4 FUNDAMENTALS OF INDUSTRIAL CATALYTIC PROCESSES

Chemistry without catalysis would be a sword without a handle, a light without brilliance, a bell without sound.

- A . Mittasch

1.1 Emergence of Catalyst Technology, A Brief History

1.1.1 Basic Variables for Control of Chemical Reactions
Since the beginning of time, man has been concerned about the control of chemical reactions. There are
presently four basic variables available to us to control chemical reactions: (1) temperature, (2) pressure, (3)
concentration, and (4) contact time.
In the 19hand early 20thcenturies most industrial reactions were run at high temperatures and pressures
in order to achieve reasonable rates of production. This is the dedgehamrner approach. Unfortunately, these
severe conditions are ( I ) energy intensive, (2) corrosive or otherwise damaging to equipment and materials,
and (3) nonselective-that is, they result in undesirable side reactions and side products.
However, in the last 4-5 decades, two important technological developments have enabled us to run most
chemical reactions under less severe conditions:
1. First, extensive use of catalysts, substances which speed up reaction rate, has enabled us to operate at
lower pressures and temperatures. We call this thefeather approach.
2. Second, improved methods of contacting, such as packed and fluidized catalyst beds, have enabled us
to operate under continuous flow conditions at much higher efficiencies.
1.1.2 A Brief History of Catalyst Technology Development
Lets briefly trace the historical developments leading to the present extensive use of catalytic
processes. Catalyst technology was practiced on a small scale for centuries in inorganic form to make soap
and in the form of enzymes to produce wines, cheeses, and other foods and beverages (Heinemann, 1981).
The word catalysis was coined by Berzelius in 1836; moreover, catalysts were identified and studied by
Berzelius, Davy, Faraday, and other scientists in the early 1800s. However, industrial catalyst technology
had its real beginning about 1875 with large-scale production of sulfuric acid on platinum catalysts, although
sadly the inventor of this catalyst, Peregrin Philips (British Patent No. 6096, 1831), did not live to see the
first contact sulfuric acid plant constructed (Burwell, 1983).
I n the ensuing 100 years, catalyst technology expanded exponentially, although the timeline can be
highlighted with several major breakthroughs (summarized in Table 1.1). The first of these was ammonia
oxidation on Pt gauze developed by Ostwald and leading to the production of nitric acid in 1903. The
discovery of promoted iron for ammonia synthesis by Mittasch, and the subsequent development of the
ammonia synthesis process by Bosch and Haber occurred in the period of about 1908 to 1914; however, this
important advance was no accident, since Mittasch, with typical German thoroughness, investigated over
2500 catalyst compositions in his search for the optimum. Ninety years later, it is still the most widely used
catalyst for this reaction. Consider what impact this single discovery has had on agriculture and our ability to
feed the masses of the world.
In the early 1900s (1920-1940), catalytic processes for hydrogenation of CO to methanol or liquid
hydrocarbons paved the way for using synthesis gas from natural gas or coal to produce liquid fuels and
chemicals.

The history of catalytic technology has been reviewed by Heinemann (l98l), while Davis and Hettinger (1983) have edited a
volume that reviews selected histories of developments in heterogeneous catalysis with emphasis on those in the United States.
Laidlers text on kinetics ( I 987) includes biographical sketches of important contributors to the fields of kinetics and catalysis
research and technology.