Catalysis Advances forSustainmable Energy

Jens Rostrup-Nielsen

Haldor Topsøe A/S

CATALYSIS WILL PLAY KEY ROLE

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

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

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

Oil reserves and price level The challenge is investment and

environment

Kilde: IEA, 2005

Flared gas:5% of production

2 mio bpd synfuelsca. 50 Sasol GTL plants

New role for coal?

Biomass conversion

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

HDS - Hydrodesulphurisation

+ 2 H 2 + H 2SS

Hydrodesulphurisation

Gasification

CO H2

CO2

BiomassNatural gasCoal

HydrogenMethanol

DMEGasolineDiesel

Syngas

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

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%

Electrons or hydrogen or ?

Elgrid

Electriccars

FCcars

ICEcars

Wind

Bio

Natural gas

H2

Chemical recuperation of nuclear energy

HTREva Adam

ADAM / EVA Energy Transportation System. Kernforschungsanlage Jülich 1970-85

Concentrated solar power

Imaging the sunImaging the Moon

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

TOOLS FOR CATALYSIS

It is the know-how which counts

Mittasch

Input from Surface Science

Noble Art of CharacterisationThere is a risk that we learn more and more

about less

In Situ MethodsToday it is possible to study the catalyst

structure during operation

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)

Particle migration and coalescence

H2, 600°C

Ni/MgAl2O4

Ostwald ripening

H2, 700°C– Atom migration– Vapour

migration

Ni/MgAl2O4

Nucleation of whisker carbon

Cs-corrected HRTEM of Au/TiO2

CM300 (300keV), Cs = 1.4mm

Titan (300kV), Cs 0.0mm

2nm 2nm

Confidential

Uncorrected image Cs-corrected image

What is a site ?

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)

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)

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

Bright brim

Region with higheletron density(metallic character)

Topsøe researchers with Besenbacher’s group (2001)

Important discovery:MoS2 has metallic brim states!!

Whisker GrowthNickel Catalyst

Snapshots of the Whisker

Mechanism and Step

Abild-Pedersen et al 2006

• INPUT FROM THEORY

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)

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

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)

Scaling model

ΔE(CH4) = ΔE(C) + ξ

Abild-Pedersen

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

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

)

Activity for steam reforming (log10. TOF) as function of C and O adsorption energies.

500oC, 1 bar abs.

Jones et al

Conclusions

Bench-scaleBench-scale PilotPilot

In-situIn-situ

Noble Art of ModellingThe model is no better than the accuracy of

the main constants involved

Multiple Approach

• Development– Catalyst– Process– Catalyst production methods

• Research to understand (and market)

• Explorative research (2nd S-curve)

Catalyst R&D

Basic researchFundamental studies

Catalyst characterization

Catalyst formulationProcess development

Scale-upPilot operationComputer modeling

Industry

A future for a hydrogen economy ?