CO2 splitting with plasma on a power efficient and scalable ......• Dissociation energy CO 2 > 5.5...

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)