new catalysis advances for a sustainable energetic development_jens r. nielsen
TRANSCRIPT
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Catalysis Advances forSustainmable Energy
Jens Rostrup-Nielsen
Haldor Topsøe A/S
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CATALYSIS WILL PLAY KEY ROLE
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Energy sources
Naturalgas
Coal
Oil
Syngas
Synfuel
Methanol
DME
Hydrogen
EthanolBiomass
Automotive FC
Solar
Windhydro
Electric powervia thermal
Electric powervia FC
Heating
Electricapplications
Energy carriers Energy conversion
NuclearGasoline diesel Automotive ICE
Electric power
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Energy sources
Naturalgas
Coal
Oil
Syngas
Synfuel
Methanol
DME
Hydrogen
EthanolBiomass
Automotive FC
Solar
Windhydro
Electric powervia thermal
Electric powervia FC
Heating
Electricapplications
Energy carriers Energy conversion
NuclearGasoline diesel Automotive ICE
Electric power
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Energy sources
Naturalgas
Coal
Oil
Syngas
Synfuel
Methanol
DME
Hydrogen
EthanolBiomass
Automotive FC
Solar
Windhydro
Electric powervia FC
Heating
Electricapplications
Energy carriers Energy conversion
NuclearGasoline diesel
Electric power
Electric powervia thermal
Automotive ICE
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Oil reserves and price level The challenge is investment and
environment
Kilde: IEA, 2005
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Flared gas:5% of production
2 mio bpd synfuelsca. 50 Sasol GTL plants
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New role for coal?
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Biomass conversion
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Biomass conversion
• Fermentation: 1. generation, 2. generation to ethanol
• Catalytic conversion of sugars to fuels• Transesterfication of oil to biodiesel + glycerol• Hydrogenation of oil to synfuel, green diesel• Pyrolysis or steam conversion to ”oil”• Hydrotreating of ”oil” to synfuel, green diesel• Gasification to syngas to FT, DME, SNG
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HDS - Hydrodesulphurisation
+ 2 H 2 + H 2SS
Hydrodesulphurisation
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Gasification
CO H2
CO2
BiomassNatural gasCoal
HydrogenMethanol
DMEGasolineDiesel
Syngas
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The synfuel cycles i f i c
m reform
ATRCoal
CnHm
Syngas H2
F-T
TIGAS
G D M E M
M ethana t
CH4
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SOFC - high flexibility
KeroseneDiesel
Syngas
MethanolEthanolBiogas (landfil) gasBio (digestive) gas
Hydrogen
Ammonia
SOFC
Nat. gas Oil
Coal
Biomass
Solar Wind
Agricul.
Power
ηel = 40-50%
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Electrons or hydrogen or ?
Elgrid
Electriccars
FCcars
ICEcars
Wind
Bio
Natural gas
H2
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Chemical recuperation of nuclear energy
HTREva Adam
ADAM / EVA Energy Transportation System. Kernforschungsanlage Jülich 1970-85
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Concentrated solar power
Imaging the sunImaging the Moon
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Routes forsolar hydrogen
Concentratedsolar energy
Solarthermolysis
Solarthermochemical
cycles
Solarreforming
Solarcracking
Solargasification
H2OH2O
H2OFossil fuels
(NG, oil, coal)
CO2/Csequestration
Solar hydrogenAdopted from Steinfeld/Solar Energy 78 (2005) 605
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TOOLS FOR CATALYSIS
It is the know-how which counts
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Mittasch
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Input from Surface Science
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Noble Art of CharacterisationThere is a risk that we learn more and more
about less
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In Situ MethodsToday it is possible to study the catalyst
structure during operation
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Formation of Whisker CarbonFormation of Whisker CarbonIn Situ HRTEMIn Situ HRTEM
(CH4/H2 = 1:1, P = 5 mbar, T = 720°C)(CH4/H2 = 1:1, P = 5 mbar, T = 720°C)
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Particle migration and coalescence
H2, 600°C
Ni/MgAl2O4
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Ostwald ripening
H2, 700°C– Atom migration– Vapour
migration
Ni/MgAl2O4
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Nucleation of whisker carbon
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Cs-corrected HRTEM of Au/TiO2
CM300 (300keV), Cs = 1.4mm
Titan (300kV), Cs 0.0mm
2nm 2nm
Confidential
Uncorrected image Cs-corrected image
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What is a site ?
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Gas-induced shape changes in Cu nanocrystals on ZnO
H2 H2O/H2= 1:3 CO/H2=1:6
P=1.5 mbar, T= 220 ºC
(111)
(110)
P.L. Hansen et al. Science 295, 2053 (2002)
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Michel Boudart“A catalyst is a complex and resilient self-assembly in space and time…. to treat an active site or a catalyst as a dead object in time with a fixed structure in space is a wrong model of the catalytic cycle”.
(Vilamoura 1999)
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In situ EXAFS, Mössbauer and FTIR measurements: MoS2-like; ~10-20 Å at 400°C; Co substituted at edge sites
of the MoS2 nanoparticles; often single layers
SMoCo
Co9S8
MoS2-like
nanoparticles”Co-Mo-S”
Co:Al2O3
Al2O3 (alumina)
support
Topsøe, et al. (1981)
Co-Mo-S modelBased on in situ characterisation
studies
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Bright brim
Region with higheletron density(metallic character)
Topsøe researchers with Besenbacher’s group (2001)
Important discovery:MoS2 has metallic brim states!!
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Whisker GrowthNickel Catalyst
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Snapshots of the Whisker
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Mechanism and Step
Abild-Pedersen et al 2006
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• INPUT FROM THEORY
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DFT-calculations for CH4 ActivationDFT-calculations for CH4 Activation
CH3,HCH2,2HCH,3H
H,4H
Graphene,4HC,5H,OH
C,6H,O
CO,6H
6H
CO
3H2H2OCH4 Ni(111)
Ni(211)
300
200
100
0
-100
-200
Bin
din
g e
ner
gy
(kJ/
mo
l)
(JRN et al 2002)
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Optimal CatalystAmmonia Synthesis
1000
100
10
1
0.1
0.01
0.001
0.0001
0.00001
0.000001-150 -100 -50 0 50 100
Relative nitrogen binding energy/kJ/mol
TO
F/s
-1
Mo
FeCo
Ni
OsRu
450°C100 bar
3:1 H2/N2
10%
NH 3
1% N
H 3
0.1%
NH 30.
01%
NH 3
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THE ELECTRONIC FACTORactivation energy for CH4 activation
(Abild Pedersen et al)
1.6
1.4
1.2
1.0
0.8-1.9 -1.8 -1.7 -1.6 -1.5
d band center (eV)
Ea(
eV)
Ni/Au(111)
2C/Ni(211)
S/Ni(211)
C/Ni(211)
Ni(111)
Ni(211)
Nistrain(111)
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Scaling model
ΔE(CH4) = ΔE(C) + ξ
Abild-Pedersen
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SCALING MODELadsorption energies of CHx and of C
(Abild Pedersen et al)
-1
-2
-3
-4
-5
-6
-7-7 -6 -5 -4 -3 -2
EC (eV)
EC
Hx(
eV)
Fit: y=0.76x-1.2
Fit: y=0.75x-1.04
Fit: y=0.49x-1.24
Fit: y=0.25x+0.11
Fit: y=0.26x+0.14
Fit: y=0.47x-1.46
AgAgAu
AuCuCu
AuAu
AgAg
Ag
AgAu
Au
Cu
CuNi
Ni
Ni
Ni
Ni
PtPt
PtPt
Pd
PdPd
Pd
Ru
Ru
Ru
RuRh
Rh
Rh
Rh
Ir
Ir
Ir
Ir
Ir
Ir
Ru
PtPt
Rh
Ni
PdCo
Ru
Cu
Rh
Ir
Pd
CHX
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STEAM REFORMING OF CH4 ON Nireaction scheme from DFT calculations
(Jones et al)
2
1
0
CH 4
(g) +
H2O
(g)
Fre
e en
ergy
/eV
6737739731173
CH 3
* + H
2O
(g) +
0.5
H 2(g
)
CH 2
* + H
2O
(g) +
H2(g
)
CH
* + H
2O
(g) +
1.5
H 2(g
)
C* +
H2O
(g) +
2H 2
(g)
C* +
OH
* + 2
.5H 2
(g)
C* +
O* +
3H 2
(g)
3H2(g
) + C
O*
3H2(g
) + C
O(g
)
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Activity for steam reforming (log10. TOF) as function of C and O adsorption energies.
500oC, 1 bar abs.
Jones et al
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Conclusions
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Bench-scaleBench-scale PilotPilot
In-situIn-situ
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Noble Art of ModellingThe model is no better than the accuracy of
the main constants involved
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Multiple Approach
• Development– Catalyst– Process– Catalyst production methods
• Research to understand (and market)
• Explorative research (2nd S-curve)
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Catalyst R&D
Basic researchFundamental studies
Catalyst characterization
Catalyst formulationProcess development
Scale-upPilot operationComputer modeling
Industry
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A future for a hydrogen economy ?