Die schönsten Sagen der stofflichen CO -NutzungDie schönsten Sagen der stofflichen CO2-Nutzung The...

Die schönsten Sagen der stofflichen CO2-Nutzung (frei nach Gustav Schwab)

André Bardow

Lehrstuhl für Technische Thermodynamik, RWTH Aachen UniversityInstitut für Energie- und Klimaforschung (IEK-10), FZ Jülich

CO2Plus – Stoffliche Nutzung von CO2zur Verbreiterung der Rohstoffbasis1. Statuskonferenz, 17.-18. April 2018, Kalkscheune, Berlin

2

Acknowledgments

Die schönsten Sagen der stofflichen CO2-Nutzung

The CO2 Team at LTT

Funding

Our Project Partners

25.04.2018

Niklas von der Assen

AndréSternberg

ArneKätelhön

LeonardMüller

JohannaKleinekorte

ChristianJens

KaiLeonhard

RaoulMeys

SarahDeutz

JanScheffczyk

Technical Chemistry:• Martin Scott• Jürgen Klankermayer• Walter Leitner

Process Systems Engineering:• Dominik Bongartz• Luisa Schulze Langenhorst• Alexander Mitsos

Combustion Engines:• Benedikt Heuser• Ahmad Omari• Marius Walters • Stefan Pischinger

3

Mitigating climate change – A herculean task

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Pacala; Socolow. Stabilization wedges: Solving the Climate Problem for the Next 50 Years with Current Technologies, Science, 2004

4

Here comes HERccuLES: Carbon capture and utilization

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Climate mitigation HERccuLES= Carbon Capture

and Utilization

5

Here comes HERccuLES: Carbon capture and utilization

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What is the role of CO2 capture and utilization in mitigating climate change ?

God ?Mortal ?Climate mitigation

6

The Labours of HERccuLES

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It‘s a matter of ….

RateTime

Scale

7


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It‘s a matter of ….

Rate

8

CCU is happening today

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9

Chemical conversion of CO2: Dream Production

Energy

CO2

Epoxide

Polyols

Langanke et al., Green Chem.,2014,16,1865–1870


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10

Dream Production: Life-cycle assessment


conventional polyol

kg CO2-eq /

(1.00 kg polyol +0.36 kWh electricity)

0.0

0.5

1.0

1.5

2.0

2.5

3.0

CO2-based polyol(20 mass-% CO2)

3.57

−0.47+0.08 3.03

Substitution ofraw materials

−0.15

CO2capture

3.5

Epoxides Epoxides

Epoxides

1 kg CO2 as feedstock can avoid

3 kg of CO2 emissions

von der Assen, Bardow, Green Chem., 2014, 16, 3272

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11


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It‘s a matter of …

• CO2 utilization can save GHG emissions• By replacing energy-intensive fossil-based feedstock

Rate

12

The Chemical Tree

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Carbon dioxide

C1-Chemicals

13

CO2 hydrogenation to C1-chemicals


Formic acid

Formaldehyde

Methanol

Methane

Energy

O = C = O

H2

H2O

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Carbon monoxide

Klankermayer; Leitner, Phil. Trans. R. Soc. A 2016, 374, 1–8.

14



Formic acid

Formaldehyde

Methanol

Methane

O = C = O

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1 1 1 1

0? ???

Carbon monoxide

15

Fossil-based production of formic acid

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HCOOH + 3 H2CO + 3 H2+ H2OCH4

HCOOCH3+ 3 H2

+ H2O+ CH3OH- CH3OH

0 1 2 3

Methane Carbon monoxide Formic acid

16



Formic acid

Formaldehyde

Methanol

Methane

O = C = O

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1 1 1 1

013

Carbon monoxide

17

0

2

4

6

8

10

12

14G

W re

duct

ion

/ (kg

CO

2-eq

/kg

H2

used

)

Efficiency = climate change mitigation per hydrogen used

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CH4 HCOOHCO

1 0 1 311

Sternberg, Jens, Bardow, Green Chem., 2017,19, 2244-2259 C

O2,

eqem

issi

onsa

ving

spe

r H2

used

18

0

2

4

6

8

10

12

14G

W re

duct

ion

/ (kg

CO

2-eq

/kg

H2

used

)

Efficiency = climate change mitigation per hydrogen used

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CH4 HCOOHCO

1 0 1 311

Sternberg, Jens, Bardow, Green Chem., 2017,19, 2244-2259 C

O2,

eqem

issi

onsa

ving

spe

r H2

used

CO2 utilization can reduce complexity

Reduction of GHG emissions

19


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• CO2 utilization can save GHG emissions• By replacing energy-intensive fossil-based feedstock• By leading to more efficient process routes

ScaleRate

20

A matter of scale: CO2-based fuels

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21

Novel CO2-based fuels: Oxymethylene Ether (OME)

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Oxymethylenether

OMEx (1; 3 < x < 6)H3C

O OCH3x

Direct reductive synthesis of OME1 (= dimethoxymethane)

K. Thenert, K. Beydoun, J. Wiesenthal, W. Leitner and J. Klankermayer, Angew. Chem. Int. Ed., 2016, 55, 12266-12269.

22

OME1 diesel blend: Cradle-to-grave GHG emissions


ΔGW = 22 %

wsubstituted = 23.5 %

OME1

OME1 = (almost) carbon neutral blending component

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Deutz, Bongartz, Heuser, Kätelhön, Schulze Langenhorst, Omari, Walters, Klankermayer, Leitner, Mitsos, Pischinger, Bardow, Energy Environ. Sci., 2018, 11, 331

23


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• CO2 utilization can save GHG emissions• By replacing energy-intensive fossil-based feedstock• By leading to more efficient process routes• By producing fuels using renewable energy

(if available)

ScaleRate

24

OME1 Footprint: Sensitivity to power supply

Electricity global warming impact in g CO2,e / kWh

Fuel

glo

bal w

arm

ing

impa

ctin

g C

O2,

e / k

m

[1] European Commission, EU energy, transport and GHG emissions Trends to 2050. Reference Scenario 2013, Luxemburg, 2013. 25.04.2018

25

OME1 Footprint: Sensitivity to power supply


Fuel

glo

bal w

arm

ing

impa

ctin

g C

O2,

e / k

m

[1] European Commission, EU energy, transport and GHG emissions Trends to 2050. Reference Scenario 2013, Luxemburg, 2013. 25.04.2018

• OME1 as fuel requires very low carbon electricity

26

CO2-based fuels: Sensitivity to power supply

Life-Cycle Assessment for Carbon Dioxide Utilization

Wind EU grid mix 2020EU grid mix 2050

Iceland

Norway France Switzerland

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

0 50 100 150 200 250 300 350 400

GWI fue

l / (k

g CO

2_eq

/MJ fue

l)

GWI electricity / (g CO2_eq/kWh electricity)

Methane (LCA: Sternberg et al., Process: Müller et al.)Methane (LCA: Sternberg et al., Process: Saint Jean et al.)GTL‐type fuel (LCA: Giesen et al., Process: Giesen et al.)Jet fuel (LCA: Falter et al., Process: Shell GTL‐plant)DME (LCA: Schakel et al., Process: Schakel et al.)DMM, oxidative route (LCA: Deutz et al., Process: Bongartz et al.)DMM, reductive route (LCA: Deutz et al., Process: ‐ )Fossil diesel

Artz, et al., Chem. Rev., 2018, 118, 2, 434-504


Fuel

glo

bal w

arm

ing

impa

ctin

g C

O2,

e / M

J

27

CO2-based fuels: Sensitivity to power supply

Life-Cycle Assessment for Carbon Dioxide Utilization

Wind EU grid mix 2020EU grid mix 2050

Iceland

Norway France Switzerland

0

0.02

0.04

0.06

0.08

0.1

0.12

0.14

0.16

0.18

0.2

0 50 100 150 200 250 300 350 400

GWI fue

l / (k

g CO

2_eq

/MJ fue

l)

GWI electricity / (g CO2_eq/kWh electricity)

Methane (LCA: Sternberg et al., Process: Müller et al.)Methane (LCA: Sternberg et al., Process: Saint Jean et al.)GTL‐type fuel (LCA: Giesen et al., Process: Giesen et al.)Jet fuel (LCA: Falter et al., Process: Shell GTL‐plant)DME (LCA: Schakel et al., Process: Schakel et al.)DMM, oxidative route (LCA: Deutz et al., Process: Bongartz et al.)DMM, reductive route (LCA: Deutz et al., Process: ‐ )Fossil diesel

Artz, et al., Chem. Rev., 2018, 118, 2, 434-504


Fuel

glo

bal w

arm

ing

impa

ctin

g C

O2,

e / M

J

• Benefits requires very green electricity

but not 100% renewables

• Regional potential already today

28

Power-to-What?

Renewable power = limited resource


Sternberg, Bardow, Energy Environ. Sci., 2015, 8, 389

Given 1 MWh of surplus electricity, which energy storage system

brings the greatest environmental benefit?

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29

Efficiency in using renewable H2

25. April 2018

André Bardow | Power-to-What ?

P2X efficiency =

GHGP2X GHGconv

1 MWh

Renewable

electricty

ConventionalProductPower-to-X (P2X)

Sternberg und Bardow, Energy Environ. Sci., 2015,8, 389-400.

GHGreduction= -

Given 1 MWh of surplus electricity, which energy storage system

brings the greatest environmental benefit?

30

Power to What?

25.04.2018



P2X-

effic

ienc

y in

t C

O2,

eq/ M

Wh

31

Power to What?

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P2X-

effic

ienc

y in

t C

O2,

eq/ M

Wh

32

Power to What?

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P2X-

effic

ienc

y in

t C

O2,

eq/ M

Wh

• Winner: Efficient routes replacing inefficient processes• Power-to-Chemicals and Power-to-Fuels

not as energy storage butbecause we need chemicals and fuels

33

HERccuLES: God or Mortal ?

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(if available)

• CO2 utilization can be useful beyond climate change

ScaleRate

34

OME1-blend as diesel fuel: NOx & soot trade-off

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Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0

OME1: Diesel (vol. %) 0:100

Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0


Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0

OME1: Diesel (vol. %) 0:100 100:0

Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0

OME1: Diesel (vol. %) 0:100 35:65 100:0


35

OME1-blend as diesel fuel: NOx & soot trade-off

25.04.2018


Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0


Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0


Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0

OME1: Diesel (vol. %) 0:100 100:0

Euro 6 NOx level

Filte

r Sm

oke

Num

ber /

-

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

Ind. spec. NOx / g/kWh0.0 0.2 0.4 0.6 0.8 1.0

OME1: Diesel (vol. %) 0:100 35:65 100:0

OME1 strongly reduces both NOx and soot emissions


36

HERccuLES: God or Mortal ?

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(if available)

• CO2 utilization can be useful beyond climate change

ScaleRate Storage

37

Life Cycle Assessment (LCA) scope in this talk

CO2 conversionCO2 transportCO2 source

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conventional productiontransportfossil

resources

Good = Carbon-efficientthrough substitution


Cradle-to-Gate comparison

38

HERccuLES: God, or mortal ?

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Further impacts, e.g., local air pollutionClimate mitigationEnergy & Resource

Security

39

HERccuLES: God, or mortal ?

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God ?Mortal ?Further impacts, e.g., local air pollutionClimate mitigation

Energy & ResourceSecurity

40

Conclusions for Policies


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Further impacts, e.g., local air pollutionClimate mitigationEnergy & Resource

Security

• Policy has to recognize different CCU services

• Harmonised LCA methodologies

• Best use of limited resources

• Market support for CCU with benefits

Thank you for your attention!

Prof. Dr.-Ing. André Bardow

Head of InstituteChair of Technical Thermodynamics

E-Mail: [email protected]: +49 241 80 95 380

Die schönsten Sagen der stofflichen CO -NutzungDie schönsten Sagen der stofflichen CO2-Nutzung The...

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