ppt-wm-3-huebner- lamnet-ws-brasilia
TRANSCRIPT
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Dr.-Ing. Peter Hbner
LAMNET Workshop, Brasilia, Dec. 2 - 4, 2002
Research on the reforming of ethanol
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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
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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
regenerative power sources:
until now neglegiblemarket penetration
2. Reforming of biogenic (CO2-neutral) fuels
- solid biomass (wood, wood pellets)
- biogas
- pyrolysis oil
- biogenic ethanol
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:
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
potential contribution of
ethanol to energy supply
is significant
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
100
62,9
50
31,425
15,7
0
20
40
60
80
100
1980 1990 2000
cost in $/ barrelcost in EUROC/l
Cost reduction potent ial: the Brazilian example
Source: Jos Goldberg in Tagungsband zur Veranstaltung Biotreibstoffe, 22. Juni 1999, Rschlikon, Switzerland
1 Barrel = 159 liter
assumption: 1 Dollar = 1 Euro
Introduction: Motivation forethanol as fuel
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
allothermal reforming
heat is transferred via a burner,
special burner design required
high hydrogen content of the
reformate
convective
heat transfer
Radiative
burner
Reforming reactor
400
600
800
1000
1200
Reformer
Off-gas
Off-gas burner
Temperature/ C
Reaction path
H2 75-78 Vol %
CO2 10-12 Vol%
CO 8-10 Vol %
CH4 2- 5 Vol%
H2O
25 % C of HC
75 % H2 O
Reforming of fossil fuels
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reforming of fossil fuels
partial oxidation
2
HCO2N 2
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 catalystat 1300 C - 1400 C
good dynamic behaviour
simple construction
lowest hydrogen content
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reforming of fossil fuels
autothermal reforming
heat is released in the
catalyst bed
quick start-up
good dynamic behaviour
temperature peak at
the reactor inlet
HCO2N2H2O
CO2 (8-10 Vol%)CO (9-11Vol%)CH4 (0,2-4 Vol%)N2 (48-52 Vol%)H2O
H2 (28-32 Vol%)
Reforming reactor
400
600
800
1000
1200
Temperature / C
Reaction path
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
Reforming of fossil fuels
steam reforming of alcohols,
general equationCnH2n+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
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
Partnership:
Fraunhofer ISE Reforming of bioethanol,CO-conversion
Co-ordination
Universtity of Duisburg Fine purification by PSA
Nuvera Fuel cell requirements,implementation and dissemination of the result s
Bioethanol as fuel for fuel cell vehicles and small scale stationaryapplications JOR3-CT97-0174
Summary of results: May, 2001
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
Reformer- PEM fuel cellsystem with ethanol asfuel
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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 reactor5. Gas cooling heat exchanger
European project: bioethanol reforming
Reformer
700 - 1000C
HT-shift
350-400C
NT-shift
180-220C
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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
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project: advantages of the porous burnerbioethanol 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)
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project: catalyst screeningbioethanol reforming
name composition sign. operation range
nickel-cat. nickel on Al2O3 Ni treact ion < 800
ruthenium-cat. ruthenium on Al2O
3Ru t
react ion< 800
plat inum cat . platinum on Al2O3 Pt treact ion < 800
palladium cat . palladium on Al2O3 Pd treact ion < 800
Perovskite-cat . lanthanum, manganese, cobalt , st ront ium Pe treact ion < 800
nickel-platinum-cat. nickel; platinum on Al2O3 PtNi treact ion < 800
nickel-palladium-cat. nickel; palladium on Al2O3 NiPd treakt 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/(lcath)
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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
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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-yield[(mole/h)H2
/(mole/h)
Eth.]
Ni Pd Pt Ru Pe PtNi NiPd
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
Ni catalyst
T = 700 Cp = 2 bar
influence of S/C
H2
CH4
CO2
CO
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]
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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]
H2
CH4
CO2
CO
European project:bioethanol reforming
Ni catalyst
T = 700 Cp = 9 bar
influence of S/C
higher pressuredue to PSA
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
European project:bioethanol reforming
HTS
Fe-oxide-catalystGHSV = 4000/h
S/C = 4
377 374 372
422 424 425
402 402 403
2,72
2,03
2,23
0
50
100
150
200
250
300
350
400
450
2 5 9
pressure [bar]
temperature[C]
0
0,5
1
1,5
2
2,5
3
COcontent[
mole%]
temperature top temperature middle temperature bottom CO content
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European project:bioethanol reforming
184
173 175
193 195196
177 177184
0,0860,087
0,135
0
50
100
150
200
2 5 9
pressure [bar]
temperature[C]
0,00
0,02
0,04
0,06
0,08
0,10
0,12
0,14
CO
content[mole%]
temperature top temperature midd le temperature bottom CO content
LTS
Cu/Zn-catalystGHSV = 4000/hS/C = 4
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
45,442,4 40,5
38,5
41,7 43,4
10,313,6 14,9
4,71,2 0,1
1,1 1,1 1,2
0
5
10
15
20
25
30
35
4045
50
gascomposition[mole%
]
Reformer HT-shif t LT-shif t
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 forPEM- fuel cell
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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 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 reformingSummary
Summary
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Reforming of Ethanol, LAMNET-Workshop, Brasilia
Outlook
5 kW Fuel processor unitfor stationary electricitygeneration
Source: Nuvera Fuel Cells Europe, Milan, methanol reformer
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Thank you very much for your attention!