Potential disadvantages of catalysis

Therefore the following factors should also be considered when assessing a

catalyst:

• separation of catalyst residues from product

• recycling of the catalyst
• degradation of the catalyst
• toxicity of the catalyst, of the catalyst residues and of catalyst degradation
products.

In general, it is greener to use catalysts than to not use them

4.I6 4 - 5
Case study: Boots synthesis of Ibuprofen

AcOH, HCl,
Al waste HCl

AcOH

NH3

4.I6 4 - 6
Case study: Hoechst synthesis of Ibuprofen

All three steps

are catalytic

AcOH

Less waste 99 % conversion

generated 96 % selectivity

4.I6 4 - 7
Some definitions

Homogeneous catalysis
Reagents and catalyst are all in the same phase (typically all are in
solution).

Heterogeneous catalysis ('surface catalysis')

Reagents are in a different phase from the catalyst - usually the
reagents are gases (or liquids) and are passed over a solid catalyst
(e.g. catalytic convertors in car exhausts).

Biocatalysis
Using enzymes to catalyse a reaction.

4.I6 4 - 8
Heterogeneous versus Homogeneous

General features:

Heterogeneous Homogeneous

Readily separated  Difficult to separate 

Readily recycled / regenerated 
Long-lived 
Cheap 
Lower rates (diffusion limited) 
Sensitive to poisons 
Lower selectivity 
High energy process 
Poor mechanistic understanding 
Difficult to recover 
Short service life 
Expensive 
Very high rates 
Robust to poisons 
Highly selective 
Mild conditions 
Mechanisms often known 

Ultimate goal: to combine the fast rates and high

selectivities of homogeneous catalysts with the ease
of recovery /recycle of heterogeneous catalysts

4.I6 4 - 9
Heterogeneous Catalysis

Used in refining / bulk chemical syntheses much more than in fine chemicals
and pharmaceuticals (which tend to use homogeneous catalysis).

Seven stages of surface catalysis:

1. Diffusion of the substrate(s) towards the surface.

2. Physisorption - i.e. physical absorption via weak interactions, e.g. van der
Waals, adhering the substrate(s) to the surface.
3. Chemisorption - formation of chemical bonds between the surface and the
substrate(s).
4. Migration of the bound substrate(s) to the active catalytic site - also known as
surface diffusion.
5. Reaction.
6. Desorption of product(s) from the surface.
7. Diffusion away from the surface.

4.I6 4 - 10
Heterogeneous Catalysts

Stage 4: Surface diffusion Stage

Stage
Stage
Stage
Stage
3:
2: 6:
Chemisorption
Physisorption
1:
5:
7:Desorption
Diffusion
Reaction
Diffusion

A B C C

A C B C

Surface
Heterogeneous Catalysts

Active sites
are in pores

Surface
Heterogeneous Catalysts

Typical features:

Metal or metal oxide impregnated onto a support (typically silica and / or alumina).

Three dimensional highly porous structure with very high surface area

A B Reactants
Products C C
A C
1. Diffusion to surface
2. Physisorption
B C 3. Chemisorption

1-3
1-3
6,7

4,5
6. Desorption 4. Surface diffusion
7. Diffusion out of pore M
5. Reaction
porous support
4.I6 4 - 11
Heterogeneous acid-base catalysis

ca. 130 industrial process use solid acid-base catalysts

• Mainly found in bulk/ petrochemicals production e.g. dehydration,

condensation, alkylation, esterification etc.

• Most are acid-catalysed processes.

ca. 180 different catalysts employed

• 74 of these are zeolites, ZSM-5 is the largest group.

• Second largest group are oxides of Al , Si , Ti , Zr.

4.I6 4 - 12
Zeolites - Asahi Cyclohexanol process

Traditional synthesis

225 °C
10 atm

For selectivity reasons, the reaction is run at low conversions (approx 6% per
tank) and the hot cyclohexane stream is continuously recycled.

Zeolite catalysed process:

98 % selectivity

100 °C

4.I6 4 - 15
Why is the Asahi process important?

Flixborough 1974 - 28 deaths

225 °C Tank 5 removed

10 atm 1 2 3 4 6
for repairs

Tanks 1, 2 and 3

Temporary pipework between

tanks 4 and 6 ruptured and
cyclohexane cloud exploded

4.I6 4 - 16
Zeolites - shape selective alkylation of toluene

H-ZSM-5 catalyses: H-ZSM-5

• toluene alkylation (acidic ZSM-5)
• xylene isomerisation

Channel size only allows para-xylene to emerge

Only para-xylene is required for PET synthesis:

poly(ethylene terephthlate) - PET

4.I6 4 - 17
A rare example of solid base catalysis

Traditional synthesis of 5-ethylidene-2-norbornene (ENB) via VNB:

VNB ENB

key component
of EPDM rubber

The base used for the isomerisation is typically Na/K alloy in liquid ammonia:
• ammonia easily recycled 
• metal recycle difficult 
• Na/K is very dangerous (much more reactive than either Na or K) 
Sumitomo process:

Base is a heterogeneous catalyst composed of Na and NaOH on alumina.

• High activity (isomerisation proceeds at room temperature) 
• Catalyst is readily recycled 
• Catalyst is much safer than Na/K 
4.I6 4 - 18
Homogeneous catalysis - principles

Well-defined active site allows rational catalyst development.

Typical single-site catalyst:

X
Ln M

sterically bulky ligand(s) e.g. Cp2ZrMe+ for the

controls stereochemistry polymerisation of ethene

substrate approaches
vacant coordination site
and may then react with X

4.I6 4 - 19
Homogeneous asymmetric catalysis

Most of the industrially important homogeneous catalysed processes are

found in asymmetric syntheses - e.g. pharmaceuticals.

e.g. Monsanto synthesis of L-DOPA (Parkinson's disease):

L* =

28 % e.e. 60 % e.e. 85 % e.e. 95 % e.e.

0.1% catalyst loading; Rh readily recovered (some L* is lost)

4.I6 4 - 20
Conclusions

The learning objectives of lecture 4 were:

• explain how catalysis may be considered green

Catalysis may reduce materials, waste and energy

• identify the characteristics of heterogeneous and homogeneous catalysis

Heterogeneous are easily recycled and long-lived but ill-defined
Homogeneous are more active and selective but expensive and hard to recover

• describe three examples of green heterogeneous catalysis

Asahi Cyclohexanol process
H-ZSM-5 alkylation of toluene/ isomerisation of xylene
Sumitomo base-catalysed isomerisation of vinylnorbornene

•describe one example of green homogenous catalysis

Asymmetric hydrogenation - e.g. Monsanto L-DOPA synthesis
4.I6 4 - 21
Another exam-style question

The traditional synthesis of ethylbenzene is a Friedel-Crafts alkylation, such as

that shown below:

The modern industrial synthesis involves mixing ethylene and benzene in the
presence of a zeolite (ZSM-5). In what ways would you consider this method to
be greener than the Friedel-Crafts reaction?

4.I6 4 - 22