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The end of the oil age?A Transition to Hydrogen?
Maurizio Fermeglia – University of Trieste
Department of Engineering and Architecture
www.mose.units.it
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Sexten, Monday, July 01, 2013- slide 2Tomorrow’s Energy
Agenda
Hydrogen Era
� Motivation: reduce emissions
� Efficiency of energy transformation
� Why Hydrogen?
Production and distribution of hydrogen
� Sources
� Production processes
� Distribution
Hydrogen utilization
� Fuel cells: fundamentals
� Fuel cells for vehicles
� Fuel cells for power generation
Conclusions
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"The Stone Age didn't end because they ran out of stones; the Oil Age won't end because we run out of oil.“
Don Huberts, Shell Hydrogen
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Sexten, Monday, July 01, 2013- slide 4Tomorrow’s Energy
The green house effect…
N2O
CO2
CH4
N2O
CH4
CO2
2010: 380ppm
1900: 280ppm
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Sexten, Monday, July 01, 2013- slide 5Tomorrow’s Energy
Energy utilization in 2009
Cars production in the world (by year)
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Sexten, Monday, July 01, 2013- slide 6Tomorrow’s Energy
0
20
40
60
80
100
120
140
1985 1990 1995 2000 2005 2010 2015
Em
issio
ns,
% o
f 1995 l
eve
l
CO
NOx
PM-diesel
VOC
Benzene
SO2
CO2
Source : European Commission
Significant progress has been made in reducing local emissions and the focus is now shifting to Greenhouse Gases
Future challenge: Reduce CO2
while
maintaining low regulated emissions
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Sexten, Monday, July 01, 2013- slide 7Tomorrow’s Energy
Changes to transport fuels are required to meet sustainability challenges
Need to balance the requirements of affordable mobility while reducing local and global environmental impacts
� Cleaner Hydrocarbon Fuels enable more fuel efficient/low emission engine technology.
� Renewable Biofuels - e.g. ethanol and vegetable oil esters
� Radical new technologies - e.g. Fuel cells & Hydrogen
Alternatives need to meet economic and social sustainability criteria as well as contributing to environmental objectives.
Need to understand the challenge of consumer acceptance.
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Sexten, Monday, July 01, 2013- slide 8Tomorrow’s Energy
Well-to-Wheel Greenhouse Gases - US Study
0
100
200
300
400
500
600
700
800
Ga s
o li n
e I C
ED
i es e
l I C
E
Ga s
o li n
e F u
e l C
e ll H
E V
Di e
s el I
CE
HE
V
Na p
h th a
Fu e
l Ce l
l HE
V
F T D
i es e
l IC
EC
NG
I CE
F T N
a ph t
h a F
C H
EV
L iq u
i d H
2 F C
HE
V
Me t
h an o
l Fu e
l Ce l
l HE V
Ga s
e ou s
H2
F C H
EV
E- 8
5 I C
E
El e
c ro l
y si s
GH
2 F C
HE
V
Et h
a no l
Fu e
l Ce l
l HE
Vg CO
2/mile Petroleum Natural Gas
Renewable/
Electricity
Better
ICE: internal combustion engine FT: Fisher Tropsch diesel
HEV: hybrid electric vehicle GTL: gas to liquid fuel
CNG: compressed natural gas E-85: 85% ethanol and 15% gasoline
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Sexten, Monday, July 01, 2013- slide 9Tomorrow’s Energy
Shell’s Interpretation of existing Well-to-Wheel Studies
ICE hybrids can deliver significant further benefits (benefit bigger for gasoline).
Fuel cell vehicles have potential for further gains but dependent on how Hydrogen produced.
Methanol fuel cell vehicles do not offer a worthwhile GHG advantage vs. gasoline/naphtha fuel cell vehicles. On board reforming gives relatively little benefit versus ICE hybrids (main value as a transition pathway).
CNG does not on average offer GHG benefit vs. conventional fuels for internal combustion engine (ICE) vehicles (depending on gas source assumed). No benefit for H2 in ICE.
GTL broadly comparable with conventional diesel on a full systems basis.
Renewable fuels offer the lowest greenhouse gas emissions
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Sexten, Monday, July 01, 2013- slide 10Tomorrow’s Energy
Hydrogen Economy........ a compelling vision
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Sexten, Monday, July 01, 2013- slide 11Tomorrow’s Energy
The Hydrogen age: the transition is uncertain...
Internal Combustion Engine
led to the Oil Age
THE PAST THE FUTURETHE TRANSITION IS
UNCERTAIN
Pro
du
ct
Pe
rfo
rm
an
ce
Time
Coal Oil Gas Hydrogen
1.5 : 1 1 : 2 1 : 4 0: 1
Underlying Decarbonisation
The Fuel Cell can lead to
the Hydrogen Age
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Sexten, Monday, July 01, 2013- slide 12Tomorrow’s Energy
Cost ($/GJ)Hydrogen Production Method
Central Production
Natural Gas 5-8
Coal 9-12
Electrolysis of Water 20
Gasified Biomass 8-13
Distributed Production
Onsite
Natural Gas 8-15
Electrolysis (hydroelectric) 10-20
Electrolysis (wind) 20-40
Electrolysis (solar/thermal) 40-60
Electrolysis (photovoltaic) 50-100
Relative Costs of Energy
(Hydrogen from Natural Gas)
$0,00
$1,00
$2,00
$3,00
$4,00
$5,00
$6,00
$7,00
$8,00
$9,00
Coal Oil Gas Hydrogen
US
Do
llar
pe
r G
J
With Gas priced at $3/MBTU
Hydrogen is not prohibitively expensive to get started today.
(Sources: British Petroleum, Hoffmann, Ogden, and
Bossel/Eliasson.)
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Sexten, Monday, July 01, 2013- slide 13Tomorrow’s Energy
(*) DER
efficiencies
improve with
heat recovery
0 20 40 60 80 100
Hydro
Hybrid fuel cell
Gas combined cycle
Fuel cell
Coal
Gas turbine
Nuclear
Wind
Photovoltaic
Geothermal
Biomass1
8
10
25
33
38
43
50*
58*
66*
80
Technology efficiencies
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Sexten, Monday, July 01, 2013- slide 14Tomorrow’s Energy
One possible view of the future - not a forecast
The next 10 years will see a wider range of technologies
and fuel types, especially in the developed world
30
40
50
60
70
80
90
100
2000 2010 2020
% of New cars
Diesel (inc Bio-diesel/GTL)
Gasoline (inc Ethanol)
Hydrogen
Fuel cell
Sparkignition
Compressionignition engines
LPG/CNG
Hybrid
Naphtha/Methanol20
10
0
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Sexten, Monday, July 01, 2013- slide 15Tomorrow’s Energy
Timeline for Hydrogen Economy
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Sexten, Monday, July 01, 2013- slide 16Tomorrow’s Energy
The Power of Innovation
Heavier-than-air flying machines are impossible,... � Lord Kelvin, President Royal Society, 1895
I think that there is a world market for maybe five computers� Thomas Watson, chairman of IBM, 1943
Computers in the future may weigh no more than 1.5 tons� Popular mechanics, 1949
There is no reason anyone would want a computer in their home� Ken Olson, President, Chairman, and founder of Digital Equipment Corp., 1977
64K ought to be enough for anybody� Bill Gates, 1981
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Sexten, Monday, July 01, 2013- slide 17Tomorrow’s Energy
Time Taken to achieve 25% access in the US
The Original Gasoline Automobile > 55 years
Electricity c. 40 years
The Microwave 18 to 20 years
The PC 15 years
The Web 7 years
Facebook …….
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Sexten, Monday, July 01, 2013- slide 18Tomorrow’s Energy
Congressional Record 1875
A new source of power…called gasoline has been produced by a Boston engineer. Instead of burning the fuel under a boiler, it is exploded inside of the cylinder of an engine….The dangers are obvious. Stores of gasoline in the hands of people interested primarily in profit would constitute a fire and explosive hazard of the first rank. Horseless carriages propelled by gasoline might attain speeds of 14, or even 20 miles per hour. The menace to our people of this type hurdling through our streets and along our roads and poisoning the atmosphere would call for prompt legislative action even if the military and economic implications were not so overwhelming ….The cost of producing [gasoline] is far beyond the capacity of private industry…In addition the development of this new power may displace the use of horses, which would wreck our agriculture.
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Sexten, Monday, July 01, 2013- slide 19Tomorrow’s Energy
So Why Hydrogen?
Hydrogen Combustion:� H2 + ½ O2 → H2O ∆H= -57.8 kcal/mole
H2 is an energy carrier, is converted to water which has minimal environmental impact.
H2 is a non-polluting fuel for transportation vehicles and power production
Currently road vehicles emit about the same quantity of CO2 as power production in developed economies.
H2 can be produced from fossil fuels with CO2 capture and storage or from renewables
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Sexten, Monday, July 01, 2013- slide 20Tomorrow’s Energy
0
10
20
30
40
50
60
70
80
90
100
110
120
0 10 20 30 40 50 60 70 80 90 100
Ethanol
Hydrogen
CH4
C2H6Propane
Butane
Gasoline / DieselRME
Coal
Low Heating
Value in MJ/kg
“Real Useable
Heat in the
Engine”
[H] in %w
Cleaner combustion
Higher Energy content
Methanol
DME
In the long run, hydrogen has the potential to be the ultimate fuel
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Sexten, Monday, July 01, 2013- slide 21Tomorrow’s Energy
Agenda
Hydrogen Era
� Motivation: reduce emissions
� Efficiency of energy transformation
� Why Hydrogen?
Production and distribution of hydrogen
� Sources
� Production processes
� Distribution
Hydrogen utilization
� Fuel cells: fundamentals
� Fuel cells for vehicles
� Fuel cells for power generation
Conclusions
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Sexten, Monday, July 01, 2013- slide 22Tomorrow’s Energy
CO2 Capture and Storage:Hydrogen Production from Fossil Fuels
H2 production from fossil fuels will predominate
H2 for transportation fuel only makes sense if CO2 is captured and stored
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Sexten, Monday, July 01, 2013- slide 23Tomorrow’s Energy
Production of HydrogenOptions
Method Characteristics
Photolysis catalytic-water splitting
Electrolysis water
Power for electrolyser ambient → high temperature
ambient → high pressure
Thermal splitting water
high temperature
Fossil fuel Conversion Heat, water, oxygen, catalytic
Far Future Non fossil fuel alternatives based on sunlight, renewables and nuclear
Present Fossil fuels
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Sexten, Monday, July 01, 2013- slide 24Tomorrow’s Energy
Renewable Hydrogen Production via Electrolysis
Typical 2 MW Turbine
gives 100 tonnes/year
Hydrogen
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Sexten, Monday, July 01, 2013- slide 25Tomorrow’s Energy
Production of Hydrogen: Reactions
Reforming With Steam - Catalytic
Natural gas and light hydrocarbons CH4 + H2O ↔ CO + 3H2 + ∆H
CO + H2O ↔ H2 + CO2 - ∆H
Partial Oxidation - Non Catalytic
Any hydrocarbon or carbonaceous feedstock
C + ½O2 → CO - ∆H
CO + H2O ↔ CO2 + H2 - ∆H
Thermal Decomposition
Only limited application as co-product in carbon black manufacture
CH4 → 2H2 + C +∆H
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Sexten, Monday, July 01, 2013- slide 26Tomorrow’s Energy
Production of Hydrogen: Process Characteristics
Open Systems
� External heating of a catalytic reactor
� Combustion products vented to atmosphere
50,000 Nm3/hr
Steam Natural
Gas Reformer
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Sexten, Monday, July 01, 2013- slide 27Tomorrow’s Energy
Production of Hydrogen: Process Characteristics
Closed Systems
� Pressurised reactors with heat supplied by direct oxidation with oxygen
� No venting of combustion products
Partial Oxidation Autothermal Reformer
Natural Gas
Oxygen Steam
Natural Gas
Oxygen POX
Catalyst
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Sexten, Monday, July 01, 2013- slide 28Tomorrow’s Energy
Worldwide Market Scenario in 2020
Transit Buses*
� 130,000-150,000 buses in service
Light Duty Vehicles*
� 17- 80 million vehicles in service
Hydrogen Required†
� 2.5 - 9 million tonnes per year
Current Largest Merchant H2 Plant
� 100,000 tonne/year
HUGE INFRASTRUCTURE TO BE BUILT
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Sexten, Monday, July 01, 2013- slide 29Tomorrow’s Energy
Agenda
Hydrogen Era
� Motivation: reduce emissions
� Efficiency of energy transformation
� Why Hydrogen?
Production and distribution of hydrogen
� Sources
� Production processes
� Distribution
Hydrogen utilization
� Fuel cells: fundamentals
� Fuel cells for vehicles
� Fuel cells for power generation
Conclusions
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Sexten, Monday, July 01, 2013- slide 30Tomorrow’s Energy
Fuel cells: Power station & Automotive
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Sexten, Monday, July 01, 2013- slide 31Tomorrow’s Energy
What is a fuel cell?
DC Voltage Source with low emissions
Makes electricity chemically
Like a battery, but doesn’t run down
Emits only water vapor
High fuel-to-electric efficiency
Low noise
No moving parts
48 V dc 7.5 kW Fuel CellAre they the microchip of the hydrogen age?
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Sexten, Monday, July 01, 2013- slide 32Tomorrow’s Energy
A fuel cell system
For top efficiency, you must use the heat!
Ultimately, hydrogen is needed!
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Sexten, Monday, July 01, 2013- slide 33Tomorrow’s Energy
Electricity
Electrical current is the flow of electrons.
Need a source of electrons, a medium in which they can flow, and a driving force.
e- e-
e-e-
Source of Electrons Sink for Electrons
Electrons Produced
Anode (-)
low E (V)
Electrons consumed
Cathode (+)
high E (V)
conductor
∆E (V)
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Sexten, Monday, July 01, 2013- slide 34Tomorrow’s Energy
Oxidation and Reduction
Electrons are produced and consumed in oxidation and reduction reactions.
Oxidation is loss (OIL)of electrons:� Fe → Fe2+ + 2e- Fe → Fe3+ + 3e-
� Ca → Ca2+ + 2e- Mg → Mg2+ + 2e-
� Na → Na+ + e- H2 → 2H+ + 2e-
Reduction is gain (RIG) of electrons:� Cl2 + 2e- → 2Cl- Br2 + 2e- → 2Br-
� Ag+ + e- → Ag Mn5+ + 3e- → Mn2+
� Ni3+ + e- → Ni2+ O2 + 4e- → 2 O2-
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Sexten, Monday, July 01, 2013- slide 35Tomorrow’s Energy
Half Reactions
Individual oxidation and reduction reactions are half reactions.
Must occur together to make an overall oxidation-reduction reaction.
EX. Mg (s) → Mg2+ + 2 e-
+ Cl2 (g) + 2 e- → 2 Cl-
Mg (s) + Cl2 (g) → MgCl2 (s)
OXIDATION
REDUCTION
OVERALL
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Sexten, Monday, July 01, 2013- slide 36Tomorrow’s Energy
Reduction PotentialEach half-reaction has a characteristic reduction potential (E°).
� E° is a relative measure of energy released by adding electrons.
EXAMPLE.
2H+ + 2e- → H2(g) E° = 0.000 V
4H+ + O2(g) + 4e- → 2H
2O E° = +1.23 V
Positive E° indicates that energy is obtained by adding electrons.
� ∆G = - n F E°
� F= Faraday’s constant; n= n. of electrons
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Sexten, Monday, July 01, 2013- slide 37Tomorrow’s Energy
Overall Reaction
For hydrogen and oxygen:
OX: 2H2 (g) → 4H+ + 4e- E° = 0.00 V
RED: O2 (g) + 4H+ + 4e- → 2H2O(g) E° = 1.23 V
TOTAL: 2H2 + O2 → 2H2O ∆E° = +1.23 V
Large, positive ∆E° → more energy
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Sexten, Monday, July 01, 2013- slide 38Tomorrow’s Energy
Fuel Cells
Fuel and oxidant react to produce electricity directly without combustion.
� Oxidation: 2 H2 (g) → 4 H+ + 4 e-
� Reduction: O2 (g) + 4 H+ + 4 e- → 2 H2O
� Overall: 2 H2 + O2 → 2 H2O, ∆E° = +1.23 V
How does this happen without combustion occurring or H2and O
2coming
into contact with each other?
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Sexten, Monday, July 01, 2013- slide 39Tomorrow’s Energy
Combustion vs. Electron Transfer
Chemical reactions are the same!
Reaction rate and types of energy produced are different.
ReactionChemical
ProductsEnergy Produced Rate
Combustion CO2, H
2O Noise, heat, light Fast
Electron Transfer CO2, H
2O
Electrical, some
heatSlow
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Sexten, Monday, July 01, 2013- slide 40Tomorrow’s Energy
Basic Operation of Fuel Cells
Fuel and oxidant are separated.
Ions conducted through electrolyte, electrons carried through external circuit
Electrodes are catalysts that facilitate the reactions
O2HO2H :Overall
OH244HO :Cathode
2H2H :Anode
222
22
2
→+
→++
+→
−+
−+
e
e
H2
and O2
never come into contact, only H+ and O2-!!
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Sexten, Monday, July 01, 2013- slide 41Tomorrow’s EnergyFrom Ballard Power Systems
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Sexten, Monday, July 01, 2013- slide 42Tomorrow’s Energy
Fuel Cell
Cathode
Anode
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Sexten, Monday, July 01, 2013- slide 43Tomorrow’s Energy
Basic Electrochemistry for Fuel Cell
Basic Electrochemistry for Fuel Cell� Chemical Energy = Electrical Energy – Energy losses
� ∆Grxn = Current*Voltage*time – Energy losses
� ∆Grxn = V*(charge passed) – Energy losses� As current � 0 the energy losses �0
� ∆Grxn= V*(charge passed)= V*(moles reacted)*(electrons transferred per molecule)*(coulombs per mole)= V*n*F
� For H2+O2 �H20 ∆G=240 kJ/mol H2, n=2 electrons/H2
� V=240 kJ/mol / (2*96485 coulomb/mol) = 1.23 Volt
Advantages of Fuel cells� Fuel cells can be made very tiny.
� µm, nm instead of mm, cm.
� Power the product of current (I) and potential difference (V)� P = I*V so ↑ I and/or ↑ V means ↑ P.
� Higher fuel and oxidant flows increase I.
� Stacking of fuel cells increases V.
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Sexten, Monday, July 01, 2013- slide 44Tomorrow’s Energy
Ideal (Nernst) potential as a function of T
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Sexten, Monday, July 01, 2013- slide 45Tomorrow’s Energy
Basic Principles
Thermodynamics
∆G = - n F V
Theoretical Efficiency
η = ∆G/ ∆H ~ 0.83
Actual Efficiency (best
conditions) ~ 0.5 0
0.2
0.4
0.6
0.8
1
1.2
1.4
0 1 2 3 4 5 6
Current Density (A/cm2)
Vo
lta
ge
(V
)
Ohmic PolarizationMass
Transport
Limited
Activ
atio
n P
ola
rizatio
n
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Sexten, Monday, July 01, 2013- slide 46Tomorrow’s Energy
Energy Losses
Activation Polarization
� Energy barrier associated with catalytic reactions at the electrodes
Ohmic Polarization
� Resistive losses of proton transport through the electrolyte
Mass Transfer Polarization
� Limit of getting the reactants to the active catalyst surface
H
H+
2
H+
1
H 2Ha2
2
H e- + H+a
3
5
6
7
O 2O a2
2e- + O O=
a
10
11
Polymer
Electrolyte
Anode Cathode
e-
=2H+ +O
2H O
5
H O2
4
O2
8
9
Carbon Fiber
Sheet
7
2H O
2H O
electro-migration
diffusion
5
porous
carbon
Pt
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Sexten, Monday, July 01, 2013- slide 47Tomorrow’s Energy
Voltage – current relationships
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Sexten, Monday, July 01, 2013- slide 48Tomorrow’s Energy
Fuel utilization
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Sexten, Monday, July 01, 2013- slide 49Tomorrow’s Energy
First Fuel CellBasic principle developed in 1839
by William Grove. Reversal of
current after turning off water
electrolysis
Fuel cell stack sketched by
Grove in 1843
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Sexten, Monday, July 01, 2013- slide 50Tomorrow’s Energy
Brief History
1839 William Grove demonstrates principle of fuel cell operation
1894 Ostwald initiates efforts to replace heat engine with a carbon fuel cell operating at 1100°C
1938 Baur demonstrates coal fuel cell with oxygen ion conducting electrode
1923 Schmid develops gas diffusion electrode
Post WWII Attention directed towards indirect cells using H2, CO and alcohols
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Sexten, Monday, July 01, 2013- slide 51Tomorrow’s Energy
Fuel Cell Types & Efficiencies
Fuel Cell TypeOperating Temp. (°C)
Projected Efficiency
Suitable Applications
Alkaline (AFC) 80-100 60% Space, Automotive
Molten Carbonate (MCFC) 600-650 45-60% Large Stationary
Phosphoric Acid 200-220 40-45% Large Stationary
Proton Exchange Membrane (PEMFC)
70-80 35-45%Small Stationary, Automotive, Portable
Solid Oxide (SOFC) 800-1000 50-65% Stationary, Automotive
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Sexten, Monday, July 01, 2013- slide 52Tomorrow’s Energy
Alkaline Fuel CellElectrolyte: 85%wt KOH @ ~250°C35 to 50%wt KOH @ <120°CCatalyst: Ni, Ag, metal oxides, spinels, and noble metalsAdvantages: � Excellent Performance on H2 and O2
compared to other due to its active O2 electrode kinetics
� flexibility to use wide range of electro-catalyst
Disadvantages: � Sensitive to CO2 and CO� Needs pure H2
� CO2 must be removed if ambient air is used
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Sexten, Monday, July 01, 2013- slide 53Tomorrow’s Energy
Molten Carbonate Fuel CellElectrolyte: combination of alkali carbonates retained in a ceramic matrix of LiAlO2
Electrodes: Nickel & nickel oxideAdvantages: � No expensive electro-catalysts needed� both CO & certain hydrocarbon can be
use as fuel� High temperature waste heat allows
use of bottoming cycle to increase system efficiency
Disadvantages: � Very corrosive electrolyte� Material problems, affecting
mechanical stability and stack life. � Large size & weight and slow start-up
times
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Sexten, Monday, July 01, 2013- slide 54Tomorrow’s Energy
Phosphoric Acid Fuel CellElectrolyte: 100% Phosphoric Acid retained by silicon carbideCatalyst: PlatinumElectrodes: Porous CarbonAdvantages:� Less Sensitive to CO, ~1% tolerance� Relatively low temperature to use
common construction materials� Waste heat can be used in
cogeneration/bottoming cycle application
Disadvantages:� Cathode-side oxygen reduction is
slower than AFC� Use of expensive materials in the stack
(especially the graphite separator plates) due to corrosive phosphoric acid.
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Sexten, Monday, July 01, 2013- slide 55Tomorrow’s Energy
Proton Exchange Membrane Electrolyte: Ion Exchange Membrane (fluorinated sulfonic acid polymer or similar)Electrodes: Porous CarbonCatalyst: PlatinumAdvantages:� Solid electrolyte resistant to gas crossover� Rapid start-up� Absence of corrosive constituents, exotic
materials are not required. � High current densities of over 2kW/l & 2
W/cm2
Disadvantages:� Difficult to use rejected heat. � Must balance sufficient hydration of
electrolyte against flooding� Higher catalyst loading (platinum)� Anode is easily poisoned by CO
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Sexten, Monday, July 01, 2013- slide 56Tomorrow’s Energy
Solid Oxide Fuel CellElectrolyte: Solid, non porous metal oxide Y2O3-stabilized ZrO2.Advantage:� Solid electrolyte enable casting of the cell in various shapes, such as tubular, planar, or monolithic
� Solid ceramic construction alleviates any corrosion problems
� Fast kinetics and CO is directly usable as fuel
� No requirement for CO2 at the cathode and resistant to sulfur.
� Modest cost materials� High temperature allows use of waste heat for cogeneration or bottoming cycle and internal reforming of fuel.
Disadvantage:� Thermal expansion mismatches among materials and sealing between cells is difficult in the flat plate configurations.
� Slow startup
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Sexten, Monday, July 01, 2013- slide 57Tomorrow’s Energy
Effect of temperature
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Sexten, Monday, July 01, 2013- slide 58Tomorrow’s Energy
Types of fuel cells
Fuel used
� Hydrogen: 2 H2 (g) + O2 (g) → 2 H2O (g)
� Methanol: CH3OH (g) + O2 (g) → CO2 (g) + H2O (g)
� Propane: C3H8 (g) + 5 O2 (g) → 3 CO2 (g) + 4 H2O (g)
Configuration
Planar ConfigurationTubular Configuration
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Sexten, Monday, July 01, 2013- slide 59Tomorrow’s Energy
Typical Fuel Cell Vehicles
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Sexten, Monday, July 01, 2013- slide 60Tomorrow’s Energy
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Sexten, Monday, July 01, 2013- slide 61Tomorrow’s Energy
Commercial Hydrogen Fuelling Installations
PA110008.JPG (303 KB)
Air Products’ Hydrogen
Fuelling Systems
Supplied to major oil
companies
BP, Singapore
Shell, Washington, DC, USA
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Sexten, Monday, July 01, 2013- slide 62Tomorrow’s Energy
The Process
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Sexten, Monday, July 01, 2013- slide 63Tomorrow’s Energy
Process: simplified version (external reformer)
CleanupReformer
Burner
Anode
Cathode
Natural
Gas
Water
Exhaust
Gas
Air
H2
Cleanup
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Sexten, Monday, July 01, 2013- slide 64Tomorrow’s Energy
Internal reforming
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Sexten, Monday, July 01, 2013- slide 65Tomorrow’s Energy
Energy from waste (Ansaldo)
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Sexten, Monday, July 01, 2013- slide 66Tomorrow’s Energy
Biomass gassification and MCFC
Pre treatment GasificationGas
Clean-up
Evaporator
Reforming
Co generation
An. Cath.
Pre heating
BurnerBiomass
Water
Air/Oxygen
Air
Turbine Compr
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Sexten, Monday, July 01, 2013- slide 67Tomorrow’s Energy
Il processo nuovo
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Sexten, Monday, July 01, 2013- slide 68Tomorrow’s Energy
Agenda
Hydrogen Era
� Motivation: reduce emissions
� Efficiency of energy transformation
� Why Hydrogen?
Production and distribution of hydrogen
� Sources
� Production processes
� Distribution
Hydrogen utilization
� Fuel cells: fundamentals
� Fuel cells for vehicles
� Fuel cells for power generation
Conclusions
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Sexten, Monday, July 01, 2013- slide 69Tomorrow’s Energy
The Alternative to a Hydrogen Future
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Modeling fuel cells
Steady state and dynamic modeling of fuel cells: Molten carbonate Fuel Cell MCFC
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Sexten, Monday, July 01, 2013- slide 71Tomorrow’s Energy
Modeling MCFC
Goals� Develop a dynamic model for the MCFC
� Bi dimensional geometry cross-flow
� Density and chemical reaction distributed
� Considers conduction and convention
� Solids are considered with their physical properties
� Anode and Cathode are independent
� Check steady state and dynamic cell behavior� Sensitivity analysis
� Develop a steady state simulation of the process� Simplified model for the cell (based on the rigorous model)
� Sensitivity analysis
Topics covered� The cell model
� The Results of the cell steady state and dynamic simulation
� The plant model and the sensitivity analysis
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Sexten, Monday, July 01, 2013- slide 72Tomorrow’s Energy
MCFC simulation: model equations development
The cell: a Molten carbonate Fuel Cell – second generation
Assumptions of the model
Flow and reaction scheme
Equations of change
Electrochemical equations
Balances and boundary conditions at cathode
Balances and boundary conditions at anode
Balances and boundary conditions at electrolyte
Physical properties
� From Aspentech™ Data base (except for Nu)
� From Literature correlations (electrolytic properties)
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Sexten, Monday, July 01, 2013- slide 73Tomorrow’s Energy
Assumptions and Input data (1)
Anode feed: vectors of stoichiometric coefficients for the electrochemical and water gas shift reaction
Cathode feed: vector of stoichiometric coefficients
Electrolyte composition: potassium, sodium and lithium carbonates are considered.
Ideal gases: mixture effects on densities are ignored; the ideal gas law is assumed and the activities are assumed to be equal to partial pressures.
Adiabatic system: no heat exchanged perpendicularly to the overall flow; electrolytes do not exchange heat with the borders.
Reaction rate: full Butler-Volmer equation is applied (quasi equilibrium reaction and negligible ion conduction resistance of the electrolyte)
Cudicio A., Fermeglia M., Pricl S., J. Power Sources, (2005)
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Sexten, Monday, July 01, 2013- slide 74Tomorrow’s Energy
Flow and reaction scheme
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Sexten, Monday, July 01, 2013- slide 75Tomorrow’s Energy
Assumptions (2)Thick channel distribution on the cell plane
Plug flow: parabolic profiles on different channels are approximated by a velocity on a single direction (vx for cathode and vy for anode).
Perfect mixing: negligible diffusion flow.
Bi dimensional model: � velocities and their derivatives along the z-axis are neglected
� characteristic dimension for calculating the fluxes along the z-axis is the geometric mean of the bi-dimensional extensions
Equal current distribution at the electrodes, due their negligible thickness.
Nitrogen effects: nitrogen oxides at the cathode and ammonia at the anode are ignored.
Nusselt number is function of Prandtl number, Reynolds number and geometrical factor: Brinkman and Grashof numbers are neglected.
Cudicio A., Fermeglia M., Pricl S., J. Power Sources, (2005)
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Sexten, Monday, July 01, 2013- slide 76Tomorrow’s Energy
Equations of change: application to anode
( )D
v rDt
ρρ= − ∇ • +
DvP
Dtρ τ= −∇ • −∇
( ) ( ) ( ):v
V
DT Pc q T v v S
Dt Tρ τ
∂ = − ∇ • − ∇ • − ∇ +
∂
Example: anode
Cudicio A., Fermeglia M., Pricl S., J. Power Sources, (2005)
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Sexten, Monday, July 01, 2013- slide 77Tomorrow’s Energy
Electrochemistry equations
Nerst equation
Polarization equation Butler – Volmer equation
0 0ln
RT a aV E
nF a a
π κ
ψ ξ= +
0 0ln
RT a aV E
nF a a
π κ
ψ ξ= +
0
e A CR
V V i
η η η
η
= + +
⇓
= −0
e A CR
V V i
η η η
η
= + +
⇓
= −
( )
( )
2 2
0
0 0 0
1
0
, ,
CO CO
nF inF i
RT RT
i i i P P
i i e e
β ηβ η −
−
=
⇓
= −
( )
( )
2 2
0
0 0 0
1
0
, ,
CO CO
nF inF i
RT RT
i i i P P
i i e e
β ηβ η −
−
=
⇓
= −
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Sexten, Monday, July 01, 2013- slide 78Tomorrow’s Energy
Degrees of freedom analysis
• Method Of LINES
• Variable Step Implicit EULER
• Fast NEWTON
• Method Of LINES
• Variable Step Implicit EULER
• Fast NEWTON
Fermeglia M., Cudicio A., Desimon G., Longo G, Pricl S. Chem. Eng. Trans. 4: 391 (2004)
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Sexten, Monday, July 01, 2013- slide 79Tomorrow’s Energy
Aspen Custom Modeler™
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Sexten, Monday, July 01, 2013- slide 80Tomorrow’s Energy
Base Case and Sensitivity analysisBASE CASE v(0.27,1.7) T(840,830) P(2.5,3.5) i(1.7)
Input variables
v(x,0) – m/s 0.33 0.27
v(0,Y) – m/s 1.52 1.70
T(x,0) - K 870.0 840.0
T(0,y) - K 860.0 830.0
P(x,0) - bar 3.500 3.380 2.500
P(0,y) - bar 3.500 3.378 3.500
i - kA/m2 1.500 1.700
Output Variables
U H2 - % 75.000 82.279 75.132 89.450 80.746
U O2 - % 30.000 28.041 30.955 30.812 34.780
Ta out - K 930.3 930.2 909.5 936.1 946.3
Tc out - K 952.9 954.1 932.4 963.6 974.4
Te av. - K 938.9 940.8 919.7 948.5 957.8
i00 - kA/m2 0.024 0.025 0.015 0.029 0.027
V av. - V 1.092 1.081 1.069 1.083 1.076
W av. - kW/m2 1.636 1.620 1.599 1.625 1.827
Fermeglia M, Cudicio A., DeSimon G., Longo G., Pricl S., Fuel cells, 5:66-79 (2005)
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Sexten, Monday, July 01, 2013- slide 81Tomorrow’s Energy
Base case distributions
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Sexten, Monday, July 01, 2013- slide 82Tomorrow’s Energy
Results of dynamic open-loop simulation
Input: Pressure perturbation� Anode pressure perturbation
� Step input (1 bar)
Output: Temperature profile at anode� Inverse response
� Fast phenomena (P prop T)
� Slow response (heat of reaction)
Output: Voltage distribution� Inverse response
� Fast phenomena: potential rises as V ~ ln(PA-1) ~ PA-1
� Slow phenomena: decrease of E0 with decreasing T dominates
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Sexten, Monday, July 01, 2013- slide 83Tomorrow’s Energy
Dynamic Results: temperature effectTemperature perturbation
� Anode and Cathode
� Semi - sinusoidal ramp (different time)
Fermeglia M, Cudicio A., DeSimon G., Longo G., Pricl S., Fuel cells, 5:66-79 (2005)
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The power generation process
Based on simplified model of MCFC
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Sexten, Monday, July 01, 2013- slide 85Tomorrow’s Energy
The Process
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Sexten, Monday, July 01, 2013- slide 86Tomorrow’s Energy
Process: simplified version (external reformer)
CleanupReformer
Burner
Anode
Cathode
Natural
Gas
Water
Exhaust
Gas
Air
H2
Cleanup
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Sexten, Monday, July 01, 2013- slide 87Tomorrow’s Energy
Internal reforming
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Sexten, Monday, July 01, 2013- slide 88Tomorrow’s Energy
A conceptual diagram of 50 MWMCFC power generation plant
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Sexten, Monday, July 01, 2013- slide 89Tomorrow’s Energy
Steady state process simulation
De Simon G., Parodi F., Fermeglia M., Taccani R., J. Power Sources, 115, 210, (2003)
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Sexten, Monday, July 01, 2013- slide 90Tomorrow’s Energy
Steady State Process Simualtion: details
Electrochemical model
Modular Integrated Reformer
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Sexten, Monday, July 01, 2013- slide 91Tomorrow’s Energy
Steady State process simulation
Fuel cells efficiency defined as the ratio of electric power produced by the stack and chemical power of the fuel actually consumed
De Simon G., Parodi F., Fermeglia M., Taccani R., J. Power Sources, 115, 210, (2003)
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Sexten, Monday, July 01, 2013- slide 92Tomorrow’s Energy
Base Case & Sensitivity analysis
Base Case:In accordance with 500 kW MCFC from
ANSALDO
Base Case:In accordance with 500 kW MCFC from
ANSALDO
Sensitivity analysis on H2O / CH4
Sensitivity analysis on H2O / CH4
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Sexten, Monday, July 01, 2013- slide 93Tomorrow’s Energy
Fuel cell module sensitivity analysis
De Simon G., Parodi F., Fermeglia M., Taccani R., J. Power Sources, 115, 210, (2003)
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Sexten, Monday, July 01, 2013- slide 94Tomorrow’s Energy
Process simulation sensitivity analysis
Air flow rate sensitivity analysis
Pressure sensitivity analysis
De Simon G., Parodi F., Fermeglia M., Taccani R., J. Power Sources, 115, 210, (2003)
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Energy from biomass
MCFC based process
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Sexten, Monday, July 01, 2013- slide 96Tomorrow’s Energy
Energy from waste (Ansaldo)
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Sexten, Monday, July 01, 2013- slide 97Tomorrow’s Energy
Biomass gassification and MCFC
Pre treatment GasificationGas
Clean-up
Evaporator
Reforming
Co generation
An. Cath.
Pre heating
BurnerBiomass
Water
Air/Oxygen
Air
Turbine Compr
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Sexten, Monday, July 01, 2013- slide 98Tomorrow’s Energy
Il processo nuovo
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Sexten, Monday, July 01, 2013- slide 99Tomorrow’s Energy
Biomass gassification
Gassification
LiteratureGas
• Mole fraction
• Temperature
• Pressure
DATA FITTING
Model
ULTIMATE
ANALYSIS
PROXIMATE
ANALYSIS
Biomass
Oxidant
Steam
Gassification
Model
Gas
Mole fraction
Temperature
PressureBiomass
Oxidant
Steam
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Sexten, Monday, July 01, 2013- slide 100Tomorrow’s Energy
Simulation strategyFLow rate of biomass
under investigationNumber of cells in the stack
Model Input
• I
• n. of cells
• boundary
conditions
•...
• I
• Fule conversion
(CO + H2
75%)
• boundary conditions
• ...
N of cells
(different for different
biomasses)
originalmodified
Gassification
Model
Felxibility of the tool
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Sexten, Monday, July 01, 2013- slide 101Tomorrow’s Energy
Different biomass investigated
Sugarcane bagasse (BG) : residue from sugar cane treatment
Switchgrass (SW)
Nut shells (NT): mix 20% nut shell, 40% hazel nut shell, 40% wood
Proximate
analysisbg sw nt
Ash 6,99 5,24 2,38
Volatile
Subst.80,06 80,09 76,28
C residual 12,95 14,67 21,34
HHV (MJ/kg)17,77 18,62 19,80
Ultimate
analysisbg sw nt
C 46,46 47,73 48,51
H 5,4 5,56 5,65
N 0,18 0,67 0,77
S 0,06 0,01 0,01
Ash 8,5 5,24 3,07
O 39,36 40,68 41,98
Cl 0,04 0,11 0,01
Source: Gas Technology Institute, 2002
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Sexten, Monday, July 01, 2013- slide 102Tomorrow’s Energy
in
biomassa
out
coH
)kg(
)kgkg(R
2
+
=
biomass bg sw nt
R 0,24 0,34 0,38
Type of
Biomass
Electrical
Efficiency
(%)
Cogeneration
Efficiency (%)
Biomass
Flow rate
Kg/h
Total
Electrical
Power kW
Gasifier
efficiency
%
Conversion
at anode
Bg 36.5 68.4 1900 2739 76.5 75%
Sw 40.3 69.1 1550 2841 82.2 75%
nt 40.2 69.9 1450 2802 84.5 75%
biomass bg sw nt
Humidity 20 % 12 % 12,5 %
Comparison of biomass feeds for constant conversion in the cell
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Sexten, Monday, July 01, 2013- slide 103Tomorrow’s Energy
Agenda
Hydrogen Era
� Motivation: reduce emissions
� Efficiency of energy transformation
� Why Hydrogen?
Production and distribution of hydrogen
� Sources
� Production processes
� Distribution
Hydrogen utilization
� Fuel cells: fundamentals
� Fuel cells for vehicles
� Fuel cells for power generation
Conclusions
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Sexten, Monday, July 01, 2013- slide 104Tomorrow’s Energy
Summary - Conclusions
Environmental legislation will continue to tighten.
The next 3 decades will see a multitude of fuels and technologies employed on a regional basis.
Automotive development will improve the efficiency of use of remaining fossil fuels
The necessary technology for a viable H2 infrastructure of production, distribution and storage already exists.
Hydrogen production from fossil fuels with CO2 capture and storage is likely to provide the bulk of hydrogen required in the next 30-50 years
R&D should concentrate on cost reduction for production, transport and storage alternatives, and demonstration projects
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Sexten, Monday, July 01, 2013- slide 105Tomorrow’s Energy
The Alternative to a Hydrogen Future