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)

5000 2000 1000* 600 300*

Power Density, /Specific Power 750 (W/l, W/kg)

Energy Efficiency (%)

80 78* 85*

15* 6* 30 <1

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

10

Cost ($/kW)

<0.5 10*

Start-Up to Full Power (min)

Inner Circle 2000 Targets Outer Circle 2004 Targets Status indicated by asterisk *

CO Content Steady State (ppm)

The PEM System Gasoline Fuel Processor

Air Fuel
Vaporize Preheat

)H<0
Reformer 700C

)H~0
Sulfur Removal

)H<0
Shifter 350-200C

)H<0 CO Removal
100-200C

Fuel Cell
80C

Water

350C

Heat

)H<0 Burner Exhaust

Challenges to On-Board Fuel Processing

o Complexity Complete reformer includes

multiple steps.
Fuel
ATR Reactor Shift Reactor 1 Shift Reactor 2 PROX 1 Sulfur Removal

H2 - Rich Gas

Fuel Vaporizer

Controls & Sensors

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 60

Product Composition, % (Dry)

H2

50 40 30 20 10 0 600 CH4 620 640 660 680 700 720 740 760 780 CO2 CO

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

Systems
l l l

Fuel Processing
l l l l l l l l

Stack Subsystem Components

l

Plug Power/NUVERA IFC Energy Partners, Honeywell ANL

NUVERA IFC McDermott

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

Plug Power Honeywell Arcadis U. Michigan/Nextech ANL, LANL, PNNL

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

l l l

Spectracorp LANL, LBNL

FY01: $7.6M

FY01: $21.5M

FY01: $12.4M

Total FY 01 Budget: $41.5M

Fuel-flexible Fuel Processors Under Development

Nuvera

Argonne

McDermott International Fuel Cells

Shift Catalyst Work

U. of Mich Nextech NUVERA IFC - McDermott
H2O

Gasoline Or Alcohol

10% CO

2,000 ppm CO

<100 ppm CO

REFOR MER or PARTIAL OXIDIZER

WATER GAS SHIFT REACTOR

PREFERENTIAL OXIDIZER

H2

O2
FUEL CELL STACK

CO + H2O CO2 + H 2

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

l l

13kW Achieved 98.6 Fuel Conversion 2100 W/L

%
40.00

=2.3
20.00

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

0 10 20 30

Conversion Selectivity to H 2 %H2 in effluent

0.00 40 50 60

time on stream (min)

Progress in Fuel-Flexible Fuel Processing

Full Scale Fuel Processing Being Demonstrated
Gasoline Fuel Cell

1997: 1999: 2000:

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

70 Product, % (dry, N2-free) 60 50 40 30 20 10 0 550 CH4 600 650 700 750 Temperature, C 800 CO CO2 850
Oxygen/Fuel = 8, Water/Fuel = 8

H2

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

60

Product, % (dry, N2-free)

50 40 30 20 10 0 760

H2
Oxygen/Fuel = 8, Water/Fuel = 8

CO 2 CO CH4
780 800 820 840 860 880

Temperature, C

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