Homogeneous vs.

heterogeneous
catalysis

Dr. habil. Marko Hapke

Leibniz-Institut für Katalyse e.V.

an der Universität Rostock
 Heterogeneous Homogeneous
Catalysis Catalysis
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Biocatalysis

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 2
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 Catalyst and reactant(s) are in the same phase.

Heterogeneous Homogeneous
Definitions
Catalysis Catalysis
Catalyst and reactant(s) are in different phases.

General features: General features:

 Different reaction phases possible: „classic“  Liquid phase reactions dominate the field.
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gas/solid; liquid/solid or liquid/liquid systems.  Industrially less relevant; but complex orga-
 High industrial relevance (about 85% of all nic or asymmetric transformations possible!
catalytic processes are heterogeneously  Reaction conditions milder than required for
catalysed). heterogeneous reactions (-78 °C - ~200 °C).
 In general wide range of operating conditions  Investigation of reactions by spectroscopic
(high temperatures/pressures). methods (NMR, MS, IR, UV-Vis) directly in
 Specialised set of analytic methods required solution possible.
(e.g. X-ray methods, Operando spectros.).  Fine-tuning of catalyst properties using
 Major advantage: Ease of separation of different ligands/additives easy possible.
reactants/products/catalysts.  Major challenge: Separation of products
and catalysts/additives.

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 3
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 porous carrier (catalyst
support)

Heterogeneous
Catalysis
bed of
catalyst particles

reactants substrate product

reactor reaction desorption

adsorption

products
catalyst support

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Technical setup: active site

product substrate C
substrate C B B
A

Mechanism: A

catalyst surface catalyst surface

Langmuir-Hinshelwood Eley-Rideal
Source: Gadi Rothenberg, Catalysis – Concepts and Green Applications, Wiley-VCH, 2008

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 4
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 Heterogeneous Major industrial processes using
Catalysis heterogeneous catalysis

Process Catalyst Reactants Products Application

Haber-Bosch process Magnetite (Fe) H2, N2 NH3 Fertiliser, explosives

Methanol synthesis Cu/ZnO/Al2O3 CO, CO2, H2 Methanol 5

Bulk chemicals, fuel

Fischer-Tropsch process Co, Fe Coal, natural gas C5-C11 hydrocarbons Automotive fuel

Cracking Clays Long alkanes, C12+ C7-C9 alkanes Fuel, detergents

Alkylation Zeolites, Clays, C3-C5 alkanes C7-C9 isoalkanes High-octane fuel

Silicates
Dehydrogenation/ Pt/Al2O3 Alkanes Alkenes Polymers, bulk
Reforming chemicals
Polymerisation Ti, Ziegler-Natta Ethylene Polyethylene Polymers

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 5
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Heterogeneous Major industrial processes using
Catalysis heterogeneous catalysis

An example from daily life: the three-way catalyst

-alumina Pt/Pd/Rh
ceramic
monolith
washcoat catalyst 6

catalytic converter 1 mm 1 m

Pt, Pd Rh
CO + 1/2O2 CO2 CO + NO CO2 + 1/2N2
Pt, Pd Rh
HC's + O2 CO2 + H2O H2 + NO H2O + 1/2N2

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 6
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 reactants
Heterogeneous
Catalysis Setup:
aqueous phase recycle
products

The Ruhrchemie/Rhône-
Poulenc Hydroformylation
(the oxo process) organic
phase 7

aqueous
Ligand L is "tppts": phase
H2

NaO3S SO3Na L CO
Rh
L H

SO3Na CO

Source: Gadi Rothenberg, Catalysis – Concepts and Green Applications, Wiley-VCH, 2008

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 7
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General procedure:
t s
l ven tr ate
So s Homogeneous
Ad

ub
PrecaSta
dit

lyst Catalysis
ive
s

Reaction
mixture

h
8

Mechanism for
Pd-cataysed
reactions – cross-
coupling and
carbonylation:

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 8
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 Major industrial processes using
homogeneous catalysis Homogeneous
Catalysis

The Monsanto process /Cativa Process

Acetic acid
Catalyst system: Rh / Ir complexes The Wacker Oxidation Process
Oxidation of olefins to carbonyl compounds
Catalyst system: Pd(II)- and Cu(I)-salts,
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The Shell Higher Olefins Process
oxygen
(SHOP)
Oligomerization of ethen to medium The Ciba-Geigy Metolachlor Process
and long-chain -olefins (C4-C20) Enantioselective Hydrogenation of an imine
Catalysts: Ni(II)-complexes Catalyst system: Josiphos-Ir complexes

The DuPont Adiponitril Synthesis

Hydrocyanation of butadiene to
hexanedinitrile
Catalyst system: Ni(0)-complexes

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke 9
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 O Me I CO
H2O Ir
CH3COOH I CO CH3I
I

I
I

O CH3
Homogeneous
Reaction CH3
I CO
mechanism
I
Ir
CO Catalysis
Ir I CO
I CO

CH3 CO
I CO
Ir
I CO
CO

The Cativa process: 10

Synthesis of acetic acid

Source: http://www.catalysis-ed.org.uk/ethacid/ethacid9.htm

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke
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Interplay: homogeneous and heterogeneous catalysis

Traditional BHC process

synthesis

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Heterogeneous
Catalysis

Homogeneous
Catalysis

Gadi Rothenberg, Catalysis – Concepts and Green Applications, Wiley-VCH, 2008

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke
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Heterogeneous Homogeneous
Catalysis Catalysis

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Biocatalysis

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke
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Final example: Artificial metalloenzymes
Merging the advantages of different types of catalysis – here:
enzymatic and transition metal catalysis

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Highlight: M. Hapke, C. C. Tzschucke, Angew. Chem. 2013, 52, 3317

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke
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 Manuskript der Vorlesung unter:
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http://www.catalysis.de/Cycloadditionen.42.0.html

Homogeneous vs. heterogeneous catalysis July 2, 2015

Dr. habil. Marko Hapke
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