die schönsten sagen der stofflichen co -nutzungdie schönsten sagen der stofflichen co2-nutzung the...
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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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Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
Climate mitigation HERccuLES= Carbon Capture
and Utilization
5
Here comes HERccuLES: Carbon capture and utilization
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Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of ….
RateTime
Scale
7
The Labours of HERccuLES
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Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of ….
Rate
8
CCU is happening today
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Die schönsten Sagen der stofflichen CO2-Nutzung
9
Chemical conversion of CO2: Dream Production
Energy
CO2
Epoxide
Polyols
Langanke et al., Green Chem.,2014,16,1865–1870
Die schönsten Sagen der stofflichen CO2-Nutzung
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10
Dream Production: Life-cycle assessment
Die schönsten Sagen der stofflichen CO2-Nutzung
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
The Labours of HERccuLES
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Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
Carbon dioxide
C1-Chemicals
13
CO2 hydrogenation to C1-chemicals
Die schönsten Sagen der stofflichen CO2-Nutzung
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
CO2 hydrogenation to C1-chemicals
Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
HCOOH + 3 H2CO + 3 H2+ H2OCH4
HCOOCH3+ 3 H2
+ H2O+ CH3OH- CH3OH
0 1 2 3
Methane Carbon monoxide Formic acid
16
CO2 hydrogenation to C1-chemicals
Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
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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Die schönsten Sagen der stofflichen CO2-Nutzung
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
The Labours of HERccuLES
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of …
• 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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Die schönsten Sagen der stofflichen CO2-Nutzung
21
Novel CO2-based fuels: Oxymethylene Ether (OME)
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Die schönsten Sagen der stofflichen CO2-Nutzung
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
Die schönsten Sagen der stofflichen CO2-Nutzung
ΔGW = 22 %
wsubstituted = 23.5 %
OME1
OME1 = (almost) carbon neutral blending component
25.04.2018
Deutz, Bongartz, Heuser, Kätelhön, Schulze Langenhorst, Omari, Walters, Klankermayer, Leitner, Mitsos, Pischinger, Bardow, Energy Environ. Sci., 2018, 11, 331
23
The Labours of HERccuLES
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of …
• 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
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
• 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
Electricity global warming impact in g CO2,e / kWh
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
Electricity global warming impact in g CO2,e / kWh
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
Die schönsten Sagen der stofflichen CO2-Nutzung
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?
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Die schönsten Sagen der stofflichen CO2-Nutzung
Sternberg und Bardow, Energy Environ. Sci., 2015,8, 389-400.
P2X-
effic
ienc
y in
t C
O2,
eq/ M
Wh
31
Power to What?
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Die schönsten Sagen der stofflichen CO2-Nutzung
Sternberg und Bardow, Energy Environ. Sci., 2015,8, 389-400.
P2X-
effic
ienc
y in
t C
O2,
eq/ M
Wh
32
Power to What?
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
Sternberg und Bardow, Energy Environ. Sci., 2015,8, 389-400.
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 ?
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of …
• 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)
• CO2 utilization can be useful beyond climate change
ScaleRate
34
OME1-blend as diesel fuel: NOx & soot trade-off
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Die schönsten Sagen der stofflichen CO2-Nutzung
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
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
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
Deutz, Bongartz, Heuser, Kätelhön, Schulze Langenhorst, Omari, Walters, Klankermayer, Leitner, Mitsos, Pischinger, Bardow, Energy Environ. Sci., 2018, 11, 331
35
OME1-blend as diesel fuel: NOx & soot trade-off
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
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
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
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
Deutz, Bongartz, Heuser, Kätelhön, Schulze Langenhorst, Omari, Walters, Klankermayer, Leitner, Mitsos, Pischinger, Bardow, Energy Environ. Sci., 2018, 11, 331
36
HERccuLES: God or Mortal ?
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
It‘s a matter of …
• 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)
• CO2 utilization can be useful beyond climate change
ScaleRate Storage
37
Life Cycle Assessment (LCA) scope in this talk
CO2 conversionCO2 transportCO2 source
25.04.2018
conventional productiontransportfossil
resources
Good = Carbon-efficientthrough substitution
Die schönsten Sagen der stofflichen CO2-Nutzung
Cradle-to-Gate comparison
38
HERccuLES: God, or mortal ?
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
Further impacts, e.g., local air pollutionClimate mitigationEnergy & Resource
Security
39
HERccuLES: God, or mortal ?
25.04.2018
Die schönsten Sagen der stofflichen CO2-Nutzung
God ?Mortal ?Further impacts, e.g., local air pollutionClimate mitigation
Energy & ResourceSecurity
40
Conclusions for Policies
Die schönsten Sagen der stofflichen CO2-Nutzung
25.04.2018
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