‫ِبْس ِم الَّلِه الَّر ْح َمِن الَّر ِح يم‬

In the name of Allah, The Most Gracious and The Most Merciful

LECTURE 10-CH 623

Catalysis & Green Chemistry

Dr. Sohail Nadeem

Department of Chemistry
School of Science
University of Management and Technology,
Lahore
 Catalyst
• A material which changes (usually increases) the
rate of attainment of chemical equilibrium without
itself being changed or consumed in the process.
• e.g.

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 Catalysis
• Nitrogen and hydrogen will sit happily together in a sealed
vessel without reacting to form ammonia.
• According to Le Chatelier’s principle the equilibrium will
be shifted to the right-hand side by high pressures.
• Haber showed that at 200 oC and 300 atm 90% of NH3.
• While at the same pressure but at 700 oC the %age of
NH3 at equilibrium would be less than 5%.
• Unfortunately the activation energy is such that
temperatures well in excess of 1000 oC are needed to
overcome this energy barrier.
• In 1900s Haber and, later, Bosch discovered that the
reaction proceeded at reasonable temperatures (around
500 oC) in the presence of osmium.
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 Catalysis- A Green Initiative
• By increasing the rate of attainment of equilibrium through
lowering the activation energy, catalysts reduce the energy
requirement of a process and therefore can be considered to be
inherently green.
• Today it is estimated that some 90% of the chemicals used have,
at some stage in their manufacture, come into contact with a
catalyst.
• The range is truly broad from bulk chemicals such as acetic acid
and ammonia to consumer products such as detergents and
vitamins. 5
 Catalysis- A Green Initiative
• Virtually all major bulk chemical and refining processes employ
catalysts. The number of fine, specialty and pharmaceutical
processes currently using catalysts is still relatively small by
comparison, but a combination of economic and environmental
factors is focusing much research on this area.
• The great economic benefit of catalysts lies in their incredible
activity, sometimes converting tens of millions of times their
own weight of chemicals.
• This results in a catalyst market worth less than 1% of the value
of the products they create. 6
 Parameters for Green Catalyst
• There are three important parameters that impact on both the
commercial viability and the inherent greenness of a particular
catalyst:
• 1. Selectivity – the amount of substrate converted to the desired
product as a percentage of the total consumed substrate (a
catalyst will be of limited benefit if it also enhances the rate of
by-product formation).
• 2. Turnover frequency – the number of moles of product
produced per mole of catalyst per second (low turnover
frequencies will mean large amounts of catalyst are required,
resulting in higher cost and potentially more waste).
• 3. Turnover number – the amount of product per mole of
catalyst (this is related to catalyst lifetime and hence to cost and
waste).
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 Types of Catalysis
• 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 catalyze a reaction
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Heterogeneous versus Homogeneous Catalysis

Heterogeneous Homogeneous

Readily separated ✔ Difficult to separate 🗶

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

Ultimate goal: to combine the fast rates and high

selectivities of homogeneous catalysts with the ease of
recovery /recycle of heterogeneous catalysts 9
Heterogeneous versus Homogeneous Catalysis

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 Important Types of Catalyst
• By definition all catalysts must be heterogeneous or
homogeneous; within and across these two categories there are
other classifications that are important to green chemistry. Most
important among these are:
• Asymmetric catalysts: These are still relatively rare in
industrial processes but they are playing an increasingly
important role in the development of pharmaceuticals. This is
because they offer one of the most efficient, low-waste
methods for producing enantiomerically pure compounds.

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 Important Types of Catalyst
• Biocatalysts: these are essential for life and play a vital role in
most processes occurring within the body as well as in plants.
In the laboratory biocatalysts are usually natural enzymes or
enzymes produced in situ from whole cells. They offer the
possibility of carrying out many difficult transformations under
mild conditions and are especially valuable for producing
enantiomerically pure materials. Their huge potential is
currently largely untapped, due to the time and expense of
isolating and screening enzymes.

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 Important Types of Catalyst
• Phase transfer catalysts: these have been around for about 40
years and were developed to increase the rates and yields of
reactions in which the reactants are in two separate phases. In
these cases, poor mass transport often limits the reaction. Phase
transfer catalysts act by transporting the reactants from one
phase into another, thus overcoming mass-transport limitations.
• Photocatalysts: these harness energy from the sun to carry out
chemical transformations. These energy-efficient catalysts are
proving especially beneficial in destroying harmful waste and
for water clean-up.
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 Features of Heterogeneous Catalysts:
• Heterogeneous catalysts have been used industrially for
well over 100 years. Amongst the first processes was the
catalytic hydrogenation of oils and fats to produce margarine
using finely divided nickel. It is quite likely that when this
process was first operated in the late nineteenth century
unhealthy amounts of nickel remained in the product.

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 Surface area
• Surface area is one of the most important factors in determining
throughput (amount of reactant converted per unit time per unit mass of
catalyst). Many modern inorganic supports have surface areas of 100
to >1000 m2g-1.
• The vast majority of this area is due to the presence of internal pores;
these pores may be of very narrow size distribution to allow specific
molecular sized species to enter or leave, or of a much broader size
distribution.
• Materials with an average pore size of less than 1.5–2 nm are termed
microporous whilst those with pore sizes above this are called mesoporous
materials. Materials with very large pore sizes (>50 nm) are said to
be macroporous. 15
 Reaction on Catalyst Surface
• The next stage in the catalytic cycle is adsorption of the
reactants onto the catalyst surface. There are two types of
adsorption process:
• Physisorption, originating from Van der Waals interaction
between reactant and surface. This weakly exothermic
process is reversible and does not result in any new
chemical bonds being formed. In general physisorption does
not lead to catalytic activity but may be a precursor to
chemisorption.

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 Reaction on Catalyst Surface
• Chemisorption results in new chemical bonds being formed
between reactant and catalyst and is usually more exothermic
than physisorption. Understanding orbital interactions between
reactant and catalyst during chemisorption can enhance the
development of efficient catalysts for specific reactions.
Bonds formed during chemisorption should be strong enough
to prevent desorption yet not too strong to prevent reaction with
other reactant molecules.

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 Reaction on Catalyst Surface
• The Catalytic cycle

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 Zeolites and the Bulk Chemical Industry
• Zeolites are made of three-dimensional frameworks of
crystalline hydrated alumino-silicates consisting of TO4
tetrahedra (T being Si or Al in most zeolites). Around 45
naturally occurring zeolites have been discovered, some of
which have well-known names such as mordenite,
clinoptilolite and chabazite. The hydrated nature of zeolites
imparts significant Brønsted Acidity.

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 Zeolites and the Bulk Chemical Industry
• Although natural zeolites are widely used (around 4 million tpa) they
are not particularly valuable as commercial catalysts. This is due to a
number of factors including natural variations in crystal size and
porosity.
• To overcome the limitations of natural zeolites, synthetic zeolites have
been manufactured since the 1950s. The basic synthesis involves
mixing a source of silica, usually sodium silicate or colloidal SiO 2,
with a source of alumina, often sodium aluminate, and a base such as
sodium hydroxide.
• The mixture is heated at temperatures up to 200 oC under autogenous
pressure for a period of a few days to a few weeks to allow
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 Commercial Uses of ZSM-5
• Zeolite Y (synthetic faujasite) is commonly employed in FCC
• Zeolite Socony Mobil–5, in 1974 ZSM-5 zeolites have had
considerable commercial success. ZSM-5 has a 10-
membered ring-pore aperture of 0.55 nm (hence the 5 in
ZSM-5), which is an ideal dimension for carrying out selective
transformations on small aromatic substrates. Being the
feedstock for PET, p-xylene is the most useful of the xylene
isomers. The Brønsted acid form of ZSM-5, H-ZSM-5, is
used to produce p-xylene selectively through toluene
alkylation with methanol, xylene isomerization. 21
Commercial Uses of ZSM-5

NanAlnSi96–nO192·16H2O (0<n<27)

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 FCC or Fluid Catalytic Cracking Processes

Some basic reactions involved in FCC

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 Disproportionation of Toluene

Disproportionation of toluene using H-ZSM-5

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Heterogeneous Catalysis in the Fine Chemical and Pharmaceutical
Industries
• A highly unusual synthesis developed by Merck (not yet fully
commercialized) involves the reaction of the imine formed from acetone
and methyl amine with sulfur dioxide over Cs-doped ZSM-5.
• The product, obtained in 70% yield at 470 oC, is 4-methylthiazole, a key
intermediate for the fungicide thiabenzazole. Whilst the moderate yield, high
temperature, and less-than-ideal starting materials detract from the overall
greenness of this atom efficient route, it is much more environmentally
benign than that currently used. This involves a five-step reaction sequence
involving chlorine, carbon disulfide and ammonia as starting materials and
producing stoichiometric amounts of hydrogen chloride, sodium bisulfite and
ammonium chloride waste.
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Heterogeneous Catalysis in the Fine Chemical and Pharmaceutical
Industries

Greener route to 4-methylthiazole

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Heterogeneous Catalysis in the Fine Chemical and Pharmaceutical
Industries
These reactions are widely used for production of pharmaceutical, perfumery and
agrochemical intermediates

Michael addition – used in synthesis of methylpiridine-based herbicides

Routes to nicotinic acid

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Heterogeneous Catalysis in the Fine Chemical and Pharmaceutical
Industries
Catalysed acylation of anisole

Benzylation catalysed by Clayzic

Clayzic is based on an acid-treated clay containing zinc chloride

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 Catalytic Converters
• Control of car exhaust emissions using three-way catalytic converters
is the single largest use of a catalyst and has had a significant impact on the
price of the platinum group metals from which the catalysts are made;
around 150000 kg of these precious metals are used annually.
• The term ‘three-way catalytic converter’ arises from the three environmental
pollutants that the device is designed to remove: carbon monoxide,
nitrogen oxides and hydrocarbons.
• Even though engine efficiencies are continually improving, in the absence
of any ‘end-of-pipe’ clean up technology an average family car would
emit 10 g of CO, 2 g of NOx and 1 g of hydrocarbon for every
kilometre driven.
• These emissions have been the major cause of poor air quality 29in
 Catalytic Converters
• The catalytic converter consists of several parts:
• A ceramic monolith catalyst support, cordierite, consisting of silica, alumina
and magnesium oxide. The purpose of this is to provide support,
strength and stability over a wide temperature range.
• A washcoat, which provides a high surface area onto which the active
catalyst is impregnated. The washcoat typically consists of a mixture of
zirconium, cerium and aluminium oxides. Apart from providing high
surface area the washcoat also acts as an oxygen storage system.
• The active catalyst: platinum, palladium and smaller amounts of
rhodium. The total weight of these metals used per converter is less than 2 g.
• A high-quality steel housing to provide additional support and
protection. 30
 Catalytic Converters
The main catalytic reactions occurring in the converter are depicted in Scheme

Catalytic converters have a design life of approximately 160000 km.

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 Homogeneous Catalysis
• Unlike heterogeneous catalysis, industrial applications of
homogeneous catalysis are relatively rare, and largely restricted
to the specialty and pharmaceutical sectors.
• Homogeneous catalysts have been well researched since their
catalytic centers can be relatively easily defined and understood,
but difficulties in separation and catalyst regeneration have
prevented their wider use.

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 Homogeneous Catalysis
• The most widely used homogeneous catalysts are simple acids
and bases which catalyze well-known reactions such as ester
and amide hydrolysis, and esterification.
• Such catalysts are inexpensive enough that they can be
neutralized, easily separated from organic materials, and
disposed of.
• This is not a good example of green chemistry and contributes
to the huge quantity of aqueous salt waste generated by
industry.

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Transition Metal Catalysts with Phosphine Ligands
• Many of the green benefits of homogeneous catalysis,
especially that of high selectivity, arise from ‘designer’
catalysts made from transition metals and appropriate
ligands.
• It is the partially filled d-orbitals that make transition
metals attractive catalysts; these orbitals are of relatively
high energy enabling electrons to be readily transferred in
or out.
• Ligands bond with transition metals via these partially
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filled d-orbitals.
Transition Metal Catalysts with Phosphine Ligands
• Phosphines, for example triphenyl phosphine, are probably the
most common type of ligand encountered. There are good
reasons for this.
• Firstly phosphines are very good electron donors and hence
form quite stable bonds with many transition metals, enabling
isolation and characterization of complexes.
• Secondly, a wide variety of phosphines can be made
synthetically, giving a high degree of control over steric effects;
this is especially noticeable when bidentate phosphines are used
to completely block off one side of a catalyst. 35
Transition Metal Catalysts with Phosphine Ligands
• Hydroformylation is an important industrial process carried out
using rhodium phosphine or cobalt carbonyl catalysts.
• The major industrial process using the rhodium catalyst is
hydroformylation of propene with synthesis gas

Basic elements of hydroformylation

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Carbonylation Process using a Phosphine Ligand
• Carbonylation process using a phosphine ligand to control
the course of the reaction is a highly atom efficient route to
the widely used monomer methyl methacrylate.
• In this process the catalyst is based on palladium acetate
and the phosphine ligand, bisphenyl(6-methyl-2-pyridyl)
phosphine.
• This catalyst is remarkably (>99.5%) selective for the 2-
carbonylation of propyne under the relatively mild
conditions of <100 oC and 60 bar pressure.
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Carbonylation Process using a Phosphine Ligand
• The environmental benefit of this route is evident when
compared to the traditional methyl methacrylate
manufacturing process, which uses hazardous hydrogen
cyanide and produces stoichiometric amounts of
ammonium hydrogen sulfate waste.

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Routes to methyl methacrylate
Thousand Dreams
One Place

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