Heterogeneous Catalysis

CM- 15,75 h
ELENA R. SAVINOVA, PR.
LMSPC-UMR 7515 (R3, Niveau 1)
Elena.Savinova@unistra.fr
@

Structure of the course

1. Introduction: setting the scene

2. Adsorption at solid surfaces

+ Exercises
3. Heterogeneous kinetics

4
4. Processes
1
 The objectives of the course

Understand the basic principles of heterogeneous catalysis, including:

- Adsorption
- Heterogeneous kinetics

Learn about:
- How to investigate adsorption and catalytic properties of materials
- Most important catalytic processes in the chemical industry, oil refinery
and pprocessingg and environmental protection
p

At the end of the course the students should know:

- How to solve kinetic equations for surface reactions;
- From a set of experimental data be able to calculate essential parameters,
such as specific surface area, specific catalytic activity, TOF, product
selectivity apparent activation energy,
selectivity, energy etc.
etc
- Catalytic cycles for industrially important processes

Background:
- Chemical kinetics and thermodynamics, 2
introduction in catalysis
 Recommended literature

Fundamental of Industrial Catalytic Processes, C.H. Bartholomew, R. J. Farrauto, 2nd Edition (2005), Wiley
ISBN 978-0-471-45713-8

Principles and Practice of Heterogeneous Catalysis, J. M. Thomas, W.J. Thomas, VCH, Weinheim, 1997, reprinted in
2005, 669 p., ISBN: 29288-8.

Reactions at Solid Surfaces,, Ertl,, Gerhard,, Baker Lecture Series 2009. 208 Pages
g

Chemical kinetics and catalysis; R.I. Masel, Wiley Interscience, 2001

Principles
p of Adsorption
p and Reaction on Solid Surfaces,, R.I. Masel,, Wiley,
y, ISBN: 978-0-471-30392-3

Introduction to Surface Chemistry and Catalysis, G. Somorjai, Wiley, 1994 (Bibliothque Esplanade)

y ; R.A. van Santen and J.W. Niemantsverdriet,, 1995,, Wiley,

Chemical kinetics and catalysis; y, (Bibliothque
( q Sciences))

Kinetics of heterogeneous catalytic reactions; Michel Boudart and G. Djga-Mariadassou, 1984; (Bibliothque IPCMS )

Concepts
p of Modern Catalysisy and Kinetics, I. Chorkendorff, J. W. Niemantsverdriet, 2nd, Completely
p y Revised and
Enlarged Edition, 2007, Wiley

Handbook of Heterogeneous Catalysis, G. Ertl, H. Knoezinger, J. Weitkamp (Eds.), 8 Volumes, 2nd Edition, February
2008, Wiley,
y ISBN: 978-3-527-31241-2

3
Chapter 1. Introduction: setting the scene
I
Importance
t off h
heterogeneous
t catalysis
t l i iin the
th modern
d economy
Heterogeneous Catalysis industry

Petroleum refinery Prevention and abatement of pollution

~20% ~37%
Production of
Catalyst cost in petroleum refinery is bulk and fine chemicals
~0.1% of the product cost ~43%
1 $ invested in the catalyst technology
leads to ca. 1000 $ of gross world ~ 90% of the chemical products are
product obtained in catalytic processes

Advantages of catalytic processes:

- Numerous industrial processes would not be possible without catalysts
- Higher energy efficiencies
- Higher Atom efficiencies ((molecular weight of the desired product)/(total molecular weight
of all products))
- Higher selectivities
- Environmental friendliness (decrease of the amount of by-products, etc.)
4
- Allow reaction rate control (NATURE: ENZYMES)
Largest processes based on heterogeneous catalysis

5
Concepts of Modern Catalysis and Kinetics, I. Chorkendorff, J. W.
Niemantsverdriet, 2nd, Completely Revised and Enlarged Edition, 2007
The largest catalyst producers (From:Fundamental of Industrial Catalytic
Processes, C.H. Bartholomew, R. J. Farrauto, 2nd Edition (2005)

Company Country Chemicals Petroleum refining Environmental

Advanced Catalyst Systems US
Advanced Refining US
Technologies LLC
Akzo Nobel Inc. Netherlands
Axens Procatalyse US
BASF G
Germany
Catalysts & Chemicals
Catalyst Plant of Fushun China
Petrochemical
Chevron Lummus Global LLC US
Criterion Catalyst UK/Netherlands
Davison Catalysts USA
Degussa AG Germany
Engelhard Corporation Now part of
BASF
Exxon Research
E R h andd USA
Engineering Co.
Haldor Topsoe Denmark
Heraeus Germany
Instituto Mexicano del Mexico
Petroleo 6
Johnson Matthey UK
Important names

Jns Jakob Wilhelm Ostwald: 1909 Gerhard Ertl: 2007

Berzelius 1835

Nobel prize in 1909 for his achieve- Nobel Prize in Chemistry for his
ments, including the understanding of pioneering studies of chemical
the catalysis phenomenon
phenomenon. processes on solid surfaces

Oswald: Catalytic action consists in the modification, by the acting substance, named
th catalyst,
the t l t off the
th rate
t att which
hi h a chemical
h i l reaction
ti occurs, without
ith t that
th t substance
bt
itself being part of the end-products formed.

7
 Catalytic cycle
ABCat

A B
Cat
P A + B + Cat PCat
P + Cat

The nature of the catalytic rate enhancement

W
G #f ,u AB# Transition State Theory:
gy
bs Energ

kf
G #f ,cat kf
K
Gibb

kb
Heterogeneous catalysis

A+B
A+B+Cat G r0
ABCat
P
P+Cat
Reaction coordinate 8
How a catalyst may influence the reaction rate?
Example 1: catalytic CO oxidation
D
Decrease off the
th activation
ti ti b barrier
i via
i compensation
ti off th
the energy llosses

Non-catalyzed reaction: Catalytic reaction:

Energy required to split O-O bond: Ea ~ 50100 kJ mol1
~500 kJ mol1 Pt-O 375 kJ mol1

Key factors: Energy and structure

Example 2: benzene formation

Putting reactants in a close proximity

3C 2 H 2
Pd
C6 H 6

C C
C C
C C Concepts of Modern Catalysis and Kinetics, I.
Chorkendorff, J. W. Niemantsverdriet, 2nd, 9
Completely Revised and Enlarged Edition, 2007
Important catalyst properties Activity
Selectivity
y
Lifetime
Cost
Activity
y
Definition of the catalytic activity:
Mass activity
activity, specific activity,
activity TOF

S l ti it
Selectivity P1
A P2
P3
CH 3 CH CH 2

O
CH 3 CH CH 2 C CH CH 2 CO2
O H

10
 Introduction into catalytic materials

Active component Support Promoter

Role Role Role

Requirements Requirements

Types and examples

Types and examples: Types and examples

Metals
y g
Hydrogenation ((Ru, Pd, Pt, Ni)) Simple and complex metal oxides
Hydrocarbon aromatization (Pt)
Al2O3, SiO2, MgO, CaO
Transition metal oxides: ZnO, NiO,
Fe2O3, SnO2, etc. ZnO, TiO2, NiO, Fe2O3, SnO2
Selective oxidations (alcohols to
aldehydes; alkyl to aldehydes, etc.) Carbon materials
Solid acids
hydrocracking of heavy petroleum
distillates 11
 Morphology of catalytic materials
Powders: from few to 500 m
Granules: few mm
Pellets: 1- 3 cm
Monoliths

IC-1-6M Catalysts for oxidation Thermostable catalyst ICT-

ICT
of sulfurous anhydride into 12-40 for of toxic organic
sulfuric anhydride in the sulfuric impurities and carbon
acid production: granules, monoxide in industrial
tubes, monoliths waste gases
gases.
IC- 42 series
IC i Iron(II) oxide powder
nonplatinum
honeycomb catalysts
to produce nitric acid

12
Boreskov Institute of Catalysis SB RAS: http://www.en.catalysis.ru/
Relevant length scales in heterogeneous catalysis
C t l ti reactor
Catalytic t Catalyst pellets/granules
m cm cm m

Supported Catalyst particles

m nm

http://www.psenterprise.com/gproms/applica
tions/reaction/info fixed bed.html
tions/reaction/info_fixed_bed.html
Pt nanoparticles
Catalytic surface
nm
nm
BALSAC picture
gallery of Prof. K.
Hermann, FHI,
Berlin

13
http://www.nanostellar.com/characterization.htm
Chapter 1: Summary

14