re-use of co2 and intermittent renewablesproduction hydrogen storagequality co 2 sequestration gas...
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Re-use of CO2 and
intermittent renewables
W.G. Haije
February 2013
ECN-L--13-049
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www.ecn.nl
Re-use of CO2 and intermittent
renewables Wim Haije
CATO2 meeting, Utrecht 05-02-2013
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Current situation
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Intermittent renewable
Energy storage problem
Poly generation:Electricity
Fuel Chemicals
CO2 capture
(from large point
sources)
Fossil Fuels (base load)
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Intermittency
• At present, countries like Germany and Spain have > 30 % power from intermittent sources, and are no longer able to “store” it in the grid when demand is low.
• IGCC installations cannot run in partial load
• In general this kind of large scale utilities, if they can be run at lower load, need quite some time for ramping up and down.
• Storage in the form of electricity on this scale is very difficult
• Storage in the form of hydrogen on this scale is not feasible.
• The gas grid (if present) has some capacity but H2 concentrations are typically 10 % max
• “Wish storage material”: something like gas(oline)!
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High gravimetric & volumetric
density
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Intermittency
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Storage-only efficiency
electrolysis Methanation
CO
2
E H2 SNG 1000 MWe 710
MWth
570 MWth
1 Mton CO2
55-60% storage Rather than No storage
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Why CO2 re-use/solar fuels
• CO2 is an enabler for hydrogen transport and storage (energy carrier)
• CO2 is available to answer the intermittent H2 production from renewables (CO2 is available continuously from a variety of sources)
• Chemicals/Fuels from CO2 are a means to sustain a carbon based economy (infrastructure, plants etc..) during the transition towards a completely renewable energy based economy (using carbon at least twice)
• CO2 emissions are reduced by saving primary resources and optionally, depending on regional configuration, CO2 storage/mineralisation – In chemical products (minor)
– In energy systems (significant)
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G- GRID
P- GRID
Electricity from Renewable
Coal & Gas
CO2 Capture
CO2 Transport &
Storage
Gas Storage
Electrolysis->H2
BULK CHEMICALS
FUELS
Oil & Gas
CO2 reuse technologies
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Chemistry and technology
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Coupling of H2 to CO2
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Intermittency versus base load of power
production
Hydrogen storage
CO2 sequestration
Gas quality
• Gas from high CO2 content gas fields Up to 60% CO2
• Digester gas is produced at small scale by manure digestion at farms. Digester gas consists of 50 to 75%
methane and 25 to 50% CO2 • Producer gas from biomass gasification
Biomass has higher carbon content than methane, which means that either CO2 has to be removed from the gas or hydrogen has to be added.
But also • Pure CO2 from capture plants, industrial
point sources etc..
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How nature does it
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Theoretical 40%, Practical 15%, from light to H2
0.2-1.0%
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What we do with it
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Methane
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Can we do the same trick?
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Yes we can!.............
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Reaction ΔH
kJ/mol
CO2 + 4H2 ↔ CH4 + 2H2O -167.0 methanation
CO + 3H2 ↔ CH4 + H2O -206.0 methanation
CO2 + H2 ↔ CO + H2O +41.3 reverse water gas shift reaction
nCO + 2nH2 → −(CH2)n− + nH2O -126.0 Fischer-Tropsch
CO2 +3H2 ↔ H2O + CH3OH -49.6 methanol synthesis
CO + 2H2 ↔ CH3OH -90.8 methanol synthesis
………. because CO2 is always in equilibrium with other components and just needs a little help to go beyond that equilibrium!
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Fundamentals
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1
10
100
1000
10000
100 300 500 700
Water gas shift
CO + H2O ↔ CO2 + H2 0 = -41 KJ/mol
Conversion limited by equilibrium:
Keq =( PH2 PCO2 )/( PCO PH2O)
T(0C)
Keq
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How to produce pure H2 and
CO2?
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CO + H2O H2
CO2
CO2 CO2
CO2
CO2
CO2
sorbent sorbent catalyst
CO2
Le Chatelier’s Principle 1 cm
CO32-
H2O
Mg(OH)6 -octahedron
Al(OH)6 -octahedron
Promoted with K2CO3
Mg6Al2(OH)16CO3.4H2O
Hydrotalcite (layered clay)
Fe-Cr
Sorption enhanced water gas shift (SEWGS)
CO + H2O ↔ CO2 + H2
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SEWGS the process
High temperature (400oC), high pressure (35 bar) production of H2 from Syngas.
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CO2 H2
H2O
H2O
CO
H2
CO2
H2O H2O
CO2
Water-Gas Shift: CO + H2O CO2 + H2
Carbonate Formation
Decarbonisation
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SEWGS and what you can learn
from it……….
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100% CO2
100% H2
+
Thermodynamics @ 400oC: 34% conversion
Two patent applications • Sorbent • Process for CO2/H2S separation
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Consequently:
• The reverse of the previous, the reverse sorption enhanced WGS, should work as well:
• Idea: take out the water, yielding full conversion to CO, and with more H2 any syngas composition can be tuned!!
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CO2 + H2↔ CO + H2O
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Wonderful…..
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CO2 + H2 ↔ H2O + CO
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100% conversion!!
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Experimental
Thermodynamics
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Artist impression
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Efficiency estimate
• PV State of the Art :19%.
• High pressure electrolysis State of the Art: 85%
►Solar hydrogen: 16%.
• Including a mismatch between photo-voltage and electrolysis potential : this number reduces to 13%.
• SERWGS: 90% (The only new technology in the process!)
• Fischer-Tropsch : 70%
►Overall efficiency: Solar to fuels : 8.2%
• Including Carbon Capture penalty of 150 kJ/mol of CO2: 7.7%
• Alternative routes generally 1-2 orders of magnitude lower!!
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Take home messages
• Hydrogen will not prevail as sole energy carrier besides electricity
• CO2 can be pushed into reaction with a.o. hydrogen (separation enhancement)
• Synthetic fuels are a logical route in intermittent demand/supply energy system on large scale
• There are many routes to chemicals and fuels
• There are clearly options on industrial scale in the near future
• What you don’t take out of the earth’s crust will not burn
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Developments in The
Netherlands
• Program DIFFER (Dutch institute for fundamental energy research) – Four themes
– Photons related
– Out of equilibrium processes (plasmas)
– Bio –mimetic photo systems
– Downstream chemical processing
• Follow-up of CATO2 – CO2GO (use and storage)
– Main message: CO2 is not waste but feedstock
– Small impact: chemicals in industry
– Big impact: energy storage related to intermittent energy sources
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Ready to beat intermittency!
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Thank you for your attention
This research was performed in close cooperation with the TU Delft group Materials for Energy Conversion and Storage
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ECN
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The Netherlands The Netherlands
T +31 88 515 4949
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info@ ecn.nl
www.ecn.nl