Reaction Kinetics and Catalysis

Ib Chorkendorff
Interdisciplinary Research Center for
Catalysis ICAT,
Dept. of Physics and Dept. of Chem.
Eng. DTU

Understand the basics

Micro-kinetic modeling
Compare to real system

rk

RLS

Pi
2
K (1
)*
K eq
ni

IC-1/41 Lecture-1 02-09-2004

Where is Catalysis Used?

Catalysis is involved in more than 20% of industrial production
Involved in more than 90% of all industrial chemical processes
Synthesis of chemicals: NH3 (85% for fertilizer)
Synthesis gas,
Polymers, etc.

Environmental Cat.: HDS (removal of sulfur)

DeNOx (cleaning of flue gas)
SO2 oxidation (H2SO4)

Energy Production:

Fuel Cells
Cleaning of flue gasses
IC-2/41 Lecture-1 02-09-2004

Organic Chemicals USA

Organic chemical production in the USA (1999)
source: Chemical & Engineering News, June 26, 2000
organic chemicals
ethylene
propylene
ethylene dichloride
urea
ethylbenzene
styrene
ethylene oxide
p-xylene
cumene
1,3-butadiene
acrylonitrile
benzene (billions of gallons)
aniline
isopropyl alcohol
o-xylene
2-ethylhexanol

billion lb
55,777
29,105
22,836
18,660
13,106
11,898
8,884
8,802
6,970
4,282
3,120
2,357
1,586
1,475
1,148
0,878
IC-3/41 Lecture-1 02-09-2004

Inorganic Chemicals USA

Inorganic chemical production in the USA (1999)
inorganic chemicals
ktons
sulfuric acid
ammonia
phosphoric acid
chlorine
sodium hydroxide
nitric acid
ammonium nitrate
hydrochloric acid
ammonium sulfate
titanium dioxide
aluminum sulfate
nitrogen gas,
excl ammonia synthesis
sodium chlorate
oxygen
sodium sulfate
hydrogen, excl refineries
455

45113
18959
13764
13284
11391
9000
8169
4526
2903
1493
1186
866
791
691
660
IC-4/41 Lecture-1 02-09-2004

Catalysis
A catalyst is a material which causes a chemical process
to proceed faster towards thermodynamical equilibrium
without it self being consumed.
Note: Equilibrium cannot be crossed.

1817 Sir Humphry Davy (Michael Faraday)

oxidation of alcohol
1836 Berzelius
1895 Ostwald (Nobel prize 1909)
1909 Haber & Bosch Ammonia synthesis
IC-5/41 Lecture-1 02-09-2004

The Car Catalyst

Or the so-called three-way catalyst is Pt/Rh based
on a monolit. The following processes takes place:

1. CxHy + O2

CO2 + H2O

2. 2CO + O2

2CO2

3. 2NOx

N2 + (O2)

Since 1 and 2 are oxidizing

and 3 is reducing is
the control of the reduction
potential essential

Sensor
Motor

CAT

Exhaust
IC-6/41 Lecture-1 02-09-2004

Environmetal Catalysis
Effect of Smog and environmental catalysis
Before
After

IC-7/41 Lecture-1 02-09-2004

Hydrodesulfurization Catalysis
Large Environmental Impact
New Technological Challenges
SO2 emissions from fuels

New S regulations world wide

EU :

S-polluted crude oil + H2(g)

300-400 C
10-50 bar

Year

ppm S in diesel

2000

350

2005

50

2010

10(?)

Desulfurized oil + H2S(g)

IC-8/41 Lecture-1 02-09-2004

Ammonia Synthesis
Daily production ~2 x 1350 ton
2 x 150 Fe/K/CaO/Al2O3

CH4 + H2O
CO + H2O
CH4 + Air

CO+3H2
CO2+H2
CO2 +H2+N2

N2 + 3H2

2NH3

IC-9/41 Lecture-1 02-09-2004

Steam Reforming Process

CH4 + H2O

CO + 3H2 Strongly endothermic process

IC-10/41 Lecture-1 02-09-2004

Methane Activation
CH4 + 2O2

CO2 + 2H2O (Combustion)

CH4 + H2O

CO + 3H2 (Steam Reform.)

CH4 + O2

CO + 2H2 (Partiel Ox.)

CO + H2O

CO2 + H2 (Water Gas Shift)

CH3OH + H2O

CH4 + O2

CO2 + 3H2

CH3OH
IC-11/41 Lecture-1 02-09-2004

Steam reforming Plant

IC-12/41 Lecture-1 02-09-2004

Length scales in Catalysis

10 mm

One of the very few

commercial Nano-materials
1 nm

shaped catalyst
particles
catalytic
surface

Why does it look like that?

What are the requirements?

1m
catalyst bed
in a reactor
1 m

catalytically active
particles on a support

microscopic

mesoscopic

macroscopic
IC-13/41 Lecture-1 02-09-2004

Shaped catalysts

pellets
Strength
Pressure drop
Mass transport
Heat transport

fused catalyst
Courtesy of Haldor Topse A/S

extrudates
IC-14/41 Lecture-1 02-09-2004

Carbon formation
Ni/SiO in a CH /H mixture at 1 bar at 763 K

IC-15/41 Lecture-1 02-09-2004

Environnemental EM from Haldor Topse A/S

Ni

Graphite

~1000
IC-16/41 Lecture-1 02-09-2004

Modifications of Surfaces
Reactivity
Activity

Selectivity

Over all yield

Products

Stability
Poisoning

Connection to industrial heterogeneous catalysis

(what to modify)
Fundamental insight into the catalytic processes
(where to modify)
IC-17/41 Lecture-1 02-09-2004

The surface science approach

Simpler system - Detailed studies
Fundamental insight
Input to catalyst design
The structure gap
The pressure gap
The materials gap

Single crystal surfaces

as model catalysts.
IC-18/41 Lecture-1 02-09-2004

Surface Physics/Chemistry

Surface composition
Surface symmetry
Adsorbed
molecules/atoms
Concentration
Geometry- and bonding
Intermediate species
Reaction rates
Etc, etc.

Photons
Electrons
Ions
Molecules

P~10

-13

bar

Ideal
Surfaces

Photons
Electrons
Ions
Molecules

IC-19/41 Lecture-1 02-09-2004

STM of the Au-Ni(111) Alloy

75x75 2 AuML
A Two-dimensional
Alloy

IC-20/41 Lecture-1 02-09-2004

Methane dissociation on Au-Ni(100)

P. Kratzer, B. Hammer,
and J. K. Nrskov
JCP 105 (1996) 5595

IC-21/41 Lecture-1 02-09-2004

Measurements on real catalysts

F. Besenbacher, I. Chorkendorff,
B. S. Clausen, B. Hammer,
A. M. Molenbroek, J. K.
Nrskov, and I. Steensgrd,
SCIENCE 279 (1998) 1913.

C4H10+ H2O

CO + H2

IC-22/41 Lecture-1 02-09-2004

Ammonia Synthesis
Daily production ~2 x 1350 ton
2 x 150 Fe/K/CaO/Al2O3

CH4 + H2O
CO + H2O
CH4 + Air

CO+3H2
CO2+H2
CO2 +H2+N2

N2 + 3H2

2NH3

IC-23/41 Lecture-1 02-09-2004

Trends in reactivity
Variation in activity for ammonia synthesis as
function of d-band filling
A. Ozaki and K. Aika, in Catalysis vol. 1
Eds. J. Anderson and M. Boudart
(Springer-Verlag, Berlin, 1981 p87.

IC-24/41 Lecture-1 02-09-2004

N2 dissociation on Ru(0001)Theoretical
Calculation

What does the potential

energy surface look like?

IC-25/41 Lecture-1 02-09-2004

N2 on Ru(0001) - N2 on Au/Ru(0001)

-10

S 0 o f N 2 o n R u (0 0 0 1 )

Step sites nine are orders

of magnitude more active
than terrace sites at 500 K.

clean Ru(0001)
Ea=42kJ/mol

-11

-12

-13

1-2% gold on Ru(0001)

Ea = 126 21 kJ/mol

-14
0.0015

0.0020

S. Dahl, A. Logadottir, R. C. Egeberg, J. H. Larsen, I. Chorkendorff,

E. Trnqvistm, and J.K. Nrskov, Phys Rev. Lett. 83 (1999) 1814.

0.0025

0.0030

0.0035

1/T (1/K)
IC-26/41 Lecture-1 02-09-2004

Microkinetic model for Ammonia Synthesis over

Ruthenium
From assuming 1% of active sites on the clean Ru(0001) surface.
k+1 = 105exp(-37 kJ/mol / RT) (bar-1s-1)
The rest of the parameters are in agreement with tailing edge of
TPD spectra of N2, H2 and NH3 desorption from Ru(0001)
H2 TPD:

Shi and Jacobi, Surf. Sci. 313 (1994) 599.

NH3 TPD:

Sun, Wang, Mullins and Weinberg, Langmuir, 7 (1991) 1689.

N2 + 2 *
H2 + 2 *
N* + H*
NH* + H*
NH2* + H*
NH3*

k+
k-

2 N*
2 H*
NH* + *
NH2* + *
NH3* + *
NH3 + *

ni

2
i
r k RLS K (1
)*
K eq

IC-27/41 Lecture-1 02-09-2004

Micro-Kinetic Model

N2 dissociation rate-determining.

N2 dissociation rate equal to measured rate at steps

10
at Ru(0001).

Realistic active site

density assumed.

Model connects
surface science
and catalysis.

rk

RLS

Pi
2
K (1
)*
K eq
ni

Model output (% NH3)

0.1

Ru/MgAl2O4

0.01

0.001

Ru Single Crystal
0.0001
0.0001

0.0010

0.0100

0.1000

1.0000

10.0000

Experimental output (% NH3)

IC-28/41 Lecture-1 02-09-2004

Active sites on Ruthenium

1
surface sites/total atoms

Surface

Particle
0.1

edge sites/total atoms

edge sites and optimal geometry

10

Particle size (nm)

IC-29/41 Lecture-1 02-09-2004

Size distribution
before and after annealing
PDSP01 (Ru/MgAl2O4)

0.45
0.4
0.3
0.25
0.2
0.15
0.1
0.05
0
4 - 4,5

3,5 - 4

3 - 3,5

2,5 - 3

2 - 2,5

1,5 - 2

1 - 1,5

0,5 - 1

0 - 0,5

Diameter [nm]

PDSP01 Ru/MgAl2O4
Temp.: 475 C
gas: H2:N2 = 3:1

Partikelfordeling fr aktivitetsmling Partikelfordeling efter

P: aktivitetsmling
50 bar ;

Activity [mmol/(g*s]

Normalizednumber of
particles

0.35

170 hours at 500 C.

6,0

600 particles analyzed

2 hours at
500 C

5,0

4,0

3,0
0

50

100

150

200

Time [h]

250

300

IC-30/41 Lecture-1 02-09-2004

Long term interest

On the long term will natural resources diminish and the prices will
eventually increase. How fast is disputable.
Known Fossil Reserves
Oil:
Natural Gas:
Coal:

1997

141 x 109t
130 x 109t
1030 x 109t

(1977)
(89 x 109t)
(64 x 109t)

Reserves/production/year
Oil
41 years
Natural Gas: 64 years
Coal:
219 years
Demands and prices will dictate the transition

IC-31/41 Lecture-1 02-09-2004

The sun supplies plenty of energy

Some data on energy consumption and sources
Total Earth
DK
Human related energy consumption: 3,8E20 J/year
8,4E17 J/year
Total incoming sun energy:
3,8E24 J/year ca. 1,6E20 J/year
Total power production:
4,6E19 J/year
1,2E17 J/year
Roughly 10% of the area in DK must be used if we should get all the
energy from solar cells or wind mills.
Even photo synthesis is not particular efficient : In principle can 6.7%
be captured but in practice is only 1% utilized and then there is
expenses for fertilizers, harvesting and transport.
The most efficient solar cells utilize up to 21-28%
of the sunlight (but are way to expensive)
IC-32/41 Lecture-1 02-09-2004

The Future Power Distribution

Sustainable sources

H2
Gas distribution
lines and storage
IC-33/41 Lecture-1 02-09-2004

The Fuel Cell

IC-34/41 Lecture-1 02-09-2004

Working Principles
4e

2H2

~0.7 V
O2
WHY Pt/Ru????????

Purge
Pt or Pt/Ru clusters
2H2+4*
4H*

4H*
4*+4e+4H+

2H2O
Nafion
H+
H+
H+
H+
Protron membrane

Pt clusters
O2+2*
4H+ +4e+4*
4H*+2O*

2O*
4H*
2H2O

IC-35/41 Lecture-1 02-09-2004

Prices of Precious Metals a Show Stopper?

USD ($)/gram

40

Pd
Pt
Au
Rh
Ru

30
20
10

Annual (2003) Pt
production ~190 ton
or 19 mio. Cars!!!

Year

Typical Pt loading 0.1-1.0 mg/cm2

Typical power production 0.2-0.35 w/cm2
Typical car 35-100 kW
1 car ~ 10g (min)
Strong demandsIC-36/41
for Lecture-1
alternatives
02-09-2004

Parallel Screening with Surface Science Insight

SEM picture of sample array preparred by
Physical Vapor Deposition (PVD)

Pd/Ni

Au

IC-37/41 Lecture-1 02-09-2004

H-D Exchange on Pd/Ni (new Anode Materials)

H2

HD

1.4 % H2, 1.4% D2 in Ar. T=150 oC, p=1 bar, Q=57.6 ml/min.
IC-38/41 Lecture-1 02-09-2004

Shift in d-band Center for a Pseudomorfic Overlayer

Overlayer

Fe

Co

Ni

Cu

Ru

Rh

Pd

Ag

Ir

Pt

Au

Fe

-0.92

0.24

-0.04

-0.05

-0.73

-0.72

-1.32

-1.25

-0.95

-1.48

-2.19

Co

-0.01

-1.17

-0.20

-0.06

-0.70

-0.95

-1.65

-1.36

-1.09

-1.89

-2.39

Ni

0.96

0.11

-1.29

0.12

-0.63

-0.74

-1.32

-1.14

-0.86

-1.53

-2.10

Cu

0.25

0.38

0.18

-2.67

-0.22

-0.27

-1.04

-1.21

-0.32

-1.15

-1.96

Ru

0.30

0.37

0.29

0.30

-1.41

-0.12

-0.47

-0.40

-0.13

-0.61

-0.86

Rh

0.31

0.41

0.34

0.22

0.03

-1.73

-0.39

-0.08

0.03

-0.45

-0.57

Pd

0.36

0.54

0.54

0.80

-0.11

0.25

-1.83

0.15

0.31

0.04

-0.14

Ag

0.55

0.74

0.68

0.62

0.50

0.67

0.27

-4.30

0.80

0.37

-0.21

Ir

0.33

0.40

0.33

0.56

-0.01

-0.03

-0.42

-0.09

-2.11

-0.49

-0.59

Pt

0.35

0.53

0.54

0.78

0.12

0.24

0.02

0.19

0.29

-2.25

-0.08

Au

0.53

0.74

0.71

0.70

0.47

0.67

0.35

0.12

0.79

0.43

-3.56

Substrate

EF

Ed

Ed

Ed

A. Ruban, H. Skriver, P. Stoltze, and J. K. Nrskov J. Mol. Cat. A 115 (1997) 421
IC-39/41 Lecture-1 02-09-2004

Nano scale-design:
The Ultimate art of Engineering

3 nm

IC-40/41 Lecture-1 02-09-2004

Competences from this course

Understand fundamental principles of reaction kinetics
(what are the ks and where do they come from)

Gain basic insight in gas-phase reactions

Gain basic insight in surface reactions
Being able to formulate models in both areas
Get an overview of some important gas-phase reactions
Get an overview of some important catalytic reactions
Understand the trends in reactivity for metals
Understand some of the design principles for catalysts
You will get the exams set from the last 4 years

IC-41/41 Lecture-1 02-09-2004