Carbon Dioxide Hydrogenation...Kashid, Renken, Kiwi-Minsker, Microstructured devices for chemical...
Transcript of Carbon Dioxide Hydrogenation...Kashid, Renken, Kiwi-Minsker, Microstructured devices for chemical...
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Transport Processes and Reactions LaboratoryInstitute of Process EngineeringHelena Reymond
Carbon Dioxide HydrogenationSynthetic Perspectives for Chemical Energy Carriers
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Carbon Dioxide
Carbon Capture and Storage
Carbon Dioxide Utilisation
Valuable Chemicals / Fuels
Economic and Environmental IncentivesEmission Mitigation Strategies
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1970 1975 1980 1985 1990 1995 2000 2005 2010 2015
Gt
CO
2
World emissions from fuel combustion
32.2 Gt CO2
2013
?
PBL Netherlands Environmental Assessment Agency, trends in global CO2 emissions, 2015 report
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Carbon Dioxide
Renewable Energies
Energy Storage
Water splitting
Hydrogen Economy
Electricity and Heat
42%
Transport23%
Industry19%
Others16%
Emissions shares by sector
Economic and Environmental IncentivesEmission Mitigation Strategies
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1970 1975 1980 1985 1990 1995 2000 2005 2010 2015
Gt
CO
2
World emissions from fuel combustion
32.2 Gt CO2
2013
International Energy Agency (IEA) highlights 2015
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Carbon Dioxide
Carbon Capture and Storage
Carbon Dioxide Utilisation
Valuable Chemicals / Fuels
Economic and Environmental IncentivesEmission Mitigation Strategies
Renewable Energies
Energy Storage
Water splitting
Hydrogen Economy Methanol3 H2 + CO2 CH3OH + H2O
Graves et al., Renewable Sustainable Energy Rev 15 (2011) 1-23
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Carbon Dioxide
Carbon Capture and Storage
Carbon Dioxide Utilisation
Valuable Chemicals / Fuels
Economic and Environmental IncentivesEmission Mitigation Strategies
Renewable Energies
Energy Storage
Water splitting
Hydrogen Economy Methanol
Formic Acid
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1 2
H2 H2
CO2
HCOOH
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Thermodynamically hampered Sensitive equilibrium Non-spontaneous
Homogeneous catalysis› Basic media to stabilise HCOOH
Heterogeneous catalysis› Economically advantageous› Unsuccessful: yields methanol
Formic acid synthesis
H2 + CO2 HCOOH
H2 H2
CO2
HCOOH
Noyori et al., Nature 368 (1994) 231.Noyori et al., Science 269 (1995) 1065.
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Reactants diffusion1. External diffusion 2. Internal diffusion
Reaction3. Adsorption of reactants on the surface4. Catalytic reaction on the surface5. Desorption of the products
Products diffusion6. Internal diffusion of products7. External diffusion of products
Rate determining step? Kinetically controlled Mass transfer limited
Heterogeneous catalysis
Kashid, Renken, Kiwi-Minsker, Microstructured devices for chemical processing Wiley Verlag, 2015
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Continuous 2-step process
CO2 + H2
REACTOR 1REACTOR 1
HCOOHCatalyst 1
> 100 bar, 200 – 300°C
MAJOR PROBLEM
Formic acid decomposition back to H2 and CO2
› Conventional heterogeneous catalysts are active in the reverse reaction (metal supported on metal oxides)› Microscopic reversibility suggests some activity in the foward reaction under appropriate conditions
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Continuous 2-step process
IDEA
Mitigate the thermodynamic barrier› Shift the reaction equilibrium to the right› Include a reaction consuming FA faster than its decomposition
CO2 + H2
HCOO(H)
???
Stable compound
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
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IDEA TO MITIGATE THERMODYNAMIC BARRIER
Secondary reaction to transform the FA before decomposition
› Reacting FA with alcohols to yield formate esters
Methyl formate synthesis
M or MOX
CO2 + H2
CO
O
H
CO
O
H
CO
O
H
Formic acid
CO-H
O
H
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IDEA TO MITIGATE THERMODYNAMIC BARRIER
Secondary reaction to transform the FA before decomposition
› Reacting FA with alcohols to yield formate esters
Methyl formate synthesis
M or MOX
CO2 + H2
CO
O
H
CO
O
H
CO
O
H
MeOH
Formic acid
Methyl formate
CO-CH3
O
H
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IDEA TO MITIGATE THERMODYNAMIC BARRIER
Secondary reaction to transform the FA before decomposition
› Reacting FA with alcohols to yield formate esters› In-situ formed MeOH
Methyl formate synthesis
M or MOX
CO2 + H2
CO
O
H
CO
O
H
CO
O
H
Methyl formate
Formic acid
MeOH
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METHYL FORMATE› Good chemical properties as fuel› Not economically viable
transient intermediate
Continuous 2-step process
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
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METHYL FORMATE› Good chemical properties as fuel› Not economically viable
transient intermediate
Continuous 2-step process
HCOOHCatalyst 3
FORMIC ACID› Industrially produced by hydrolysis of MF (BASF)› MeOH as by-product› Batch or chromatographic reactors
HCOOCH3
CH3OH
REACTOR 210 bar, 40 - 120°C
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METHYL FORMATE› Good chemical properties as fuel› Not economically viable
transient intermediate
Continuous 2-step process
FORMIC ACID› Industrially produced by hydrolysis of MF (BASF)› MeOH as by-product› Batch hydrolysis
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
REACTOR 2
HCOOH
CH3OH
Catalyst 3
10 bar, 40 - 120°C
HCOOCH3
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The overall process requires the rational design of a robust heterogeneous CO2 hydrogenation catalyst selective for formic acid
Catalyst and reactor design
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
REACTOR 2
HCOOH
CH3OH
Catalyst 3
10 bar, 40 - 120°C
HCOOCH3
Reaction mechanismPhase behaviour
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Sinergia collaboration
The overall process requires the rational design of a robust heterogeneous CO2 hydrogenation catalyst selective for formic acid
Reaction mechanismPhase behaviour
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Reactor 1: synthesis of methyl formate
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
REACTOR 2
Catalyst 3HCOOH
CH3OH
10 bar, 40 - 120°C
HCOOCH3
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High-pressure hydrogenation setupCatalytic activity measurements and simultaneous in-situ Raman spectroscopy at reaction conditions
3H2 + CO2 CH3OH + H2O
H2 + CO2 CO + H2O
H2 + CO CH3OH
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High-pressure hydrogenation setupCatalytic activity measurements and simultaneous in-situ Raman spectroscopy at reaction conditions
Diaphragm compressorpmax = 3000 bar
Pressure transducers
H2 storage in coiled pipe
Hydrogen
Carbon dioxide
Pressure relief valvepmax = 1300 bar
Nickel-clad fused silicaID = 1 µm
Operando Raman microspectrometerλ1 = 355 nmλ2 = 532 nmλ3 = 785 nm
Online gas chromatograph
Pressure regulating valvepmax = 1300 bar
Microreactorwith
view-cell
High-pressure syringe pumppmax = 1300 bar
Stainless steel microreactor ID = 1 mm
Maximum operating conditionsPressure 500 barTemperature 300°C
Flowrate rangeCO2H2 (via ∆p_capillary)
5 – 25000 µL/min40 – 500 µL/minTidona et al., J. Supercrit. Fluids 78 (2013) 70-77
Tidona et al., Chem. Eng. Process.: Process Intensif. 65 (2013) 53-57
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High-pressure micro view-cell
Metal sealingsSapphire window
WD = 14 mm
NA = 0.34 40°
FP 1 mm below window
Inner diameter ID = 1 – 1.5 mmLength L = 50 mm
Maximum operating conditionsPressure 500 barTemperature 300°C
Flow or static conditions
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The Raman effect
SPECTROSCOPY = LIGHT – MATTER INTERACTION› Incident electric field› Induced dipole moment› Oscillating molecule
Fingerprint of molecule
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H2 CO2CH4CO
H2OCH3OH
HCOOCH3A
S RI S¦
S
A
A
catalyst packed bed
in situ analysis
SURFACE SPECIES ANALYSIS BY RAMAN SPECTROSCOPY
› Main carbon oxide source ?› Parallel or consecutive RWGS ?› Common or different intermediate species ?
PHASE BEHAVIOUR OF REACTIVE MIXTURES
› Number and nature of phases in reactor ?› Chemical and phase equilibrium ?
3H2 + CO2 CH3OH + H2O
H2 + CO2 CO + H2O
H2 + CO CH3OH
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Methanol synthesis: equilibrium conversion
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170 190 210 230 250 270 290 310 330
CO
2co
nver
sion
[-]
Temperature [°C]
50 bar V 100 bar V 350 bar V 500 bar V 700 bar V50 bar VL 100 bar VL 350 bar VL 500 bar VL 700 bar VL
PR
ESS
UR
E
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Temperature [°C]
170 180 190 200 210 220 230 240 250 260 270 280 290 300
Sele
ctiv
ity [%
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CO
Methanol
Methylformate
Reaction performance GHSV = 22’300 h-1
H2:CO2 = 3:1
Temperature [°C]
170 180 190 200 210 220 230 240 250 260 270 280
CO2 c
onve
rsio
n [%
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Temperature [°C]
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Yiel
d [m
mol
/g h
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90350 bar500 bar700 bar
CO
Methanol
Methylformate
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Raman spectrum of reaction effluent
Raman shift [cm-1]1000 1500 2000 2500 3000 3500 4000
Rel
ativ
e in
ten
sity
[a.u
]
500
350 bar240 °CH2:CO2 = 3:1GHSV = 22’300 h-1
H2 CO2 ProductsProducts Products
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Methanol synthesis: in situ condensation
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CO
2co
nver
sion
[-]
Temperature [°C]
50 bar V 100 bar V 350 bar V 500 bar V 700 bar V50 bar VL 100 bar VL 350 bar VL 500 bar VL 700 bar VL
Van Bennekom et al., Ind. Eng. Chem. Res., 51 (2012)
Van Bennekom et al., Chem. Eng. Sci., 87 (2013)
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Condensation
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Reactor 2: hydrolysis of methyl formate
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
REACTOR 2
Catalyst 3HCOOH
CH3OH
10 bar, 40 - 120°C
HCOOCH3
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Hydrolysis setup
Stainless steel reactor ID = 2 mm
Maximum operating conditionsPressure 100 barTemperature 300°C
Flowrates range 0.001 – 100 mL/min
MF Water catalyst packed bed
Methyl formate + Water Formic acid + Methanolcatalyst
MF
MF
MF
MF
MF
WaterFormic acidMethanolMF
MFMF
MFMF
MFP P
P
PPP PP
P
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Ternary Map (Mole Basis)
WATER
MF
MEO
H
0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 0.8 0.85 0.9 0.95
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0.55
0.6
0.65
0.7
0.75
0.8
0.85
0.9
0.95
0.95
0.9
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
0.45
0.4
0.35
0.3
0.25
0.2
0.15
0.1
0.05
Water
Simultaneous phase and chemical equilibria
H2Oaq + MFaq MeOHaq + FAaq
H2Oorg
H2Oaq
MForg
MFaq
MeOHorg
MeOHaq
FAorg
FAaq
H2Oorg + MForg MeOHorg + FAorg
ORG
AN
IC
PHA
SEA
QU
EO
US
PHA
SE
Keq/org(T)
Keq/aq(T)
10 bar, 23°C
Reac
tion
coor
dina
te
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Parametric study
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XM
F[%
]
Temperature [°C]
Water molar excess
14.2
3.6
1.8
0.9
0.000
0.002
0.004
0.006
0.008
0.010
0.012
0.014
0.016
20 30 40 50 60 70 80 90 100 110 120C
once
ntr
atio
n [
mol
/m
L]
Temperature [°C]
Water molar excess
R = 1.8
MF
MeOH
p = 10 barWHSV = 650 h-1
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Outlook
CO2 + H2
HCOO(H)
CH3OH
HCOOCH3
Catalyst 1
Catalyst 2
REACTOR 1> 100 bar, 200 – 300°C
CO2
H2HCOOCH3
CH3OH
HCOOH
CH3OH
H2OREACTOR 1 REACTOR 2
CO
REACTOR 2
HCOOH
CH3OH
Catalyst 3
10 bar, 40 - 120°C
HCOOCH3
Thank you for your attention