feature

A brief history of catalysis

Brd Lindstrma and Lars J. Petterssonb
a Volvo Technology Corporation, Alternative Drivetrains, Dept 06120 CTP, Sven Hultins gata 9D, SE-412 88 Gteborg, Sweden, e-mail [email protected]
b KTH-Royal Institute of Technology, Department of Chemical Engineering and Technology, Teknikringen 42, SE-100 44 Stockholm, Sweden, email [email protected]

Historical studies are usually divided into segments of time that were marked by intellectual
progress or specific achievements. Some periods are clearly identified by great events or an individual
accomplishment that revolutionizes the entire concept. However, in most cases the advancement from
one period to another is not marked by distinct accomplishments, but rather the result of a series of
advances. This paper follows this conventional style and we have divided our subject of catalysis into
five distinct periods.
The fi rst period of catalysis dates back to the dawn of
civilization, at a date lost in time when mankind began to
produce alcohol by fermentation. The work done during the
fi rst period of catalysis consists mainly of isolated observations
that were sporadically documented without any effort made
to explain these phenomena. The fi rst period of catalysis
ended stridently when Jns Jacob Berzelius systematically
investigated the recorded observations and classified them
as catalysis in 1835 [1,2] . The conclusions drawn by Berzelius
were based upon discussions and experimental work with
contemporary scientists in Europe [3].
If the first period of catalysis was chaotic then the second
period was characterized by systematic research and the
discovery of new catalytic processes. During this period
it became quite clear that catalysis was applicable in most
chemical processes and that by implementing catalysis in an
industrial process there could be significant financial gains. This
new perception of catalysis was clearly formulated by Wilhelm
Ostwald, who once wrote that there is probably no chemical
reaction which can not be influenced catalytically[1,4].
The point in time when the shift from the second
to the third period occurs is not as clear as between the
fi rst and the second. The third period of catalysis begins
sometime during the end of the nineteenth century, when
the growth of academic knowledge translated into industrial
applications. At this point the number of catalytic processes
that had been developed had grown into hundreds and the
economic potential of some of these processes were highly
feasible. There was also a general growth in the demand for
bulk chemicals and therefore minimization of by-products,
by catalysis, had evident economic advantages. The industrial
production of bulk chemicals of this period was at an all time
high during World War 1[1] , when the demands on explosives
based upon nitric acid reached preposterous proportions.
130
Volume 7, no. 4, 2003

The fourth period of catalysis began at the end of the First

World War, when the demand for explosives diminished, and
the industrial production shifted towards the manufacturing
of synthetic fuels and new innovative processes such as FisherTropsch. The most significant new process innovation of this
period was the FCC (Fluid Catalytic Cracking) process,

Figure 1 Front cover of Alchemia (1597) by Andreas Libavius [5]

From alchemy to chemistry (1834)

The art of producing alcohol from sugar, by fermentation,
has ancient roots and the origins of this process are too
remote to trace [1]. However, it was during the alchemic era
that the process was fi rst clearly formulated. The fi rst known
reference to the use of inorganic catalysis is from 1552, when
Valerius Cordus used sulfuric acid to catalyze the conversion
of alcohol to ether [1,5] .
The alchemical period[1,5] was dominated by the search for
a magical catalyst that could convert base metals into noble
metals. The knowledge of chemical reactions during this
period was mainly empirical. The discoveries made during
this period were often isolated and collaboration between
the scientists of the period was sparse. It was when, in 1957,
Andreas Libavius wrote his masterpiece Alchemia (see
Figure 1)[6], which is often referred to as the first textbook
of chemistry, that it was first possible for the scientists to
compare their work with others. The work is particularly
interesting for us as it is the first historical reference to
catalysis as a chemical phenomenon. Libavius (see quotation
below), however, uses the term catalysis to describe the
decomposition of base metals into silver and gold rather than
the catalytic phenomena described by Berzelius[2].
De magisteriis substantiae, ubi primum det metallorum
transformatione, magisterium substantiae fit vel genesi
vel catalysi
The formulation of the laws for the conservation of matter
made it possible to distinguish between chemical and

A brief history of catalysis

which enabled the Allied forces to provide fuel to its fighters

during World War Two. When the war ended there was a
notable change in the trend of the catalytic industry and thus
the end of the fourth period of catalysis.
The fi fth period, which lasted to some undefi ned point
at the beginning of the 1970s, was strongly characterized
by the petrochemical industry and various catalytic
processes for the manufacturing of synthetic polymers. The
dominating role of the petrochemical industry was the result
of the explosive automotive market that had developed in
Europe and North America after World War Two.
At some point during the early 70s the world started
to become aware of the impacts that industry had on the
environment, partially sparked off by Rachel Carsons
Silent Spring.
This new trend of thought gave birth to the discipline of
environmental catalysis. Environmental catalysis was the first
step towards the modern chemical industry where catalysis
is applied to almost every process, including the production
of fine chemicals for pharmaceutical applications to the
production of bulk chemicals and exhaust gas catalysts. The
sixth period, which started in the seventies, and that can only
be characterized by continuous invention of new catalytic
processes, has not yet clearly passed into a seventh stage. The
use of enzymatic bio-catalysis could possibly be the start of a
new catalytic era; however it is too early yet to tell.

Figure 2 Humphry Davy (17781829)

catalytic reactions [1]. The conservation of matter was based

upon the ideas of Lavoisier, Cavendish, Priestley, Berthollet,
Proust, Gay-Lussac and Dalton [1,79].
The principle features of catalysis were fi rst presented by
Fulhame in 1794 [1,10] when she suggested that the presence
of small quantities of water was required for the oxidation
of carbon monoxide and that the water was unaffected by
the chemical reaction. Similar observations were made by
Kirchhoff who hydrolyzed starch to sugars by using dilute
acids in 1812. Kirchhoff observed that the acids were not
altered by the chemical reaction [1,9,11].
Sir Humphry Davy (see Figure 2) suggested in 1817 that
combustible gases, when mixed with oxygen, could explode
if they were exposed to heated platinum at temperatures
below the ignition temperature [11]. From his own words it
is quite clear that Davy was uncertain of what caused this
peculiar phenomenon:
I have shown, that the temperature of the flame is infinitely
higher than necessary for the ignition of solid bodies.
It appeared to me, therefore, probable, that in certain
combinations of gaseous bodies, for instance, those above
referred to, when increase of temperatures was not sufficient
to render the gaseous matters themselves luminous; yet it
might be adequate to ignite solid matters exposed to them.
From this passage it appears that Davy believed that the
catalyst itself was ignited rather than the combustible gases.
The work of Davy was followed up in 1818 by Erman,
who showed that it was possible to perform the combustion
at 50 C [1,9] .
Thenard [13,14] showed in 1818 that it was possible to
stabilize hydrogen peroxide in acidic solutions while it
decomposed in the presence of water. (Thenard is also
131

A brief history of catalysis

accredited with the discovery of hydrogen peroxide [14].)

He was also able to show that it was possible to decrease
the rate of decomposition by adding noble metals and that
the rate of decomposition was dependent on the metal
used. The influence of noble metals on decomposition was
investigated further by Edmund Davy who demonstrated
in 1820 that it was possible to rapidly oxidize alcohol to
acetic acid over platinum when exposed to air [15]. This was
later verified by Dbereiner in 1822[16]. Dbereiner also
showed it was possible to combust hydrogen and oxygen at
room temperature over platinum. This discovery led to the
construction of the hydrogen lamp. [17].
Inspired by Dbereiners discoveries, Dulong and
Thenard began investigating a series of materials to examine
whether it was possible to promote the reaction of hydrogen
and oxygen with materials other than platinum. In the
course of their study they discovered that several substances
(e.g. gold, silver and even glass) were able to promote the
combustion of hydrogen and that the activity was dependent
on the material used [9,18,19].
The deactivation of platinum-based catalysts was fi rst
studied by Henry in 1825 [20] . Henry discovered that certain
substances (for example hydrogen sulfide and carbon
disulphide) inhibited the combustion of hydrogen. Henry
also noted that platinum catalysts were less active for the
combustion of methane and ethylene than for hydrogen and
carbon monoxide. With this new discovery Henry developed
models for separating and analyzing combustible gases
based upon their reactivity in the presence of platinumbased catalysts.
Turner[21] showed that it was possible to combine
hydrogen with chlorine by using a platinum-based catalyst.

Figure 3 Michael Faraday (17911867)

132

Prompted by this discovery, Phillips developed the fi rst

commercial catalytic process, the oxidation of sulfur dioxide
over platinum-based catalysts [22] .
The work of Faraday [79,23] was not mentioned by
Berzelius in his summary of the catalytic phenomena;
however it is an excellent study of the catalytic properties of
platinum for the oxidation of hydrogen. When describing
the required properties of platinum for ignition, Faraday
came to the following conclusion:
The only essential condition appears to be a perfectly clean and
metallic surface, for whenever that is provided, the platina
acts, whatever form and condition in other respects may be.
In his study Faraday (see Figure 3) also investigated both
the effects of pretreatment and poisoning. He made a clear
distinction between permanent and temporary poisons that
could be removed by regeneration.
Mitscherlich performed detailed studies on the effects
of sulfuric acid on the conversion of ethanol to ether.
Mitscherlich concluded that only small quantities of acid
were required to convert large amounts of ethanol [1,24] . In
1835 Berzelius analyzed Mitscherlichs work and came to
the conclusion that the promotional effects of sulfuric acid
did not simply depend on the affi nity of sulfuric acid for
water, as it was possible to control the product composition
by varying the conditions. Berzelius continued to draw
analogies between the effect of sulfuric acid on ethanol to
the decomposition of hydrogen peroxide and the conversion
of starch into sugar. Based upon these analyses, Berzelius
presented the following analogy in 1835 [1,2,79,25] .
It is then shown that several simple and compound bodies,
soluble and insoluble, have the property of exercising on
other bodies and action very different from chemical
affinity. The body effecting the changes does not take
part in the reaction and remains unaltered through the
reaction. This unknown body acts by means of an internal
force, whose nature is unknown to us. This new force, up
till now unknown, is common to organic and inorganic
nature. I do not believe that this force is independent of
the electrochemical affinities of matter; I believe on the
contrary, that it is a new manifestation of the same, but,
since we cannot see their connection and independence,
it will be more convenient to designate the force by a
new name. I will therefore call it the Catalytic Force
and I will call Catalysis the decomposition of bodies by
this force, in the same way that we call by Analysis the
decomposition of bodies by chemical affinity.
With these famous words Berzelius (see Figure 4) started a
new era of catalysis.
From empirics to science (18351887)
The second period of catalysis was marked not only by
systematic research and the discovery of new catalytic
processes but also by an enhanced perception of chemical
reactions. We have therefore tried to show how an increase
in the understanding of chemical reactions influenced the

development of catalysis, rather than only listing the new

processes chronologically.
Wilhelmy proved in 1850 that the rates of chemical
reactions were dependent on the concentration of the
reactants. In his experiments Wilhelmy showed that the
rate at which sugar cane was reversed was dependent on the
concentration of sugar used [1,26] . The establishment of a rate
dependency of chemical reactions led to the recognition of
reversibility of chemical reactions. Williamson showed in
1851 that esters could easily be reversed back to alcohol.
Berthelot and Pean de St. Gilles, inspired by the discoveries
of Williamson, began investigations of the etherification
of alcohol. In 1862 they were able to prove that the
etherification of ethanol was a simple reversible reaction.
The investigations of Berthelot and Pean de St. Gilles
also showed that the rate of etherification was directly
proportional to the concentration of the acid [1].
Guldberg and Waage continued the work of Berthelot
and were able to derive a more precise interpretation of
the experimental results, and subsequently formulated the
fi rst quantitative law. In a paper presented in 1864 [1,9,27] ,
Guldberg and Waage proposed that there was a relationship
between the tendency of a chemical reaction and the active
masses of the reactants. The term active mass referred to
the relationship between the number of molecules and the
volume, which is synonymous with the concentration of the
species. The degree of a chemical reaction was, according
to Guldberg and Waage, dependent on the concentration of
the reactants and a constant which could only be determined
experimentally.

A brief history of catalysis

Figure 4 Jns Jacob Berzelius (17791848)

The results of Guldberg and Waage were not accepted

until Vant Hoff pointed out in 1877 that the constant was
in reality a rate constant, which could be used to measure the
chemical change. Vant Hoffs defi nition was much clearer
than Guldberg and Waages and as a result of his defi nition
the concept of affi nity was immediately accepted[1,9] .
The dependency of a chemical reaction on the
temperature and pressure were originally presented by Le
Chatelier in 1884. By combining the results of Le Chatelier
with that of Guldberg and Waage, it was possible to deduce
a mathematical expression that quantitatively described
the relationship between the rate of reaction and the
temperature and pressure of the reaction. The developments
achieved in this field are the result of several prominent
researchers including Vant Hoff, Horstmann, Gibbs and
Nernst (see Figure 5).
The results presented so far in this section can be applied
to all chemical reactions, not only catalytic reactions, and
we will now present these discoveries from a catalytic
perspective.
In 1877 Lemoine [28] showed that by applying a catalyst to
a chemical reaction the rate at which equilibrium was reached
could be increased, but the position of the equilibrium was
not altered. During the same period the same conclusion
was reached from a thermodynamic perspective:
A catalyst which contributes no energy to a chemical system
cannot change the position of the equilibrium, it can only
alter the rate at which it is reached [9,28] .

Figure 5 Walther Nernst (18641941)

133

A brief history of catalysis

This view was modified by Ostwald (see Figure 6) who

claimed that a catalyst cannot initiate a chemical change, it can
only accelerate or retard[1,5,9]. This definition received strong
reservation from several researchers as many investigators
had noted that several reactions could only take place in
the presence of a catalyst. The difference between the two
definitions is however merely hypothetical, as, for practical
reasons, there is no difference between a reaction with an
infinitely small rate and one not taking place at all.
In this section we have tried to present the change of ideas
rather than listing the hundreds of new catalytic processes
that were developed during the second period of catalysis.
This is to recognise that the change of thought of chemical
reaction engineering was the main driving force of the second
period. We begin the third period of catalysis in 1898, as this
was the year that saw the birth of one of the most important
industrial processes of the twentieth century.
The birth of industrial catalysis (18981918)
The industrial catalytic production of bulk chemicals
in Europe and America did not begin at the end of the
nineteenth century, as one might suspect when reading our
motivation for setting this time as the start of the third period
of catalysis. The production of sulfuric acid was, for instance,
above 50 tons per year in the UK alone. However it was not
until 1898 that the production problems with contact
sulphuric acid were solved by Knietsch[1]. The work of
Knietsch enabled a remarkable expansion in the worldwide
production of sulfuric acid, which was near one million tons
per year at the end of the period.
The third period was marked by the discovery and
implementation of new catalytic processes. We have therefore
tried to show how these new processes were linked with the
events of the period and how the catalytic industry changed
as Europe entered the Great War.
The ammonia process, which was without a doubt
the most significant process of the period, was originally
developed to provide Europe with a fertilizer to prevent
a famine. However most of the ammonia produced ended
up as a major bulk chemical in the production of nitrogenbased explosives. The possibility of using ammonia in the
production of explosives can in large part be accredited
to Ostwald, who developed a process for the oxidation of
ammonia to nitric acid in 1902[1,9,29].
The first important advancement in the development
of the ammonia process came in 1903 when Haber and
Nernst discovered that in order to obtain significant activity
the process had to be operated at high pressure. During the
course of their work Haber and Nernst also realized that high
activity and equilibrium concentration could be achieved
by operating the process at both elevated temperature and
pressure. The first small scale catalytic production of ammonia
began in 1905, when Haber used an iron-based catalyst[2932].
The development of an industrial process for synthesizing
ammonia can mainly be accredited to the work of Haber,
134

Figure 6 Wilhelm Ostwald (18531932)

Bosch and Mittasch. Carl Bosch began working for BASF

in 1908 and was immediately assigned to the development
of the ammonia process. In 1909 Mittasch developed the
first industrial catalyst for the production of ammonia from
hydrogen and nitrogen, and one year later the first large scale
production of ammonia based upon the Haber process was
constructed at the BASF plant in Ludwigshafen. By the end of
1913 most of the ammonia produced in Europe was designated
for the production of explosives, and by this time BASF had
constructed two new ammonia plants. BASF were by now also
producing nitric acid on an industrial scale, using the Ostwald
process, solely for military applications. By 1914, when war had
broken out in Europe, all of BASFs production of ammonia
was designated for the production of explosives[29,3336].
The progress of catalysis during the war was slow, but
there are a few developments worth mentioning. In 1915
Irving Langmuir presented his theories on the adsorption
isotherm based upon early work done by Haber[37].
Langmuir is also accredited with the developing Temperature
Programmed Desorption the following year[38].
In 1918, at the end of the third period, Haber received
the Nobel Prize in chemistry for the synthesis of ammonia.
The decision to give Haber the award sparked off protests all
over Europe due to his role in the development of chemical
weapons (chlorine gas), which was used against the Allied
troops during the war. The third period of catalysis ended
somewhat in shame as the catalytic developments were
dominated by the production of weapons of destruction.

A brief history of catalysis

The increase in global mobility by developing

catalytic fuel processes (19181945)
The catalytic developments of the fourth period were
dominated by the petroleum industry. In this section we
will try to follow the catalytic evolution chronologically as
there are a large number of significant events that need to
be highlighted. Special attention will however be paid to
the petroleum industry as it defi ned the catalytic progress
of the period.
The fi rst significant development came in 1920 when
the Standard Oil Company began large scale industrial
production of isopropanol from petroleum. The production
of isopropanol is significant as it was the fi rst large scale
process which used petroleum in the feed.
In 1922 Franz Fischer and Hans Tropsch managed
to synthesize hydrocarbons from carbon monoxide and
hydrogen (from coal gasification) at room temperature.
This discovery is without a doubt one of the most important
chemical achievements of the period. Fischer and Tropsch
continued development of their process and in 1925 were
able to obtain high yields by operating the process at high
pressure. The process was particularly important during
World War Two when the demands for hydrocarbons rapidly
increased. The process is as relevant today as it was 80 years
ago, and is employed by several companies, including Shell
and SASOL[3941].
Methanol has been one of the most important bulk
chemicals of the twentieth century with a vast amount of
applications, ranging from functioning as a base chemical in
the production of formaldehyde and MTBE, to being used
as a fuel in fuel cell vehicles. The fi rst large scale industrial
production of methanol started in 1926 when DuPont
began producing synthetic methanol [42,43] .
In 1927 the knowledge of catalysis took a gigantic step
when Hinshelwood presented his kinetic theory based upon
earlier fi ndings by Langmuir. The principles of LangmuirHinshelwood kinetics are still being applied in catalytic
modeling today and gave Irving Langmuir the Noble Prize
in 1932. The discoveries of Langmuir and Hinshelwood
was popularized by Olaf Hougen and Kenneth Watson who
applied Langmuir and Hinshelwoods theories to reactor
design and chemical engineering principles [44].
1921 was the year that, after investigating over 2,000
different substances, Thomas Midgley at General Motors
Chemical Company discovered that tetraethyl lead could be
added to gasoline as an antiknocking agent. The discovery
of tetraethyl lead was extremely significant as it both
increased the performance of the automobile engine as well
as prevented destruction of the engine by knocking [45].
Steam reforming has been vital for the production of
hydrogen in the modern petroleum industry. The fi rst
commercial steam reforming plant was constructed in 1930
by the Standard Oil Company in New Jersey.
The knowledge of surface chemistry developed at a
significant rate during the 1930s. Special attention should

be paid to Igor Tamm, who performed ground breaking

work on electron states on metallic surfaces, and to John
Barden for his investigations on the structure of electrons
on metallic surfaces [5].
The catalytic cracking of petroleum was developed by
Eugne Houdry in 1936 and is certainly one of the most
important chemical processes ever developed. Houdry
originally developed the process for the Sun Oil Company,
who did not want to resort to tetraethyl lead as an additive
in petroleum. The process became incredibly relevant during
World War Two when there developed a sudden demand for
aviation gasoline. Between 1938 and 1950 construction was
completed on several cracking units all over the world and
several improvements were made to the process. The most
important modification came in 1941 when fluid catalytic
cracking (FCC) technology was introduced. The FCC
technology was developed by Lewis and Gilliland, at MIT,
for the Standard Oil Company. The modification made by
Lewis and Gilliland solved most of the problems associated
with the fi xed-bed Houdry process and played a very
important part in providing the vast quantities of gasoline
that was needed during World War Two [39,46,47].
The ammonia process, which was incredibly important
during the third period of catalysis, was investigated further
during the fourth period of catalysis. The most significant
development came in 1940 when Temkin published a
detailed description of the kinetics of the ammonia process.
Hendrik Kramer published the same year a detailed study on
the kinetics of catalytic reactions [5,48].
The fourth period of catalysis ended with that of World
War Two in 1945. The most important catalytic event at the
end of the period is the Allies decision to split I. G. Farben
into BASF, Bayer and Hoechst as a result of their role during
the war.
From war to peace (19461970)
As the world moved away from a war-based economy there
was a natural shift in the demands of chemicals. In Europe
there was an explosion in the market for automobiles, which
in turn caused a swift increase in the demand for petroleum.
The catalytic production of polymers from petrochemicals
also played a vital role. The petroleum industry that forged
the fourth period of catalysis therefore played an equally
important part in the fi fth period, with the only real
difference being the commodities produced. In order to
avoid missing any of the significant events of this period we
will present the events of this period chronologically.
In 1949 the first organized catalysis meeting took place at
the University of Pennsylvania. The meeting was organized by
Prof. Farkas, who was later elected chairman of the Catalysis
Club which held its first meeting in December of the same
year. 1949 was also important from a commercial viewpoint
as it was the year that the first commercial naphtha reforming
plant became operational. The plant was constructed and
operated by Universal Oil Products (UOP)[47].
135

A brief history of catalysis

1950 is undoubtedly one of the most important years

in the history of catalysis. It was this year that the Faraday
Society organized the fi rst conference ever devoted to
heterogeneous catalysis. The meeting was attended by
most of the dignitaries of catalysis, and some of the topics
presented at the meeting were [49]:
D. D. Eley, The heat of adsorption of hydrogen on metals.
G. M. Schwab, Alloy catalysts for dehydrogenation
D. D. Dowden and P. W. Reynolds, Electronic effects in
catalysis by metal alloys
W. Selwood and L. Lyon, Magnetic susceptibility and
catalyst structure
M. W. Tamele, Surface chemistry and catalytic activity of
silica-aluminum catalysts
John Turkevich, H. H. Hubbell and James Hillier,
Electron microscopy and small angle X-ray scattering
During the same year a linear relationship between quinoline
chemisorption and catalytic activity for gasoline cracking
was developed by Oblads group [47,50] .
In 1951 Wheeler discovered that diffusion had a
significant impact on the activity and selectivity of a catalytic
system. Wheelers work has played a crucial role in the design
of industrial catalytic systems [51].
In 1953 there were two major catalytic discoveries,
those of Karl Ziegler and Oblads group. The first and most
important was Karl Zieglers discovery of a catalytic system
for polymerizing ethylene at low temperatures and pressures
to form linear crystalline polyethylene[52]. One year later in
1954 Giulio Natta invented stereo-specific polymerization of
propylene to form crystalline propylene. Ziegler and Nattas
discovery gave birth to a new industry, and new products based
upon their original ideas are continuously being developed
today[53]. Karl Ziegler and Giulio Natta were awarded the
Nobel Prize in 1963 for their work on polymerization.
1953 was also the year that Oblads group discovered
that naphtha reforming takes place by dual functional
catalysis which enabled increased activity and selectivity in
industrial naphtha reforming [47] .
A significant development in catalysis came in 1954 when
the first method for characterization of catalysts was developed
by Eischen and co-workers. Eischens group developed a
method for studying carbon monoxide adsorption on copper
catalysts, with IR-spectroscopy. Eischens group also developed
methods for the characterization of active sites on metal and
metal oxide surfaces by adsorption, as well as a method for
distinguishing between Brnsted and Lewis acid sites[54].
Other advances in 1954 worth mentioning are the
introduction of chromium-based catalysts for the production
of polyethylene by Phillips Petroleum and the announcement
of the Gulf Oil company to use Ziegler-Natta catalysts in the
production of synthetic rubber [47] .
The Phillips process developed in 1954 became in 1956
the worlds largest source for polyethylene. The process
appeared at the time to be superior to the Ziegler-Natta
Process; however the key to Phillips success was a result of
136

clever engineering and large scale manufacturing[55]. 1956

was also the year that the first International Congress on
Catalysis (ICC) was held in Philadelphia. There were more
than 500 delegates present at the conference and the forum
still exists today as an independent organization.
In 1960 there were three industrially important processes
introduced on the commercial market [47]:
Ethylene to acetaldehyde Wacker Chemistry[56]
Benzene to Cyclohexene (Hydrar process) UOP
Worlds first Acrylonitrile Plant SOHIO
1962 was an important year for catalysis both academically
and commercially. It was the year that saw the birth of
Journal of Catalysis, the fi rst journal devoted solely to
catalysis, and the Nickel-based steam reforming catalyst was
introduced. The NiK 2Al 2O3 catalyst had higher activity and
selectivity than all other previous steam reforming catalysts,
increasing the economic gains of the process [57].
In 1964 there was an extraordinary number of new
catalysts and processes developed. The most important was
Mobil Oils development of the rare earth metal stabilized
X-zeolite for catalytic cracking. The development of this
zeolite revolutionized the petroleum industry and is today
one of the most important catalytic materials available [58].
Other developments worth mentioning are:
The metathesis of olefins by Banks et al.[59]
The development of the mechanism for hydro-cracking
by Coonradt and Garwood[60]
The mechanism for CO adsorption on transition metals
explained by Blyholder[61]
When Wilkinson developed a homogeneous catalyst
for hydrogenation in 1965, he started a new branch of
catalysis [62]. Today, homogeneous catalysis plays an important
role in the production of pharmaceuticals and fi ne chemicals.
The discovery gave Wilkinson the Nobel Prize in 1973.
In 1966 ICI developed a copper-based methanol
synthesis catalyst that enabled the process to operate at
low temperature and moderate pressure. The modification
of the methanol process played an important part when an
alternative for tetraethyl lead was to be developed, as vast
quantities of the substitute were required [63].
Other developments of 1966 that are worth mentioning
are:
The introduction of the concept of hard and soft acid sites
by Pearson[64]
The development of a method for calculating the
coordination number of surface atoms in the stable form of
small metal particles by van Hardeveld and Montfoort[65]
We have decided to end the fi fth period of catalysis at the
end of the sixties as there is no clear transition into the sixth
period and therefore the beginning of a new decade seems as
good a starting point as any.
Environmental catalysis (197020??)
The sixth and current period of catalysis has been
characterized and influenced by environmental driving forces

A brief history of catalysis

and the Sciences integration with new technologies, such

as super computers. The development of rapid inexpensive
computational systems has in fact created a new branch of
catalysis, namely mathematical modeling, which has had a
significant impact on the methods used today for developing
new catalytic systems.
The amount of new processes, catalysts and discoveries
during the sixth period are countless and listing them all
chronologically would be implausible for this paper. We have
therefore indentified the most significant developments and
how they influenced the progress of catalysis and affected
the world.
The negative impact of the exhaust gas from automobiles
was debated heavily during the late sixties and early seventies.
The first commercial exhaust after-treatment system
was developed by Engelhard in the mid sixties[66]. The
development of exhaust gas catalysts has led to incredibly large
reductions in emissions and has also governed the evolution
of the combustion engine. The exhaust gas catalyst system is
now the most common catalytic reactor in the world.
The role of the zeolite increased steadily during the sixth
period as research groups all over the world attempted to
fi nd new areas of application for zeolites. The most notable
new processes using zeolites during the sixth period are
Mobil Oils methanol-to-gasoline process which operates
with a ZSM-5-zeolite catalyst (1976) [67] and the oxidation
of benzene to phenol over a Fe-ZSM-5 zeolite catalyst
(1990).
During the eighties there were several new catalytic
processes introduced to the market. One of the most
important process developments was the introduction of
Selective Catalytic Reduction (SCR) for controlling the
NOx emitted from nitric acid and stationary power plants[68].

SCR technology is today implemented in several mobile

applications ranging from large ships to heavy-duty trucks.
There were also several developments in catalytic processes
for the production of synthetic polymers during the eighties.
In 1980 Shell and Union Carbide developed a process for
producing linear low-density polyethylene. The process was
revolutionary as it gave the producers total control over the
material properties of the product. The process was later
extended to the production of polypropylene. The advantages
of using homogeneous catalysts in the production polymers
were clearly demonstrated [69].
The ammonia process is today as relevant as it was
during the second period of catalysis and improvements and
investigations into the nature of the process are constantly
being carried out. In 1982 Ertls group defined the energy
profile of the synthesis of ammonia and in 1992 the first
commercial use of a catalyst without iron was presented[70].
Other process developments of the period worth
mentioning are the introduction of Reduced Crude Cracking
(RCC) by Ashland Petroleum., the use of Fischer-Tropsch
as a source for producing alpha-olefins and UOPs Cyclar
process for the production of aromatics from Liquefied
Petroleum Gas (LPG).
Epilogue
The point in time when the transition into a new area of
catalysis will take place is today impossible to predict. What
we can however say with certainty is that the future of catalysis
all will be as exciting tomorrow as it was during the early
years. Without a doubt there will be scientific contributions
from the catalytic scientists of tomorrow that will be
remembered by future generations in the same manner that
we remember the accomplishments of Berzelius and Davy.

Curricula vitae

Lars J. Pettersson is an associate professor

Brd Lindstrm obtained

in chemical engineering at the Department

his

of

Chemical Engineering from

Chemical

Engineering

and Technology,

Masters
Royal

degree
Institute

in

Royal Institute of Technology in Stockholm. He

the

received his Master of Science and PhD at the

Technology-KTH

same university. Lars has more than 20 years of

holm and stayed on for

experience in using heterogeneous catalysis for

doctoral

improving efficiency and lowering emissions in

group of Ass. Prof. Lars J.

the transportation sector. Exhaust gas catalysts

Pettersson. His PhD thesis

work

of

in Stockin

the

for alternative-fuelled vehicles and onboard

focused on the development

hydrogen generation for vehicles with fuel cells or international combustion

of a compact methanol reformer for generating hydrogen

engines as power sources are some examples of his work. Lars has a

for fuel cell vehicles. The result of his PhD studies resulted

particular interest in the history of science and technology with a special

in several publications in international journals.

focus on Berzelius activities and the early years of the petroleum industry.
He teaches Reaction and Separation Engineering, Environmental Catalysis,
Material and Energy Balances, and Chemical Reaction Engineering, as well
as various courses on a postgraduate level.

137

A brief history of catalysis

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