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1

Mahmoud Galal Zidan


University of Tanta , faculty of science

SlideShare
Reviewed by Prof.
Paula Bruice

PRENTICE HALL Upper Saddle River , NJ 07458


Some Of General Types Of Catalyst

Brief Contents
Chapter 1

History of Catalysis
1.1 Humphry Davys Classic Paper
1.2

1.3
1.4
1.5

Chapter 2

2.3.

2.4.
2.5.
2.6.

Whats catalyst 9
Catalysts Can Be Atoms, Molecules, Enzymes and Solid
Surfaces 10
Why is Catalysis Important? 10
2.3.1. Catalysis and Green Chemistry
2.3.2. Atom Efficiency, E Factors and Environmental
Friendliness
Catalysis as a Multidisciplinary Science 12
2.4.1. The Many Length Scales of a Catalyst
2.4.2. Time Scales in Catalysis
The Scope of This Book 14
Catalysis in Journals 14

Types of Catalysis
3.1.
3.2.
3.3.

3.4.

3.5.

Chapter 4

Introduction to Catalysis
2.1.
2.2.

Chapter 3

5
Dobereiners Experiment 6
Faradays Review
6
Fusinieris Theory
7
The Beginnings of Industrial Catalysis

Types of catalytic reactions 16


What is a phase? 16
Heterogeneous catalysis 17
3.3.1. How the heterogeneous catalyst works (in general
terms)
3.3.2. Examples of heterogeneous catalysis
3.3.2.1. The hydrogenation of a carbon-carbon
double bond
3.3.2.2. Catalytic converters
3.3.2.2.1. The use of vanadium(V) oxide in the
Contact Process
Homogeneous catalysis 21
3.4.1. Examples of homogeneous catalysis
3.4.1.1. The reaction between persulphate ions and
iodide ions
3.4.1.2. The destruction of atmospheric ozone
Autocatalysis 23
3.5.1. The oxidation of ethanedioic acid by manganate (VII)
ions

Heterogeneous catalysis
4.1.
4.2.

Some Of General Types Of Catalyst

Principles of heterogeneous catalysis 25


CLASSIFICATION OF REACTION MECHANISMS 29

4.3.
4.4.
4.5.
4.6.

Chapter 5

Homogeneous industrial catalysis Examples 44

Bio-catalysis
8.1.
8.2.
8.3.

8.4.

8.5.

Reference

Whats Homogeneous catalysis 42


Acid catalysis 42
Organometallic chemistry 42
Other forms of homogeneous catalysis 43
6.4.1. Contrast with heterogeneous catalysis

Industrial Uses of Homogeneous catalysis


7.1.

Chapter 8

Heterogeneous industrial catalysis Examples 33


General requirements for a heterogeneous catalyst 36
Aluminium oxide, silicon dioxide, aluminosilicates and zeolites
37
5.3.1. Zeolite catalysts

Homogeneous catalysis
6.1.
6.2.
6.3.
6.4.

Chapter 7

32

Industrial Uses of Heterogeneous catalysis


5.1.
5.2.
5.3.

Chapter 6

Coadsorption 33
Poisons and Promoters 31
Electropositive impurities 31
Determination of the Reaction Rate

Whats Biocatalysis 47
Definition 48
BIOTECHNOLOGY 53
8.3.1. What is biotechnology
8.3.2. Liquid fuels
8.3.3. The Starch industry
8.3.4. BIOTECHNOLOGY TODAY
Enzyme Technology 54
Genetic Engineering 56

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Some Of General Types Of Catalyst

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ne hundred and forty years ago it was possible for one man to prepare an annual report on the
progress of the whole of chemistry, and for many years this task was undertaken by the noted Swedish
chemist J. J. Berzelius for the Stockholm Academy of Sciences. In his report submitted in 1835 and
published in 1836 Berzelius reviewed a number of earlier findings on chemical change in both
homogeneous and heterogeneous systems, and showed that these findings could be rationally coordinated by the introduction of the concept of catalysis. In a short paper summarizing his ideas on
catalysis as a new force, he wrote (I):
It is, then, proved that several simple or compound bodies, soluble and insoluble, have the property
of exercising on other bodies an action very different from chemical affinity.
By means of this action they produce, in these bodies, decompositions of their elements and different
recombination of these same elements to which they remain indifferent.
Berzelius proceeded to propose the existence of a new force which he called the catalytic force and
he called catalysis the decomposition of bodies by this force. This is probably the first recognition
of catalysis as a wide-ranging natural phenomenon.
Metallic catalysts had in fact been used in the laboratory before 1800 by Joseph Priestley, the
discoverer of oxygen, and by the Dutch chemist Martinus van Marum, both of whom made
observations on the dehydrogenation of alcohol on metal catalysts. However, it seems likely that these
investigators regarded the metal merely as a source of heat. In 1813, Louis Jacques Thenard
discovered that ammonia is decomposed into nitrogen and hydrogen when passed over various red-hot
metals, and ten years later, with Pierre Dulong, he found that the activity of iron, copper, silver, gold,
and platinum for decomposing
ammonia decreased in the order given. This is one of the earliest recorded examples of a pattern of
catalytic activity.
Thenard, the son of a peasant, after experience with Vauquelin in Paris as a laboratory boy, became
assistant and later Professor at the lkole Polytechnique. In 1857, then a peer, he became Chancellor of
the University of Paris. His collaborator Dulong was Professor of Physics in the &ole Polytechnique,
later becoming Director. He is, of course, famed for the law of Dulong and Petit. He also proposed a
hydrogen theory of acids independently of Davy. Homogeneous catalytic processes have been used by
mankind for some thousands of years, for example in fermentation. Perhaps the first attempt at a
rational theory of catalysis is the intermediate compound theory proposed by Charles Bernard
Desormes and Nicolas
Clement (2) for the homogeneous catalytic effect of nitrogen oxides in the lead chamber process for
the manufacture of sulphuric acid.
This particular process was later discussed more fully by Humphry Davy, and has received a huge
amount of attention and discussion since these early times.
Clement studied science in Pans and became assistant at the Ecole Polytechnique.
Later he became Professor at the Conservatoire des A r t s et Mtiers, and after winning a lottery,
married the daughter of Dtsormes. That a chemical substance can speed up a chemical reaction
without itself being chemically changed became clear in a research on the decomposition of hydrogen
peroxide, carried out by L. J. Thenard, who announced his discovery of this substance in 1818.

Some Of General Types Of Catalyst

5
Thenard had become interested in barium peroxide, probably because of the notable discovery by
Davy in 1807 of sodium and potassium, which he prepared by the electrolysis of their moist
hydroxides. Davys first Bakerian lecture in 1806 On some Chemical Agencies of Electricity
described work of such importance that the 3000 francs prize given by Napoleon I was awarded to
him. Napoleon seems to have been somewhat peeved that the prize went to an Englishman when a
state of war existed between England and France, and, noting the vital part the large Royal Institution
voltaic pile had played in the research, he ordered two large voltaic piles to be built. Perhaps he
adopted the type of argument we note even now from some political circles, that two voltaic piles will
do twice as much useful work as one, irrespective of who originates the ideas to be tried out with the
piles. Thtnard probably investigated the alkaline earth oxides with the initial aim of electrolyzing
them. The work he did on the reaction of barium peroxide with nitric or hydrochloric
acid led to the discovery of hydrogen peroxide. This he found to decompose when in contact with
many solids, some of which were not chemically changed. He also found that the action of metals in
bringing about decomposition became more vigorous as the metal was reduced to a finer state of
subdivision.

1.1. Humphry Davys Classic Paper


The first clear realization that chemical
reaction between two gaseous reactants
can occur on a metal surface without
the metal being chemically changed is
found in a paper by Humphry Davy (3)
published by the Royal Society in 1817.
This describes the discovery of a new
and curious series of phenomena.
During the researches which led to the
miners safety-lamp, Davy fixed a fine
platinum wire above a coal-gas flame in
a safety-lamp. When additional coal gas
was introduced into the lamp, the flame
went out
but the platinum wire remained hot for
many minutes. Davy immediately
deduced that the oxygen and coal gas
combined without flame when in
contact with the hot wire, thereby
producing enough heat to keep the wire
incandescent.
A hot platinum wire introduced into a
mixture of coal gas and air immediately
became incandescent. Furthermore
many combustible vapors mixed with
air were found by Davy to produce the
same effect.
Davy had discovered the phenomenon
of heterogeneous catalytic oxidation.
Only platinum and palladium wires were effective; wires of copper, silver, gold and iron were
ineffective. This is one of the earliest recorded patterns of catalytic activity.
In these researches Davy was assisted by Faraday but it is unclear whether Faraday contributed to the
development of the ideas or acted mainly by carrying out Davys instructions. The two-man team
which made
these discoveries about heterogeneous catalysis must have been one of the strongest in the whole
history of chemistry.

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In order to initiate catalytic oxidation the wires used by Davy needed to be hot, but in 1820 Edmund
Davy , Professor of Chemistry at Cork in Ireland, formerly Assistant: at the Royal Institution, and
cousin of Humphry Davy, prepared a finely-divided platinum catalyst of such high activity that it
acted at room temperature. When this catalyst was dropped on to any porous substance moistened
with alcohol, oxidation occurred so rapidly that the catalyst became red hot.

1.2. Dobereiners Experiment


J. W. Dobereiner , Professor of Chemistry at Jena and formulator of the law of triads, reduced a
catalyst prepared by the procedure Edmund Davy had described and obtained a spongy platinum
which brought about the combination of hydrogen and oxygen at room temperature and quickly
became red hot as a result. This remarkable discovery was rapidly followed up by Dulong and
Thenard in Paris, who discovered that palladium and iridium could also act at ordinary temperatures
whereas cobalt, nickel,
rhodium, silver and gold acted catalytically only at higher temperatures. Their note
actually appeared in the Annales de Chimie et de Physique before Dobereiners paper because
his discovery was communicated privately by Liebig to Dulong and Thenard.
Dobereiners work had, however, been communicated from Paris to Faraday in a letter of September
16th, 1823, from J. N. P. Hachette and within a few days Faraday had proceeded to repeat the
experiment and confirm the findings. In a brief note signed merely M. F. he wrote it was
communicated to me by M. Hachette and having verified it I think every chemist will be glad to hear
its nature.

1.3. Faradays Review


Dulong and Thenard in a later paper reported that the ability to bring about gaseous combination is a
general property of sufficiently- heated solids, while Faraday , in a very good review of early work on
heterogeneous catalysis, drew attention to the merits of their experiments. He wrote (paragraph 611):
In the two excellent papers by MM. DULONG and Thenard ,philosophers show that elevation of
temperature favors the action, but does not alter its character, Sir HUMPHRY DAVYSin candescent
platina wire being the same phenomenon with DBEREINWS spongy platina. They show that all
metals have this power in a greater or smaller degree, and that it is even possessed by such bodies as
charcoal, pumice, porcelain, glass, rock crystal, etc., when their temperatures are raised; and that
another of DAVYs effects, in which oxygen and hydrogen had combined slowly together at a heat
below ignition, was really dependent upon the property of the heated glass, which it has in common
with the bodies named above.
Later in the paper Faraday wrote (paragraph 618): The effect is evidently produced by most, if not
all, solid bodies, weakly perhaps by many of them, but rising to a high degree in platina. DULONG d
Thenard philosophically extended our knowledge of the property to its possession by all the metals,
and by earths, glass, stones, etc. (611); and every idea of its being a known and recognized electric
action is in this way removed. This last sentence in effect rejects a somewhat vague suggestion made
by Dulong and
Thenard that the power of solids to bring about reactions of gases is electrical in origin, although, as
Faraday noted, Dulong and Thenard expressed themselves with great caution on the theory of the
effect.
Additional significant experimental discoveries concerning heterogeneous catalytic oxidation were
made by William Henry (IO), who used as a catalyst either platinum sponge or molded balls made of
china clay and spongy platinum. These catalytic balls were first described by Dobereiner, to whom
Henry refers. The two papers by Dobereiner and Henry were the first to describe the use of a
supported platinum catalyst. Dobereiners contributions to catalysis have been reviewed in more detail
by McDonald .
Henry found that ethylene prevented the surface combination of a mixture of hydrogen and carbon
monoxide with oxygen, and carbon monoxide slightly slowed down the surface reaction between

Some Of General Types Of Catalyst

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hydrogen and oxygen. He also found, when working with mixtures of hydrogen, carbon monoxide
and methane, that selective catalytic oxidation on platinum is possible.
Henry had studied under Joseph Black in Edinburgh and had also worked with the noted Scottish
chemist Thomas Thomson. Later he directed his fathers chemical works. He is famed for Henrys
law concerning gaseous solubilities.

1.4. Fusinieris Theory


The first attempt to give a detailed theoretical discussion of heterogeneous catalytic oxidation on
platinum was made by the Italian physician Ambrogio Fusinieri in a paper published in 1824. He
discussed the effects discovered by Dobereiner and others. He also explained in more detail his own
experimental observations (first expounded in a note) and remarked that these would dispel all
confusion and doubt, writing : Ora espongo in pih dettaglio le mie osservazione che dissipano ogni
confusione ed ogni dubbio; ed altre ancora ve ne soggiungo di pih recenti. Fusinieri contended, in
opposition to Day, that in fact the combustion of ether on platinum occurs with flame, which may be
obscured by light from the platinum, or may be invisible. He further contended that during the
oxidation of ether concrete laminae of the combustible substance could be seen with the naked eye,
the laminae running over the platinum surface and then disappearing by burning. Fusinieri thought
that the ether forming the laminae was solidified, although he noted a relation between the appearance
and disappearance of the laminae and capillary action of liquids. According to Fusinieri, the platinum
catalyst acted like a candle wick with the laminae burning like candle wax. As an explanation of the
formation and burning of the concrete laminae, which Fusinieri thought he saw, he proposed the
concept of native caloric (Faradays translation).
Faraday in his momentous paper of 1834 , which proposed the idea (increasingly supported since the
researches of Langmuir) of simultaneous adsorption of both reactants on a platinum surface, reviewed
Fusinieris views at some length, but he confessed that he could not form a distinct idea of the concept
of native caloric, and remarked that his knowledge of the language in which the Fusinieri memoir is
written was imperfect. Faraday during his European tour with Davy and Lady Davy, in which he
acted as scientific assistant and unofficial valet, had learnt Italian, but the Fusinieri paper of 1824 uses
Italian which is as out-dated as Chaucerian English, and sentences in which caloric nativo appears
have been said to be totally incomprehensible . It is not surprising that Faraday was unable to form a
distinct idea of what Fusinieri meant by caloric nativo.

1.5. The Beginnings of Industrial Catalysis


The industrial possibilities of heterogeneous catalytic oxidation were appreciated as early as 1831 by
Peregrine Phillips, Junior, who in that year took out a British Patent (No. 6096) for Certain
Improvements in Manufacturing Sulphuric Acid commonly called Oil of Vitriol. The specification
states :The first improvement then, namely, the instantaneous union of sulphurous acid with the
oxygen of the atmosphere, I effect by drawing them in proper proportions by the action of an air pump
or other mechanical means thro an ignited tube or tubes of platina, porcelain, or any other material
not acted on when heated by the sulphurous acid gas. In the said tube or tubes I place fine platina wire
or platina in any finely-divided state, and I heat them to a strong yellow heat, and by preference in the
chamber of a reverberatory furnace; and I do affirm that sulphurous acid gas being made to pass with
a sufficient supply of atmospheric air through tubes as described, properly heated and managed, will
be instantly converted into sulphuric acid gas, which will be rapidly absorbed as soon as it comes into
contact with
water.
This far-sighted patent has made Phillips one of the inventors who have devised a really new process
of manufacture of an important chemical substance. The process was first worked to make fuming
sulphuric acid by Messel in 1875. Very little is known about the inventor, despite a search of local
records made by E. Cook except that he was the son of a tailor and was born in Milk Street, Bristol.

Some Of General Types Of Catalyst

8
The first to use platinum as a catalyst for ammonia oxidation was C. F. Kuhlmann who reported his
results to the Scientific Society of Lille, France, in 1838. An account of early developments with
platinum catalysts for the ammonia oxidation process for nitric acid manufacture has been given by L.
B. Hunt From these small beginnings vast industries based on catalysis have arisen and a huge
quantity of scientific information has been accumulated. Despite numerous theoretical discussions
catalytic action is still to some extent a mystery-indeed it is notable that large-scale processes are
based on catalysts which from a theoretical point of view can hardly be described. Catalysis a century
and a half after Davys discovery still remains a challenge to the chemist.

Some Of General Types Of Catalyst

2
sk the average person in the street what a catalyst is, and he or she will probably tell you that a
catalyst is what one has under the car to clean up the exhaust. Indeed, the automotive exhaust
converter represents a very successful application of catalysis; it does a great job in removing most of
the pollutants from the exhaust leaving the engines of cars. However, catalysis has a much wider
scope of application than abating pollution.
For example, living matter relies on enzymes, which are the most specific catalysts one can think of.
Also, the chemical industry cannot exist without catalysis, which is an indispensable tool in the
production of bulk chemicals, fine chemicals and fuels.
For scientists and engineers catalysis is a tremendously challenging, highly multidisciplinary field.
Let us first see what catalysis is, and then why it is so important for mankind.

2.1. Whats catalyst ?


A catalyst accelerates a chemical reaction. It does
so by forming bonds with the reacting molecules,
and by allowing these to react to a product, which
detaches from the catalyst, and leaves it unaltered
such that it is available for the next reaction. In
fact, we can describe the catalytic reaction as a
cyclic event in which the catalyst participates and
is recovered in its original form at the end of the
cycle.
Let us consider the catalytic reaction between
two molecules A and B to give a product P, see
Fig. 1.1. The cycle starts with the bonding of
molecules A and B to the catalyst. A and B then
react within this complex to give a product P,
which is also bound to the catalyst. In the final
step, P separates from the catalyst, thus leaving
the reaction cycle in its original state.
To see how the catalyst accelerates the reaction,
we need to look at the potential energy diagram
in Fig. 1.2, which compares the non-catalytic and the catalytic reaction.
For the non-catalytic reaction, the figure is simply the familiar way to visualize the Arrhenius
equation: the reaction proceeds when A and B collide with sufficient energy to overcome the
activation barrier in Fig. 1.2. The change in Gibbs free energy between the reactants, A + B, and the
product P is G.
The catalytic reaction starts by bonding of the reactants A and B to the catalyst, in a spontaneous
reaction. Hence, the formation of this complex is exothermic, and the free energy is lowered. There
then follows the reaction between A and B while they are bound to the catalyst. This step is associated
with an activation energy; however, it is significantly lower than that for the uncatalyzed reaction.
Finally, the product P separates from the catalyst in an endothermic step.
Some Of General Types Of Catalyst

10
The energy diagram of Fig. 1.2 illustrates several
important points:
The catalyst offers an alternative path for
the reaction, which is obviously more
complex, but energetically much more
favorable.
The activation energy of the catalytic
reaction is significantly smaller than that of
the uncatalyzed reaction; hence, the rate of
the catalytic reaction is much larger
The overall change in free energy for the
catalytic reaction equals that of the
uncatalyzed reaction. Hence, the catalyst
does not affect the equilibrium constant for
the overall reaction of A + B to P. Thus, if a
reaction is thermodynamically unfavorable,
a catalyst cannot change this situation. A
catalyst changes the kinetics but not the
thermodynamics.
The catalyst accelerates both the forward and the reverse reaction to the same extent. In other
words, if a catalyst accelerates the formation of the product P from A and B, it will do the
same for the decomposition of P into A and B. Thus far it is immediately evident that there
are also cases in which the combination of catalyst with reactants or products will not be
successful.
If the bonding between reactants and catalyst is too weak, there will be hardly any conversion
of A and B into products. Conversely if the bond between the catalyst and one of the
reactants, say A, is too strong, the catalyst will be mostly occupied with species A, and B is
not available to form the product. If A and B both form strong bonds with the catalyst, the
intermediate situation with A or B on the catalyst may be so stable that reaction becomes
unlikely. In terms of Fig. 1.2, the second level lies so deep that the activation energy to form
P on the catalyst becomes too high. The catalyst is said to be poisoned by (one of) the
reactants.
In the same way, the product P may be too strongly bound to the catalyst for separation to
occur. In this case the product poisons the catalyst. Hence, we intuitively feel that the
successful combination of catalyst and reaction is that in which the interaction between
catalyst and reacting species is not too weak, but also not too strong. This is a loosely
formulated version of Sabatiers Principle, the catalyst has been an unspecified, abstract body,
so let us first look at what kind of catalysts exist.

2.2. Catalysts Can Be Atoms, Molecules, Enzymes and Solid Surfaces


Catalysts come in a multitude of forms, varying from atoms and molecules to large structures such as
zeolites or enzymes. In addition they may be employed in various surroundings: in liquids, gases or at
the surface of solids. Preparing a catalyst in the optimum form and studying its precise composition
and shape are an important specialism, which we describe in later chapters.
It is customary to distinguish the following three sub disciplines in catalysis:
Homogeneous .
Heterogeneous .
Bio catalysis .

2.3. Why is Catalysis Important?


The chemical industry of the 20th century could not have developed to its present status on the basis of
non-catalytic, stoichiometric reactions alone. Reactions can in general be controlled on the basis of

Some Of General Types Of Catalyst

11
temperature, concentration, pressure and contact time. Raising the temperature and pressure will
enable stoichiometric reactions to proceed at a reasonable rate of production, but the reactors in which
such conditions can be safely maintained become progressively more expensive and difficult to make.
In addition, there are thermodynamic limitations to the conditions under which products can be
formed, e.g. the conversion of N2 and H2 into ammonia is practically impossible above 600 C.
Nevertheless, higher temperatures are needed to break the very strong N_N bond in N2. Without
catalysts, many reactions that are common in the chemical industry would not be possible, and many
other processes would not be economical.
Catalysts accelerate reactions by orders of magnitude, enabling them to be carried out under the most
favorable thermodynamic regime, and at much lower temperatures and pressures. In this way efficient
catalysts, in combination with optimized reactor and total plant design, are the key factor in reducing
both the investment and operation costs of a chemical processes. But that is not all.

2.3.1. Catalysis and Green Chemistry


Technology is called green if it uses raw materials efficiently, such that the use of toxic and
hazardous reagents and solvents can be avoided while formation of waste or undesirable byproducts is
minimized. Catalytic routes often satisfy
these criteria.
A good example is provided by the
selective oxidation of ethylene to
ethylene
epoxide,
an
important
intermediate towards ethylene glycol
(antifreeze) and various poly-ethers and
polyurethanes (Fig. 1.6).

The old, non-catalytic route (called the epichlorohydrine process) follows a three step synthesis:

Cl2 + NaOH
HOCl + NaCl (1)
C2H4 + HOCl
CH2ClCH2OH (epichlorohydrine) (2)
CH2ClCH2OH + 1/2Ca(OH)2
1/2CaCl2 + C2H4O +H2O (3)
or in total:
Cl2 + NaOH + 1/2Ca(OH)2 + C2H4
C2H4O + 1/2CaCl2 + NaCl + H2O
Hence, for every molecule of ethylene oxide, 1 molecule of salt is formed, creating a waste problem
that was traditionally solved by dumping it in a river. Such practice is of course now totally
unacceptable. The catalytic route, however, is simple and clean, although it does produce a small
amount of CO2. Using silver, promoted by small amounts of chlorine, as the catalyst, ethylene oxide
is formed directly from C2H4 and O2 at a selectivity of around 90 %, with about 10% of the ethylene
ending up as CO2. Nowadays all production facilities for ethylene oxide use catalysts.

2.3.2. Atom Efficiency, E Factors and Environmental Friendliness


Numerous organic syntheses are based on stoichiometric oxidations of hydrocarbons with sodium
dichromate and potassium permanganate, or on hydrogenations with alkali metals, borohydrides or
metallic zinc. In addition, there are reactions such as aromatic nitrations with H 2SO4 and HNO3, or
acylations with AlCl3 that generate significant amounts of inorganic salts as byproducts.
Fine chemicals are predominantly (but not exclusively!) the domain of homogeneous catalysis, where
solvents present another issue of environmental concern.
According to Sheldon, the best solvent is no solvent, but if a solvent is unavoidable, then water is a
good candidate.

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12
Sheldon has introduced several indicators to measure the efficiency and environmental impact of a
reaction. The atom efficiency is the molecular weight of the desired product divided by the total
molecular weight of all products. For example the conventional oxidation of a secondary alcohol

3C6H5CHOHCH3 + 2CrO3 + 3H2SO4

3C6H5COCH3 + Cr2(SO4)3 + 6H2O

has an atom efficiency of 360/860 = 42%. By contrast, the catalytic route

C6H5CHOHCH3 + 1/2O2

C6H5COCH3 + H2O

offers an atom efficiency of 120/138 = 87%, with water as the only byproduct. The reverse step, a
catalytic hydrogenation, proceeds with 100% atom efficiency:

C6H5COCH3 + H2

C6H5CHOHCH3

as does the catalytic carbonylation of this molecule:

C6H5CHOHCH3 + CO

C6H5CH(CH3)COOH

Another useful indicator of environmental acceptability is the E factor the weight of waste or
undesirable byproduct divided by the weight of the desired product.
As Table 1.1 shows, the
production of fine chemicals
and pharmaceuticals generate
the highest amounts of waste
per unit weight of product.
Atom efficiencies and E factors
can be calculated from each
other, but in practice E factors
can be higher due to yields
being less than optimum and
reagents that are used in excess. Also, loss of solvents should be included, and perhaps even the
energy consumption with the associated generation of waste CO2.
To express that it is not just the amount of waste but rather its environmental impact, Sheldon
introduced the environmental quotient EQ as the E factor multiplied by an unfriendliness quotient, Q,
which can be assigned a value to indicate how undesirable a byproduct is. For example, Q = 0 for
clean water, 1 for a benign salt, NaCl, and 1001000 for toxic compounds. Evidently, catalytic routes
that avoid waste formation are highly desirable, and the more economic value that is placed on, for
example, the unfriendliness quotient, the higher the motivation to work on catalytic alternatives.
Waste prevention is much to be preferred over waste remediation.

2.4. Catalysis as a Multidisciplinary Science


2.4.1. The Many Length Scales of a Catalyst
Catalysis is a very broad field of study that is
closely interwoven with numerous other scientific
disciplines. This becomes immediately evident if
we realize that catalysis as phenomenon
encompasses many length scales. Figure 1.8
illustrates this for the case of heterogeneous
catalysis. For the examples given above, the
bonding of reactant molecules to a catalyst to give
a reactive complex and the final separation of
catalyst and product is catalysis on the molecular
level. For heterogeneous, homogeneous or
enzymatic catalysis, this is the level on which the
chemistry takes place. Understanding reactions at
the elementary level of the rupture of bonds in
reactants and the formation of bonds in products
is at the heart of the matter, and requires the most
advanced experimental techniques and theoretical

Some Of General Types Of Catalyst

13
descriptions available. This is the domain of spectroscopy, computational chemistry and kinetics and
mechanism on the level of elementary reaction steps. The length scales of interest are in the
subnanometre region. Publications on research at the molecular scale are found predominantly in
general journals in chemistry, physical chemistry and physics.
The next level is that of small catalytically active particles, with typical dimensions of between 1 and
10 nm, and inside the pores of support particles (_m range). The questions of interest are the size,
shape, structure and composition of the active particles, in particular of their surfaces, and how these
properties relate to catalytic reactivity. Although we will deal with heterogeneous catalysis, the
anchoring of catalytic molecules or even enzymes to supporting structures is also of great interest in
homogeneous and biocatalysis. This is the domain of catalyst preparation, characterization, testing on
the laboratory scale, and mechanistic investigations. Transport phenomena such as the diffusion of
molecules inside pores may affect the rate at which products form and become an important
consideration on this level. Much academic research as well as exploratory work in industry occurs on
this scale. Journals dedicated to catalysis deal largely with catalysis on this mesoscopic length scale.
The next level is that of shaped catalysts, in the form of extrudates, spheres, or monoliths on length
scales varying from millimeters to centimeters, and occasionally even larger. Such matters are to a
large extent the province of materials science. Typical issues of interest are porosity, strength, and
attrition resistance such that catalysts are able to survive the conditions inside industrial reactors. This
area of catalysis is mainly (though not exclusively) dealt with by industry, in particular by catalyst
manufacturers. Consequently, much of the knowledge is covered by patents. The macroscopic level is
that of reactors, be it the 25 cm test reactor in the laboratory or the 10 m high reactor vessel in an
industrial plant. The catalyst forms the heart of the reactor. Nevertheless catalysis as a discipline is
only one of many other aspects of reaction engineering, together with, for example, the design of
efficient reactors that are capable of handling high pressure, offer precise control of temperature,
enable optimized contact between reactants and catalyst and removal of products, are resistant to
corrosion, make optimum use of energy resources, and are safe during operation. In describing the
kinetics of catalytic reactions on the scale of reactors, extrinsic factors dealing with the mass and heat
transport properties of reactants and products through the catalyst bed are as important as the intrinsic
reactivity of the molecules reacting at the catalytic site. The catalysts mechanical stability, sensitivity
to trace impurities in the reactant feed, and degradation of particles, e.g. due to exposure to high
temperatures, are important in addition to its intrinsic properties such as activity and selectivity.
Literature on these aspects of catalysis is largely found in chemical engineering journals and patents.

2.4.2. Time Scales in Catalysis


The characteristic times on which catalytic events occur vary more or less in parallel with the
different length scales discussed above. The activation and breaking of a chemical bond inside a
molecule occurs in the picosecond regime, completion of an entire reaction cycle from complexation
between catalyst and reactants through separation from the product may take anywhere between
microseconds for the fastest enzymatic reactions to minutes for complicated reactions on surfaces. On
the mesoscopic level, diffusion in and outside pores, and through shaped catalyst particles may take
between seconds and minutes, and the residence times of molecules inside entire reactors may be
from seconds to, effectively, infinity if the reactants end up in unwanted byproducts such as coke,
which stay on the catalyst.

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14

2.5. The Scope of This Book


The emphasis of this book is on the fundamental level of catalytic reactions on the molecular and
themesoscopic scale. Dealing with the acceleration of reactions, catalysis is a kinetic phenomenon.
Hence, we start with a chapter on kinetics to describe how the rate of the catalytic reaction cycle
depends on the main external process variables by which reactions can be influenced: concentration,
pressure and temperature. Next is a chapter on the theory of reaction rates, which aims to make the
connection between the properties of reactant molecules and their reactivity. To make the connection
between fundamental catalysis and real life, we also describe what catalysts look like on
themesoscopic level, how they are made and how they are characterized. Owing to the spectacular
advances in theoretical chemistry and computational facilities over the last decade it is now possible
to predict reaction rates from first principles, albeit for idealized cases only. We intend to provide the
reader with the necessary background to have at least a feeling for what fundamental catalysis
currently means. Consequently, we describe phenomena such as adsorption and reaction on surfaces,
along with the tools needed to investigate this. Finally, we describe a number of industrially important
catalytic processes, from both applied and fundamental points of view. The emphasis is on concepts
and general trends rather than on specific details, and the aim has been to provide students with the
necessary background to appreciate the more specialized literature on fundamental catalysis. The
literature section gives references to a number of general books in catalysis and related disciplines.

2.6. Catalysis in Journals


The results of research in catalysis are published in a wide range of general and more specialized
journals. This reflects the highly multidisciplinary nature of the field. Referring to the different length
scales in Fig. 1.8, research in the microscopic domain, dealing with the fundamentals of adsorbed
molecules and elementary reaction steps is often reported in general journals, such as the Journal of
Chemical Physics, the Journal of Physical Chemistry, Physical Chemistry-Chemical Physics, Surface
Science, Langmuir and Physical Review, and sometimes even Science and Nature. Also, the
specialized Journal of Catalysis and Catalysis Letters publish articles in this area. The mesoscopic
domain of real catalysts is mostly covered by the typical catalysis periodicals, such as Applied
Catalysis, the Journal of Catalysis, Catalysis Letters, Topics in Catalysis, Catalysis Today,
Microporous Materials and Zeolites, although occasionally articles also appear in Journal of Physical
Chemistry and Physical Chemistry-Chemical Physics, and many others. The macroscopic domain is
largely covered by journals dedicated to chemical engineering: Chemical Engineering Science,
Industrial & Engineering Chemistry Research, and the Journal of the American Institute of Chemical
Engineers (AIChE Journal) are some of the best known in this field.
Exciting, new results that may not yet be fully understood but for which it is important that the
catalysis community learns about them, are published in the form of Letters, Notes and Rapid
Communications. Specialized Letter Journals are Chemical Communications, Catalysis Letters,
Chemical Physics Letters and Physical Review Letters, while several regular journals have sections
for letters, such as the Priority Communications in the Journal of Catalysis.
In addition, there are the highly appreciated review journals, which publish overviews of the status of
certain topics of interest in the field. Advances in Catalysis, Catalysis Reviews: Science &
Engineering and Catalysis, Specialist Periodical Reports publish the most exhaustive reviews.
CaTTech is a colorful magazine that publishes shorter reviews along with news from the catalysis
community. Also the News Brief section of Applied Catalysis fulfills this important role. As in all
scientific fields, conferences are frequently followed up by a book of proceedings, containing short
accounts of the presentations. However, proceedings are becoming less popular among scientists. As
refereeing procedures tend to be less strict, and the amount of information that can be included is
usually limited, the quality of these proceedings is not always what it should be. Often, work
published in expensive proceedings is also published in regular papers, rendering proceedings too
often a waste of effort and money.
Midway between conference proceedings, reviews and regular research papers are the topical issues
published by Catalysis Today and Topics in Catalysis. Rather than publishing the proceedings of an

Some Of General Types Of Catalyst

15
entire conference, the editor makes a selection of particularly interesting contributions and invites the
presenters to write a not too short article about their work. Such topical issues often give a valuable
overview of the status of a certain field, while the quality of the publications is much higher than that
of the average conference proceedings.
To get an impression of which journals are the most read and cited, the Institute of Scientific
Information (Philadelphia, PA, USA) provides two interesting indicators (Journal Citation Reports,
Science Edition). The impact factor for a given journal is the number of citations in that year to
articles published by the journal in the two previous years. Thus, if each article published in, for
example, either 1998 or 1999 is cited exactly once in 2000, the journal will have an impact factor of 1
in that year.
Authors use impact factors to decide where to submit their publications. For specialized journals, e.g.
those focusing on catalysis, impact factors of 3 and higher are considered high. Review journals
usually have higher impact factors, whereas letter journals usually score lower.
A much less appreciated but in fact highly informative parameter and indicator of quality is the
citation half-life of a journal. This is the period in years (going back from the current year) during
which cited papers were published, from which it received half of all the citations in the current year.
A long citation half-life indicates that the journal has published quality articles that have long kept
their value to the scientific community. Care should be exercised with these numbers, as relatively
young journals need years before they can reach an appreciable citation half-life to prove that they
indeed published papers of long lasting value. Table 1.5 lists the impact factor and citation half-life
for several relevant journals.

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3
3.1

Types of catalytic reactions

Catalysts can be divided into two main types - heterogeneous and homogeneous. In a
heterogeneous reaction, the catalyst is in a different phase from the reactants. In a
homogeneous reaction, the catalyst is in the same phase as the reactants.

3.2

What is a phase?

If you look at a mixture and can see a boundary between two of the components, those
substances are in different phases. A mixture containing a solid and a liquid consists of two
phases. A mixture of various chemicals in a single solution consists of only one phase,
because you can't see any boundary between them.

You might wonder why phase differs from the term physical state (solid, liquid or gas). It
includes solids, liquids and gases, but is actually a bit more general. It can also apply to two
liquids (oil and water, for example) which don't dissolve in each other. You could see the
boundary between the two liquids.

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17

If you want to be fussy about things, the diagrams actually show more phases than are
labelled. Each, for example, also has the glass beaker as a solid phase. All probably have a
gas above the liquid - that's another phase. We don't count these extra phases because they
aren't a part of the reaction.

3.3

Heterogeneous catalysis

This involves the use of a catalyst in a different phase from the reactants. Typical examples
involve a solid catalyst with the reactants as either liquids or gases.
Note: It is important that you remember the difference between the two terms heterogeneous and
homogeneous.
hetero implies different (as in heterosexual). Heterogeneous catalysis has the catalyst in a different phase from
the reactants.
homo implies the same (as in homosexual). Homogeneous catalysis has the catalyst in the same phase as the
reactants.

3.3.1

How the heterogeneous catalyst works (in general terms)

Most examples of heterogeneous catalysis go through the same stages:


One or more of the reactants are adsorbed on to the surface of the catalyst at active sites.
Adsorption is where something sticks to a surface. It isn't the same as absorption
where one substance is taken up within the structure of another. Be careful!
An active site is a part of the surface which is particularly good at adsorbing things
and helping them to react.
There is some sort of interaction between the surface of the catalyst and the reactant
molecules which makes them more reactive.
This might involve an actual reaction with the surface, or some weakening of the
bonds in the attached molecules.
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18

The reaction happens.


At this stage, both of the reactant molecules might be attached to the surface, or one
might be attached and hit by the other one moving freely in the gas or liquid.
The product molecules are desorbed.
Desorption simply means that the product molecules break away. This leaves the
active site available for a new set of molecules to attach to and react.
A good catalyst needs to adsorb the reactant molecules strongly enough for them to react, but
not so strongly that the product molecules stick more or less permanently to the surface.
Silver, for example, isn't a good catalyst because it doesn't form strong enough attachments
with reactant molecules. Tungsten, on the other hand, isn't a good catalyst because it adsorbs
too strongly.
Metals like platinum and nickel make good catalysts because they adsorb strongly enough to
hold and activate the reactants, but not so strongly that the products can't break away.

3.3.2 Examples of heterogeneous catalysis


3.3.2.1
The hydrogenation of a carbon-carbon double bond
The simplest example of this is the reaction between ethene and hydrogen in the presence of a
nickel catalyst.

In practice, this is a pointless reaction, because you are converting the extremely useful
ethene into the relatively useless ethane. However, the same reaction will happen with any
compound containing a carbon-carbon double bond.
One important industrial use is in the hydrogenation of vegetable oils to make margarine,
which also involves reacting a carbon-carbon double bond in the vegetable oil with hydrogen
in the presence of a nickel catalyst.
Ethene molecules are adsorbed on the surface of the nickel. The double bond between the
carbon atoms breaks and the electrons are used to bond it to the nickel surface.

Hydrogen molecules are also adsorbed on to the surface of the nickel. When this happens, the
hydrogen molecules are broken into atoms. These can move around on the surface of the
nickel.

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If a hydrogen atom diffuses close to one of the bonded carbons, the bond between the carbon
and the nickel is replaced by one between the carbon and hydrogen.

That end of the original ethene now breaks free of the surface, and eventually the same thing
will happen at the other end.

As before, one of the hydrogen atoms forms a bond with the carbon, and that end also breaks
free. There is now space on the surface of the nickel for new reactant molecules to go through
the whole process again.

3.3.2.2

Catalytic converters

Catalytic converters change poisonous molecules like carbon monoxide and various nitrogen
oxides in car exhausts into more harmless molecules like carbon dioxide and nitrogen. They
use expensive metals like platinum, palladium and rhodium as the heterogeneous catalyst.
The metals are deposited as thin layers onto a ceramic honeycomb. This maximises the
surface area and keeps the amount of metal used to a minimum.
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20

Taking the reaction between carbon monoxide and nitrogen monoxide as typical:

Catalytic converters can be affected by catalyst poisoning. This happens when something
which isn't a part of the reaction gets very strongly adsorbed onto the surface of the catalyst,
preventing the normal reactants from reaching it.
Lead is a familiar catalyst poison for catalytic converters. It coats the honeycomb of
expensive metals and stops it working.
In the past, lead compounds were added to petrol (gasoline) to make it burn more smoothly in
the engine. But you can't use a catalytic converter if you are using leaded fuel. So catalytic
converters have not only helped remove poisonous gases like carbon monoxide and nitrogen
oxides, but have also forced the removal of poisonous lead compounds from petrol.
3.3.2.2.1

The use of vanadium(V) oxide in the Contact Process

During the Contact Process for manufacturing sulphuric acid, sulphur dioxide has to be
converted into sulphur trioxide. This is done by passing sulphur dioxide and oxygen over a
solid vanadium(V) oxide catalyst.

This example is slightly different from the previous ones because the gases actually react
with the surface of the catalyst, temporarily changing it. It is a good example of the ability of
transition metals and their compounds to act as catalysts because of their ability to change
their oxidation state.
The sulphur dioxide is oxidised to sulphur trioxide by the vanadium(V) oxide. In the process,
the vanadium(V) oxide is reduced to vanadium(IV) oxide.

The vanadium(IV) oxide is then re-oxidised by the oxygen.

This is a good example of the way that a catalyst can be changed during the course of a
reaction. At the end of the reaction, though, it will be chemically the same as it started.

3.4

Homogeneous catalysis

This has the catalyst in the same phase as the reactants. Typically everything will be present
as a gas or contained in a single liquid phase. The examples contain one of each of these . . .

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3.4.1 Examples of homogeneous catalysis


3.4.1.1 The reaction between Persulphate ions and iodide ions
This is a solution reaction that you may well only meet in the context of catalysis, but it is a
lovely example!
Persulphate ions (peroxodisulphate ions), S2O82-, are very powerful oxidizing agents. Iodide
ions are very easily oxidized to iodine. And yet the reaction between them in solution in
water is very slow.
If you look at the equation, it is easy to see why that is:

The reaction needs a collision between two negative ions. Repulsion is going to get seriously
in the way of that!
The catalyzed reaction avoids that problem completely. The catalyst can be either iron(II) or
iron(III) ions which are added to the same solution. This is another good example of the use
of transition metal compounds as catalysts because of their ability to change oxidation state.
For the sake of argument, we'll take the catalyst to be iron(II) ions. As you will see shortly, it
doesn't actually matter whether you use iron(II) or iron(III) ions.
The persulphate ions oxidize the iron(II) ions to iron(III) ions. In the process the persulphate
ions are reduced to sulphate ions.

The iron(III) ions are strong enough oxidizing agents to oxidize iodide ions to iodine. In the
process, they are reduced back to iron(II) ions again.

Both of these individual stages in the overall reaction involve collision between positive and
negative ions. This will be much more likely to be successful than collision between two
negative ions in the uncatalyzed reaction.
What happens if you use iron(III) ions as the catalyst instead of iron(II) ions? The reactions
simply happen in a different order.

3.4.1.2

The destruction of atmospheric ozone

This is a good example of homogeneous catalysis where everything is present as a gas.


Ozone, O3, is constantly being formed and broken up again in the high atmosphere by the
action of ultraviolet light. Ordinary oxygen molecules absorb ultraviolet light and break into
individual oxygen atoms. These have unpaired electrons, and are known as free radicals.
They are very reactive.

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22

The oxygen radicals can then combine with ordinary oxygen molecules to make ozone.

Ozone can also be split up again into ordinary oxygen and an oxygen radical by absorbing
ultraviolet light.

This formation and breaking up of ozone is going on all the time. Taken together, these
reactions stop a lot of harmful ultraviolet radiation penetrating the atmosphere to reach the
surface of the Earth.
The catalytic reaction we are interested in destroys the ozone and so stops it absorbing UV in
this way.
Chlorofluorocarbons (CFCs) like CF2Cl2, for example, were used extensively in aerosols and
as refrigerants. Their slow breakdown in the atmosphere produces chlorine atoms - chlorine
free radicals. These catalyse the destruction of the ozone.
This happens in two stages. In the first, the ozone is broken up and a new free radical is
produced.

The chlorine radical catalyst is regenerated by a second reaction. This can happen in two
ways depending on whether the ClO radical hits an ozone molecule or an oxygen radical.
If it hits an oxygen radical (produced from one of the reactions we've looked at previously):

Or if it hits an ozone molecule:

Because the chlorine radical keeps on being regenerated, each one can destroy thousands of
ozone molecules.

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3.5

Autocatalysis
3.5.1 The oxidation of ethanedioic acid by manganate(VII) ions

In autocatalysis, the reaction is catalysed by one of its products. One of the simplest examples
of this is in the oxidation of a solution of ethanedioic acid (oxalic acid) by an acidified
solution of potassium manganate(VII) (potassium permanganate).

The reaction is very slow at room temperature. It is used as a titration to find the
concentration of potassium manganate(VII) solution and is usually carried out at a
temperature of about 60C. Even so, it is quite slow to start with.
The reaction is catalysed by manganese(II) ions. There obviously aren't any of those present
before the reaction starts, and so it starts off extremely slowly at room temperature. However,
if you look at the equation, you will find manganese(II) ions amongst the products. More and
more catalyst is produced as the reaction proceeds and so the reaction speeds up.
You can measure this effect by plotting the concentration of one of the reactants as time goes
on. You get a graph quite unlike the normal rate curve for a reaction.
Most reactions give a rate curve which looks like this:

Concentrations are high at the beginning and so the reaction is fast - shown by a rapid fall in
the reactant concentration. As things get used up, the reaction slows down and eventually
stops as one or more of the reactants are completely used up.

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24

An example of autocatalysis gives a curve like this:

You can see the slow (uncatalyzed) reaction at the beginning. As catalyst begins to be formed
in the mixture, the reaction speeds up - getting faster and faster as more and more catalyst is
formed. Eventually, of course, the rate falls again as things get used up.

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4
4.1

Principles of heterogeneous catalysis

About 90% of all industrial processes involve heterogeneous catalysis, the catalyst being
typically a solid while the reactants are in gas or in the liquid phase. The advantage compared
to homogeneous catalysts is that they are easier to prepare, handle and separate from the
reaction mixture. The catalytic process is run inside a reactor typically operated with
continuous flow under steady-state conditions. The rate is determined, apart from the nature
of the catalytically active surface, by external parameters like temperature, partial pressures
and flow rate.
Usually heterogeneous catalysts consist of fine, often Nano sized, powders supported on
nominally inert oxide substrates (Alumina, MgO,...) which exhibit all possible
crystallographic faces. The catalyst is often a metal to which chemical and structural
promoters or poisons are added to enhance the efficiency and /or the selectivity.
A catalytic reaction is said to be homogeneous if the catalyst is in the same phase as the
reactants Examples:
1. the molecule chlorine-tris(triphenylphosphine)-rodium(I) [RhCl(PPh3)3] is added to
alkene solutions for hydrogenation reactions (Wilkinson catalyst)
2. Nickel(IV) acetylacetonate (benzene synthesis)
3. Dicarbonyl diiodine-iridium(III) (acetic acid synthesis, Cativa process)
4. di-cobalt(II) Octacarbonyl (hydroformylation of akenes to aldehydes)
A classic example are the iron powders used in the Haber process to enable the reaction of H
and N to NH . The H2 N2 NH3. triple bond between the nitrogen atoms in the N2 molecules is
then broken by dissociative chemisorption.
A catalytic reaction is said to be heterogeneous if the catalyst is in a different phase than the
reactants, e.g. when the reactants chemisorb on a solid surface. The weakening of the internal
bonds makes the formation of new bonds with other molecules easier. The product must have
a lower affinity with the catalyst in order to be released into the gas phase (desorption).
Other Examples:
1) Pt/Rh (Ostwald process for the production of nitric acid)
2) Titanium tetrachloride and an organometallic composite of Al (Ziegler- Natta process
for polymerization)
3) Chromium oxide for the Phillips process for the polymerization of ethylene to
polyethylene.
4) Zeolite ZSM-5 for hydrocarbon conversion.

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26

An example of heterogeneous catalysis from everyday life is the automobiles


catalytic converter transforming poisonous gases like carbon monoxide and nitrogen
oxides, generated from the combustion of gasoline, into much less
dangerous molecules like carbon dioxide and nitrogen.

The catalyst is composed by a thin metal film of Pt, Pd and Rh deposited on a ceramic
surface. In this way the amount of expensive metal is minimized and the active
surface maximized allowing to keep down costs at an affordable
level.

The catalyst causes the


dissociative adsorption of
NO. The N atoms recombine
to N2 which desorbs. The O
atoms react with adsorbed
CO yielding CO2 which
desorbs, too.

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28

Industrial catalysis is still governed by empirical experience. The single crystal surfaces
studied under ultra-high vacuum conditions, necessarily differ from the real catalysis
conditions. One speaks in particular of material and pressure gaps. The material gap can be
bridged by studying the reaction for different single crystal surfaces including surfaces with
well-defined defects such as monoatomic steps or using particles with uniform particle size.
Analysis of the catalyst composition enables the deliberate modification of the chemical
composition studying the way in which the reaction digs its own bed.
The reaction rate is determined by the surface concentration of the reactants and by barriers
to the adsorption which determine the pressure gap. It can be bridged using lower
temperatures to increase the surface coverage and supersonic molecular beams to study the
high energy tail of the Boltzmann distribution of the reactants

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4.2

CLASSIFICATION OF REACTION MECHANISMS

A(gas)+B(gas) C(gas)+(D(ad) or D(gas))

Langmuir-Hinshelwood: both reactants are adsorbed at the surface and the reaction occurs
between surface species
A(gas)+B(gas)A(ad)+B(ad)
A(ad)+B(ad) Cg+ D(ad) (or D)
Four processes are involved: adsorption of A and B at the surface diffusion of A(ad) and
B(ad) reaction between A(ad) and B(ad) desorption of C Example: Haber-Bosch synthesis of
NH ;
Eley-Rideal: only one reactant has to be adsorbed at the
surface
A(gas)A(ad)
B(gas)+A(ad) C +D (ad) (or D)
Example: H(g) +D/Cu(111) HD
H+Dad
HD energy balance: E(HD)=Ediss(HD)+Ekin(H) + Eads(D)=2.3 eV on Cu(111) This energy
is carried away by the products of the reaction which keep memory of the velocity of the
impinging H atoms On Ni(110), however, also D2 is formed indicating that part of the
impinging H ends up in a translationally hot precursorwhich may transfer its energy to the D
atoms which then react by collision with other D ad atoms.
3

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4.3

Coadsorption

In the limit in which one can assume that the mutual


interaction of the reactants acts pairwise and
independently with interaction energies: AA , AB ,

BB one has: If AA + BB - 2AB <0 the two species


will repel each other and one has competitive
adsorption If AA + BB - 2AB >0 the two species will
attact each other and one has cooperative adsorption
Competitive adsorption may inhibit the sticking
probability of one of the reactants, which may be
enhanced adding a promoter (electropositive atoms
like alkali atoms) .

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4.4

Poisons and Promoters

Typically electronegative species act as poisons, electropositive species as


promoters
CO methanation on Ni (powders as well as supported clusters). Sulphur attenuates the
catalytic activity of Ni, 10 sites deactivated per S atom Two possibilities:
1) S blocks 10 sites and the reaction sequence needs for a critical step of the reaction
2) S has an electronic effect which extends on nearest neighbor sites
a. If holds changing the poison has little effect,
b. if holds a less electronegative adsorbate has a smaller effect
phosphorus is less poisoning than S electronic effect

4.5

Electropositive impurities:

Potassium may accelerate certain steps in a reaction. CO methanation over Ni occurs by CO


dissociation and subsequent reaction of the carbidic carbon produced with H. The carbidic C
coverage saturates at 50% of a ML. Large H2 pressure needed to find sites where to
dissociate.
The presence of K does not modify the reaction barrier, but 0.1% of K increase the carbon
coverage in working conditions from 0.1 ML to 0.3 ML on Ni(100).
The reaction is poisoned above T=650 K since carbidic carbon coalesces into unreactive
graphite.
Structural Promoter:
Adsorbate which modifies
the surface structure to
make it more or less
reactive .

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4.6

Determination of the Reaction Rate


a.

Power laws

a b
r
Partial pressure of reactants pi and products j = k pA pB useful approach but contains still
no information about the progress of the reaction
b.
Attempt to describe the elementary steps: Langmuir approach
The various steps of the reaction are described in terms of rate equations for adsorption ,
desorption and surface reaction. If adsorption and desorption processes are fast then the
partial coverages of the reactants are related to the relative partial pressures through
adsorption isotherms.
This approach may look hopeless given the various structural elements of a real catalyst.
However, it works, and the reason why it works is the same of why catalysts are robust and
can stand a wide range of operative conditions

For constant T the reaction passes through a maximum since A blocks


the sites for the adsorption of B
c.
c) Micro kinetics parameters obtained by DFT calculations of the elementary
steps involved
d.
d) Kinetic Monte Carlo: takes into account the actual neighborhood of the
adsorbed particle detailed insight but heavy computational effort.

Selectivity
A catalyst may lead to different products which then need to be separated. The selectivity
towards one particular reaction channel is thus often more valuable than the overall reactivity.
the desired product it must then be interrupted at such point The reaction has two branches
characterized by reaction rates r1 and r2.
The selectivity is then s1= r1 / (r1 + r2 ) and can be affected by poisoning one of the pathways
Ostwald process: Ammonia oxidation for the production of Nitric acid In industry the catalyst
is Pt based and used at T>1000 K Surface science demostrated that the reaction may work at
T=500 K on RuO2 .

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5
5.1.

Heterogeneous industrial catalysis Examples

The most common examples of heterogeneous catalysis in industry involve the reactions of
gases being passed over the surface of a solid, often a metal, a metal oxide or a zeolite (Table
1).
Process
Making ammonia
Making synthesis gas
(carbon monoxide and
hydrogen)
Catalytic cracking of gas
oil

Catalyst
Iron
Nickel

Equation

Zeolite

Produces:
a
gas
(e.g.
a
liquid
a residue (e.g. fuel oil)

Reforming of naphtha

Platinum
and
rhenium
on
alumina
Silver on alumina

Making epoxyethane
Making sulfuric acid
Making nitric acid

ethene,

propene)
(e.g.petrol)

Vanadium(V)
oxide on silica
Platinum
and
rhodium

Table 1 Examples of industrial processes using heterogeneous catalysis.


The gas molecules interact with atoms or ions on the surface of the solid. The first process
usually involves the formation of very weak intermolecular bonds, a process known as
physisorption, followed by chemical bonds being formed, a process known as chemisorption.
Physisorption can be likened to a physical process such as liquefaction. Indeed the enthalpy
changes that occur in physisorption are ca -20 to -50 kJ mol-1, similar to those of enthalpy
changes when a gas condenses to form a liquid. The enthalpies of chemisorption are similar
to the values found for enthalpies of reaction. They have a very wide range, just like the
range for non-catalytic chemical reactions.
An example of the stepwise processes that occur in heterogeneous catalysis is the oxidation
of carbon monoxide to carbon dioxide over palladium. This is a very important process in
everyday life. Motor vehicles are fitted with catalytic converters. These consist of a metal

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34

casing in which there are two metals, palladium and rhodium, dispersed very finely on the
surface of a ceramic support that resembles a honeycomb of holes. The converter is placed
between the engine and the outlet of the exhaust pipe.
The exhaust gases contain carbon monoxide and unburned hydrocarbons that react with the
excess oxygen to form carbon dioxide and water vapour, the reaction being catalyzed
principally by the palladium:

The exhaust gases also contain nitrogen(II) oxide (nitric oxide, NO), and this is removed by
reactions catalyzed principally by the rhodium:

The accepted mechanism for the oxidation of carbon monoxide to carbon dioxide involves
the chemisorption of both carbon monoxide molecules and oxygen molecules on the surface
of the metals. The adsorbed oxygen molecules dissociate into separate atoms of oxygen. Each
of these oxygen atoms can combine with a chemisorbed carbon monoxide molecule to form a
carbon dioxide molecule. The carbon dioxide molecules are then desorbed from the surface
of the catalyst. A representation of these steps is shown in Figure 1.

Figure 1 A mechanism for the oxidation of carbon monoxide.


Each of these steps has a much lower activation energy than the homogeneous reaction
between the carbon monoxide and oxygen.
The removal of carbon monoxide, unburned hydrocarbons and nitrogen(II) oxide from car
and lorry exhausts is very important for this mixture leads to photochemical smogs which
aggravate respiratory diseases such as asthma.

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35

Platinum, palladium and rhodium are all used but are very expensive metals and indeed each
is more expensive than gold. Recently, much work has been devoted to making catalysts with
very tiny particles of the metals, an example of the advances being made by nanotechnology.
It is not simply the ability of the heterogeneous catalyst's surface to interact with the reactant
molecules, chemisorption, that makes it a good catalyst. If the adsorption is too exothermic,
i.e. the enthalpy of chemisorption is too high, further reaction is likely to be too endothermic
to proceed. The enthalpy of chemisorption has to be sufficiently exothermic for
chemisorption to take place, but not so high that it does not allow further reaction to proceed.
For example, in the oxidation of carbon monoxide, molybdenum might at first sight be
favoured as a choice, as oxygen is readily chemisorbed by the metal. However, the resulting
oxygen atoms do not react further as they are too strongly adsorbed on the surface. Platinum
and palladium, on the other hand, have lower enthalpies of chemisorption with oxygen, and
the oxygen atoms can then react further with adsorbed carbon monoxide.
Another point to consider in choosing a catalyst is that the product must not be able to adsorb
too strongly to its surface. Carbon dioxide does not adsorb strongly on platinum and
palladium and so it is rapidly desorbed into the gas phase.
A testimony to the importance of catalysis today is the award of the Nobel Prize in Chemistry
in 2007 to Gerhard Ertl for his work in elucidating, amongst other processes, the mechanism
for the synthesis of ammonia (the Haber Process):

Ertl obtained crucial evidence on how iron catalyses the dissociation of the nitrogen
molecules and hydrogen molecules leading to the formation of ammonia
(Figure 2):

Figure 2 A mechanism for the catalytic synthesis of ammonia.


Figure 3 shows how the activation energy barriers are much lower than the estimated
activation energy barrier (which would be at least 200 kJ mol1) for the uncatalysed synthesis
of ammonia.

Some Of General Types Of Catalyst

36

Figure 3 The activation energy barriers for the reactions occurring during the catalytic
synthesis of ammonia.

5.2.

General requirements for a heterogeneous catalyst

To be successful the catalyst must allow the reaction to proceed at a suitable rate under
conditions that are economically desirable, at as low a temperature and pressure as possible.
It must also be long lasting. Some reactions lead to undesirable side products. For example in
the cracking of gas oil, carbon is formed which is deposited on the surface of the catalyst, a
zeolite, and leads to a rapid deterioration of its effectiveness. Many catalysts are prone to
poisoning which occurs when an impurity attaches itself to the surface of the catalyst and
prevents adsorption of the reactants. Minute traces of such a substance can ruin the process,
One example is sulfur dioxide, which poisons the surface of platinum and palladium. Thus all
traces of sulfur compounds must be removed from the petrol used in cars fitted with catalytic
converters.
Further, solid catalysts are much more effective if they are finely divided as this increases the
surface area.

Some Of General Types Of Catalyst

37

Figures 4 and 5 Two ways by which the surface area of a catalyst can be increased.
In Figure 4, the platinum-rhodium alloy (used in the manufacture of nitric acid) is in the form of very fine
wire that has been woven to construct a gauze.
By kind permission of Johnson Matthey.
In Figure 5, vanadium(V) oxide (used in the manufacture of sulfuric acid) has been produced in a
'daisy'shape.
By kind permission of Haldor Topse A/S.

At high temperatures, the particles of a finely divided


catalyst tend to fuse together and the powder may 'cake',
a process known as sintering. This reduces the activity
of the catalyst and steps must be taken to avoid this. One
way is to add another substance, known as a promoter.
When iron is used as the catalyst in the Haber Process,
aluminum oxide is added and acts as a barrier to the
fusion of the metal particles. A second promoter is
added, potassium oxide, that appears to cause the
nitrogen atoms to be chemisorbed more readily, thus
accelerating the slowest step in the reaction
scheme. Figure 6 A platinum-rhodium gauze is used as
a catalyst in the reaction between ammonia and methane
to produce hydrogen cyanide, an intermediate in the
production of methyl 2-methylpropenoate. The gauze
operates at 1270 K and is thus glowing. The photograph
was taken though a sight glass located on the reactor.

5.3.

Aluminium oxide, silicon dioxide, aluminosilicates and zeolites

One of the most important reactions in which aluminium oxide, Al2O3, (often referred to as
alumina) takes part in an industrial reaction is in platforming, in which naphtha is reformed
over aluminina impregnated with platinum or rhenium. Both the oxide and the metals have
catalytic roles to play, an example of bifunctional catalysis. There are hydroxyl groups on the
surface of alumina which are, in effect, sites which are negatively charged to which a
hydrogen ion is attached that can act as an acid catalyst.

Some Of General Types Of Catalyst

38

Silicon dioxide (silica) is another acidic oxide used in industry. It becomes particularly active
if it has been coated with an acid (such as phosphoric acid), thereby increasing the number of
active acidic sites. For example, the manufacture of ethanol is achieved by the hydration of
ethene using silica, coated with phosphoric acid:

The mechanism involves the formation of a carbocation (Figure 7):

Figure 7 A mechanism for the hydration of ethene to ethanol.


Aluminosilicates are also used as catalysts when an acid site is required. These are made from
silicon dioxide (silica) and aluminium oxide. They contain silicate ions, SiO44- that have a
tetrahedral structure which can be linked together in several ways. When some of the Si
atoms are replaced with Al atoms, the result is an aluminosilicate. Hydrogen ions are again
associated with the aluminium atoms:

Some Of General Types Of Catalyst

39

5.3.1. Zeolite catalysts


A particular class of aluminosilicates that has excited huge interest in recent years is the
zeolites. There are many different zeolites because of the different ways in which the atoms
can be arranged. Their structure of silicate and aluminate ions can have large vacant spaces in
three dimensional structures that give room for cations such as sodium and calcium and
molecules such as water. The spaces are interconnected and form long channels and pores
which are of different sizes in different zeolites.

Figure 8 The structure of a zeolite (example figure)

A zeolite which is commonly used in many catalytic reactions is ZSM-5 which is prepared
from sodium aluminate (a solution of aluminium oxide in aqueous sodium hydroxide) and a
colloidal solution of silica, sodium hydroxide, sulfuric acid and tetrapropylammonium
bromide.
It is, for example, a very effective catalyst for the conversion of methylbenzene (toluene) to
the three dimethylbenzenes (xylenes). Alas, the mixture produced only contains about 25%
1,4-dimethylbenzene, (p-xylene) the isomer needed for the manufacture of the polyesters and
the rest, 1,2- (o-xylene) and 1,3-dimethylbenzenes (m-xylene), is not wanted in such large
quantities.

Some Of General Types Of Catalyst

40

However, if the zeolite is washed with phosphoric acid and heated strongly, minute particles
of phosphorus(V) oxide are deposited on the surface making the pores slightly smaller. This
restricts the diffusion of the 1,2- and 1,3-isomers and they are held in the pores until they are
converted into the 1,4-isomer and can escape (Figure 9).
This remarkable selectivity enables the yield of the 1,4-isomer to be increased from 25% to
97%.

Figure 9 A zeolite acting as a molecular sieve and a catalyst during


the formation of 1,4-dimethylbenzene from methylbenzene.

Some Of General Types Of Catalyst

41

The ability of the zeolite to adsorb some molecules and to reject others gives it the ability to
act as a molecular sieve. For example, in the manufacture of ethanol from ethene or from
biomass, an aqueous solution of ethanol is produced, in which there is 4% water still present
even after repeated distillations. Further purification of ethanol requires the use of a zeolite
which absorbs the water preferentially. Table 2 gives examples of industrial processes
involving zeolites.
Process
Catalytic cracking of gas oil

Catalyst
Zeolite

Equation

Produces:
a gas (e.g. ethene, propene)
a liquid (e.g.petrol)
a residue (e.g. fuel oil)

Reforming of naphtha

Disproportionation
methylbenzene

Dealkylation
methylbenzene
Making
cumene
methylethyl)benzene<

Platinum
rhenium
zeolite
of Zeolite

and
on

of Zeolites

(1- Zeolite
5)

(ZSM-

Table 2 Examples of industrial processes using zeolites.

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42

6
6.1.

Whats Homogeneous catalysis ?

In chemistry, homogeneous catalysis is catalysis in a solution by a soluble catalyst. Strictly


speaking, homogeneous catalysis are catalytic reactions where the catalyst is in the same
phase as the reactants, so homogeneous catalysis applies to reactions in the gas phase and
even in a solid. Heterogeneous catalysis is the alternative to homogeneous catalysis, where
the catalysis occurs at the interface of two phases, typically gas-solid. The term is used
almost exclusively to describe solutions and it is often implies catalysis by organometallic
compounds. The area is one of intense research and many practical applications, e.g., the
production of acetic acid. Enzymes are examples of homogeneous catalysts.

6.2.

Acid catalysis

The proton is the most pervasive homogeneous catalyst because water is the most common
solvent. Water forms protons by the process of self-ionization of water. In an illustrative case,
acids accelerate (catalyze) the hydrolysis of esters:
CH3CO2CH3 + H2O

CH3CO2H + CH3OH

In the absence of acids, aqueous solutions of most esters do not hydrolyze at practical rates.

6.3.

Organometallic chemistry

Processes that utilize soluble organometallic compounds as catalysts fall under the category
of homogeneous catalysis, as opposed to processes that use bulk metal or metal on a solid
support, which are examples of heterogeneous catalysis. Some well-known examples of
homogeneous catalysis include hydroformylation and transfer hydrogenation, as well as
certain kinds of Ziegler-Natta polymerization and hydrogenation. Homogeneous catalysts has
also been used in a variety of industrial processes such as the Wacker process Acetaldehyde
(conversion of ethylene to acetaldehyde) as well as the Monsanto process and the Cativa
process for the conversion of MeOH and CO to acetic acid.
Many non-organometallic complexes are also widely used in catalysis, e.g. for the production
of terephthalic acid from xylene.

Some Of General Types Of Catalyst

43

6.4.

Other forms of homogeneous catalysis

Enzymes are homogeneous catalysts that are essential for life but are also harnessed for
industrial processes. A well-studied example carbonic anhydrase, which catalyzes the release
of CO2 into the lungs from the blood stream.

6.4.1. Contrast with heterogeneous catalysis


Homogeneous catalysis differs from heterogeneous catalysis in that the catalyst is in a
different phase than the reactants. One example of heterogeneous catalysis is the
petrochemical alkylation process, where the liquid reactants are immiscible with a solution
containing the catalyst. Heterogeneous catalysis offers the advantage that products are readily
separated from the catalyst, and heterogeneous catalysts are often more stable and degrade
much slower than homogeneous catalysts. However, heterogeneous catalysts are difficult to
study, so their reaction mechanisms are often unknown.
Enzymes possess properties of both homogeneous and heterogeneous catalysts. As such, they
are usually regarded as a third, separate category of catalyst.

Some Of General Types Of Catalyst

44

7
7.1.

Homogeneous industrial catalysis Examples

Homogeneous catalysts are less frequently used in industry than heterogeneous catalysts as,
on completion of the reaction, they have to be separated from the products, a process that can
be very expensive.
Manufacture
Ethane-1,2-diol

Catalyst
Sulfuric acid

Equation

2,2,4-Trimethylpentane Hydrogen fluoride


(iso-octane)

Phenol and propanone

Sulfuric acid

Bisphenol A

Sulfuric acid

Table 3 Examples of industrial processes using homogeneous catalysis.


However, there are several important industrial processes that are catalyzed homogeneously,
often using an acid or base (Table 3).
One example is in the manufacture of ethane-1,2-diol from epoxyethane where the catalyst is
a trace of acid:

Some Of General Types Of Catalyst

45

Figure 12 A mechanism for the formation of ethane-1,2-diol from epoxyethane.


In the mechanism for this reaction a hydrogen ion is added at the start, and lost at the end.
The hydrogen ion functions as a catalyst.
Two other examples are concerned with the production of 2,2,4-trimethylpentane from 2methylpropene, again using an acid as the catalyst. One uses 2-methylpropane (Table 3)
which yields the alkane directly. The other uses only 2-methylpropene.
The mechanism of the reaction also involves the addition of a hydrogen ion to a reactant
(Figure 13).

Figure 13 Part of a mechanism for the formation of 2,4,4-trimethyl-2-pentene from 2methylpropene.


The alkene is then hydrogenated, using nickel as the catalyst, to 2,2,4-trimethylpentane
(isooctane):

Some Of General Types Of Catalyst

46

2,2,4-trimethylpentane is often added to petrol to enhance its anti-knock properties, now that
methyl t-butyl ether (MTBE) is being phased out.

Some Of General Types Of Catalyst

47

8
8.1.

Whats Biocatalysis

Biocatalysis can be broadly defined as the use of biological molecules (usually enzymes) to
catalyse specific chemical reactions. Enzymes are complex protein molecules. They are
produced by living organisms to catalyse the biochemical reactions required for life.
Although enzymes are formed within living cells, they can continue to function in vitro (in
the test-tube) and their ability to perform very specific chemical transformations is making
them increasingly useful in industrial processes. Biocatalysis is a major part of
biotechnology. Biotechnology is defined by the European Federation of Biotechnology as
.the integration of natural sciences and organisms, cells, parts thereof, and molecular
analogues for products and services. which can be translated from legalese to .a technology
which employs practical applications of living organisms or the components of living
organisms.. Biotechnology is not a single field and there is danger viewing it as a unified
body of scientific knowledge. It is multi-disciplinary and has its roots in many areas a
smorgasbord of subjects including: engineering, chemistry, plant and animal biology,
microbiology, immunology and many more. Industrial Biotechnology encompasses to
varying degrees the life sciences, chemistry and engineering and it is now being applied so
widely that it has even made skirmishes into such unlikely territories as the manufacture of
silicon chips and gold mining.
Biotechnogy is almost as old as history, people having used it to make sourdough, alcoholic
beverages, vinegar, yoghurt and cheese as far back as 700 BC. It came of age in the 19th
century when Louis Pasteur discovered that it was yeast which converted sugars to ethanol
and that bacteria caused spoilage by converting ethanol to acetic acid. War brought further
advances - the conversion of sugar into glycerol for making nitroglycerine in Germany in
World War 1, and turning it into acetone and butanol in Britain in World War 2.
At present, only about 20 enzymes are produced on a truly industrial scale. These enzymes
are made by 35 producers with 4 major companies holding 75% of the market. In 1992, the
market value of these enzymes was approximately US$800 million with a predicted yearly
increase of around 10-15%. The market is highly competitive, suffers from overcapacity, has
small profit margins and is technologically intensive. Nonetheless, there is room for growth
as long as new markets can be found. A breakdown of enzyme production and their uses is
given in Table 1 Industrial .

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48

8.2.

Definition

Biocatalysis can be broadly defined as the use of biological molecules (usually enzymes) to
catalyse specific chemical reactions. Enzymes are complex protein molecules. They are
produced by living organisms to catalyse the biochemical reactions required for life.
Although enzymes are formed within living cells, they can continue to function in vitro (in
the test-tube) and their ability to perform very specific chemical transformations is making
them increasingly useful in industrial processes.

Most of us use biocatalysis around the home - often without realizing. If you use .biological
detergents or contact lens cleaners, or even cook ham with pineapple you are using
biocatalysis. In each one of these actions you are applying a proteinase enzyme to hydrolyze

Some Of General Types Of Catalyst

49

a protein substrate. If you make home-made bread, you are also using biocatalysis. Many
commercial preparations of yeast include a purified xylanase, an enzyme that partially breaks
down the hemicellulose polymer xylan that can make bread heavy, and the yeast itself,
Saccharomyces cerevisiae, uses its own -and -amylases to hydrolyze the starch in the flour.
Next the yeast converts the sugars to ethanol and CO2 and the CO2 that makes the bread rise.
Biocatalysis is also found in industry most commonly in food production and processing.
Familiar examples are cheese, yoghurt, beer and wine production, but also many food
additives and sugars are produced by enzymes. In the past, many sectors of the chemical
industry were more restrained in embracing this technology, largely because enzymes were
perceived as being too delicate to survive the extreme conditions in the reaction vessels.
Many enzymes have very specific requirements of pH and temperature before they will
function and more often than not, these requirements are quite different from those for which
an industrial plant was designed. But attitudes are changing. A new awareness of the diversity
of microbial life has pushed microbiology from a rather academic subject to the fore-front of
biotechnology. We now know that some microorganisms can produce enzymes which can
survive and function in extreme conditions. Whats more, we are not short of new candidates.
It is estimated that less than 1% of all known micro-organisms have so far been identified:
there are probably in excess of 50 million bacterial species still undiscovered*! We are no
longer forced to change industry to accommodate an enzyme; research and development now
focuses on finding enzymes which will function in existing industrial processes. Find a
natural environment which resembles the conditions in your reaction vessel, and with luck, it
will contain many organisms that produce enzymes which fit your needs.
In this article we will focus on biocatalysis and look at a single case study; the application of
enzymes in the pulp and paper industry. But first, we will take a broader view of
biotechnology, its history and its structure.

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50

8.3. BIOTECHNOLOGY
8.3.1. What is biotechnology?
Biotechnology is defined by the European Federation of Biotechnology as .the integration of
natural sciences and organisms, cells, parts thereof, and molecular analogues for products and
services. which can be translated from legalese to .a technology which employs practical
applications of living organism or the components of living organisms..
Biotechnology is not is single field and there is danger viewing it as a unified body of
scientific knowledge. It is multi-disciplinary and has its roots in many areas - a smorgasbord
of subjects including: engineering, chemistry, plant and animal biology, microbiology,
immunology and many more (see figure 1). Industrial Biotechnology encompasses to varying
degrees the life sciences, chemistry and engineering and it is now being applied so widely
that it has even made skirmishes into such unlikely territories as the manufacture of silicon
chips and gold mining.

The word .biotechnology. may be a relatively new addition to the English language, but the
application has been around for many years. Micro-organisms have been used for millennia
in the production of beer, wine, vinegar, yoghurt and cheese. The Egyptians, Sumerians and
Babylonians produced alcoholic beverages from barley, and the Greek epic poems The Iliad
and The Odyssey, written around 700 BC, both refer the uses of calf.s and kid.s stomachs
(sources of rennet) for the production of cheese. Sour dough bread appeared in Europe
around 800 BC and early Christian and Sanskrit writings describe fermented dairy products.
The first purified chemical to be produced by biotechnology was ethanol, which by the 14th
Century, was being produced to fortify wines and beers. Throughout the centuries, nobody
understood the underlying chemistry or even that living organisms were involved.
Biotechnology came of age in the 19th Century. French wine merchants were searching for a
way to prevent spoilage when their beers and wines were shipped over long distances. They
enlisted the help of Louis Pasteur who discovered that it was yeast converting the sugars to
ethanol and that spoilage was caused by bacteria which converted the ethanol to acetic acid.
Pasteur developed the method of .Pasteurization. which kills the bacteria without spoiling the
Some Of General Types Of Catalyst

51

flavor. Not everybody was in agreement with Pasteur. He had a vocal adversary in the
chemist Justus Von Liebig who maintained it was nothing to do with living organisms but
fermentation was a simple chemical reaction. Both Von Liebig and Pasteur died before the
dispute was finally settled and in a way, they were both partly correct. In 1897, the Buchner
brothers proved that yeast extract could convert glucose to ethanol and CO2 without the need
for any living organisms. Such reactions were called .unorganized ferments. and William
Khne named the agents responsible for catalyzing the reactions .enzymes.. This wasn.t a
great leap in understanding, the word .enzyme. Meanwhile, a Japanese scientist named
Takamine was developing a fermentation process for industrial production of enzymes from
the fungus Aspergillus oryzae. The product, called .Takadiastase. was a mixture of amylases
and other glycolytic enzymes and although rather crude, Takadiastase production can claim
to be the true beginnings of enzyme technology.
(Takadiastase can still be purchased in many Eastern countries where it is considered an aid
to digestion). Shortly afterwards in Europe, the textile industry moved from chemicals to
enzymes for .desizing.. Size is starch which is added to strengthen the warp during weaving,
but once the fabric has been woven, the size must be removed. The first attempts used malt
extract or pancreas extract, but by 1917, the industry was converted to bacterial amylases
from Bacillus subtilis.
A rather less attractive traditional biotechnological process was .Bating. carried out by the
leather tanning industry. Bating is the method by which leather is rendered softer and more
pliable by the action of proteinases. The traditional source of these enzymes was dog and
pigeon faeces. To compound the unpleasantness, the breakdown of sulphur-containing
compounds in hair produced H2S gas. Your neighborhood took a sharp .nose.-dive if a
tannery moved in next door! The image of the tanning industry remained at rock-bottom until
the German industrial magnate Otto Rhm became convinced that the excrement contained
secretions from the digestive tract. He produced an extract of pancreas which seemed to work
well and he took this as confirmation of his theory. In fact, later experiments showed that it
wasn.t the animal enzymes at all but enzymes produced by bacteria living in the gut. Rhm
also brought us the first .biological. detergent which despite his 1913 patent, didn.t score a hit
for another 50 years. The early preparations, marketed under the brand name of Burnus had
limited success. The enzyme .pancreatin. (Trypsin) was not particularly active in the alkaline
conditions used in detergent washes. Modern detergents use bacterial alkaline serine
proteinases which are far more suited to high pHs.
As is often the case, it was war which provided the biggest impetus for the development of
biotechnology. During World War 1, a British naval blockade prevented Germany from
importing vegetable oils - the raw material for glycerol and hence nitroglycerine. In response
German biochemists developed a method using yeast grown in the presence of sodium
Bisulphite. Bisulphite blocks key enzymes in the biochemical pathway for the conversion of
sugars to alcohol and so the yeast is forced to use an alternative pathway which has glycerol
as its end product (see Figure 2).
Meanwhile on the other side, Britain was having difficulties in obtaining butanol and acetone
which were required for the production of explosives and rubber. Scientists turned to a
bacterium called Clostridium acetobutylicum which produces these two chemicals as
endproducts of its rather unusual biochemical utilisation of sugar. Unfortunately, C.
acetobutylicum also produces H2 gas and the combination of the two volatile solvents and
hydrogen resulted in a number of plants being destroyed by explosions. But despite its
hazards, the process proved so successful that it was used until the 1950s in Europe and the
last plants were only recently closed in South Africa which had limited access to raw
materials during the apartheid trade embargo.

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52

From the 1940s to the 1960s, the most dramatic developments came from the pharmaceutical
industry. New antibiotics were discovered and organisms were genetically altered to enhance
production. The first (and still the most successful) of these antibiotics was penicillin but
soon afterwards, pharmaceutical companies realized the utility (and profitability) of
antibiotics and so an intense research program was implemented. Streptomycin was isolated
from Streptomyces griseus and many hundreds of new antibiotics from filamentous bacteria
of the genus Actinomyces. The micro-organisms needed to be grown in large quantities
without contamination. New processes were developed such as the use of steam for
sterilisation, stirred tank bioreactors, aeration with sterile air and pressurization of bioreactors
which prevents the in-flow of contaminated air. In parallel, microbiologists were improving
the production organisms. The first strain of Penicillium produced only 2 mg of penicillin per
litre of culture. Today.s Penicillium strains produce in excess of 20g per litre - a 20,000-fold
improvement! By the 1960s the technology had developed sufficiently that plant and animal
cells could be cultured and now many viral vaccines are produced from animal tissue
cultures.

8.3.2. Liquid fuels


An expanding biotechnology is the production of ethanol as a liquid fuel. Ethanol has been
known as a fuel for many years. In fact the Model T Ford was originally designed for ethanol
and at around that time, ethanol was considered to be the obvious fuel for the future. It is
plentiful and cheap and whereas most fuels (petrol, diesel, natural gas etc.) are produced from
fossil hydrocarbons, ethanol is produced from renewable biological feedstock, such as
agricultural crops and forestry by-products. Furthermore, ethanol is safer, less polluting,
requires lower engine compression and less cooling. So why did petrol take over the market?
There are two key reasons: first, per kilometer petrol originally cost less, and second, the
large investments made by the oil and auto industries in capital, human skills and technology

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53

made the entry of a new industry difficult. However, in countries with a surplus agricultural
capacity, liquid fuels from biomass can be a viable alternative to petrochemicals.
The biggest fuel ethanol user is Brazil where approximately 3.2 billion gallons are made from
sugar cane for automotive use every year. Brazil began its ethanol program (called
.Proalcool.) in 1979, in an effort to use its sugar cane crops and to reduce dependence on oil
imports. Since then, many people cite the noticeable improvement in air quality as
justification for continuing the effort. Most of Brazils vehicles are fuelled by 22% ethanol
blends, and more than 4 million operate on 95% ethanol. Ten years ago, 96% of the cars sold
in Brazil were made to run solely on alcohol. Today the trend has reversed somewhat, mainly
because popular imported cars are not designed for ethanol. The down-turn is more indicative
of Brazil.s lonely pioneering rather than a failure of the technology.
In other countries, ethanol is used mainly as a fuel additive. In America, ethanol-blended
petrol accounts for about 9% of the sales. In a country as large as the USA (and a country so
dependent on the car) this is a significant amount, equating to 1.2 billion gallons - roughly the
entire Canadian consumption of petrol. Blending began in the USA in the late 1970.s and it is
estimated that over two trillion kilometers have been travelled using fuel ethanol blends.
Environmentally, ethanol blends have been shown to reducing carbon monoxide and nitrogen
dioxide emissions and in countries where the farming economy has slumped, the fuel market
has help to stabilize farmers. incomes. Fuel ethanol may be relatively old biotechnology, but
it is destined to have a large impact in the future.

8.3.3. The Starch industry


Enzymes have proved to be of great value in the starch industry for around 20 years. In the
1950s, fungal amylase was used to manufacture syrups that contained sugars which could not
be produced by conventional acid hydrolysis, but it was Amyloglucosidase which
revolutionized the industry in the 1960s. Amyloglucosidase can completely break down
starch into glucose and so within a few years, almost all glucose production converted from
chemical to enzyme hydrolysis. Among the benefits were: greater yield, higher degree of
purity and easier crystallization. The modern enzymes are more thermostable than their
predecessors and these are favored because starch is heated (liquefaction) to facilitate enzyme
hydrolysis and pumping. Since then, interest has widened to other enzymes; in particular
glucose isomerases. Using these enzyme, glucose containing an aldehyde group can be
converted into the corresponding ketone sugar, fructose. This has the same calorific value as
glucose, but is twice as sweet and hence less is needed - which is popular with dieters and
food manufacturers. Considering that starch is universally available, and frequently cheaper
than cane sugar and beet sugar, it makes economic sense to use High Fructose Corn Syrup
(HFCS) in many products where sugar has hitherto predominated.

8.3.4. BIOTECHNOLOGY TODAY


Biotechnology today extends from public and private companies and includes multi-national
corporations and governments. In 1996, the journal Nature Biotechnology estimated total
biotechnology revenue at around US$8.5 billion (give or take a million or two) with 230
public companies sharing in this income. However, if you include funding for Research and
Development, this figure is closer to US$30 billion. Despite the large figures for income,
many companies are still making an annual loss in this area because of their investment in R
& D, but clearly, the high level of investment reflects confidence in the technology. The

Some Of General Types Of Catalyst

54

processes involved in the production of a commodity by modern industrial biotechnology are


summarized as a flow diagram in Figure 3.

Details vary considerably from process to process but in all cases, the technology should be
able to compete with existing industries. Raw materials should be cheap and accessible and
preferably a waste product from another industry. The bioreactor itself may use whole
organisms (bacteria, fungi, plant, or animal cells) or enzymes. Energy input is required for
mechanical functions such as stirring, pumping and aeration, and as most Biocatalysis
reactions are exothermic, refrigeration is also required to prevent the organisms from being
cooked or the enzymes denatured. Sterility is critical - particularly with whole organisms.
Very often, organisms are genetically modified to enhance production levels and as the
modifications are not for benefit of the organism, they almost invariably produce strains
which are weaker and which are rapidly outgrown by their wild-type counterparts. With
traditional enzymes and the more familiar organisms, contamination is a considerable
problem but new, high-temperature enzymes and thermophilic organisms (which are
discussed later) can alleviate this by allowing processes to be run at temperatures where
common contaminating organisms cannot survive.

8.4.

Enzyme Technology

Enzyme-catalyzed processes are gradually replacing chemical processes in many areas of


industry. Enzymes have all the properties of true catalysts. In the presence of an appropriate
enzyme, a chemical reaction occurs at a much higher rate but the enzyme is not consumed by
the reaction. Their ability to perform very specific chemical transformations
(biotransformation) has made them increasingly popular in industries where less specific
chemical processes produce unwanted by-products. Purity and predicability are of particular
Some Of General Types Of Catalyst

55

importance in food manufacture where by-products may be harmful or affect flavour, and
because of their specificity, pharmaceutical companies favour biotransformations in the
development of novel therapeutic agents. In addition, enzymes are chiral catalysts which
means that they can be used to produce optically active, homochiral compounds of a kind that
are often difficult to make using traditional organic chemistry. Recently, a greater awareness
of conservation issues have forced industries with a history of polluting to consider
alternative, cleaner methods so there is now significant growth of biotechnology outside of
the pharmaceutical and food industries.
At present, only about 20 enzymes are produced on a truly industrial scale. These enzymes
are made by 35 producers with 4 major companies holding 75% of the market. In 1992, the
market value of these enzymes was approximately US$800 million with a predicted yearly
increase of around 10-15%. The market is highly competitive, suffers from over-capacity, has
small profit margins and is technologically intensive. Nonetheless, there is room growth as
long as new markets can be found. A breakdown of enzyme production and their uses is
given in Table 1.
Matching an enzyme with a process is the greatest challenge to a research and development
program. Often an industrial plant can be modified to accommodate the limitations of an
enzyme but this is costly and a better approach is to find an enzyme more suited to the
existing process. Increasingly, new organisms are being found living in unusual environments
and these are proving an excellent source of novel enzymes. Living organisms are now
generally divided into three groups (or domains): the Eukarya (still often called the
eukaryarotes), the Bacteria and the Archaea (or archaebacteria). The Eukarya, which include
all animals and plants are limited in their ability to withstand hostile conditions such as
extreme ranges of temperature or pH. Some worms that can live above 60_C have been found
living around deep ocean volcanic vents, but these are exceptional. Bacteria and Archaea are
not so constrained and can thrive in quite unbelievable conditions; from freezing to boiling
water and from an acidic pH 2 to alkaline pH 12. The record holder for temperature at present
is the wonderfully named Archaea Pyrococcus furiosa which grows optimally at around
113C and finds it too chilly if temperatures fall to 100C. These are the organisms of the
future for biotechnology. Many industrial processes are designed to run at elevated
temperatures where viscosity is reduced and chemical reactions are faster. By using enzymes
with optimal activities at these temperatures, changes to existing industrial plants can be
minimised. Furthermore problems with contamination are reduced, and less cooling is
required where the reactions are exothermic.
It was once thought that the .thermophiles. (Greek for .heat-lovers.) survived by having a
rapid turnover of cellular components. Nobody really believed that proteins or other
biomolecules could withstand such extremes of temperature. In the early 1980.s this theory
was proven to be largely incorrect. The macromolecules used by thermophilic organisms are
intrinsically heat-stable and optimally active at the same temperature as the environment in
which their owners grow. In fact, a close look at the reaction kinetics of biochemical
reactions above 100C suggest that it is us that are living in a hostile, frigid environment and
that the natural place for life is in boiling water. Where we have a large energy expenditure to
create macromolecules, in the chemical and physical environment of a geothermal hot pool
many of the same reactions are energetically favored (have a negative G) - it seems that
thermophiles actually gain energy when building the same molecules which cost us so much
to make. The properties of an .extremophiles. protein (such as thermal stability) are a direct
result of the proteins sequence of amino acids. This means that enzymes can be isolated and
purified and they will still function at high temperatures. The application of thermostable
biocatalysis is still relatively limited with most thermostable enzymes being used in the
detergent or starch industries. However, they are rapidly expanding into other areas and

Some Of General Types Of Catalyst

56

usurping their mesophilic (mid-temperature loving) counterparts. Outside of industry,


thermostable enzymes have specialized uses in medical diagnostics and molecular genetics
research. Perhaps the best example is a DNA polymerase isolated from Thermus aquaticus
which is used in the Polymerase Chain Reaction (PCR). The half-life of this enzyme is 40
minutes at 95C and so Taq DNA polymerase can be repeatedly heated during the DNA
denaturation steps of the reaction. PCR has so revolutionized molecular genetics that its
inventor, Kary Mullis, shared the Nobel Prize for Chemistry in 1993.
The way forward sounds fairly straightforward; find an organism growing at a suitable
temperature and extract its enzymes. Unfortunately it is not so simple. Many enzymes are
produced in very small quantities or the organisms that produce them are extremely difficult
grow in the laboratory. In fact with most micro-organisms, we still dont.t know how to grow
them at all. Even if suitable growth conditions can be found, many grow in such difficult
conditions (such as 110C, 2000 atmospheres pressure and in the total absence of oxygen) or
at such pitiful cell densities, that to extract as little as milligram of enzyme would be all but
impossible and yet kilograms or tons of enzyme are often needed by an large industrial
enduser. To the rescue came recombinant DNA technology or Genetic Engineering.

8.5.

Genetic Engineering

Genes are the fundamental basis of all life. The genetic code is similar to a computer program
but instead of using a binary code of .1.s and .0.s, the basis for the genetic code is the
chemical sequence within DNA (deoxyribonucleic acid). DNA is heteropolymer. a polymer
of more than one monomeric unit. With DNA there are four units or .bases.: A = adenine, C =
cytosine, G= guanine and T = thymine. DNA is often described as a .blueprint., but this is
misleading. A better description is a .recipe.. When you see a blueprint of a building you can
immediately tell whether it is the plan of a house, a block of flats or a bridge. If you were
given a recipe for a building (a set of instructions without pictures) you would have to
perform a lot of the instructions before it became apparent what you were building. It is the
same with DNA. DNA is a set of instructions which cannot be interpreted at a glance and
DNA from one organism looks pretty much like that from another. However, as our
knowledge increases, our ability to identify and discriminate between genes and organisms
increases; but we still have a long way to go.
The sequence of the four bases along a DNA molecule, is translated into the amino acid
sequence of proteins and the rules are the same for all organisms (except for a few minor
differences here and there). As a consequence of the common language, a gene can be
transferred from one organism to another and it will be translated correctly. The
characteristics of an enzyme are defined by the sequence of its amino acids, and in turn, the
amino acid sequence is defined by the gene from which it is translated. Therefore, if we can
locate and isolate a gene from the chromosome of an organism which we have difficulty
growing, we can insert it into a new host which is much easier to handle and use this to
produce our enzyme. Isolating genes is becoming increasingly simplified as new methods are
devised. In fact, methods have advanced to such an extent that we dont even need the
original organisms. PCR allows us to isolate genes directly from environmental samples.
simply treat the mixture of organisms as a gene pool. The latest strategy for obtaining suitable
enzymes for industry is:
1) Find a pool which is similar in temperature and pH to the conditions within an
existing process.
2) Extract genes directly from the pool water or sediment by using the polymerase chain
reaction.
3) Transfer the genes to a production host.

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57

4) Engineer the new host to produce the gene product in large quantities.
If you are having trouble finding a pool which is a natural counterpart to your process, you
may find suitable organisms actually living within your existing industrial plant. If reactions
are carried out in conditions which arent too harsh, then micro-organisms may be growing
on vessel walls or in the outlet and waste pipes.
Once you have cloned your gene, enhancing production levels of the recombinant enzyme
can be relatively simple if the production organism is well understood. A gene comprises the
translatable code and DNA sequences upstream and downstream which specify when to
activate the gene and how much of the product to make. It is possible to swap these control
sequences and trick the host into believing it is making something else - something useful for
its own survival. It is also possible to modify the gene so that the organism secretes the
protein through the cell wall into the surrounding medium and this action greatly simplifies
purification. Genetic systems have now been developed where it is possible to produce more
than 20 grams of protein for every litre of culture. With this sort of production level, costs are
reduced dramatically and the amounts of enzyme needed by industry become achievable
goals.

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58

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Some Of General Types Of Catalyst