Dr.-Ing. Peter Hübner LAMNET Workshop, Brasilia, Dec. 2 - 4, 2002 Research on the reforming of ethanol Seite 2 Reforming of Ethanol, LAMNET-Workshop, Brasilia 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 Summary, Outlook CH 3 CH 2 OH H 2 O H 2 -rich gas
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Dr.-Ing. Peter Hübner
LAMNET Workshop, Brasilia, Dec. 2 - 4, 2002
Research on the reforming of ethanol
Seite 2
Reforming of Ethanol, LAMNET-Workshop, Brasilia
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
Summary, Outlook
CH3CH2OH
H2O
H2-rich gas
Seite 3
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Introduction regenerative energy sources for hydrogen fuel cells
1. Electrolysis of water with electricityfrom regenerative sources like
CO2 (0,6-2 Vol%)CO (14-18 Vol%)CH4 (0 Vol%)N2 (43-52 Vol%)
O
H2 (24-30 Vol%)Reforming reactor
400
800
1200
Reaction path
Temperature / °C
1600
H
without catalyst at 1300 °C - 1400 °C
good dynamic behaviour
simple construction
lowest hydrogen content
Seite 8
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reforming of fossil fuels
autothermal reforming
heat is released in thecatalyst bed
quick start-up
good dynamic behaviour
temperature peak atthe reactor inlet
HCO2N2H2O
CO2 (8-10 Vol%)CO (9-11 Vol%)CH4 (0,2-4 Vol%)N2 (48-52 Vol%)H2O
H2 (28-32 Vol%)Reforming reactor
400
600
800
1000
1200Temperature / °C
Reaction path
Seite 9
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reforming of fossil fuels
steam reforming of alcohols,general equation CnH2n+1OH + (2n -1) H2O ⇔ 3n H2 + n CO2
steam reforming of ethanol C2H5OH + 3H2O ⇔ 6 H2 + 2 CO2 ∆RH = 173,5 kJ/mol
endothermal cracking of ethanol C2H5OH + H2O ⇔ 4 H2 + 2 CO ∆RH = 255,9 kJ/mol
exothermal CO-conversion CO + H2O ⇔ H2 + CO2 ∆RH = -41,2 kJ/mol
Seite 10
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Partnership:
Fraunhofer ISE Reforming of bioethanol,CO-conversionCo-ordinat ion
Universt ity of Duisburg Fine purif icat ion by PSA
Nuvera Fuel cell requirements,implementat ion and disseminat ion of the results
Bioethanol as fuel for fuel cell vehicles and small scale stationaryapplications JOR3-CT97-0174
Summary of results: May, 2001
Seite 11
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project: bioethanol reforming
Reformer- PEM fuel cellsystem with ethanol as fuel
Seite 12
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reformer und CO-conversion device at Fraunhofer ISE
1
2
34
5
1. Water/ethanol pump
2. Reformer
3. HT-shift reactor
4. NT-shift reactor
5. Gas cooling heat exchanger
European project: bioethanol reforming
Reformer700 - 1000°C
HT-shift350-400°C
NT-shift180-220°C
Seite 13
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Experimental set-up:
Reformer:
Height: 150 mm
Diameter: 121 mm
Catalyst Volume: 600 cm3
Burner:
Height: 150 mm
Diameter: 81 mm
European project:bioethanol reforming
Seite 14
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project: advantages of the porous burner bioethanol reforming
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)
Seite 15
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project: catalyst screeningbioethanol reforming
name composition sign. operation rangenickel-cat. nickel on Al2O3 Ni treact ion < 800ruthenium-cat. ruthenium on Al2O3 Ru treact ion < 800platinum –cat. platinum on Al2O3 Pt treact ion < 800palladium –cat. palladium on Al2O3 Pd treact ion < 800Perovskite-cat. lanthanum, manganese, cobalt, strontium Pe treact ion < 800nickel-platinum-cat. nickel; platinum on Al2O3 PtNi treact ion < 800nickel-palladium-cat. nickel; palladium on Al2O3 NiPd treakt ion < 800
investigation parametersTemperature: 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)
Seite 16
Reforming of Ethanol, LAMNET-Workshop, Brasilia
Operation load 38 115 [%]Porous burner temperature 910 1100 [°C]Temperature of the fixed catalyst bed 720 - 800 390 - 880 [°C]Pressure 7,3 7,3 [bar]S/C ratio 4 4 [moleH2O/atomC]Reformer ethanol inlet stream 3,45 10,36 [mole/h]Enthalpy stream of the ethanol 1,19 3,57 [kW]Product gas stream 42,89 128,9 [mole/h]Hydrogen stream of the product gas 14,90 44,63 [mole/h]Enthalpy stream hydrogen reformer 1,00 3,00 [kW]Burner hydrogen stream 7,5 22 [lN/min]Enthalpy stream hydrogen burner 1,35 3,96 [kW]Burner exhaust stream 23,7 64,3 [lN/min]
operation parameters of the Fraunhofer ISE-ReformerEuropean project:bioethanol reforming
Seite 17
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
catalyst screening
T = 700 °CS/C = 4
⇒ selection of Ni-catalyst
0,5
0,6
0,7
0,8
0,9
1
2 3 4 5 6 7 8 9
pressure [bar]
H2-y
ield
[(m
ole/
h)H
2/(m
ole/
h)Et
h.]
Ni Pd Pt Ru Pe PtNi NiPd
Seite 18
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
Ni catalyst
T = 700 °Cp = 2 bar
influence of S/C
H2CH4CO2CO
13,9
10,9
8,7
14,0
16,4
18,4
2,4
1,0
0,5
68,5
70,5
71,2
0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0
2
3
4
S/C-
ratio
molar fractionl [%,dry]
Seite 19
Reforming of Ethanol, LAMNET-Workshop, Brasilia
10,3
8,8
7,7
17,4
18,5
19,3
10,3
7,3
4,3
61,5
65,1
67,7
0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0
2
3
4
S/C-
ratio
molar fraction [%,dry]
H2CH4CO2CO
European project:bioethanol reforming
Ni catalyst
T = 700 °Cp = 9 bar
influence of S/C
higher pressuredue to PSA
Seite 20
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
HTS
Fe-oxide-catalystGHSV = 4000/hS/C = 4
377 374 372
422 424 425402 402 403
2,72
2,03
2,23
0
50
100
150
200
250
300
350
400
450
2 5 9pressure [bar]
tem
pera
ture
[°C
]
0
0,5
1
1,5
2
2,5
3
CO
con
tent
[mol
e %
]temperature top temperature middle temperature bottom CO content
Seite 21
Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
184173 175
193 195 196
177 177184
0,0860,087
0,135
0
50
100
150
200
2 5 9
pressure [bar]
tem
pera
ture
[°C
]
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
CO
con
tent
[mol
e%]
temperature top temperature middle temperature bottom CO content
LTS
Cu/Zn-catalystGHSV = 4000/hS/C = 4
Seite 22
Reforming of Ethanol, LAMNET-Workshop, Brasilia
45,4 42,4 40,5
38,5 41,7 43,4
10,3 13,6 14,9
4,71,2 0,1
1,1 1,1 1,2
05
101520253035404550
gas
com
posi
tion
[mol
e%]
Reformer HT-shift LT-shift
CH4
CO
CO2
H2
H2O
CH4 CO CO2 H2 H2OEuropean project:bioethanol reforming
Results of reformer andCO-shift device
S/C = 4p = 9 bar
With CO fine purification:Reformate suitable for PEM- fuel cell
Seite 23
Reforming of Ethanol, LAMNET-Workshop, Brasilia
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 preheatingof liquid reformer feedstream (with burner exhaust gas) andof 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