Microchannel Fuel Processing - Energy.gov...Microchannel Fuel Processing Fuel Cells for Transportation/Fuels for Fuel Cells 2002 Annual Program/Lab R&D Review May 6-10, 2002 Kriston

Microchannel Fuel ProcessingFuel Cells for Transportation/Fuels for Fuel Cells

2002 Annual Program/Lab R&D ReviewMay 6-10, 2002

Kriston Brooks, Jim Davis, Chris Fischer, Adam Heintzelman, Dave King, Larry Pederson, Susie Stenkamp,

Ward Tegrotenhuis, Bob Wegeng, Greg Whyatt

Pacific Northwest National Laboratory

U.S. Department of EnergyPacific Northwest National Laboratory 5/19/200

22

Objectives ApproachSteam Reformation

Improve power density, specific power Demonstrate fuel flexibility, transient response, 1000-hour durability (catalyst and reactor)Redesign for rapid startup

Water Gas Shift ReactorDifferential temperature design reduces reactor sizeCollaborate on catalyst formulations from industry

Preferential Oxidation ReactorInvestigate advantages of microchannel design

Demonstrate at ~1/10 scale amicrochannel-based fuel processing system that meets FreedomCAR performance targets.

Engage industrial partner(s) to facilitate development of full scale fuel processing system.Develop reactors, vaporizers, recuperative heat exchangers, and condensers broadly applicable to other fuel processing options.

Performance Criteria

Current Performance 2004 FreedomCAR Targets

50 kWe System Volume <1 cubic foot (<28L) 2.5 cubic foot (71 L)

Power Density, Specific Power

1800 W/L, 320 W/kg

700 W/L, 700 W/kg

System Efficiency 81% 76%

Durability >1000 h 4000 h

Transient Response (10 to 90%) 5 s 5 s

Start-Up to Full Power, 20oC 30 s (low dP projection), 15 m (current reactor block) <1 min

Steady State CO Content 15 ppm 10 ppm

Project Timeline

FY 2000Designed and built

10 kWe SR with integratedHX network

FY200110 kWe reactor testing

First “low dP” vaporizersModular test stand established

2002 2003 2004 2005 2006 2007 2008

Engineered catalyst, reactordevelopment

Demonstrate rapid startup

Sulfur management

Collaborate with industrial partner(s) on manufacturing, field testing, lifetime, controls

Integrated reformer/fuel cell demonstration at ~5 kWeFY 2002

SR fuel flexibility, durability testingWGS/PROX catalyst studies

Differential temperature reactor conceptSR/WGS/PROX initial integration

Full-scale low dP vaporizers delivered

FY 1999Fast SR kinetics

demonstrated in amicrochannel reactor

FY 1998Full-size gasoline

vaporizer/combustorR&D100 Award

Reforming Reactor HT WGS Reactor

LT WGS Reactor

Combustor

Reformate Recuperator


24

Reactor Volumetric Productivity Improved(isooctane at 3:1 S:C / GHSV basis: 1atm, 25C, exit conditions, bulk catalyst volume)

0.84

0.86

0.88

0.90

0.92

0.94

0.96

0.98

1.00

0 50,000 100,000 150,000 200,000 250,000 300,000

GHSV in Steam Reforming Reactor [hr-1 ]

Frac

tion

conv

ersi

on to

C1 C

ompo

unds

662C676C

684C

661C

672CFactor of ~3X Increase

in Processing Rate

680C660C

Catalyst A

Catalyst B


25

Fuel Flexibility Demonstrated(cat. “B”, 3:1 O:C / GHSV basis: 1atm, 25C, exit composition, bulk catalyst volume)

0.80

0.82

0.84

0.86

0.88

0.90

0.92

0.94

0.96

0.98

1.00

0 50,000 100,000 150,000 200,000 250,000 300,000

GHSV in Steam Reforming Reactor [h-1]

Frac

tion

conv

ersi

on to

C1 C

ompo

unds

Methane

Propane

Butane

Ethanol

Methanol

Isooctane

Benchmark Fuel

Methanol (646-663C)

Butane (643-702C)

Isooctane (661-664C)

Ethanol (663-652C)Methane (644-657C)


26

012345678

0.0 5.0 10.0 15.0

secondsre

form

ate

flow

liquid inputsreduced from 100%

to 10%

liquid inputsincreased from 10%

to 100%

0.0%

10.0%

20.0%

30.0%

40.0%

50.0%

60.0%

70.0%

80.0%

90.0%

100.0%

0 100 200 300 400 500 600 700 800 900 1000

Elapsed Time Reforming Benchmark Fuel [hr]

% C

onve

rsio

n to

C1 C

ompo

unds

99.8%99.4%93.4% 97.0%

26 hr Steam Purge andBackpressure Regulator Change

74 wt% isooctane20 wt% xylene5 wt% methyl cyclohexane1 wt% 1-pentene

BenchmarkFuel

3:1 S:C ratio650oC

Response to step changes in liquid fuel andwater feed rates of 100% to 10% and 10%to 100% in 51 cc reactor

Durability and Transient Response1000-Hour Reforming Test 5 Second Warm Transient Response


27

Air-CooledGradient WGS

Section

Steam&Fuel-Cooled Gradient

WGS Section

Steam Reforming Reactor

Reformate Recuperator

Combustor

WaterVaporizer

Fuel Vaporizer

HT Air Recuperator

ManualAdjustment

Valves

CatalystScreening

KineticModel

ReactorModeling

Reactor Prototypes

Integrate into

system

y = 34686e-10368x

R2 = 0.9627

0.00001

0.0001

0.001

0.01

0.00150 0.00170 0.00190 0.002101/T (1/K)

Kin

etic

Co

effic

ien

t (m

ol C

O /s

.g c

at)

0

20

40

60

80

100

200 225 250 275 300 325

Temperature, C

CO

Co

nve

rsio

n, %

Equil CO Conversion

WHSV = 75393

Water-Gas Shift DevelopmentApproach / Progress


28

WGS Catalyst ScreeningSud-Chemie Copper-Zinc (T2650) and Precious Metal/Ceria (PMS5)

Low Shift Feed at 0.5 S/G

0

20

40

60

80

100

200 225 250 275 300 325Temperature, C

CO

Con

vers

ion,

%

EquilibriumT2650 @ GHSV = 60,000T2650 @ GHSV =30,000PMS5 @ GHSV=75,000

PMS5 preferred for microchannel WGS development


29

Water-Gas ShiftWhy microchannels? – To control temperature profile

HTS LTS

Hxr

Conventional 2-stage Adiabatic

200

300

400

500

600

700

0 0.2 0.4 0.6 0.8 1

Fraction of catalystTe

mpe

ratu

re (C

)250

300

350

400

450

0.0 0.3 0.5 0.8 1.0

Fraction of catalyst

Tem

pera

ture

(C)

1 Integrated Unit2.3X Less Catalyst

Based on Sud-Chemie PMS5 PM catalyst and SR reformate

Ideal profile


210

Differential Temperature Water-Gas ShiftReactor volume < 3L projected from experimental results

150,000 GHSV, 0.5 Steam/Dry Gas, 4.6% CO Feed

Differential temperature out performs isothermal operation

Prototype 7-channel ReactorPrototype 7-channel Reactor

1

1.5

2

2.5

250 275 300 325 350 375

Temperature, oC

CO

Out

let C

once

ntra

tion

(mol

e %

)

kineticallylimited

equilibriumlimited

isothermal

differential temperature(350 270oC) equilibrium

Reactor can be operated isothermally or with a temperature gradient


211

Performance of Engineered PROX Catalysts

Stage 2 PROX Performance of Precious Metal Catalyst in a Single Channel Reactor: 0.1% CO, 100oC, GHSV = 200K; S/G=0.3

010

2030

4050

6070

8090

100

0.50 1.50 2.50 3.50 4.50

O2/CO

% C

O C

onve

rsio

n or

O2 S

elec

tivity

Conversion

Selectivity

35 ppm CO 15 ppm CO

30

40

50

60

70

80

90

100

140 160 180 200 220 240

Temperature, C

CO

Con

vers

ion,

%

30

40

50

60

70

80

90

100

O2

Sele

ctiv

ity, %

Base Metal

Precious Metal

Base Metal

Precious Metal

Stage 1 PROX, Precious and Base Metal Catalysts ; 1% CO, O2/CO = 1, GHSV = 400K, S/G = 0.3

Base metal catalyst preferred for Stage 1; Precious metal catalyst preferred for Stage 2


212

Industry InteractionsFormally seeking to engage industrial partnerWater Vaporizer for 50 kWe ATR designed, built,

tested and delivered to McDermott Technology, Inc.Water Vaporizer delivered to Gas Technology

Institute for boiler-related research, funded by OIT.Interaction with Engelhard, Süd Chemie, NexTech,

and ANL for catalyst formulationsVaporizer and recuperator delivered to Innovatek for

Army reformer demonstration50 kWe Water Vaporizer Panel Size:

dimensions 22.2 cm x 10 cm x 1.8 cmweight = 2.4 kg

At max operating point:HX duty = 24.6 kWHX intensity = 60 W/cm3

Steam225oC, 425 kPa abs.

Water23oC, 4.08 g/s

Combustion Gas685oC, 69.1 kg/h

Combustion Gas157oC, ambient pressuredP = 5 in. H2O

Sample Operating Point


213

Plans, Future MilestonesComplete catalyst optimization (FY03)WGS, PROX reactor development and integration (FY03)High temperature reformation/sulfur tolerance study complete (FY02)Demonstrate rapid start-up concepts based on low dP design (FY03)Develop sulfur management approach (FY03)Engage industrial partner(s) to facilitate development (FY03)Demonstrate fast-start, integrated fuel processor at 5 kWe, and operate with a PEM fuel cell (FY04)


214

Rapid Cold Start Concept for Steam ReformerLow combustion gas dP key to rapid startup (30 second start projected)Target test system has four reformer stages with one water vaporizer

Key Data For 30-Second Startup Calculation - 2.4 kWe System∆P at Normal Cond. ∆P at Startup

(~60 SLPM, Air) (~800 SLPM, Air)

Reforming Reactor, 650C (4 stages, 600We each)

720 g (180 g, per stage)

1.6 in H2O (0.4 in H2O, per stage)

21.3 in H2O (5.33 in H2O, per stage)

Water Vaporizer (1 stage) 91 g 0.1 in H2O 1.3 in H2O

MassComponent


215

Responses to Comments from Last YearAn effort should be made to test this reformer with methanol: Tests conducted showed that methanol was the most easily reformed of all fuels evaluated. Productivity is >2x higher than rate for benchmark gasoline, or ~4 kWe/L.Engage an industrial partner to build a complete reforming system:Formal process underway.More studies evaluating catalyst performance and life:

Completed 1000 hour reformer durability test on benchmark gasoline.Commercial and prototype WGS and PROX catalysts extensively studied in powder and engineered form.Developed single channel reactors that provide flexibility in testing of engineered catalysts, provide data to develop kinetic model.

Documents

Microchannel Fuel Processing - Energy.gov...Microchannel Fuel Processing Fuel Cells for Transportation/Fuels for Fuel Cells 2002 Annual Program/Lab R&D Review May 6-10, 2002 Kriston