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Decentralized hydrogen production from diesel and biodiesel
Fuel Cells 2014 Science & Technology, 3‐4 April 2014, Amsterdam
S. Martin, G. Kraaij, A. WörnerGerman Aerospace Center, Germany
NEMESIS2+ (New Method for Superior Integrated Hydrogen Generation System) received funding from the European Union‘s Seventh Framework Programme (FP7/2007‐2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under Grant Agreement No 278138.
Slide 2 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Biological / Thermochemical conversion
B) Biomass
H2
C) Renewable electricity
A) Conventional H2 production(mainly steam reforming of natural gas)
Worldwide: ~600*109 m3N H2/year
70 % chemical industry (ammonia, methanol)30 % fuel and heating purposes
Linde‐steam reformerLocation: Texas/USAFeed: natural gasCapacity: 110,000 mN
3/hPurity: 99.99 %
WaterElectrolysis
H2 production: Which options are available?
H2
Slide 3 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
DieselFAME
BiodieselGasoline
Bioethanol
Dimethyl ether
Methane,Natural gas
LNG
LPGs
Propane
Spruce
Beech
n‐Butane
OakLarch
Pellet bed
Crude Oil
0
5
10
15
20
25
30
35
40
0 10 20 30 40 50 60 70 80 90 100 110 120
Volumetric
Ene
rgy Den
sity [M
J/l]
Gravimetric Energy Density [MJ/kg]
Liquid fuels
LH2, liquified
Biomass
Light Hydrocarbons(C1‐C4)
Hydrogen
Fischer‐Tropsch‐Diesel
Methanol
Pulverized coal
Coal briquette
Coal
Straw bale
Butanol
CGH2 (70 MPa)
atmospheric pressure
CNG
Metalhydride
Complex hydride
High volumetric and gravimetric energy density of liquid fuels + existing infrastructure
Volumetric limitations ofCGH2 and LH2 technology
On-site/on-board hydrogenproduction from liquid fuels
Slide 4 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
On‐site hydrogen production at refuelling stations from diesel and biodiesel
H2
H2
Steam reforming Liquid fuels only!
NEMESIS2+: Project Objectives
Slide 5 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
• Development of a pre‐commercial hydrogen generator (50 Nm3/h)• System efficiency > 65 % (>70 %), stable long‐term operation testing for at least 1000 hours, H2‐purity 5.0
• Total hydrogen production costs < 4 € per kg• Show feasibility of desulphurization concept based on liquid phase adsorption
• Development of improved reformer and WGS catalyst formulations
NEMESIS2+: Project Targets
Slide 6 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Pressurized steam reforming (13 bara)
Long‐term testing (1000 h)
Focus on liquid fuels(diesel, biodiesel)
„One‐reformer“‐concept(without pre‐reforming)
Scale up from 5 to 50 Nm3/h
Innovative desulph. concept (liquid phase adsorption)
Elaborated heat management (Pinch‐Analysis)
Development of S‐tolerant and coke‐resistant catalysts
Dual Fuel Burner
NEMESIS2+: Scientific Approach
Slide 7 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Fuel characterization
Biodiesel Diesel
Chemical formula C18.3H34.8O2 C13.3H24.7
S content (ppmw) 1.5 7.1
LHV (kJ/kg) 37,790 42,930
• Fossil diesel (Shell)• Biodiesel (Abengoa Bioenergy)
Boiling point curves
GC Analysis
Slide 8 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Diesel with S < 2ppmw is produced for 20 ml desulphurized diesel/gr of sorbent
‐
1
2
3
4
5
6
7
8
0 5 10 15 20 25 30 35 40 45deS fuel (ml) / sorbent (g)
Remaining
sulphu
r (pp
mw)
LAB‐scale experiments Fresh DIESEL: [S] = 7.1
Diesel desulphurization breakthrough curve
…achieved in an adsorption bed of activated carbon(lab scale) with low particle size and high surface area
Lab‐scale deS reactor Pilot‐scale deS unit
Liquid Desulphurization
x 10
Process scaling up:
Production of 1.5‐2 l/h of desulphurized fuel
Slide 9 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Lab scale steam reforming of desulphurized B7 Diesel (T=850 °C, p=5 bar, S/C=5)
Stable product gas concentration over 100 hours
Slide 10 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
No signs of catalyst deactivation! Diesel conversion > 99 % Coking (mixing zone, catalyst surface) cannot be completely avoided → foreseeperiodic regeneration with steam and/or air
Thermocouples1/8"
23 mm
25 mm49 mm
TATBTC
TD
51 mm
TA
TB
TC
TD
Lab scale steam reforming of desulphurized B7 Diesel (T=850 °C, p=5 bar, S/C=5)
Slide 11 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Single-tube testing
Burner
Single‐tub
e
ReformateCooler
Mass and energy balance
Axial temperature profile
Single tube
Single tube integrated in LIFT test facility
Mixing chamber(H2O + Diesel)
Slide 12 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Water gas shift durability testing (Lab scale)
100 hour continuous tests carried out with addition of 1 ppm H2S and 600 ppm of hydrocarbons (C2, C3 and C4) → No degrada on observed
y = ‐1E‐05x + 0,0296
0%
2%
4%
6%
8%
10%
12%
0%
10%
20%
30%
40%
50%
60%
0 20 40 60 80 100
CO, C
H4 mol %
H2, H2O
, CO
2 m
ol %
t (h)
H2 H2Ocalc CO2 CO CH4
Assessment of operating conditions and reactor design:
• Steam to carbon ratio• Temperature• Gas Hour Space Velocity• Dimension of reactor
R. C. Neto et al., Int. J. Hydrogen Energy 39 (2014) 5242‐5247
Slide 13 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Dual Fuel Burner Development: Simulation
• Challenges to use three different fuels alone or combined in a single burner: Biodiesel, Natural Gas and Off‐Gas.
• Existing furnace with small volume and requirements to produce a short flame and distribute the gases uniformly through the multiple reformer tubes.
• Use of CFD based numerical models to evaluate effects of swirl number, air and fuel velocity on flame shape.
• Model also used to transpose the results from test work to the final furnace dimensions.
Flow Stream Lines
Temperature (K)
Slide 14 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Dual Fuel Burner Development: Experiments • Tests on atomization and combustion were carried out to show relative
advantages of atomizers:– Pressure atomizers: fine atomization but very sensible to flow rate– Air assisted atomizers: acceptable atomization but air mass flow
restrictions• Final burner designed with high swirl and air assisted atomizer.
900
1000
1100
1200
1300
1400
1500
‐50 0 50 100 150 200 250 300
Tem
pera
ture
(ºC
)
Radial distance (mm)
Above reformer tubes
Below reformer tube caps
Slide 15 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Design Study NEMESIS2+ Hydrogen Generator
‐ System has been designed based on HyGear HGS‐L system
‐ Additional hardware for water‐gas‐shift reactor and heat exchangers designed and built:
‐ Control temperature of 300‐350 °C in shift reactor ‐ Increase steam temp. for biodiesel reforming‐ Vaporize and dose (bio)diesel feed
‐ Next steps: Build up system and test with‐ Biodiesel‐ Fossil diesel‐ GtL Diesel
Newly designed water gas shift reactor
Slide 16 • Decentralized hydrogen production from diesel and biodiesel• Fuel Cells 2014 Science & Technology• S. Martin, G. Kraaij, A. Wörner • 04.04.2014
Thank you for your attention!www.nemesis‐project.eu Stefan.Martin@dlr.de
NEMESIS2+ (New Method for Superior Integrated Hydrogen Generation System) received funding from the European Union‘s Seventh Framework Programme (FP7/2007‐2013) for the Fuel Cells and Hydrogen Joint Technology Initiative under Grant Agreement No 278138.
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