Research on the reforming of ethanol

LAMNET Workshop, Brasilia, Dec. 2 - 4, 2002

Dr.-Ing. Peter Hbner

Reforming of Ethanol, LAMNET-Workshop, Brasilia

CH3CH2OH H2O

Introduction - regenerative energy sources for hydrogen fuel cells - motivation for ethanol as fuel Reforming of fossil fuels - allothermal reforming - partial oxidation - autothermal reforming European Project: bioethanol reforming - reformer and shift conversion device - burner development - catalyst screening

H2-rich gas

Summary, Outlook
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Introduction

regenerative energy sources for hydrogen fuel cells 1. Electrolysis of water with electricity from regenerative sources like - windenergy - hydropower - solar energy 2. Reforming of biogenic (CO2-neutral) fuels - solid biomass (wood, wood pellets) - biogas - pyrolysis oil - biogenic ethanol

regenerative power sources: until now neglegible market penetration

bio-ethanol - can be reformed most easily - is economically attractive (see following slides) motivation for ethanol

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Introduction:

motivation for ethanol as fuel - economic potential Preliminary estimation of worldwide market penetration:

potential contribution of ethanol to energy supply is significant

550 million tons per year in the transport sector (20 % of present consumption) 500 million tons per year for co-generation capacity (10 % of present capacity) several hundred million tons per year in the domestic market 200 million tons per year for the chemicals market
Source: Guiliano Grassi, Bioethanol - Industrial world perspectives in Renewable Energy World, May-June 2000, p. 86 - 97
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Introduction: Motivation for ethanol as fuel Cost reduction potential: the Brazilian example 100 100
80 60 40 20 0 62,9 50 31,4 25 15,7 cost in $/ barrel cost in EUROC/ l

1 Barrel = 159 liter assumption: 1 Dollar = 1 Euro

1980

1990

2000
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Source: Jos Goldberg in Tagungsband zur Veranstaltung Biotreibstoffe, 22. Juni 1999, Rschlikon, Switzerland

Reforming of Ethanol, LAMNET-Workshop, Brasilia

Reforming of fossil fuels

Temperature/ C

allothermal reforming

1200 1000 800

Off-gas burner

heat is transferred via a burner, special burner design required high hydrogen content of the reformate

600 400

Reformer

Reaction path

25 % C of HC 75 % H2 O
Reforming reactor

Off-gas
convective heat transfer Radiative burner

H 2 75-78 CO 2 10-12 CO 8-10 CH 4 2- 5 H 2O

Vol % Vol % Vol % Vol %

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Reforming of fossil fuels partial oxidation

without catalyst at 1300 C - 1400 C good dynamic behaviour simple construction lowest hydrogen content
HC O2 N2
Temperature / C
1600 1200 800 400

Reaction path

Reforming reactor

H2 (24-30 Vol%) CO (0,6-2 Vol%) 2 CO (14-18 Vol%) CH (0 Vol%) 4 N2 (43-52 Vol%) H2O
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Reforming of fossil fuels autothermal reforming

Temperature / C 1200 1000

heat is released in the catalyst bed quick start-up good dynamic behaviour temperature peak at the reactor inlet
HC O2 N2 H2O

800 600 400 Reaction path

Reforming reactor

H2 (28-32 Vol%) CO2 (8-10 Vol%) CO (9-11 Vol%) CH4 (0,2-4 Vol%) N2 (48-52 Vol%) H2O
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Reforming of fossil fuels

steam reforming of alcohols, general equation steam reforming of ethanol CnH2n+1OH + (2n -1) H2O 3n H2 + n CO2 6 H2 + 2 CO2 RH =

C2H5OH + 3H2O 173,5 kJ/mol endothermal cracking of ethanol C2H5OH + H2O exothermal CO-conversion CO + H2O

4 H2 + 2 CO

RH = 255,9 kJ/mol RH = -41,2 kJ/mol

H2 + CO2

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Bioethanol as fuel for fuel cell vehicles and small scale stationary applications JOR3-CT97-0174
Part nership: Fraunhof er ISE Ref orming of bioet hanol, CO-conversion Co-ordinat ion Fine purif icat ion by PSA Fuel cell requirement s, implement at ion and disseminat ion of t he result s

Universt it y of Duisburg Nuvera

Summary of results: May, 2001

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

Reformer- PEM fuel cell system with ethanol as fuel

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming Reformer und CO-conversion device at Fraunhofer ISE
4 3

1. Water/ethanol pump
2

2. Reformer 3. HT-shift reactor 4. NT-shift reactor 5. Gas cooling heat exchanger

Reformer 700 - 1000C

HT-shift 350-400C

NT-shift 180-220C

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

Experimental set-up: Reformer: Height: 150 mm Diameter: 121 mm Catalyst Volume: 600 cm3 Burner: Height: 150 mm Diameter: 81 mm
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

advantages of the porous burner

high effective heat conduction of the pore material ( 60 - 100 higher then the effective heat conduction of gas) large combustion reaction zone ( flame burner reaction zone thickness 1 mm) lower temperature in the reaction zone homogeneous temperature profile lower NOx- and CO-emission high flame velocity in the pore medium without flame instability ( 8 - 10 higher then a flame burner) large performance modulation range 1:20 ( flame combustion 1:3)

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

name nickel-cat. ruthenium-cat. platinum cat. palladium cat. Perovskite-cat. nickel-platinum-cat. nickel-palladium-cat.

catalyst screening
composition nickel on Al2O3 ruthenium on Al2O3 platinum on Al2O3 palladium on Al2O3 lanthanum, manganese, cobalt, strontium nickel; platinum on Al2O3 nickel; palladium on Al2O3 sign. Ni Ru Pt Pd Pe PtNi NiPd operation range t react ion < 800 t react ion < 800 t react ion < 800 t react ion < 800 t react ion < 800 t react ion < 800 t reakt ion < 800

investigation parameters
Temperature: 600; 700; 800 C steam to carbon ratio: 2; 3; 4 pressure: 2; 5; 9 bar gas hourly space velocity: 2000 - 6500 sleducts/(lcat h)
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

operation parameters of the Fraunhofer ISE-Reformer

38 910 720 - 800 7,3 4 3,45 1,19 42,89 14,90 1,00 7,5 1,35 23,7 115 1100 390 - 880 7,3 4 10,36 3,57 128,9 44,63 3,00 22 3,96 64,3 [%] [C] [C] [bar] [mole H2O/atom C] [mole/h] [kW] [mole/h] [mole/h] [kW] [l N/min] [kW] [l N/min]

Operation load Porous burner temperature Temperature of the fixed catalyst bed Pressure S/C ratio Reformer ethanol inlet stream Enthalpy stream of the ethanol Product gas stream Hydrogen stream of the product gas Enthalpy stream hydrogen reformer Burner hydrogen stream Enthalpy stream hydrogen burner Burner exhaust stream

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

1

Ni

Pd

Pt

Ru

Pe

PtNi

NiPd

catalyst screening
H2-yield [(mole/h) H2/(mole/h) Eth.]

T = 700 C S/C = 4
selection of Nicatalyst

0,9

0,8

0,7

0,6

0,5 2 3 4 5 6 7 8 9

pressure [bar]
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

71,2

Ni catalyst T = 700 C p = 2 bar influence of S/C

H2 CH4 CO2 CO

0,5 18,4 8,7

S/C-ratio

70,5

1,0 16,4 10,9

68,5

2,4 14,0 13,9

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

molar fractionl [% ,dry]

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

67,7

Ni catalyst T = 700 C p = 9 bar

S/C-ratio

4,3 19,3 7,7

65,1

influence of S/C higher pressure due to PSA

7,3 18,5 8,8

H2 CH4 CO2 CO

61,5

10,3 17,4 10,3

0,0

10,0

20,0

30,0

40,0

50,0

60,0

70,0

80,0

molar fraction [% ,dry]

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

450

temperature top
422 402 377 2,72

temperature middle
424

temperature bottom

CO content
425

3
403

HTS Fe-oxide-catalyst GHSV = 4000/h S/C = 4

400 350

402 374 372

2,5

temperature [C]

2,23

300 250

2,03

1,5 200 150 100 0,5 50 0 2 0 1

pressure [bar]

9
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CO content [mole %]

Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming

200

temperature top
193 184 0,135 177

temperature middle
195 173

temperature bottom

CO content
196

LTS
temperature [C]

177

184 175

0,14 0,12

Cu/Zn-catalyst GHSV = 4000/h S/C = 4

150 0,10
0,087 0,086

0,08 0,06 0,04 0,02

100

50

0 2 5 9

0,00

pressure [bar]
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Reforming of Ethanol, LAMNET-Workshop, Brasilia

European project: bioethanol reforming Results of reformer and CO-shift device S/C = 4 p = 9 bar
gas composition [mole%]

CH4

CO

CO2

H2

H2O

45,4

42,4 41,7 43,4

40,5

With CO fine purification: Reformate suitable for PEM- fuel cell

50 45 40 35 30 25 20 15 10 5 0

38,5

H2O
10,3 13,6 14,9

H2 CO2

4,7 1,1 1,1

1,2 1,2

0,1

CO CH4

Reformer

HT-shift

LT-shift
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CO content [mole%]

Reforming of Ethanol, LAMNET-Workshop, Brasilia

Summary

Hydrogen generation from biogenic ethanol is attractive due to - good availability, - competitive costs, - easy realisation of reforming process Research of bioethanol reforming at Fraunhofer ISE: - development of a compact steam reformer with preheating of liquid reformer feedstream (with burner exhaust gas) and of the air for the burner (with the reformer product gas) - development of a porous burner with stable combustion for offgas, methane, or ethanol - optimisation of heat losses and performance Outlook: - reduction of volume and weight of the reforming unit - reduction of start-up time - further improvement of performance - cost reduction - longtime-operation to show catalyst stability

European project: bioethanol reforming Summary

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Outlook 5 kW Fuel processor unit for stationary electricity generation

Source: Nuvera Fuel Cells Europe, Milan, methanol reformer

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Reforming of Ethanol, LAMNET-Workshop, Brasilia

Thank you very much for your attention!

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