playing with thermodynamics and kinetics: efficient
TRANSCRIPT
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Playing with thermodynamics and kinetics:
Efficient conversion of CO2 to chemical energy carriers
Atsushi Urakawa
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In New York City, 10 m CO2 spheres emerging at every 0.58 seconds
http://www.carbonvisuals.com
Scale of THE problem
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Quantity matters…
After 1 year, 54.3 Mtons of CO2
Only in NY city…
http://www.carbonvisuals.com
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Heterogeneous catalysis
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CO2 hydrogenation
CH4
CH3OH
HCOOH
higher hydrocarbons
CO
CH3OCH3
higheralcohols
H2
H2
H2
CO2 + H2
Natural energy
water electrolysis
FUEL
FUEL FUEL
FUEL
FUEL
H2 CARRIER
C1 FEEDSTOCK
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CO2 to chemical energy carriers
High-pressure approach
• Hydrogenation to methanol (and DME)
• Hydrogenation to formic acid and methyl formate
• Dimethyl carbonate (DMC) synthesis from CO2 and methanol
Unsteady-state operation
• CO2 capture and conversion in one process for syngas production
+
Conversion
Selectivity
X
S&
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CO2 to chemical energy carriers
High-pressure approach
• Hydrogenation to methanol (and DME)
• Hydrogenation to formic acid and methyl formate
• Dimethyl carbonate (DMC) synthesis from CO2 and methanol
Unsteady-state operation
• CO2 capture and conversion in one process for syngas production
+
Conversion
Selectivity
X
S&
7
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CO2 + 3H2 CH3OH + H2O ΔH298K,5MPa = - 40.9 kJ·mol-1
CO2 + H2 CO + H2O ΔH298K,5MPa = + 49.8 kJ·mol-1
4 2
2 2
Le Châtelier's principle
High pressure & low temperature are favorable for methanol synthesis
RWGS
Methanol synthesis
CO + 2H2 CH3OH ΔH298K,5MPa = - 90.7 kJ·mol-1
3 1
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180 210 240 270 300 3300
20
40
60
80
100
%
Temperature / OC
330 bar330 bar
182 bar182 bar
30 bar30 bar
180 210 240 270 300 3300
20
40
60
80
100
%
Temperature / OC
CO2 conversion MeOH selectivity
Thermodynamic equilibrium at CO2:H2=1:3
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High productivity
• Thermodynamics
• Kinetics
Supercritical phase
• High density and high diffusivity
Small reactor size
• For compressive fluids
• Economic
• Enhanced safety
liquid supercritical
Reactor
low P
high P
High-pressure advantages
NOTE: Old methanol synthesis processes were operated
at high-pressure (1920s-1960s, at 250-350 bar) 10
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Nanostructured Cu-ZnO (+Al2O3) catalysts
Cu0 ZnO
ZnO
Kasatkin et al., Angew. Chem. Int. Ed., 46, 7324 (2007)
Prepared by co-precipitation method
Active site
Spacer
Highly
active site
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260 oC, 330 bar, GHSV = 10,471 h-1, Cu/ZnO/Al2O3
95 %
98 %
1:3 1:5 1:7 1:10 1:12 1:140
20
40
60
80
100
SMeOH
XCO2
XC
O2 ,S
Me
OH
/ %
CO2:H
2 / molar ratio
0
10
20
30
40
SCO
SC
O /
%
Effects of feed CO2:H2 ratio
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30 bar
182 bar
330 bar
30 bar
182 bar
330 bar
Thermodynamic equilibrium
1:3 vs. 1:10 (CO2:H2)
180 210 240 270 300 3300
20
40
60
80
100
%
Temperature / OC
CO2 conversion MeOH selectivity
180 210 240 270 300 3300
20
40
60
80
100
Temperature / OC
%
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160 180 200 220 240 260 280 300 3200
20
40
60
80
100
SMeOH
XCO2
X C
O2,S
MeO
H /
%
Temperature / C
0
10
20
30
40
50
SC
O /
%
SCO
Kinetic
Regime
Thermodynamic
Regime
CO2:H2 = 1:10, 330 bar, GHSV = 10,471 h-1, Cu/ZnO/Al2O3
Temperature effects
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Towards full conversion of CO2 to methanol
CO2 + 3H2 CH3OH + H2O
catalyst
catalytic reactorunder high pressure
State-of-the-art Our process
CO2 conversion per pass
Methanol selectivity
Productivity
20-30%
30-60%
1 gMeOH gcat-1 h-1
(excellent case)
>95%
>98%
1-15.3 gMeOH gcat-1 h-1
Editor’s Choice in Science
Bansode & Urakawa, J. Catal. 309, 66 (2014)Granted patents: EP13724223, US9133084, CN104321293
Stoichiometric: Gaikwad, Bansode, Urakawa J. Catal. 343, 127 (2016), EP1638206215
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Capillary
Inlet Outlet
Quartz tube
Heater coil
X-ray
• Plug-flow• 300 oC & 330 bar• Fused silica capillary• Facile construction• Tunable length• Space-resolved study• Relevant activity
247 (ID), 662(OD) µm
Fixed-bed
Bansode, Urakawa, et al., Rev. Sci. Instrum. 85, 084105 (2014)
High-pressure operando XAFS
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▪ CO2:H2 = 1:3
▪ Up to 400 bar, 300 °C
▪ Fused-silica capillary (ID: 150 µm)
Detector
Heater
X-ray
source
Catalyst
High-pressure operando XRD
ZnCO3
15 20 25 30
D= Cu (0)*= ZnO• = ZnCO3
Inte
nsity /
a.u
.
2ϑ / °
••
D
D
•* * * *
200 bar, 300 °C
Reaction time
Gaikwad et al. in preparation 17
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Temperature gradients @ 200 bar, CO2:H2 = 1:3
+ operando Raman for C profiling
in out
∆T = +2 °C
CO2 CO CH3OH
endothermic exothermic
Gaikwad, Phongprueksathat et al., Catal. Sci. Technol., 10, 2763 (2020) 18
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2CH3OH → CH3OCH3 + H2O ΔH298K = - 23.5 kJ·mol-1
Cu/ZnO/Al2O3 H-ZSM-5
Mixed Bed
Reactor
Direct DME synthesis
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200 220 240 260 280 3000
20
40
60
80
100
Temperature / C
XC
O2,S
pro
d. /
%
SCO
SMeOH
XCO2
SDME
CO2:H2 = 1:10, P = 360 bar, GHSV = 10471 h-1
Cu/ZnO/Al2O3 + H-ZSM-5 mixed catalyst bed
97 %
89 %
Bansode & Urakawa, J. Catal. 309, 66 (2014)
Direct DME synthesis
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CO2 to chemical energy carriers
High-pressure approach
• Hydrogenation to methanol (and DME)
• Hydrogenation to formic acid and methyl formate
• Dimethyl carbonate (DMC) synthesis from CO2 and methanol
Unsteady-state operation
• CO2 capture and conversion in one process for syngas production
+
Conversion
Selectivity
X
S&
21
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Formic acid
Fuel cellLeather processingFeed preservationChemicals
HCOOH (FA)
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Formic acid: Promising energy carrier
H2
700 bar
39.4 g L-1
FA
Liquid at RT
53 g L-1
FA → H2 + CO2
TOYOTA
Mirai
HONDA
Clarity
HYUNDAI
Tucson
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CO2 Hydrogenation to FA
Breakthrough in the 1990s by Noyori’s group • Ru complexes
• In supercritical CO2
• CO2 as reactant and solvent
• Very high activity
CO2 + H2 HCOOH
Jessop, Ikariya, Noyori, Nature, 368, 231 (1994)
Jessop, Ikariya, Noyori, Science, 269, 1065, (1995)
Active transition-metal (Ru & Ir) catalysts since mid 1970s
Jessop
JACS 2002
Baiker
Chem Comm 2007
Nozaki
JACS 2009
Fujita
Nat Chem 2012
Sanford
ACS Catal 2013
Pidko
ACS Catal 2015
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HCOOH
CH3OH
Reactor 2
catalyst
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Reactor 1
Catalyst
Catalyst
Methyl formate (MF)
2-step synthesis
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Metal effects on MF synthesis
Wu et al., Green. Chem., 17, 1467 (2015)
Filonenko et al., J. Catal., 343, 97 (2016)
Preti et al., Angew. Chem. Int. Ed., 50, 12551 (2011)
Au catalysts for formates synthesis
Au/TiO2
Au/ZrO2
Au/Al2O3
MF
Continuous, 1 wt% M (Cu, Ag, Au)/SiO2, CO2:H2:CH3OH = 4:4:1, 6000 h-1
Ag!
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In situ DRIFTS & Raman spectroscopy
1 wt% M (Cu, Ag, Au)/SiO2
1800 1700 1600 1500 1400 1300 1200 1100
•
ÿ
ÿ
ÿ
Inte
nsity
Raman shift (cm-1)
•
ÿ
ÿ
3000 2800 2600 1800 1700 1600 1500 1400
0.01
Ag
Au
Ab
so
rba
nce
Wavenumber (cm-1)
Cu
DRIFTS Raman
H2
CO2
formatesformates
1 bar
40 bar
400 bar
200 bar• More formates with pressure
• Strongest signal of formates over Ag/SiO2
1 wt% Cu/SiO2
CO2:H2 = 1:1, 230 oC
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Transient operando DRIFTS @ 5 bar
3000 2800 2600 1800 1700 1600 1500 1400
0.01
Ag
Au
Ab
so
rba
nce
Wavenumber (cm-1)
Cu
3000 2800 2600 1800 1700 1600 1500 1400
0.01
Ag
Au
Ab
so
rba
nce
Wavenumber (cm-1)
Cu
How many surface species?
What kind of formates?
Tim
e (
s)
Wavenumber (cm-1)
Ar
CO
2+
H2
Ab
so
rba
nce
(milli
ab
s.)
1600
1680
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Source: interactive audio lab
Multivariate Analysis
Blind → No Reference
Multivariate Curve Resolution
(MCR)
Reducing spectral complexity:Blind source separation (multivariate analysis)
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Identification of surface species
Time / s1
CO2 + H2
Ar
bi-HCOO (vC-H)
bi-HCOO (vC-O)
Tim
e (
s)
Wavenumber (cm-1)
Ar
CO
2+
H2
Absorb
ance (m
illiabs.)
MCRMultivariate Curve Resolution
2700280029003000
1500160017001800
bi-HCOO (vC-H)
bi-HCOO (vC-O)
?
?
Wavenumber / cm-1
1680 cm-1
1680 cm-1
??2330 cm-1
Three different surface species:
1. 1600 & 2817 cm-1 - bi-HCOO
2. 1680 cm-1 - ?
3. 2330 cm-1 - ??
- 2 & 3 kinetically very similar
- But… different species
- Also observed for SiO2 (weak)
- Less pressure dependent
1
2
3
F
FF
F
?
F
FF
F
?
CO2,ad and…?
F
F
F
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M M M
? → important for MF formation
MF
MF
M?
F
M?
MFF
CH3OH +
CO2+H2
CH3OH
+ Ar
bi-HCOOad
?(perimeter,1680 cm-1)
Adsorbed MeOH
Transient operando DRIFTS @ 5 bar
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Reaction mechanism – Ag/SiO2
F
M?
MFF
F
CA
F
CO2
Corral-Pérez et al., J. Am. Chem. Soc., 140, 43, 13884 (2018)
• 1680 cm-1: carbonic acid on SiO2
• 2330 cm-1: adsorbed CO2 on SiO2
M
F
CA
FM
MF
FA
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Continuous FA/MF synthesis
ChemCatChem, 11, 4725 (2019) J. Catal. 380, 153 (2019)
J. Am. Chem. Soc.,
140, 43, 13884 (2018)
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CO2 to chemical energy carriers
High-pressure approach
• Hydrogenation to methanol (and DME)
• Hydrogenation to formic acid and methyl formate
• Dimethyl carbonate (DMC) synthesis from CO2 and methanol
Unsteady-state operation
• CO2 capture and conversion in one process for syngas production
+
Conversion
Selectivity
X
S&
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Dimethyl carbonate (DMC) synthesis
• Equilibrium limited
• Very low conversions < 1 %
(even at 400 bar!)
• H2O removal is effective
Electrolyte Fuel Additive Non-toxic reagent
O
OO
2 CH3OH H
2OCO
2+ +
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Tomishige et al., ChemSusChem 1341, 6 (2013)
2-cyanopyridine 2-picolinamide
DMC
Na2O/SiO2
- H2ORegeneration by
94 % DMC yield (12 h) in a batch reactor at 50 bar
State-of-the-art
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Continuous high-pressure DMC synthesis
MeOH +
2-cyanopyridine
CO2
reactor
BPR
hot-trap
cold-trap
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Continuous DMC synthesis: Pressure effects
0 50 100 150 200 250 3000
20
40
60
80
100
X
Me
OH ,
SD
MC (
%) S
DMC
XMeOH
Pressure (bar)
>92% (XMeOH)
>99% (SDMC)
Bansode & Urakawa, ACS Catalysis, 4, 3877 (2014)
MeOH : 2-cyanopyridine = 2:1 (10 µL/min), 6 NmL/min (CO2), 120 C, CeO2
Reaction & Residence time
Batch: 12 h
Continuous: 10-100 s
0 20 40 60 80 100
65
70
75
80
85
90
95
Me
OH
co
nve
rsio
n / %
Time / h
But…
30% activity decrease
after 4 days!
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Operando visualization
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Visual inspection (up to 70 bar)
Fresh CeO2
After 24 h
After MeOH
washing
After 300 °C
calcination
Before short washing Praline…
CeO2, 120 °C, 30 bar
Fused silica tube
ID:2 mm, OD: 3mm
No reactivation!
Stoian, Bansode, Medina, Urakawa, Catal Today, 283, 2 (2017)
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Origin of deactivation
60080010001200140016001800 60080010001200140016001800
Wavenumber / cm-1 Raman Shift / cm-1
IR Raman
After MeOH washing
2-picolinamide
Boiling point of 2-picolineamide: 284 °Cthe source of deactivation
2-picolinamideStoian, Bansode, Medina, Urakawa, Catal Today, 283, 2 (2017)
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Rare earth metal (REM) doping to CeO2
Less 2-PA adsorption Stoian, Medina, Urakawa. ACS Catal. 8, 4, 3181 (2018)
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CO2 to chemical energy carriers
High-pressure approach
• Hydrogenation to methanol (and DME)
• Hydrogenation to formic acid and methyl formate
• Dimethyl carbonate (DMC) synthesis from CO2 and methanol
Unsteady-state operation
• CO2 capture and conversion in one process for syngas production
+
Conversion
Selectivity
X
S&
43
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Challenge in CO2 conversion: CO2 purity
• Typical CO2 concentration: 3-15%
• Composition: CO2, N2, O2, H2O, …
▪ Most CO2 conversion processes require prior
purification steps
▪ Very expensive: 25-40% increase in energy
requirement for power plants
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Unsteady-state operation:CO2 capture and reduction (CCR)
syn
ch
ron
iza
tio
n
flue gas CO2
4-way
switching valve
H2
CO2
capture reduction
CO2-free
effluent
CO2 capture
phase
CO2-containing gas
syn
ch
ron
iza
tio
n
flue gas CO2
4-way
switching valve
H2
CO2
capturereduction
Product
stream
CO2 reduction
phase
reducing gas (e.g. H2)
CO2-free effluent Product stream45
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0 30 60 90 120 150 180 210
0.0
1.5
3.0
4.5
6.0
CO2
Co
nce
ntr
atio
n /
vo
l.%
Co
ncen
tra
tio
n /
vol.%
Time / s
0.0
0.5
1.0
1.5
2.0
Bobadilla et al., J CO2 Util, 14, 106 (2016)
5.8% CO2 in N2 (27 mL/min) vs. 100% H2 (65 mL/min) at 550 °C (107.5 s each)
CO2 H2
SiC
0 30 60 90 120 150 180 210
0.0
1.5
3.0
4.5
6.0
Co
nce
ntr
atio
n /
vo
l.%
Co
nce
ntr
atio
n /
vol.%
Time / s
0.0
0.5
1.0
1.5
2.0
CH4
CO2
COFeCrCu/K/MgO-Al2O3
CCR catalyst (FeCrCu/K/MgO-Al2O3)for syngas (COx + H2) production
CCR for methanation: Hu & Urakawa, J CO2 Util., 25 323 (2018)
CCR with DAC: Kosaka et al., submitted46
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DRIFTS cell: Urakawa et al.,
Angew. Chem. Int. Ed. 47, 9256 (2008)
Space- and time-resolved operando spectroscopy
XRD & XAFSDRIFTS
IR light
gas inlet
gas outlet
ZnSe
window
catalyst
front
back
gas inlet
gas outlet
X-ray
front
back
catalyst
47
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Spatiotemporal operando study
130015001700 1300150017001300150017001300150017000
50
100
150
200
FRONT BACK
MS
CO2
CO
Cu-K/Al2O3
350 °C
Tim
e / s
Tim
e / s
Wavenumber / cm-1
Hyakutake et al., J. Mater. Chem. A, 4, 6878 (2016)
5 10 15 20 25 30 35
2θ / °
KOH∙H2O
nano Cu
Protection of Cu
from oxidation
Cu-K/Al2O3
XRD XAS
DRIFTS
Pinto, Work in progress 48
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CH4
CH3OH
HCOOH
higher hydrocarbons
CO
CH3OCH3
higheralcohols
H2
H2
H2
MF
DMC+CO2
CO2 + H2
FUEL
FUEL FUEL
FUEL
FUEL
H2 CARRIER
C1 FEEDSTOCK
Take advantages of the thermodynamics & kinetics!!!49
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Acknowledgements
Catalysis Engineering @TU Delft, July 2020
Dr. Atul Bansode
Dr. Rohit Gaikwad
Dr. Andrea Álvarez
Nat Phongprueksathat
Donato Pinto
Dr. Dragos Stoian
Dr. Juan José Corral-Pérez
Dr. Luis Bobadilla
Dr. Tsuyoshi Hyakutake
Dr. Lingjun Hu50