR

H2- Rich
Gas

q Hydrogen can be stored and supplied directly to

the fuel cell: Storage and Infrastructure Issues

Hydrogen can be derived from fuels such as
ethanol, methanol, natural gas, gasoline or FT
fuels: Complexity, Cost, and Start-up Issues
q

Status vs Technical Targets

50-kW Gasoline Fuel Processor for PEM Fuel Cells
Emissions
<Tier II*

Durability
(hours)

Power Density, /Specific Power

750
(W/l, W/kg)

5000
600

2000

300*
1000*

Energy
Efficiency
(%)

80 78*

15*

85*

Transient
Response
(10-90% Power)
(sec)

6*
<1

30
10

Cost
($/kW)

<0.5
10*

CO Content
Steady State
(ppm)

Start-Up to Full Power

(min)
Inner Circle
2000 Targets
Outer Circle 2004 Targets
Status indicated by asterisk *

The PEM System Gasoline Fuel Processor

Fuel

Water

Vaporize
Preheat

Air
)H<0

)H~0

Reformer

Sulfur
Removal

Shifter

350C

350-200C

700C

Heat

)H<0

)H<0
CO
Removal
100-200C

)H<0
Burner
Exhaust

Fuel
Cell
80C

Challenges to On-Board Fuel

Processing
o Complexity Complete reformer includes

multiple steps.
Fuel

ATR
Reactor

Fuel
Vaporizer

Shift
Reactor 1

Shift
Reactor 2

Controls & Sensors

PROX
1

Sulfur
Removal

H2 - Rich
Gas

Heat
xchange

o Cost complexity, sophisticated catalysts,

control technology and high temperature

operation combine to make the cost goal of
$10/kW difficult.
o Fuel Gasoline may have to be tailored for the

fuel cell application - a moderate infrastructure

challenge.

Autothermal Fuel Processing

Fuel Flexible & Thermally Favorable

CnHmOp + x(O2+3.76N2) + (2n-2x-p)H2O =

nCO2 + (2n-2x-p+m/2)H 2 + 3.76xN2
o Process control thermodynamics is a function of

the oxygen-to-fuel ratio (x). H = 0 at x = 5.86

Lower heat exchange requirements, reducing the size
and weight of the fuel processor
improved cold starting initially using high oxygen to
fuel ratio
Improved transient response only requires
adjustment to feed rate while maintaining constant
feed proportions (oxygen-fuel and water-to-fuel)

Autothermal Reforming of Gasoline Using

an ANL Catalyst
70

Product Composition, % (Dry)

60

H2

50
40
30
CO2

20

CO
10
0
600

CH4
620

640

660

680

700

720

740

760

780

Reactor Temperature, C

o Theoretical maximum hydrogen percentage = 66%

o No performance degradation: 1700 hrs. on gasoline containing

0.01 wt% sulfur

1on

a nitrogen-free basis

Projects and Funding by

Budget Category
Fuel Processing

Systems
l

Plug Power/NUVERA

NUVERA

IFC

IFC

Energy Partners,
Honeywell

ANL

FY01: $7.6M

Stack Subsystem
Components
l

McDermott
l

l
l

Plug Power
Honeywell

Arcadis

U. Michigan/Nextech

ANL, LANL, PNNL

FY01: $21.5M

Energy Partners,
AlliedSignal,
IFC, Plug Power
IGT, Electrochem

3M, SwRI/Gore,
Foster-Miller
l Vairex, A.D. Little,
Honeywell, Meruit
l

l
l

Spectracorp
LANL, LBNL

FY01: $12.4M

Total FY 01 Budget: $41.5M

Fuel-flexible Fuel Processors Under

Development

Argonne

Nuvera

McDermott
International Fuel
Cells

Shift Catalyst Work

U. of Mich Nextech NUVERA IFC - McDermott
H2O

Gasoline
Or
Alcohol

2,000 ppm
CO

10%
CO

REFOR MER
or
PARTIAL
OXIDIZER

WATER GAS SHIFT

REACTOR

CO + H2O CO2 + H 2

<100 ppm
CO

PREFERENTIAL
OXIDIZER

O2

H2

FUEL CELL
STACK

H=

-9.7 kcal/mol

Microchannel Iso-Octane Steam Reforming

PNNL
Technical feasibility of microchannel steam reforming established
Complete fuel processor system: < 1 ft3
100.00

80.00

60.00

%
40.00

ms
T=650 C
S:C = 6
Feed = 2.54 ccm

Conversion
Selectivity to H 2
%H2 in effluent

0.00
0

13kW Achieved

98.6 Fuel Conversion

=2.3
20.00

10

20

30

40

time on stream (min)

50

60

2100 W/L

Progress in Fuel-Flexible
Fuel Processing
Full Scale Fuel Processing Being Demonstrated
Gasoline

1997:
1999:
2000:

Fuel Cell

Power

Worlds First Demonstration

of PEM Fuel Cell Power from
Gasoline - <1kW
Plug Power & Epyx (NUVERA)
Demonstrate 10kW System
on Multiple Fuels Including
Gasoline, Methanol, and
Ethanol
IFC Demonstrates 50 kW,
Automated System on
Gasoline. Plug
Power/NUVERA
System Demonstrated.

The Program Supports

Diesel Reforming in Two Ways
PEM Reformers Indirectly Support Diesel:
o CO clean-up projects all directly applicable to diesel reforming.
o ANL autothermal catalyst, Nextech and U. of Michigan shift catalysts

applicable to a diesel reformer.

o Initiating a significant sensors effort necessary for control of all types of

reformers.
o A large part of our program focuses on reformate tolerant stacks,

necessary for any type of reformed fuel PEM system.

Direct Support of Diesel for Solid Oxide:

o Diesel reforming work at ANL initiated by DOE Hydrogen program being

continued for solid-oxide applications.

o Work at LANL being initiated

Suitable process temperature for

hexadecane is 750C
Product, % (dry, N2-free)

70
H2

60
50

Oxygen/Fuel = 8, Water/Fuel = 8

40
30
20
10
0
550

CH4
600

650
700
750
Temperature, C

800

CO
CO2
850

Autothermal reforming of
diesel (D-2) fuel yielded 50% H2

Product, % (dry, N2-free)

60

H2

50
40

Oxygen/Fuel = 8, Water/Fuel = 8

30

CO 2

20

CO

10
0
760

CH4
780

800

820

840

Temperature, C

860

880

Issues in Diesel Processing for

SECA
o Fuel vaporization
o

o
o

Solution: liquid fuel injection

Coke formation
Solutions: catalyst, high temperature, excess water
Would like to reduce the amount of water used
Sulfur poisoning
Solution: S-tolerant catalyst, scrubber
High temperature sulfur removal is a potential issue
Byproduct hydrocarbons
Solution: catalyst selectivity, high temperature
Solid Oxide reformer potentially 1/10th the size of a PEM
reformer, except for sulfur removal issue

Current Solicitation Addresses Key

Fuel Processing Barriers
Solicitation Website:
www.doeal.gov/cpd/readroom.htm
q Advanced fuel processing technology
q Water-gas shift catalysts
q Balance of plant (sensors, actuators, heat exchangers)

Solicitation Closes February 15