Fischer2013Tropsch catalysis The basis for an emerging industry
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A history of industrial catalysis
John N. Armor* GlobalCatalysis.com L.L.C., 1608 Barkwood Dr., Oreﬁeld, PA 18069, USA
1. Scope of the assessment
The impact of catalysis and catalysts is substantial. Today over 90% of all industrial chemicals are produced with the aid of catalysts . Industrial chemicals and petroleum reﬁning are interconnected with industrial catalysis. Catalysts impact a sizable fraction of any nation’s gross domestic product. These materials achieve very high turnovers, such as those in oleﬁn polymerization with some catalysts producing over a million pounds of polymer per pound of metal (in the catalyst) per hour! In 1991 it was estimated that the total value of fuels and chemicals derived from catalysts exceeded $900 billion/year . World catalyst demand is forecast to grow to $16.3 billion through 2012  according to the Freedonia Group. In 2003 global sales of catalysts exceeded 12 billion dollars which was up from 9.3 billion dollars in 1998. . Sales are often divided into chemicals, petrochemicals and petroleum reﬁning products, polymerization, and environmental/emissions.
The story of catalysis has been told in the past by practitioners with different perspectives [5–10]. Lindstrom and Pettersson  chose to look at the development of catalysis over periods of time back to the dawn on civilization. Hans Heinemann began his summary following WI ; Kieboom et al. provided a more detailed review which ended in the late 1990s; and Neidleman focused on biocatalysis only . In 1996, Professor Burtron Davis (University of Kentucky) prepared a very nice pictorial poster presentationon50yearsofcatalysis(from1949)whichisavailable on the W  and at the NACS web site . This was originally prepared to commemorate the advances in catalysis during the formative years of the development of catalysis in America and displayed for the 50th anniversary of the International Catalysis Conferences (Baltimore, MD USA, 1996). It steps onethroughthescienceofcatalysismarkingkeyeventsincatalysis over that exciting, 50 years period. B.H. Davis, W.P. Hettinger Jr. also prepared a special symposium series book on an American History of Heterogeneous Catalysis in 1982. This contains a lot of speciﬁc chapters on the history around many valuable, catalyzed processes  in the US.
This manuscript seeks to provide, on a global basis, brief examples of the development of catalysts into commercial processes. Catalysts are often discovered by more than individuals, rather it is often a team effort. What I would like to do here is describe the history of industrial catalysis on a global perspective 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 catalysis for more than 250 years from the 18th into the 21st century and focus on the role of industry in discovering,
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Keywords: Biomass Sustainability Emissions control Energy Zeolites Industrial catalysis History Chemical and petrochemical processes
Histories of catalysis have been told by others from different perspectives. This manuscript highlights 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, but also signiﬁcantly impacting the production of commodity, specialty and ﬁne chemicals, as well as petrochemical, petroleum, emissions control, and polymerization. For centuries before 1750, catalysts were used to make beverages and foods. One sees that the Lead Chamber process for the production of sulfuric acid is among the earliest of catalytic processes and reaches back to 1750. Pursuit of a sound fundamental understanding of catalysis in the 19th century, led to the application of these materials to a variety of basic chemicals. The development of petroleum fuels led to a vast petrochemicals business whichinturnfedagrowthinspecialtyandperformancechemicals.Newdriversinthe20thcenturyfrom 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 regulatorystandards. As we move forwardinto the new century, we continue to see market pull from growing interests in biomass, sustainability, emissions control, and energy. 2009 Elsevier B.V. All rights reserved.
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0920-5861/$ – see front matter 2009 Elsevier B.V. All rights reserved. doi:10.1016/j.cattod.2009.1.019 developing, and commercializing catalysis. Also, the intent is to focus on the driving forces behind much of industrial catalysis and how those efforts were often initiated, inspired and supported by the scientists focusing on explaining the fundamentals of the science. Early sketches of key catalytic discoveries and how they led to commercial processes will be provided. The purpose, in this limited number of pages, is to provide some of the key, historical events, but not in a comprehensive or detailed treatise nor to summarize the many more commercialized processes [16,17]. Rather it is my intent to show how catalysis evolved over the last 250 years into major industries focused not only at catalyst production, but the production of commodity, specialty and ﬁne chemicals, as well as petrochemical, petroleum, emissions control, and polymerization.
2. Catalysis for commodity chemicals
Catalysis was practiced by many early societies without realizing its impact as demonstrated by the production of wine and beer (fermentation), soap, cheese, sulfuric acid (oil of vitriol), and ether. Catalysis emerged from scientistsseeking to understand the chemistry and the origin of the promotion by catalytic materials. Sir Humphrey Davy (in 1817) [throughout this manuscript, speciﬁedyears areintendedtoreﬂect the approximateyear(s)of impact of the person’s work] observed the accelerated combustion of coal gas with oxygen using a glowing Pt wire (heterogeneous, catalytic oxidation). Ultimately, society used chemicals to improve the way we produce materials in our environment. This led to the growth in applications of catalysis (often driven by the scientiﬁc knowledge generated within the academic community and industry) which began to translate into hundreds of economically attractive, industrial applications. Huge industries emerged around making chemicals, fuels and pharmaceuticals in sufﬁcient quality so that materials and products could be produced in sufﬁcient quantities and at a reasonable cost. Thus, catalysts were discovered and developedas a means to enhancethe productionof these materials. Much of the very early history of catalysis before 1934 is nicely summarized by Burwell  and Robertson .
Jons J. Berzelius, a Swedish chemist, recognized a common ‘‘force’’ governing various chemistries reported by others and provided an early deﬁnition (1836) [20,21] of catalysis: reactions thatareacceleratedbysubstancesthatremainunchangedafterthe reaction. Scientists like Berzelius, Sir Humphrey Davy , and Wilhelm Ostwald, working in the 1800s, discovered and pursued many of the early fundamental concepts of catalysis. Others like
Louis Jacques Thenard (1813 studying the decomposition of NH3), Joseph Priestley, Johann Wolfgang Dobereiner (in 1810: Pt black oxidation of alcohols), Ambrogio Fusinieri (1824, catalytic oxidation over Pt) , Michael Faraday  and Pierre Dulong appreciated the use of various materials as catalysts without deﬁning them as such or deﬁning the fundamental underpinnings .
As early as 1746, John Roebuck, an English inventor, began producing somewhat ( 35%) concentrated sulfuric acid in large lead-lined chambers . Here SO2 (produced by burning sulfur or roasting of sulfur containing metal ores) is oxidized by NO2 in large, lead-lined chambers (easier to scale-up than using glass). In
1831, Peregrine Phillips Jr. a Bristol manufacturer of vinegar, developed the more economical Contact process for the manufacture of much more concentrated sulfuric acid using a Pt or later a
V2O5 catalyst. In 1838, Frekederic Kuhlmann  ﬁled for a patent on the aerial oxidation of ammonia over platinum to nitric acid. He, and others, appreciated the strategic need for nitrates for explosives production in the event of war without a dependence on distant imports of Chilean saltpeter. Many fundamental issues of science, process chemistry, and global events delayed commercialization of this invention until 1906.
Although catalysis is practiced on a large scale by Nature in the form of digestion, fermentation, and many other forms of enzymatic processes, the ﬁrst man-made commercially catalyzed processes did not emerge until about 1750 and then there was a gap until the late 1800s. Here, catalysts ﬁrst emerged for the production of large volumes of key chemicals, including:
Sulfuric acid in 1746  Lead Chamber process.
SO2 oxidation by the Contact Process in 1831. Chlorine production in 1875 over CuCl2 (Deacon process) by HCl + O2 (now outdated) .
Sulfuric acid production enhanced by use of V2O5 in 1875. Nitric acid production enhanced by the use of Pt gauzes in 1904.
NH3 synthesis from N2 and H2 in 1905; at large scale at BASF in 1910.
Methanol synthesis developed by BASF (1923) at high pressure over a ZnO-chromia catalyst.
This marked the emergence of synthesis of large volume organic chemicals.
Fischer–Tropsch synthesis of synthetic fuels commercialized in 1930 as an alternative to processing heavy oil, although discovery of the process goes back to 1913 patents by Mittasch and Schneider .
The very ﬁrst commercial applications of catalysis occurred without a ﬁrm grasp of the science and principles like equilibrium; equipment for running reactions at high pressures did not exist. Applications of these early inventors led the way for industrial production of basic chemicals such as the synthetic production of indigo, sulfuric acid, hydrolysis of starches, and the hydrogenation of fats. Studying the oxidation of ammonia, Wilhelm Ostwald and his assistant, Eberhard Brauer, built a pilot plant in 1904 to conﬁrm their laboratory studies and theories on ammonia oxidation. In
May 1906, a 300 kg/day HNO3 plant using corrugated Pt strips was brought on stream; in 1908 production was 3000 kg HNO3/day. Details for most of above examples of early, commercial catalytic processes (largely for the production of commodity chemicals and feedstocks) are provided in Eric Rideal and Hugh Taylor’s excellent early book (in 1919) on catalysis  and the book on selected historiesbyDavisandHettinger.(Theformerbookisnolonger under copyright and can be downloaded directly from the World Wide Web .)
At ﬁrst, we see catalysis as a science being pursued by creative individuals largely in academia seeking to understand how catalysts inﬂuenced chemistry. In time as the demand for the production of substantial volumes of these catalyzed chemicals emerged, small industrial companies emerged to make these value-added chemicals. In addition an industry developed for preparing these iron, vanadium, cerium, chromium, copper, and manganeseoxides aswellasclaycatalysts.Thesecompaniesoften employed and/or were founded by those from academia; thus, creating a profession using students trained in academia to add value to the chemicals based on the understanding created in the academic labs. Later, the Kaiser–Wilhelm–Gesellschaft research institutesinGermanycreatedahome forthose pursuing technical applications of catalysis and teamed with those in industry. Some industrial companies eventually generated their own fundamentalresearchlabsinthe1940s through the 1970s tofocus onahuge growth in new chemical products (Dow, GE, DuPont, BASF, ICI, Monsanto, and others). So too, governments worldwide provided early funding of academic labs and then also started to build their own federally funded labs to use and to create new catalytic science. These included the US National Labs at Oak Ridge, Sandia, and Hanford (the latter is now PNNL National Labs); the Max
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Planck Institutes in Germany; the Boreskov Institute of Catalysis in Russia, NIOK (Netherlands Institute of Catalysis Research); as well as other government funding of individuals and centers within universities around the globe. From the 1970s to present, these national labs have served to bring together academic, industrial and government participants in catalysis research. In addition, catalysis underpins many of the different institutes withintheMaxPlankSocietyassupportedbyGermanfederal and state funding.
3. Individuals establish fundamentals; teams emerge
At the turn of the 20th century, we saw individual scientists pursuing a fundamental understanding of catalysis, eventually teaming with others to undertake the enormous efforts needed to develop industrial catalysts:
Nicolas Clement (Lead Chamber process for H2SO4) was a professor at Conservatoire des Arts et Metiers in Paris.
Wilhelm Ostwald was a chemistry professor (in Latvia and Germany) famous for his pioneering work in electrochemistry and catalysis. Paul Sabatier was a chemistry professor in France whose fundamental studies included the role of ﬁnely divided metals for hydrogenating organic compounds. Vladimir Ipatieff, a Russian nobleman working at the Mikhail Artillery Academy and later Professor of chemistry and explosives at University of St. Petersburg. He later ﬂed to the USA and had a dual appointment at UOP and Northwestern University. He led the discovery of the promoter effect (1909) and parafﬁn alkylation by oleﬁns (1935) with acid catalysts (solid phosphoric acid) [10,30,31]. He played a leading role in the development of UOP’s polymerization, alkylation, and isomerization processes, and thus made a major contribution to the development of the high-octane aviation fuel. Carl Bosch was a chemist working for BASF with his assistant,
Alwin Mittasch; they scaled up the NH3 synthesis process developed by Fritz Haber from Technische Hochschule of
Karlsruhe (later the Director of the Kaiser Wilhelm Institute for Physical Chemistry). This work on the NH3 synthesis catalyst and process is a major milestone of catalysis.
Irving Langmuir began at Stevens Tech (USA) then joined GE in 1909 working on light bulb problems while contributing to the fundamentals of catalysis especially with respect to surface chemistry. In 1915, he ﬁrst described heterogeneous catalysis as something that occurred in a single layer of gas molecules (although an oversimpliﬁcation) held on a solid surface . Sir Hugh Taylor (a chemistry professor at Princeton) and Sir Eric Rideal (a Professor of Physical Chemistry at Kings College) together authored the ﬁrst notable book on catalysis (1919) . FranzFischerwasdirectoroftheKaiserWilhelmInstituteforcoal research working with Hans Tropsch in the 1920s. Murray Raney (1926) is noted for the unique type of metal hydrogenation (particularly of vegetable oils) catalysts which bear his name . Herman Pines of UOP and Northwestern University (while working with Vladimir Ipatieff) was very active  for over 50 years (beginning in 1930) in developing acid and base catalysis, aluminas, aromatization, alkylation, dehydrogenation catalysts and metal hydrogenation catalysts, all of which were very instrumental in a number of commercial petrochemical processes (high-octane gasoline (in collaboration with Ipatieff), biodegradable detergents, and dehydrogenation of parafﬁns). Paul Emmett’s work provided additional fundamental under- standing of NH3 synthesis and he contributed to the BET method for measuring surface area .
Heinz Heinemann had an impressive career in both industry and academia. While at Berkeley, the research team he led invented the process of oxydehydrogenation; over his long career, he was associated with more than 14 commercial processes. Frank G. Ciapetta (1950) was another pioneer in catalysis who is noted for his work on a new, general class of parafﬁn isomerization catalysts (consisting of a hydrogenation-dehydrogenation agent such as Ni or Pt in combination with an acidic cracking catalyst (such as silica–alumina)) .
4. Basic chemicals industry emerges
During the building of fundamentals of catalysis, a chemicals industry emerged largely based upon the use of catalysts. First with the efﬁcient production of basic, inorganic chemicals such as sulfuric acid, ammonia, and nitric acid. These were driven by the need for NH3 as a component of agricultural fertilizer, and later by theneed forbulk chemicals,especially forexplosives in World War
I. Other food processing needs emerged such as the hardening of fats over Ni based catalysts in 1907.
Earlyinthe20th century, coalwasaprimary feedstock forbasic organic chemicals, largely based on coal liquefaction, distillation of coaltar, acetylene(from coke)orcoal gas (CO/H2). Although the ﬁrst oil well was drilled in 1859 and thermal cracking of petroleum was available, it was not until the accelerated demand for gasoline and thedevelopment of theHoudry catalytic cracking process that the modern petrochemicals industry really emerged. Petroleum, being a liquid, Houdry’s catalytic cracking (1930) played a major role in this shift away from coal feedstocks. Later, the FCC (Fluid Catalytic Cracking) process proved invaluable for high-octane aviation fuel for jet ﬁghters in W I. With the development of a petrochemicals industry, catalysis played a crucial role in producing products to enhance our quality of life through plastics, pharmaceuticals, and specialty chemicals. The many, major applications of catalysis to the petroleum industry did not begin after the 1920s with rapid growth after the 1940s. Occasionally, industrial teams developed new catalyst technology,butinmany casesspeciﬁcindividuals arecreditedwiththekey discovery.
Oxidation of benzene and aromatics to anhydrides in 1920 over
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