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A History of Industrial Catalysis

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A History of Industrial Catalysis Catalysis Today 163 (2011) 3–9 Contents lists available at ScienceDirect Catalysis Today journal homepage: www.elsevier.com/locate/cattod A history of industrial catalysis John N. Armor * GlobalCatalysis.com L.L.C., 1608 Barkwood Dr., Orefield, PA 18069, USA ARTICLE INFO ABSTRACT Article history: Histories of catalysis have been told by others from different perspectives. This manuscript highlights Available online 12 January 2010 key catalytic discoveries that led to commercialized, industrial processes. The intent to show how catalysis evolved over the last 250 years into major industries focused not only at catalyst production, Keywords: but also significantly impacting the production of commodity, specialty and fine chemicals, as well as Biomass petrochemical, petroleum, emissions control, and polymerization. For centuries before 1750, catalysts Sustainability were used to make beverages and foods. One sees that the Lead Chamber process for the production of Emissions control sulfuric acid is among the earliest of catalytic processes and reaches back to 1750. Pursuit of a sound Energy fundamental understanding of catalysis in the 19th century, led to the application of these materials to a Zeolites Industrial catalysis variety of basic chemicals. The development of petroleum fuels led to a vast petrochemicals business History which in turn fed a growth in specialty and performance chemicals. New drivers in the 20th century from Chemical and petrochemical processes the transportation and the environmental business sectors provided market pull to bring about more catalytic solutions for more industries. The often novel, catalytic properties of zeolites created new commercial applications, while environmental legislation created market pull to use catalysis to meet the new regulatory standards. As we move forward into the new century, we continue to see market pull from growing interests in biomass, sustainability, emissions control, and energy. ß 2009 Elsevier B.V. All rights reserved. 1. Scope of the assessment summary following WWII [8]; Kieboom et al. provided a more detailed review which ended in the late 1990s; and Neidleman The impact of catalysis and catalysts is substantial. Today over focused on biocatalysis only [12]. In 1996, Professor Burtron Davis 90% of all industrial chemicals are produced with the aid of (University of Kentucky) prepared a very nice pictorial poster catalysts [1]. Industrial chemicals and petroleum refining are presentation on 50 years of catalysis (from 1949) which is available interconnected with industrial catalysis. Catalysts impact a sizable on the WWW [13] and at the NACS web site [14]. This was fraction of any nation’s gross domestic product. These materials originally prepared to commemorate the advances in catalysis achieve very high turnovers, such as those in olefin polymerization during the formative years of the development of catalysis in with some catalysts producing over a million pounds of polymer America and displayed for the 50th anniversary of the Interna- per pound of metal (in the catalyst) per hour! In 1991 it was tional Catalysis Conferences (Baltimore, MD USA, 1996). It steps estimated that the total value of fuels and chemicals derived from one through the science of catalysis marking key events in catalysis catalysts exceeded $900 billion/year [2]. World catalyst demand is over that exciting, 50 years period. B.H. Davis, W.P. Hettinger Jr. forecast to grow to $16.3 billion through 2012 [3] according to the also prepared a special symposium series book on an American Freedonia Group. In 2003 global sales of catalysts exceeded 12 History of Heterogeneous Catalysis in 1982. This contains a lot of billion dollars which was up from 9.3 billion dollars in 1998. [4]. specific chapters on the history around many valuable, catalyzed Sales are often divided into chemicals, petrochemicals and processes [15] in the US. petroleum refining products, polymerization, and environmen- This manuscript seeks to provide, on a global basis, brief tal/emissions. examples of the development of catalysts into commercial The story of catalysis has been told in the past by practitioners processes. Catalysts are often discovered by more than individuals, with different perspectives [5–10]. Lindstrom and Pettersson [11] rather it is often a team effort. What I would like to do here is chose to look at the development of catalysis over periods of time describe the history of industrial catalysis on a global perspective back to the dawn on civilization. Hans Heinemann began his and how the work of individuals as well as large teams ultimately led to many of our current commercial, catalytic processes. This assessment will focus primarily on the birth and renaissance of * Tel.: +1 610 3951406. catalysis for more than 250 years from the 18th into the 21st E-mail address: [email protected]. century and focus on the role of industry in discovering, 0920-5861/$ – see front matter ß 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.cattod.2009.11.019 4 J.N. Armor / Catalysis Today 163 (2011) 3–9 developing, and commercializing catalysis. Also, the intent is to chemistry, and global events delayed commercialization of this focus on the driving forces behind much of industrial catalysis and invention until 1906. how those efforts were often initiated, inspired and supported by Although catalysis is practiced on a large scale by Nature in the the scientists focusing on explaining the fundamentals of the form of digestion, fermentation, and many other forms of science. Early sketches of key catalytic discoveries and how they enzymatic processes, the first man-made commercially catalyzed led to commercial processes will be provided. The purpose, in this processes did not emerge until about 1750 and then there was a limited number of pages, is to provide some of the key, historical gap until the late 1800s. Here, catalysts first emerged for the events, but not in a comprehensive or detailed treatise nor to production of large volumes of key chemicals, including: summarize the many more commercialized processes [16,17]. Rather it is my intent to show how catalysis evolved over the last Sulfuric acid in 1746 [10] Lead Chamber process. 250 years into major industries focused not only at catalyst SO oxidation by the Contact Process in 1831. 2 production, but the production of commodity, specialty and fine Chlorine production in 1875 over CuCl (Deacon process) by 2 chemicals, as well as petrochemical, petroleum, emissions control, HCl + O2 (now outdated) [27]. and polymerization. Sulfuric acid production enhanced by use of V O in 1875. 2 5 Nitric acid production enhanced by the use of Pt gauzes in 1904. 2. Catalysis for commodity chemicals NH synthesis from N and H in 1905; at large scale at BASF in 3 2 2 1910. Catalysis was practiced by many early societies without Methanol synthesis developed by BASF (1923) at high pressure realizing its impact as demonstrated by the production of wine over a ZnO-chromia catalyst. and beer (fermentation), soap, cheese, sulfuric acid (oil of vitriol), This marked the emergence of synthesis of large volume and ether. Catalysis emerged from scientists seeking to understand organic chemicals. the chemistry and the origin of the promotion by catalytic Fischer–Tropsch synthesis of synthetic fuels commercialized in materials. Sir Humphrey Davy (in 1817) [throughout this manu- 1930 as an alternative to processing heavy oil, although script, specified years are intended to reflect the approximate year(s) of discovery of the process goes back to 1913 patents by Mittasch impact of the person’s work] observed the accelerated combustion and Schneider [28]. of coal gas with oxygen using a glowing Pt wire (heterogeneous, catalytic oxidation). Ultimately, society used chemicals to improve The very first commercial applications of catalysis occurred the way we produce materials in our environment. This led to the without a firm grasp of the science and principles like equilibrium; growth in applications of catalysis (often driven by the scientific equipment for running reactions at high pressures did not exist. knowledge generated within the academic community and Applications of these early inventors led the way for industrial industry) which began to translate into hundreds of economically production of basic chemicals such as the synthetic production of attractive, industrial applications. Huge industries emerged indigo, sulfuric acid, hydrolysis of starches, and the hydrogenation around making chemicals, fuels and pharmaceuticals in sufficient of fats. Studying the oxidation of ammonia, Wilhelm Ostwald and quality so that materials and products could be produced in his assistant, Eberhard Brauer, built a pilot plant in 1904 to confirm sufficient quantities and at a reasonable cost. Thus, catalysts were their laboratory studies and theories on ammonia oxidation. In discovered and developed as a means to enhance the production of May 1906, a 300 kg/day HNO3 plant using corrugated Pt strips was these materials. Much of the very early history of catalysis before brought on stream; in 1908 production was 3000 kg HNO3/day. 1934 is nicely summarized by Burwell [18] and Robertson [19]. Details for most of above examples of early, commercial catalytic Jo¨ns J. Berzelius, a Swedish chemist, recognized a common processes (largely for the production of commodity chemicals and ‘‘force’’ governing various chemistries reported by others and feedstocks) are provided in Eric Rideal and Hugh Taylor’s
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