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4/22/2012
1
Fuels generated from renewable energy: a possible solution for large scale energy storage
and transport
Richard van de Sanden
m.c.m.vandesanden@differ.nl
D t h I tit t f F d t l E R hDutch Institute for Fundamental Energy Research,P.O.Box 1207, 3430 BE Nieuwegein, The Netherlands
&Group Plasma & Materials Processing, Dept. Applied Physics,
Eindhoven University of Technology
Institute for Plasma Physics Rijnhuizen
From Jan. 1st 2015 on TU/e campus
FOM Rijnhuizen Instituut for Plasma Physics
4/22/2012
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To perform leading fundamental research in the fields of fusion energy and solar fuels,
New Mission DIFFER
in close partnership with academia and industry,
and to have a national coordinating role in the field of fundamental energy research.
In short:
Science for Future Energy
The TeraWatt Challenge
see also :
M.I. Hoffert et al. Nature 385, 881 (1998)
R.E. Smalley, MRS Bulletin 30 412 (2005)
Sustainable, CO2 neutral, energy infrastructure essential
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Theoretical potential energy sources
Solar energy conversion technologies (2011)
Light low temperature heat Light high temperature heat electricity
C i l (CSP)Concentrating solar power (CSP)
Light electricityPhotovoltaic conversion (PV)
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Solar power generation: DoE Sunshot
Price-experience curve of silicon PV modules(combined effects of innovation, experience and scale)
Solar power generation: Economy of scale
Grid parity ~1 /Wp
Clear economyof scale
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Grid parity in Europe
From 2020 a significant fraction is renewable
However.
solar generation
...energy demand
Storage and transport is part of the challenge!
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PV & wind far beyond niche already
Intermittency of PV/wind is part of the challenge!
Energy storage
Electrical- Batteries
Super capacitors- Super capacitors
110l57l33l26l
Mg2FeH6 LaNi5H6 H2 (liquid) H2 (200 bar)
Chemical storage- H2- Carbon containing fuels
(>10 more energy density)
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Storing and Transport of Energy
P tl 85% f th l b l i t t d b f lPresently: 85% of the global energy is transported by fuels
Carbon containing fuels (hydrocarbons, alcohols, etc.) generated from CO2 and H2O to store sustainable energy:
Solar Fuels
Solar Fuels: from sustainable energy
sustainable energy
Artificialphotosynthesis
Solves generation, transport and storage challenges
CO2 + H2O C-fuels + O2
sustainable energy
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Solar Fuels: fuels generated from sunlight
Big efforts and initiatives
Electricity grid
Current Energy System
Gas(or fossil)
Plant
Sun or Wind Energy Plant
SunFossil
Wind
WaterLiquid fuels or raw materials for industry
Dr.WaldoBongers
Gas gridGas buffer Fossil
current infrastructure of energy system
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Electricity grid
Indirect
Towards the Renewable Energy System
Gas(or fossil)
Plant
Sun or Wind Energy Plant
CO2Solar FuelPlant
SunFossil
Wind
WaterLiquid fuels or raw materials for industry
Direct
Dr.WaldoBongers
Gas gridGas buffer Fossil
Solar Fuels Production from CO2 and H2O using sustainable energy fitted in our current infrastructure
Electricity grid
Indirect
Full Renewable Energy System
GasPlant
Sun or Wind Energy Plant
CO2Solar FuelPlant
Sun
Wind
WaterLiquid fuels or raw materials for industry
Direct
Dr.WaldoBongers
Gas gridGas buffer
Solar Fuels Production from CO2 and H2O as storage using intermittent sustainable energy
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Contents
The TeraWatt Challenge: CO2 neutral energy supply The Energy problem Sustainable Energy Generation Sustainable Energy Generation Storage and Transport of Energy
Solar Fuels from CO2 and H2O Water splitting
CO ti ti CO2 activation Solar energy conversion
Conclusions and Outlook
Fuel processing from CO2 and H2O: syngas
Basically production of syngas H2 and CO :
By splitting H2O:1) H2O H2 + O22) followed by a reverse watershift reaction
H2 + CO2 H2O + CO (endothermic)
H2 productionmain activity globally
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Fuel processing from CO2 and H2O: syngas
Basically production of syngas H2 and CO :
By splitting H2O:1) H2O H2 + O22) followed by a reverse watershift reaction
H2 + CO2 H2O + CO (endothermic)
or activating CO2: 1) CO2 CO + O22) followed by a watershift reaction
CO + H2O CO2 + H2 (exothermic)
Syngas: by means of Fisher-Tropsch process carbon containing fuels
FT=Fischer-Tropsch reaction(R)WGS=(reverse) watergas shift
CO2 Hydro-genation
MethaneMethanol
Solar Fuels
Fuel processing starting from CO2 and H2O
Captured CO2
CO2RWGSAir
Solar energy conversion:
H2 O H2 + O2 COFT Fuel
H2
CO
H2WGS
CO2 CO + O2CO
water
Courtesy Wim Haije (ECN)
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Gas-to-liquid from syngas: Fisher-Tropsch
Shell Qatari plant (2009)
Methane reformation:
CH4 + H2O CO + 3H2 C-fuels
Investment of 19 B$; Revenue 4 B$/yr
Large scale proven
Ref. Bloomberg
Solar energy conversion (direct & indirect)
Man-made, ti ifi l
Courtesy Wim Sinke (ECN)
articifical
Solar
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
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Solar energy conversion (direct & indirect)
Man-made, ti ifi l
Courtesy Wim Sinke (ECN)
articifical
Solar
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
Solar energy conversion (direct & indirect)
Man-made, ti ifi l
Courtesy Wim Sinke (ECN)
articifical
ThermochemicalConversion (> 5%)
Solar
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
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Concentrated solar power
CO2 + 2H2O CO, O2, H2
Solar Fuels: Thermochemical (direct)
Thermochemically (direct sunlight into syngas/fuels)0.7-0.8 %
Science 330 1798 (2010)
Nanostructured materials + catalysis essential
Solar energy conversion (direct & indirect)
Man-made, ti ifi l
Courtesy Wim Sinke (ECN)
PhotocatalyticNanodevices (> 5%)
articifical
ThermochemicalConversion (> 5%)
Solar
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
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Direct photocatalytic conversion of H2O
Which approach is most promising ?
The challenge
Nanostructured materials and catalysis essential
But also photon management: plasmonics, etc.
Fundamental energy research: (Generation), Storage
Choice of research themes: Solar Fuels
Approaches:
Catalysis today (2009)
Science 331 746 (2011) TiO2 loaded with Cu
Photocatalytically (direct sunlight into fuels)1-3% 0.015% CO2 + 2H2O liquid fuels
2H2O 2H2 + O2
Nanostructured materials and catalysis essential
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Solar energy conversion (direct & indirect)
Man-made, ti ifi l
PV conversion +Electrolysis (> 20%)
Courtesy Wim Sinke (ECN)
PhotocatalyticNanodevices (> 5%)
articifical
ThermochemicalConversion (> 5%)
Solar
Electrolysis (> 20%)
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
Watersplitting using PV and electrolyser
Efficiency > > 20 %
Efficiency 70-80 %
sustainable energy> 8 /kg*
>16 /kmol2H2O 2H2 + O2
Advantage: separate optimization possibleCurrent bottleneck: use of scarce materials (a.o. Pt)
>16 /kmol
*H2 generation from steam reformation
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For large scale deployment:
Watersplitting using electrochemical cell
Elements of hope
2H2O 2H2 + O2
Nocera group (MIT): basically solar cell with Co based catalyst
Watersplitting using photo-lectrochemical cell
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Direct photocatalytic conversion of CO2Research issues use of N-doped TiO2 adding co-catalysts (Pt, Ru, Ag) stability under UV exposure
i i
To tailor the catalyst to optimally use the solar spectrum for activating the catalyst
The challenge
poisoning
Difficult to activate CO2
Roy, Varghese, Paulose, Grimes, ACSNano 4, 1260 (2010)
= 0.0148%solar spectrum for activating the catalyst
CO2 + 2H2O CH4 + 2O2Nanostructured materials and catalysis essential
activate CO2
Solar energy conversion (direct & indirect)
Man-made, ti ifi l
PV conversion +Electrolysis (> 20%)
PV conversion +Plasma conversion
Courtesy Wim Sinke (ECN)
PhotocatalyticNanodevices (> 5%)
articifical
ThermochemicalConversion (> 5%)
Solar
Electrolysis (> 20%) Solar Fuels
Biomass (< 1%)
PhotosyntheticMicro organism (> 5%)
(modified) natural, living
European Science Foundation,Science Policy Briefing 34 (Sept. 2008)
Primary and secondary
biofuels
4/22/2012
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FT=FischerTropschreaction(R)WGS=(reverse)watergasshift
CO2Hydrogenation
MethaneMethanol
SolarFuels
CapturedCO2
CO2
RWGSAir
Conversion: Electrocatalysis Photocatalysis Thermocatalysis CO
FT FuelH2
CO
Plasmacatalysis
H2WGSwater
Plasmacatalysis
Directplasmaactivation ofCO2(Plasmacatalysis ofCO2)
CO2 CO + O (H=5.9 eV)If O radical can be used in subsequent reaction:
Energy cost of CO2 dissociation
CO2 + O CO+ O2This leads to
CO2 CO + O (H=2.9 eV)
This implies already efficient use of produced O !!- plasma-surface interaction important- under which conditions is process energy efficient?
A.V. Eletskii, B.M. Smirnov, Pure. Appl. Chem. 57 1235 (1985)
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Thermochemically 41% can be reached (thermal plasmas?)
Energy cost of CO2 dissociation
CO2 CO + O2 H = 2.9 eV H/ECOEnergy efficiency
Thermochemically 41% can be reached (thermal plasmas?)
Ideally vibrational temperature should be high, notranslational and rotational heating, limited excitation and ionization energy efficiency of CO production: 61%
Nonequilibrium essential to obtain high efficiencies!!
A.V. Eletskii, B.M. Smirnov, Pure. Appl. Chem. 57 1235 (1985)
Controlling Tvib essential!
http://www.pages.drexel.edu/~rpg32/Research.htm
Dielectricbarrierdischarge15mm
Non-equilibrium atmospheric plasmas
Glidingarc
Surfacedischarge
Nonthermalprocess(roomtemp) Throughputnecessary(scale!) Scalable(stackedmicroreactors?) Essentiallynonequilibrium Controle ofEEDF
DBD/PackedbedCatalyticreactionenhancedbyPlasmacatalysis. http://www.jeh
center.org/electro/plasma/theory.html
Coronadischarge
CourtesyTomohiroNozaki(TokyoInstituteofTechnology)
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Energy efficient dissociation by plasma
1.Vibrational excitation is most effective in achieving dissociation
2 Energy lost by electrons in 1 3 eV
Rusanov et al.Usp. Fiz. Nauk. 134 185 (1981)
2.Energy lost by electrons in 1-3 eVplasmas concentrates on vibrationalstates, leads to Tvib > T0
3.Dissociation by vibrational activationmuch more efficient than byelectronic excitation
Distribution of energy lost by electrons in CO2 amongother excitation channels
Note: avoid channels which consume electronsor ions such as dissociative attachment
= H/ECOCO2 CO + O2 H = 2.9 eV Energy efficiency
100
Reported results on energy efficiency
Plasma surfaceinteraction!!
Material freedom!! 2030
40
50
60
70
80
90
100
microwave 1 microwave 2 microwave 3 microwave 4 supersonic RF-CCP RF-ICP
From A. Fridman, Plasma Chemistry (Taylor&Francis 2009)
Literature reports > 50% energy efficiency of CO2
dissociation !
Material freedom!!
10-1 100 1010
10
Ev (eV/molecule)
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CO2 activation using plasma
Efficiency> 20 %
Efficiency 70-80 %
sustainable energy 4.33 kWh/m3
@ =80%CO2 CO + O2
Advantage: separate optimization possible
@ =80%
Directing Matter and Energy Five challenges for science and the imagination, Report Basic Energy Science Advisory Committee
Nonequilibrium: controlling complexity
One of the five challenges directly linked with plasma science:
How do we characterize and control matter away, especially very far away, from equilibrium?
linked with plasma science:
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Conclusions and Outlook
Sustainable energy generation within reach (2025): Clear economy of scale
Next challenge: storing renewable energy in solarfuels (directly or indirectly) Cost effective CO2 neutral energy infrastructure In line with the present energy infrastructure Several approaches are adopted: H2O splitting prominent,
CO ti ti till i i f hCO2 activation still in infancy phase
Plasma aspect highlighted: Plasma deposition of nanostructured materials Plasma activation of CO2
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