unesco desire – net project molten carbonate fuel cells state of the art & perspectives state...
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UNESCO UNESCO Desire – Net projectDesire – Net project
Molten Carbonate Fuel CellsMolten Carbonate Fuel Cells State of the Art & PerspectivesState of the Art & Perspectives
Angelo Moreno, Stephen McPhail Angelo Moreno, Stephen McPhail ENEA – Hydrogen and Fuel Cell ProjectENEA – Hydrogen and Fuel Cell Project
[email protected]@[email protected]@casaccia.enea.it
UNESCOUNESCORome , 13Rome , 13thth March 2007 March 2007
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Summary
• Fuel cell lessons programmeFuel cell lessons programme
• Hydrogen and fuel cellsHydrogen and fuel cells
• MCFC: cell, stack, system, plantMCFC: cell, stack, system, plant
• Difficulties, solutions, perspectivesDifficulties, solutions, perspectives
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FC lessons programme
13 March MCFC ENEAMoreno, McPhail
14 March MCFC Ansaldo Parodi
29 March MCFC Ansaldo Capobianco
12 AprilMCFC System configurations
ENEAMoreno, Cigolotti
PEM/SOFC lessons in planning
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H2 production plant
Fuel cell plant
HH22
Natural gas
Filling station
Depleted gas well Deep saline aquifer
Power generation plant
COCO22
HH22
Thermal solar Wind turbines
Biomass
PV plant
Hydropower
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Turbine avanzate
Efficiency, %
Plant size, MW
SOFC-GT
Steam turbinesDiesel
Gas engines
Combined cycle turbines
Internal combustion engines
PAFCPEFC
MCFC, SOFC
0,1 1 10 100 1000
80
60
70
50
40
30
20
10
0
Microturbines
Advanced turbines
Fuel cells & competing technologies
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Hydrogen and Fuel Cells
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Hydrogen and Fuel Cells – Roadmap
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Why Fuel Cells?
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Chemical Energy Thermal
conversion
Work
qloss
CO2 CO NOx SOx PM
qlossqloss
H2O (CO2)
FUEL CELL
CONVENTIONAL SYSTEM
Fuel Cells – principle
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Electric power
Hydrogen(Fuel)
Oxygen(air - oxidant)+
heat
water
No thermal cycles
Fuel Cells – principle
No thermodynamic limitations (Carnot)
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Electric power
Hydrogen(Fuel)
Oxygen(air - oxidant)+
heat
water
Thermal efficiency
Fuel Cells – principle
H
G
available
usefulT
for H2/O2 reaction: H = 285.8 kJ/mole G = 237.1 kJ/mole
With pure H2/O2: η = 0.83
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Temperature: 60-120 °C Efficiency: 60% State of the art technology: 5-150 kW Market: Special applications
(military, space) transportation
Alkaline, AFCAlkaline, AFC
Temperature: 160-220 °C Efficiency: 40-50% State of the art technology: 50 kW -1 MW
plants up to 11 MW Applications: CHP, distributed generation
Temperature: 70-100 °C Efficiency: 40% State of the art technology: 1-250 kW Applications: Transport
ResidentialPremium powerRemote generation
Polymer elctrolyte, PEFCPolymer elctrolyte, PEFC
Temperature: 600-650 °C Efficiency: 45-55% State of the art technology: 100 kW - 3 MW Applications: CHP, distributed generation
(plants up to 20 MW)
Molten carbonate, MCFCMolten carbonate, MCFC
Temperature: 800-1000°C Efficiency: 45 - 60% State of the art technology: 50 kW- 1 MW Applications: CHP, distributed
generation (plants up to 20 MW, transport (APU)
Solid oxide, SOFCSolid oxide, SOFC
Temperature: 50-100 °C Efficiency: 30-40% State of the art technology: : < 1kW Applications: portable, electronics
Direct methanol, DMFCDirect methanol, DMFCPhosphoric acid , PAFCPhosphoric acid , PAFC
Fuel Cells – types
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Anode H2 + CO3
= → H2O + CO2 + 2 e-
Cathode 1/2 O2 + CO2 + 2 e- → CO3
=
Water is produced at the anode side
CO2 is needed at the cathode side
Temperature 650 °C ELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONS
MCFC – characteristics
Electrolyte: combination of alkali carbonates – Li, K, Na
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Anode H2 + CO3
= → H2O + CO2 + 2 e-
Cathode 1/2 O2 + CO2 + 2 e- → CO3
=
CO2 is needed at the cathode side:
Temperature 650 °C ELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONS
MCFC – characteristics
• Supply CO2 from alternate source
• Produce CO2 by combustion anode off-gas
• Transfer CO2 fm anode exit to cathode inlet
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Anode H2 + CO3
= → H2O + CO2 + 2 e-
Cathode 1/2 O2 + CO2 + 2 e- → CO3
=
Temperature 650 °C ELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONSELECTROCHEMICAL REACTIONS
MCFC – characteristics
CO is a fuel:
through combination with water to H2: CO + H2O → H2 + CO2 (water-gas-shift)
through direct electrochemical oxidation: CO + CO3
= → 2 CO2 + 2 e-
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MCFC – stack
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MCFC – stack
With sealing & manifolds
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MCFC – stack
Manifolds:
Sealing:
Ensure leak-tight closing in highly corrosive atmosphere
• Between cells • Between stack & manifolds
Gas flow distribution
• Homogeneous reactant distribution to the cell • Lower pressure drops• Uniform fuel utilisation
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MCFC – stackFuel and oxidant feed
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MCFC – Fuelling
Fuel:
• H2
• CO
Oxidant:
• O2
• CO2
Possible sources:
• Natural gas• Syngas (coal gasification)• HC-rich fuel (butane, methanol…)• Biomass (gasification, digestion…)• Chemical production (electrolysis…)
Possible sources:
• Air• Reaction products (recirculation)
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MCFC – Fuelling
Fuel:
• H2
• CO
Possible sources:
• Natural gas• Light hydrocarbons (butane, methanol, …)
CxHy + x H2O (g) → x CO + (½y+x) H2
(Endothermic reaction → heat required)
Yield: • H2 75%• CO 10%• CO2 15%
Traces of NH3, CH4, SOx…
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MCFC – Fuelling
ReformingExternal
Heat provided by burn-up of anode exit gas + HX
Internal
Heat provided by cell reaction
+
Simplicity inside cell
Separation of functions
-
Complexity in system
Large coolant flow required
+
Cell cooling provided
System simplicity & lightness (=
cost)
-
Reforming catalyst required in cell
Not ideal for high P
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MCFC – Fuelling
Fuel:
• H2
• CO
Possible sources:
• Biomass, coal (gasification)• Heavy hydrocarbons (distillate, oil)
CxHy + ½x O2 → x CO + ½y H2
(Exothermic reaction → heat released)
Yield: • H2 20%• CO 25%• CO2 10%• N2 40%
CH4, NH3, SOx, H2S, HCl, …
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MCFC – Fuelling
Partial oxidation (gasification)
+High-T heat produced
Quick start & reaction
Works on many fuels
-Low H2 yield
High emission of pollutants (upgrading,
clean-up required)
Complex external components
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MCFC – stack
300 W, 10-cell stack (MTU)
With fuel & oxidant inlets & CO2 recirculation
125 kW, 150-cell (Ansaldo, Italy)
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MCFC – Heat Recovery
Thermal management of cell:
Optimum temperature for cell & system ≈ 650°C
Fuel cell reactions generate heat
Tcell ↓
• Open circuit potential ↑• Available heat quantity ↑• Electrolyte loss ↓• Corrosion effects ↓
Tcell ↑
• Polarization ↓• Reaction kinetics ↑• Reforming conditions ↑• Available heat quality ↑
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MCFC – stack
With heat recovery
250 kW, HotModule (MTU, Germany)
100 kW (KEPCO, Korea)
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MCFC – Power conditioning
• Power consolidation• Current control• Invert DC to AC• Voltage increase
Efficiency of power conditioning between 94-97%
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MCFC – system
Fuel
Treatment
Heat
Recovery
MCFC
Stack
System
Control
Fuel
Heat
Heat
Heat
H2O
H2, CO
DC
AC
Air
Power
Cond.
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MCFC – Balance of Plant (BoP)
Balance of Plant components:
• Pumps and fans • Heat exchangers• Spray nozzles• Piping• Filters• Seals• Gaskets• Valves• Regulators
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MCFC – Balance of Plant (BoP)
500 kW Joint effort (Ansaldo, Iberinco, Balke, ENEA, AMG – Madrid)
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AFCO: 500 kW system ConfigurationConfigurationConfigurationConfiguration
Cell SizeCell Size
Operating Pressure
Operating Pressure
Operating TemperatureOperating
Temperature
Modular Integrated Reformer
Modular Integrated Reformer
TWINSTACK®TWINSTACK®
0.81 m²Rectangular
shape
0.81 m²Rectangular
shape
3.5 bar3.5 bar
650°C650°C
MCFC – Plant
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MCFC – Plant
Modular build-up to MMW units!