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Reactor development for a steam reforming fuelprocessor for diesel fuel in the kW range

Marius Maximini1, Philip Engelhardt1, Martin Brenner2,Andrea De Toni3, Hans-Georg Anfang3

1Oel-Waerme-Institut GmbH, Germany2 BEHR GmbH & Co. KG, Germany

3Süd-Chemie AG, Germany

Berlin, 12.04.2012

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Outline

Project introduction and background

Reactor development for mixture preparation

Reformer development and testing

Summary

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Introduction

MÖWE 2 ProjectDevelopment of an integrated fuel cell system comprising a 10 kWth diesel fuel processorand a 4 kWel LT-PEM fuel cell

Diesel fuel High availability, existing infrastructure easy market entry High energy density compact size Easy storage

Steam reforming Highest hydrogen yield of all reforming processes No dilution of reformate gas with atmospheric N2

LT-PEM fuel cell Technical maturity High availability

Market: APU for recreational applications

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Introduction

Modular fuel cell system fuel processor adaptable for LT-PEM and HT-PEM fuel cells

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New multifunctional reactor (Prototype developed with J. Eberspächer GmbH & Co. KG)

Start-up burner

Cool Flame reactor for fuel evaporation

Diesel / steam mixer

Operation: Start-up burner + Diesel/steam mixer

on reformer side

Start-up burner + Cool Flame reactor on burner side

Electrical heating for Cool Flame and mixer operation

Reactor development

T2

Porous surfaceT1

Air / H2O

Diesel

T3

Electrical heating

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Burner operation Characteristics for safe ignition

determined

Fuel input can be increased after ignition

Operation shown for fuel inputs up to 3 kWth

Flame stabilizes in the reactor front

Air excess ratio may be increased for lower outlet temperatures less thermal stress on the reformer

Reactor development

Start-up burner, ignition

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

0.0 0.5 1.0 1.5 2.0 2.5 3.0

Fuel input / kW

Air

exce

ss ra

tio

ignition successful

Burner operation, temperatures at = 2.5

700

800

900

1000

1100

1200

1 1.5 2 2.5 3 3.5Fuel input / kW

Tem

pera

ture

/ °C

T 1

T 2

T 3

T2

T1

T3

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Cool flame start-up procedure, target temperature T1 = 420°C

0

200

400

600

800

1000

1200

00:00 00:05 00:10 00:15 00:20Runtime / hh:mm

Tem

pera

ture

/ °C

0

2

4

6

8

10

12

Fuel

inpu

t / k

W,

air e

xces

s ra

tio

Pfuel

T1

T2

T3

Steady state cool flame operation

0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

410 420 430 440 450 460 470Temperature at T1 / °C

Air

exce

ss ra

tio

1 kW 1,5 kW 2 kW 2,5 kW 3 kW

Temperature control by air excess ratio

Steady state operation shown at 1 – 5 kWth

Cool flame operation Preheating in burner mode

Cooling down to cool flame temperature level

Start of the cool flame reaction at an air excess ratio < 1

Reactor development

T2

T1

T3

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0

2

4

6

8

10

12

00:00 00:30 01:00 01:30 02:00 02:300

200

400

600

800

1000

1200Electrical heating

runtime / hh:mm

TReformer, Pos.6

Pel

PCool flame

PReformer

el. P

ower

, fue

l inp

ut /

kW

Tem

pera

ture

/ °C

Cool flame Reformer start

Deployment of the reactor in the 10 kWth fuel processor Reduction of FP start-up time > 60 % by using one multifunctional reactor as Cool

Flame reactor instead of electrical heating device

Minimal electric power consumption

Start-up time < 30 min expected when deploying a second reactor for diesel/steam mixing

(based on experimental data from P.Engehardt, 2012)

Reactor development

0

2

4

6

8

10

12

00:00 00:30 01:00 01:30 02:00 02:300

200

400

600

800

1000

1200

runtime in hh:mm

T Reformer, Pos.6

PCool flame

Fuel

inpu

t / k

W

Tem

pera

ture

°C

T

Cool flame

Start-up Burner

Reformer start

PReformer

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Reformer development on downscaled steam reformers Catalytically coated plate heat exchanger

Microchannels with 0.6 mm channel height

Scaling by plate number reduction, original plate size

Design point of Pth = 1 kW at GHSV = 25,000 h-1

Reformer testing Süd-Chemie HyProGenTM catalyst coating

Steamreforming

Combustion

Temperature measurement plate

1

2 4

5

6

8

7 9 10 11Flowdirection

3

Steam reformingCombustion

Reformer development

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Test program Variation of

steam to carbon ratio (S/C),

operating temperature,

and fuel input

Reforming of Diesel surrogate (Shellsol mixture)

Reforming of commercial diesel (Shell petrol station)

Catalyst testing

Diesel surrogateMixture of ShellSol A 100 + ShellSol D 100

SMS 1897< 2 wt.ppmSulphur

SMS 272820 wt.%Aromatics

GC32 wt.%Naphtenes

GC48 wt.%Paraffins

Method of analysisValueFraction

Commercial diesel (ULSD)Shell

DIN EN 1291621.1 wt.%Aromatics

DIN EN 140786.4 vol.%FAME

DIN EN ISO 208466.4 wt.ppmSulphur

ASTM D 5291 mod.1.3 wt.%Oxygen

DIN 51 73213.5 wt.%Hydrogen

DIN 51 73284.5 wt.%Carbon

Method of analysisValueFraction

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Gas concentrations, diesel surrogate, Pth = 1.25 kW

0

10

20

30

40

50

60

70

2 2.5 3 3.5 4 4.5S/C

Con

cent

ratio

ns /

% v

/v

(dry

bas

is)

0

3

6

9

12

15

18

21

Con

cent

ratio

ns /

% v

/v

(dry

bas

is)

Temperature T6 = 700°CTemperature T6 = 800°C

CO2

CO

H2

CH4

Catalyst testing

Diesel surrogate reforming No diesel residues found by GC analysis (CH4 and CO2 are the only by-products found)

Complete fuel conversion achieved over the entire parameter range

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Residual hydrocarbons and fuel conversion, Pth = 1.25 kW

0

5

10

15

20

25

30

35

40

45

50

675 700 725 750 775 800

Reformer outlet temperature T11 / °C

CxH

y con

cent

ratio

n /

10³ v

ppm

CH

4 equ

ival

ent

(wet

bas

is)

50

55

60

65

70

75

80

85

90

95

100

Con

vers

ion

rate

/ %

mol

/mol

S/C = 4, 30 min S/C = 4, 90 minS/C = 3, 30 minS/C = 3, 90 min

0

Conversion rate

Σ CxHy

time

time

Catalyst testing

Commercial diesel reforming Complete fuel conversion at outlet temperatures > 740°C, slight degradation after 90 min

Rapid catalyst deactivation at low temperatures, but reversible

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Coke / carbon formation, Pth = 1.25 kW

0

10

20

30

40

50

60

70

80

90

100

675 700 725 750 775 800Reformer outlet temperature T11 / °C

carb

onac

eous

dep

osits

/ m

g/kW

h

Diesel S/C = 4Diesel S/C = 3Diesel surrogate S/C = 4Diesel surrogate S/C = 3

Catalyst screening

Commercial diesel reforming Coke / carbon formation increased using commercial diesel compared to diesel surrogate

Low temperatures and low S/C increase the effect

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GC analysis, 10 h steam reforming of commercial diesel at T6 = 750°C , S/C = 4, Pth = 1.25 kW, GHSV = 31,000 h-1

0

1

2

3

4

5

6

1:00 2:00 3:00 4:00 5:00 6:00 7:00 8:00 9:00 10:00

runtime / hh:mm

Con

cent

ratio

ns /

10³ v

ppm

(d

ry b

asis

)

0

0.1

0.2

0.3

0.4

0.5

0.6

Con

cent

ratio

ns /

10³ v

ppm

(d

ry b

asis

)

CH4C2H6C2H4C3H8C3H6C4H10C5H12

CH4

Aromatic residuals in the reformate

Commercial diesel reforming Selectivity suffers from catalyst deactivation

Hydrocarbon concentrations increase due to progressing catalyst deactivation

Catalyst testing

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Commercial diesel reforming Progression of temperature profiles in the reformer

Shift of the main reaction zone through the reformer due to catalyst deactivation

Temperature profile reformer center

700

720

740

760

780

800

820

840

0 20 40 60 80 100 120 140Distance form reformer inlet / mm

Tem

pera

tur i

n °C

00:30 h

03:30 h

06:30 h

09:30 h

time

time

Temperature profile reformer periphery

700

720

740

760

780

800

820

840

0 20 40 60 80 100 120 140Distance from reformer inlet / mm

Tem

pera

ture

/ °C

00:30 h

03:30 h

06:30 h

09:30 h

time

time

2 4 6

7 910

11

1

5

8

Catalyst testing

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SummaryReactor development

Multifunctional reactor for mixture preparation has been developed and characterised

Deployment of one reactor leads to FP start-up time < 45 min,

Potential start-up time < 30 min when using a second reactor

Catalyst testing

Süd-Chemie HyProGenTM shows complete fuel conversion in reforming diesel surrogate

Complete fuel conversion achieved in reforming commercial diesel at outlet temperatures > 740 °C

Increased catalyst deactivation from carbon/coke formation and sulfur poisoning in reforming commercial diesel, deactivation is reversible

Catalyst deactivation leads to a progression of the temperature profile inside the reformer

Summary

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Thank you for your attention!

Contact:

Dipl.-Ing. Marius MaximiniOWI Oel-Waerme-Institut GmbHAffiliated Institute of RWTH-AachenKaiserstrasse 10052134 HerzogenrathTel: +49 (0) 2407 / 9518-176Mail: m.maximini@owi-aachen.de

Acknowledgement:

Funding by the

German Federal Ministry of Economics and Technology (BMWi)

Project MÖWE II, FZK: 0327724