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CO2 splitting with plasma on a power efficient and scalable wayon a power efficient and scalable way
Presented by Waldo Bongers
Dutch Institute for Fundamental Energy Research,P.O.Box 1207, 3430 BE Nieuwegein, The Netherlands
DIFFER is part of andDr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
&
Developments in power efficient dissociation of CO2 using non-equilibrium plasma activation
Introduction FOM institute DIFFERM ti ti f f l f t i bl Motivation for fuels from sustainable
energy: Solar FuelsWhy dissociation by plasma activation?Why dissociation by plasma activation?Experimental facilityResults obtained in 2012Future outlook
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
From January 2015 Present situation:
DIFFER is part of andDr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
onward: Eindhoven University campus
FOM Institute DIFFERApprox 150 FTE
Mission DIFFER
Fundamental research in: fusion energy and solar fuelsfusion energy and solar fuels
In close partnership with academia and industryIncluding Univ Stuttgart Eindhoven Twente Delft Leiden Including Univ. Stuttgart, Eindhoven, Twente, Delft, Leiden, AmsterdamIncluding Alliander, Shell and others (Dutch Top sector policy)policy)
National coordinating role in fundamental energy research, including NWO programme CO2 neutral fuels:research, including NWO programme CO2 neutral fuels:•Photo-catalysis (inorganic semi-conductors)•Smart matrices (artificial photo-synthesis)•Out of equilibrium processing (plasma chemistry)
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
q p g (p y)•Down-stream processing and reactor development
Motivation Solar Fuels
Sustainable power generation is booming but it is
German solar and wind energy
boo g bu s
with time-scales ranging from
inhomogeneous and intermittent
minutes to months
Mismatch betweensupply and demandSolution:Energy storageEnergy storage
Sustainable energy - storage needed
Storing energy: mechanicalelectricalelectricalelectro-chemicalchemical
water reservoirs
bio-chemical Artificial chemical fuel
batteriesstored heat
Solar Fuels Cycle
• Large potential to contribute to a CO2 neutral energy infrastructureneutral energy infrastructure
• Storage and transport of sustainable energy in chemical bonds
• Large efforts world wide on Solar Fuels:Basically splitting H2O or dissociating CO2using direct solar (heat & light) or sustainably
generated electrical energy: generated electrical energy:
End product carbon containing fuelsEnd product carbon containing fuels
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
CO2 Hydrogenation
MethaneMethanol
Solar FuelsCourtesy Wim Haije (ECN)
Captured CO
CO2
RWGSAir
H
COH2 O H2 + ½O2
CO2 CO + ½O2C i
CO2conversion
process
Efficiency (%)
Electro-catalysis
~6CO2
COFT Fuel
H2Conversion:• Electrocatalysis• Photocatalysis• Thermocatalysis
catalysis
Thermo-catalysis
~3-4
Photo-catalysis
~1
FT=Fischer-Tropsch reaction(R)WGS=(reverse) watergas shift
H2WGSwater
Thermocatalysis•Why not Plasma?
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
( ) ( ) g
Focus: Energy efficient CO2 dissociation by plasma
CO2 chemistry out of equilibrium Tv>T 0
CO2 CO + O H = 5.5 eVIf radical O is used:CO + O CO + O H 0 3 V
96.285 kJ/mol eV
]CO2 + O CO + O2 H = 0.3 eVTotal reaction:CO2 CO + ½ O2 H = 5.8/2
=2.9 eV 2000
3000
ergy
[cm
-1]
2.9 eV
1000Vib
. Ene
(4 26 m)
(4.26 m)
Concentrate energy on CO2 vibration state that matters for dissociation
Thermodynamic equilibrium: Energy efficiency 41% maxOut of equilibrium > 50% Classified Russian work 60`s
A. Fridman, Drexel Univ., US [Plasma Chemistry]
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
(CO production at 100%: 12.5 kJ/l or 3.5 Wh/l or 4.8 slm/kW)(CO + H2OH2+ CO2 H=-0.4 eV)
Energy efficiency
H/ECO
CO2 dissociation by plasma activation
Can it be done energy efficiently?
Plasma processing energy expensive:
CO2 potential energy96.285 kJ/mol eV
Plasma processing energy expensive:• Creating electron-ion pair > 30 eV• Dissociation energy CO2 > 5.5 eV
YES if:• Vibration excitation CO by slow electrons• Vibration excitation CO2 by slow electrons
(1 eV) creating out of equilibrium Tvib >Tgas• Low degree of ionisation (10-5)• Low reduced electric field (~10-16 Vcm2)
energy efficient dissociation possible through vibrational excitation CO in asymmetric stretch mode
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
vibrational excitation CO2 in asymmetric stretch mode
Electron energy loss in CO2 plasma
electrons
electric field
collisions
vibrationalexcitation
Electron energy loss depends on reduced electric
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013Rusanov et al. Usp. Fiz. Nauk. 134 185 (1981)
field depends on average electron energy
Reported results on energy efficiency96 28 k / l
(η = ∆H/ECO)CO2 CO + ½O2 ∆H = 2.9 eV
90
100
microwave 1microwave 2
96.285 kJ/mol eV
60
70
80 microwave 3 microwave 4 supersonic RF-CCP RF-ICP
30
40
50
10-1 100 1010
10
20
Literature reports > 50% power
Advantage plasma:No catalysts used
(no rare materials needed)
10 10 10
Ev (eV/molecule)
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
[Adapted From A. Fridman, “Plasma Chemistry” (2009)]
Literature reports > 50% power efficiency of CO2 dissociation !
( )Scalable technology (microwave)Proof of principle (microwave)
How: Using a Microwave Plasma source for CFCdestruction(IPF) for (DIFFER) CO2 dissociation
DIFFER/IPF cooperationWaldo Bongers, Adelbert Goede, Martijn Graswinckel, Pieter Willem Groen,
Martina Leins, Jochen Kopecki, Andreas Schulz, Matthias Walker en Richard van de Sanden
30 kW 915 MHz setup
Sub atmospheric CO plasmas inside microwave cavity
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
Sub atmospheric CO2 plasmas inside microwave cavityCO2 CO + ½O2
Experimental Results: subsonic region
CO produced at expense of CO2CO2 CO + ½O2 H = 2 9 eV 96 285 kJ/mol eV
12
CO2 CO + ½O2 H = 2.9 eV
1,0x10 5 1 kW
96.285 kJ/mol eV
6
8
10
ow [s
lm] CO2
6,0x10 4
8 ,0x10 42 kW
3 kW 4 kW
y [a
. u.]
0
2
4
Outp
ut flo
COO2
200 300 400 500 600 7000,0
2,0x10 4
4 ,0x10 4
inte
nsity
0 1000 2000 3000 4000 5000Power [W]
200 300 400 500 600 700
wavelength [nm ]
CO 3rd positive, 4th positive,Angstrom and triplet identified
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013Constant CO2 flow of 11.1 SLM
g p
Experimental Results: supersonic region
CO produced at expense of CO2CO2 CO + ½O2 H = 2 9 eV 96.285 kJ/mol eV
10
12
25
30Energy efficiency [%]
Conversion efficiency [%]
CO2 CO + ½O2 H = 2.9 eV
CO2 Conversion: βdiss
/
4
6
8
tput
flow
[slm
]
10
15
20
Effic
ency
[%]
CO
CO2
Energy: η
diss
0
2
0 1000 2000 3000 4000 5000
Out
Power [W]
0
5
0 1000 2000 3000 4000 5000Power [W]
COO2
Energy: ηpower
[ ]
H/EEnergy efficiency:
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013Constant CO2 flow of 11.1 SLM
H/ECO
Experimental Result: pre-supersonic region
CO produced at expense of CO2CO2 CO + ½O2 H = 2 9 eV 96.285 kJ/mol eV
8
10
12
]
COCO21000
1200
1400
1 cm3 cm/m
s]
P = 5 kW, d = 5 mm asymm, position IV
CO2 CO + ½O2 H = 2.9 eV 96.285 kJ/mol eV
2
4
6
tput
flow
[slm O2
400
600
800
1000 6 cm
nsity
[cou
nts/
0
2
0 2000 4000 6000 8000
Out
Power [W] 200 300 400 500 600 700
0
200
Inte
nwavelength [nm]
C2 Swan band A3Πg>X3Πu
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013 Constant CO2 flow of 11.1 SLM
Best results DIFFER/IPF of conversion efficiency:Low flow CO2 (2 -10 eV/CO2 molecule)
96 285 kJ/mol eV
12 100
CO produced at expense of CO2
96.285 kJ/mol eV
6
8
10
w [s
lm]
60
80
ency
[%]
CO2 CO
½O2
Conversion: βdiss
0
2
4
0 2000 4000 6000 8000
Out
put f
low
0
20
40
Effic
e½ 2
Energy: ηpower0 2000 4000 6000 8000
Power [W] 0 2000 4000 6000 8000
Power [W]
Measurements (bold) fitted on reaction scheme (open)High energy per CO2 molecule gives low efficiencyHigh energy per CO2 molecule gives low efficiencyDeviation by little C production(spectrum shows C-Swan band)
Energy efficiency (@3kW) ≈ 36%
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
Constant CO2 flow of 11.1 slm (2.3 kW@100% E. efficiency)
Energy efficiency (@3kW) 36%Conversion efficiency (@8kW) ≈ 84%
More experiments at more CO2 input flow?E ffi i ∆H/EEnergy efficiency η = ∆H/ECOCO2 CO + ½O2 ∆H = 2.9 eV
100
96.285 kJ/mol eV
70
80
90 microwave 1 supersonic microwave 2 microwave 3 microwave 4 microwave subsonic RF-CCPRF ICP
40
50
60
RF-ICP DIFFER&IPF
10
20
30
10-1 100 1010
Ev (eV/molecule)
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
Ev can be tuned by Power/flow:At same powers more input gas flow needed to reach higher efficiencies
[Adapted From A. Fridman, “Plasma Chemistry” (2009)]
Best results DIFFER/IPF of energy efficiency:High flow CO2 (0.6 -1.5 eV/CO2 molecule)
96 285 kJ/mol eV
7080
CO produced at expense of CO2
96.285 kJ/mol eV
40
50
60
y [%
]
40506070
flow
[slm
] CO2Energy: ηpower
0
10
20
30
Effic
ency
01020300
Out
put f
CO½O2Conversion: βdiss0
0 2000 4000 6000 8000Power [W]
00 2000 4000 6000 8000
Power [W]
Measurements (bold) fitted on reaction scheme (open)Low energy per CO2 molecule gives high efficiency
Energy efficiency (@3kW) ≈ 60%C i ffi i (@8kW) 20%
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
Conversion efficiency (@8kW) ≈ 20%
Constant CO2 flow of 75 slm (15.6 kW@100% E. efficiency)
Business case: How good is 60%? compare plasma, water electrolyses and steam reformation
Efficiency 70-80 %
SR: CH4+ H2O 3H2 + COWGS: CO+ H2O H2 + CO2
Comparison H2 generation by 6 :1) Fossil, CH4 3 by SR+WGS 1 : 1 €/kg2) Bio, CH4 by SR+WGS 4 : 10 €/kg3) Electrolyses H O ( =70%)2 8 €/kg3) Electrolyses, H2O ( =70%)2 8 €/kg4) Plasma, CO2 to CO and WGS:
( = 90-60%) 6-9 €/kg
2H2O 2H2 + O2
Sustainable energy
(Exclusive CO2 emission rights 5 at2011-2050: 0.17-1.7 €/500 Mole)
Comparison CO generation by 6 :2H2O 2H2 + O2Advantage: No gas separationDisadvantage:
1) Fossil, CH4 3 by SR+RWGS 1 : 9 € cts/m32) Plasma, CO2 to CO :
( = 90-60%) 15-23 € cts/m3 [1] J ff R B t l t l I t ti l J l f H d E 35 (2010) 8371
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
rare materials necessary (Pt, etc)low power density
[1] Jeffrey R. Bartels et al. Internation al Journal of Hydrogen Econ. 35 (2010) 8371[2] R. van der Krol (TUD), privé communicatie (2011)[3] J.M. Cormier et al., J. Phys. D 34 (2001) 2798–2803[4] Private communication Harry van Breen, Alliander (2011)[5] Solar Photovoltaics: competing in the energy sector, EPIA report 2011[6] CH4 8 cnts/m3 and standard electricity price 4 cts/kWh
Overview results DIFFER/IPF:How further optimization?
microwave 1 supersonic microwave 2 microwave 3microwave 4
90
100 CO2 CO + ½O2 ∆H = 2.9 eV Key issue for further
optimization: E-Field distribution over the density
microwave subsonic RF-CCP RF-ICP microwave 1 supersonic microwave 1 supersonic DIFFER&IPF 11 SLM CO2 DIFFER&IPF 75 SLM CO250
60
70
80
distribution over the density (= E/n ~ average electron
energy) to excite the optimal vibrational mode
10
20
30
40
10-1 100 1010
10
Ev (eV/molecule)
Next research DIFFER:Next research DIFFER:Insight in Plasma parameters
with more diagnostics (E, ne, Te, Tvib, Tg, etc)
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013
, , g, )Cavity design optimization on
E/n (simulation)[A. Fridman, “Plasma Chemistry”]
Conclusion and Future outlook
Sustainable energy generation within reach by storage in Solar Fuels using no scare materials
The DIFFER/IPF CO2 plasma dissociation experiments prove high efficiency >50% can be obtained
New reactor designs are now under development and production at DIFFER (INITSF 3 months-> PROTOSF 5 months ->start begin next year DEMOSF)
Additional diagnostics for better plasma chemistry d di d i i i ill b li dunderstanding and optimization will be applied
Modelling (microwave-plasma-flow-chemistry interaction) Efficient Capture and separation of CO2 to be to addressed
f(preferably using process waste energy) Direct Fuel production (CH4, etc) in plasma under investigation
using CO2 (or carbonate) and H2O combination as input
Dr. Waldo Bongers, Spring session of PINNL, Traxxys, Amersfoort, 10 April, 2013” A il 11 2013
Ultimate Goal: 100 kW plasma DEMOSF reactor (efficient fuel production from sustainable energy using CO2 and H2O)