Dehydration, Dienes, High Octane, and High Pressures: Contributions

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Dehydration, Dienes, High Octane, and High Pressures: Contributions from Vladimir Nikolaevich Ipatieff, a Father of Catalysis Christopher P. Nicholas* Exploratory Catalysis and Materials Research, Honeywell UOP, 25 East Algonquin Road, Des Plaines, Illinois 60017, United States

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S Supporting Information *

ABSTRACT: Vladimir Nikolaevich Ipatieff contributed significantly to the birth of catalysis, first in Russia, then in Chicago at Northwestern University and UOP, and provided a strong base from which those of us practicing now continue to build. Among the discoveries in which he participated are the dehydration of alcohols to alkenes including ethanol to ethylene, the elucidation of the structure of isoprene, methods of butadiene synthesis, catalysts for hydrogenation, and the discovery and commercialization of oligomerization, paraffin alkylation, and acidcatalyzed aromatic alkylation. These discoveries and his enduring contributions in the form of the Ipatieff Prize and student education have ensured Ipatieff’s place in the chronicle of catalysis. KEYWORDS: oligomerization, alkylation, catalysis, history, Northwestern University, UOP

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INTRODUCTION The son of an architect, Vladimir Nikolaevich Ipatieff was born 150 years ago on November 21, 1867 in Moscow, Russia. By the end of his career, 85 years later on November 29, 1952, Ipatieff had contributed to the birth of our field and discovered multiple catalytic transformations still in commercial practice. Among the discoveries he participated in are the dehydration of alcohols to alkenes including ethanol to ethylene, the elucidation of the structure of isoprene, methods of butadiene synthesis, catalysts for hydrogenation, the discovery and commercialization of oligomerization, paraffin alkylation, and acid-catalyzed aromatic alkylation. Much of this work was carried out at high pressure in steel autoclaves, a key innovation Ipatieff brought to catalysis. Ipatieff lived during tumultuously changing times, having been born prior to the delineation of the periodic table and passing on during the space race. He witnessed both World Wars and the Russian Revolution, events that caused him to permanently leave the USSR and a successful career to start a new life in the United States at Northwestern University and Universal Oil Products (UOP) as depicted in the timeline of Figure 1. Due in part to these transitions, Dr. Ward Evans, then chair of the Chemistry Department at Northwestern, described Ipatieff’s life as reading “like a tale from the Arabian Nights”. In this account, I highlight some of Ipatieff’s many contributions to the understanding of catalysis as a field of chemistry and engineering and describe multiple ways he continues to beneficially impact the field of catalysis.

(Figure 2A) was sick for much of her life, going to Crimea in 1878 in an attempt to find a cure for her illness, but died of consumption in 1880. As a result, much of Ipatieff’s early education was in the form of tutoring provided by his uncle Mitia. Military schools, not universities, were the only option for Ipatieff, and he was admitted to the lower-level school of the famous Mikhail Artillery Academy (Figure 2C) in St. Petersburg in 1886 after some effort. He took math and artillery courses, graduating in 1887 with a commission in the Army.1 Ipatieff then returned close to home, taking a teaching job for 1888 and 1889 in the small town of Serpukhov for these same subjects. While teaching, he taught himself chemistry by reading textbooks from two famous chemists, Mendeleev’s The Fundamentals of Chemistry and Menshutkin’s Analytical Chemistry.2,3 Later, he remarked that Mendeleev and Menshutkin were his true mentors in chemistry as it was from their books that his chemical knowledge was obtained.4 Enamored with chemistry, Ipatieff used his graduation bonus, which was supposed to allow army officers to purchase a good winter coat, to fund a home laboratory. To continue with his education, Ipatieff applied for and was accepted into the upper level Mikhail Artillery Academy in 1889, graduating in 1892. He then spent much of the next 20 years in St. Petersburg affiliated with the Artillery Academy. Ipatieff began as an Instructor teaching inorganic and organic chemistry. One of his professors and then colleagues was D. K. Chernov, who is credited with starting the field of metallurgy. Chernov recognized the importance of polymorphism and the carbon−iron phase diagram which laid the foundations

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EARLY LIFE, INFLUENCES, AND STUDIES IN ALLENES AND TERPENES Vladimir Nikolaevich Ipatieff was born in Moscow, Russia on November, 21 1867. He was the oldest of three children and had a brother, Nikolai, and a sister, Vera. Their mother Anna © XXXX American Chemical Society

Received: June 14, 2018 Revised: July 30, 2018 Published: August 2, 2018 8531

DOI: 10.1021/acscatal.8b02310 ACS Catal. 2018, 8, 8531−8539

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Figure 1. A timeline of significant events in the life of Ipatieff and the history of chemistry.

practice at the time.16 With time still left on the fellowship, von Baeyer allowed Ipatieff time to work on a project of his choosing. Ipatieff started working on bromination reactions to produce allenes (Figure 3C) and noted that the same compound was produced by hydrobromination of isoprene and the allene he was attempting to make via dehydrobromination. By comparing compounds and preparing different synthetic routes, Ipatieff was the first to determine the structure of isoprene, correctly noting the diene character.17,18

for strong steel to be utilized both in cannons the Artillery Academy was developing, but also in the autoclaves Ipatieff developed a few years later.5 Indeed, Ipatieff’s first paper was actually on the properties of steel.6 Ipatieff’s research career began because a dissertation was necessary to be named Professor. While teaching, Ipatieff studied with A.E. Favorsky at the University of St. Petersburg, reacting bromine with tertiary alcohols to prepare precursors for allene synthesis (Figure 3A).7 The dibromo-substituted compounds produced could then be doubly dehydrobrominated to the coresponding allene. He was promoted to Assistant Professor upon acceptance of his dissertation in 1895. Ipatieff then began a steady rise, becoming Professor in 1898 at the age of 31, the first chemistry teacher in the Academy to hold the title of Professor. In 1896, Ipatieff won a prestigious scholarship from the Russian government to study abroad and bring knowledge and techniquesback to Russia. Favorsky recommended that Ipatieff go to Germany and work with the powerful group of Adolph von Baeyer. von Baeyer was best known and won the 1901 Nobel Prize for his work on indigo and other synthetic dyes. Among the other group members present at the time Ipatieff spent a summer there (Figure 2D) were Richard Willstätter, who won the 1915 Nobel Prize for his studies into the structures of plant pigments including chlorophyll,8 Wilhelm Königs, discoverer of the Königs−Knorr glycosylation reaction,9 and Moses Gomberg, who worked with von Baeyer to prepare tetraphenylmethane,10 and is best known for his discovery of triphenylmethyl radical, the first known persistent radical.11 Gomberg later became President of the American Chemical Society while at the University of Michigan.12 Ipatieff’s initial project with von Baeyer was to investigate the structure of carone (Figure 3B), a terpene obtained from derivatization of carvone,13 of which von Baeyer and Thorpe had been trying to determine the structure.14,15 Ipatieff oxidized carone with permanganate and studied the structure of the caronic acids obtained to determine the structure of the first known bicyclic terpene. Baeyer was so pleased with Ipatieff’s insights that Ipatieff’s name is on the resulting paper, an unusual

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DEHYDRATION, DEHYDROGENATION, AND THE UNDERSTANDING OF CATALYSIS It was about 1900 when Ipatieff started to understand catalysis, a phenomenon he called contact reactions at the time. In his laboratory in St. Petersburg, Ipatieff was attempting to prepare butadiene by the only known method at the time, heating amyl alcohol. As it was something he had in plentiful supply, he utilized a steel tube to prepare butadiene and was surprised to find a different product than expected. Carrying out systematic observations, Ipatieff noted that primary alcohols dehydrogenate to aldehydes, secondary to ketones, and tertiary to alkenes.19 He figured out that the dehydrogenation was caused by the iron tube he utilized, and that if he used quartz as others in the field were, then butadiene and methane were obtained as expected. Because Ipatieff determined that the reaction occurred due to contact with the reactor wall, he called these reactions contact reactions.20 About this point in time, Sabatier started publishing on the phenomena of catalysis.21 Both men refused to cite each other and published in separate languages. Each correctly claimed to have contributed heavily to the development of catalysis and continued the spat until the 1930s, well after the time Sabatier had been awarded the 1912 Nobel Prize for work on hydrogenation.22,23 An offshoot of the investigation of these contact reactions resulted in the discovery of alumina as an outstanding dehydration catalyst.24 Starting with iron, and working his way through other metals and metal oxides to understand dehydrogenation 8532


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Figure 3. Early chemical work carried out by Ipatieff. (A) Bromination of tertiary alcohols to dibromides performed during his initial dissertation work. (B) The structure of carone, a monoterpene, the structure of which he solved during a postgraduate fellowship with von Baeyer. (C) Routes utilized to determine the structure of isoprene.

γ-alumina is still the catalyst utilized commercially for dehydration.30−32

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WORLD WAR I AND THE RUSSIAN REVOLUTION An offshoot of the ethanol dehydration work was Ipatieff’s discovery of a reaction where ethanol was converted to butadiene over powdered aluminum (or Al2O3) in small quantities.29 As time progressed and Ipatieff’s talents were recognized, he was asked to run larger operations. By the start of WWI in 1914, Ipatieff was named chairman of the Committee for Preparation of Explosives which wound up directing activities for much of the Russian chemical industry by the end of the war. He often reported progress directly to the Tsar and, after the Revolution in 1917, to Lenin and then Trotsky. Ipatieff continued these duties in addition to teaching until his political removal from the post in 1926 as Stalin consolidated power.33 While this took time from his own research, he was able to suggest many projects. Some were in the production of butadiene, a key raw material for rubber. Suggestions to follow up Ipatieff’s initial results culminated in the one-step Lebedev and two-step Ostromislensky processes34 that were used by the 1940s to make 100 000 tons/yr of butadiene in the USSR and 300 000 tons/yr in the U.S., or 1/3 of the U.S. supply.35 Amazingly, these processes can still be found in use today, so mechanistic investigation has continued. While crotonaldehyde is a key intermediate,36 the reaction is generally believed to run through dehydrogenation of ethanol to acetaldehyde followed by further reaction with ethanol to form butadiene.37,38

Figure 2. (A) Ipatieff’s mother Anna in 1870. (B) V.N. Ipatieff in 1897 just after studying with von Baeyer. (C) The Mikhailovsky Artillery Academy as seen in ∼1895 on the banks of the Neva River. (D) The group of Adolph von Baeyer in 1896. Identified in the photograph are (first 4 in the front row, right to left) Ipatieff, Wilhelm Königs, Adolph von Baeyer, and Johannes Thiele. Second from the right in the 2nd row is Richard Willstätter, and 3rd from the right in the 3rd row is Moses Gomberg.

effects over the course of his career, Ipatieff discovered that dispersion of the metals had significant impact on catalytic behavior.25 Understanding of the effect of small amounts of promoter metals, such as that of Zn on Cu is another discovery Ipatieff made while performing these fundamental studies.26 Ipatieff noted that many metal oxides were catalysts for dehydration of alcohols.27,28 Among the best catalysts, particularly for ethanol to ethylene, was γ-alumina.29 The Schering company noticed his paper and produced a commercial process for dehydration from it. Although the paper was in the open literature, Ipatieff received a check for 1000 Marks in the mail as gratitude.4 Even though discovered long ago, alumina surfaces continue to be investigated for this reaction and

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HIGH PRESSURES: PHOSPHORUS OXIDATION AND METALS PRODUCTION FOR INDUSTRY At the time Ipatieff started in catalysis, high pressure was difficult to work with as most instruments had to be fabricated by hand. Most scientists did not have extensive knowledge of materials properties and typical apparatuses were fabricated from glass. Ipatieff used his knowledge of high-quality steels to fabricate autoclaves with Cu seals held between knife edges on the top and bottom portions of the autoclave. If steel was not a desired material to contact the reaction, a liner of glass, copper, 8533


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ACS Catalysis or silver would often be utilized. After a year of experimentation,4 he could construct autoclaves holding 450 atm at 500 °C or up to 1300 atm at 25 °C and therefore work on reactions including the oxidation of phosphorus and highpressure hydrogenations.39 In 1927, the USSR desired to resume contact with foreign scientists. At the age of 60, Ipatieff was assigned the title of Ambassador of Russian Science and allowed to consult for foreign companies. Among the commercial processes that Ipatieff developed in Germany for Bayerische Stickstoff Werke was one for catalytic conversion of phosphorus into phosphoric acid via high pressure oxidation with water.40 Here, Ag liners were used in the autoclaves.4 Ipatieff carried out mechanistic work to understand that the primary reaction involved oxidation of P4 to H3PO3 with equimolar formation of PH3. PH3 is then consumed with additional water, leading to H3PO4 and H2 while the H3PO3 produced in the main reaction is oxidized to H3PO4 with production of H2.41 While this process for H3PO4 production has been supplanted by conversion from Ca3(PO4)2 or a thermal oxidation process, largely to avoid the formation of phosphine, these were important studies to understand how P4 oxidation occurred and guide science to the current thermal oxidation process.42 Between about 1909 and 1930, Ipatieff studied reductions to the metal of numerous aqueous salts using H2 as an alternative to known carbothermal techniques.43 Among the numerous pure metals produced via these high-pressure hydrogenations was Cu from CuSO4 solutions using 200 atm of H2 at relatively high temperatures of 90 °C, a process Ipatieff was working on for Bayerische Stickstoff Werke at the time of his leaving for the United States.4,39 By slightly lowering temperature and pressure, Cu2O could also be produced easily.

Figure 4. An undated photo of Ipatieff from the early 1930s.

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A NEW LIFE IN THE UNITED STATES Early in 1930 as Stalin’s grip on Russia tightened, Ipatieff (Figure 4) learned that he was high on a list of personnel to be picked up by Soviet intelligence.44 Many of his friends and professional colleagues had already disappeared after questioning. That summer, the USSR was sending 10 representatives to the World Power Congress in Berlin,45 and one of these representatives was arrested shortly before the conference. Surprisingly, Ipatieff was named the replacement for him and was also able to obtain a visa for his wife to leave the country at the same time for medical treatment. Together, they boarded a train with only their possessions for a two week stay. As they passed the border from the USSR into Poland, Ipatieff noted to his wife “take a good look, it may be the last we see of Mother Russia”. Hans Tropsch introduced Ipatieff to Gustav Egloff, the research director at Universal Oil Products, at the conference. The drumbeat of war was clearly approaching, and many scientists were looking to leave Europe for the United States (Figure 5). Egloff was in Europe searching for new talent and methods of increasing petroleum refining yields, and wound up offering positions at UOP as group leaders to both Tropsch and Ipatieff. Three others including the chemist Aristid von Grosse also joined UOP.46,47

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Figure 5. A 1933 partial reunion of the von Baeyer group in Chicago following the awarding of the Willard Gibbs medal to Willstätter. From left to right: Ipatieff, Richard Willstätter, Gustav Egloff, Moses Gomberg.

facilities, one of the first areas Egloff had Ipatieff consider was that of increasing the yield of gasoline from the Dubbs cracking process.46 Ipatieff initiated a series of experiments at UOP aimed at utilizing cracked gases containing propene and butenes as feeds and received reports throughout the year after he returned to Europe for his previously contracted work on the precipitation of metals with Bayerische Stickstoffwerke.4,43 Oligomerization. Ipatieff, working with Schaad, Corson, and Pines, discovered a number of acids catalyze the

HIGH-OCTANE GASOLINE AND WWII

Key to performance of aircraft critical to winning WWII for the Allied side were 100 octane gasolines generated by three processes: oligomerization, aromatic alkylation, and paraffin alkylation.48 After arriving at UOP in 1930 to view the Riverside 8534


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ACS Catalysis oligomerization of alkenes to longer, branched alkenes49 upon returning to Chicago with his family in the summer of 1931.44,46 The most successful catalyst they discovered from these fundamental studies was phosphoric acid supported on a SiO2 support,50 which they called “solid phosphoric acid” or SPA.51,52 The product gasoline from oligomerization of mixed propene and butene feeds had an octane number of 81, significantly higher than the average 65 octane of the 17.8 billion gallons of gasoline produced in the United States in 1934.35 Commercialization of the “polymerization” reaction was extremely rapid, with over 100 units constructed from 1935 to 1945 and about 250 in total. Amazingly, the technology is still practiced today at about 9% of refineries, even with newer developments in shape-selective acidic solids.53 To produce 100 octane fuels, a second version of the oligomerization was created. Known as “Selective Polymerization”, isobutene was dimerized to 2,4,4-trimethylpentenes followed by hydrogenation to 2,2,4-trimethylpentane (isooctane). Plants constructed to produce isooctane were largely secrets due to the approach of WWII.54 As detailed below, the Caribbean islands Aruba and Curacao were leading fuels producers at the time and employed CatPoly processes (Figure 6). Both selective and unselective versions were constructed on Curacao and at least one is still operating.55

Figure 7. Photos from 1940 of the combination process utilized at the former ICI facility in Billingham, England, utilizing dehydrogenation of butanes, oligomerization of the resulting alkenes, hydrogenation and fractionation to recover high octane gasoline. (A) The top image shows the dehydrogenation section on the right, and the olig/H2/frac section is the tower assembly on the left. (B) Close-up of the dehydrogenation furnace assembly.

Figure 6. The first Selective Polymerization (isobutene dimerization and hydrogenation) unit was located at the Isla Refinery in Curacao. The photo is from 1939; the identity and location of the unit were kept as a secret through WWII.

Dehydrogenation/Oligomerization Combination Processes. Although the oligomerization processes were performing well, at some locations light alkenes were in short supply, so attention turned to methods of creating alkenes from paraffins. As noted above, early in his career, Ipatieff had worked on dehydrogenation. One of his discoveries was that CrO3 was an active, but short-lived catalyst,56 a discovery later confirmed by Sabatier.57 Work by a number of groups, including that at UOP, turned to supporting metal oxides including chromia on inactive supports such as alumina to reduce crystallization of CrO3.58 The catalysts and process that Ipatieff and Aristid van Grosse invented comprised less than 10 wt % CrO3 on γ-Al2O3 in a fixed bed, atmospheric pressure process with ∼1 h catalyst life and were commercialized in combination with Shell.59,60 The first such installation is shown in Figure 7 at the Billingham location of ICI where the dehydrogenated product is fed to the polymerization apparatus

before hydrogenation to 100 octane gasoline additives.61,62 While significantly better known for his catalytic cracking process developed in the 1930s,63 Eugene Houdry improved upon the dehydrogenation process by utilizing subatomospheric pressure,64 leading to higher conversion and longer catalyst lifetime.65 The catalyst and process brought to the fore by Ipatieff has been improved subsequently and is still sold today, now as the Clariant/CB&I Catofin process. Aromatic Alkylation. A second method of producing 100 octane gasoline discovered by Ipatieff utilized the same acid catalyst as that for oligomerization, SPA. Lewis acid-catalyzed Friedel−Crafts alkylations of aromatics had long been known, so a natural extension of the oligomerization results was to explore Brønsted acid-catalyzed aromatic alkylation. By 1938, Ipatieff had invented and patented processes using SPA to produce ethylbenzene and cumene (isopropylbenzene) at 8535


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Figure 8. Dedication of the Ipatieff Teaching Laboratory at Northwestern Technological Institute, 1947. (A) The dedication ceremony was attended by Dr. Herman Pines, Dr. Virgil C. Williams, Professor Ipatieff, Dr. Robert E. Wilson, Dr. Robert K. Summerbell (front row, left to right) and Colonel J.C. Raaen, Edwin F. Nelson, Dr. K.M. Watson, Dr. Ovid W. Eshbach (back row, left to right). (B) Pines and Eugene Aristoff inspecting equipment within the teaching laboratory. (C) An Ipatieff type rotating autoclave situated within a steel safety enclosure. (D) A luncheon was held following the dedication ceremony. (E) Plaque commemorating the Ipatieff High Pressure Laboratory located within the Catalysis Center at Northwestern.

>90% selectivity using moderate pressures of 300−900 psi.66 However, due to the technological significance (EB and cumene have octane numbers of 112),67 secrecy orders from the U.S. Patent Office forbade publications of the results in the open literature until 1946.68 SPA was the catalyst then used commercially for aromatic alkylation until the advent of shape selective zeolites in the 1980s.69,70 Ipatieff continued mechanistic studies of the reaction throughout his career, noting that that for alkenes where isomerization has a competitive rate to alkylation, mixtures of aromatic products results.71,72 Paraffin Alkylation. In the early 1930s, the analytical method for determination of the alkene content in a hydrocarbon fraction was to shake with H2SO4 to sulfonate the alkene.51 Herman Pines, employed as a young analytical chemist at the Riverside, Illinois UOP site, kept noticing increases in the gasoline fraction when performing this test. While no one else among management was interested, Ipatieff mentored Pines and requested additional research with pure compounds,73 ultimately leading to the discovery of multiple acids, including HF and H2SO4, as catalysts to produce what is termed “alkylate” via the reaction of isobutane and alkenes to yield isooctane.74−76 Among the first units constructed of what is now a standard gasoline producing technology in oil refining was that at the Shell Stanlow refinery in the U.K.77 This discovery is emblematic of the approach Ipatieff took to discovering new catalysts and reactions. When an unexplained phenomenon occurred, one should step back; and rather than use the complicated refinery feed, use model compounds to establish reactivity patterns. Ipatieff would then council to figure out the reaction mechanism and intuit how to increase reactivity from there. The group screened the known acids to find the best catalyst for oligomerization and alkylation. Aviation gasoline from these three methods was produced in quantities exceeding 24 million gallons per month for the

Allied Air Forces during WWII.54 The Isla refinery in Curacao and the Lago refinery in Aruba were leading producers outside of the United States, with smaller production volumes coming out of locations in England and Iran. While the presence of the specific technologies employed may have been a secret, Axis planners certainly knew of the importance of products from these refineries. Throughout the war, harassment of tankers coming from these refineries north to Newfoundland before continuing to Europe was a continual problem.59 Early in 1942, in attempts to reduce output of the critical fuel supply, several actions during Operation Neuland included attempted shellings of the Aruba and Curacao refineries, which caused no damage to the refineries, although many tanker ships were destroyed (Supporting Information).78

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THE CONTINUING LEGACY OF IPATIEFF The Ipatieff Laboratory at Northwestern. Even as these scientific and technological successes mounted, Ipatieff remained humble and committed to science and education. While in Russia, Professor Ipatieff had been described as approachable and someone who tried to stay away from politics with a “strong dedication to universal science in which knowledge should be freely available to all”.79 As a well-regarded professor, it made sense that as UOP brought Ipatieff to Chicago, the help of a university was sought to help secure a permanent visa. It was only through the efforts of Ward Evans, chair of the Department of Chemistry at Northwestern, that Ipatieff was granted a visa to work in the United States.80 During his time in the United States, Ipatieff split time between UOP and Northwestern, having started at Northwestern in 1931 as a Saturday morning lecturer. The first years were difficult as he spoke essentially no English upon arriving in the United States. Each week, he would lecture from a script that had been practiced all that week. By 1937, Ipatieff spoke English well 8536


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The Ipatieff Prize. A final way in which the Ipatieff legacy continues is via the Ipatieff Prize. In 1943, Ipatieff funded an award to further efforts in the fields of catalysis or high pressure which would be administered by the ACS.85 The Ipatieff Prize is awarded every 3 years to a scientist of any nationality under the age of 40. Since the initial awarding of the prize in 1947 to Lou Schmerling for work on understanding the reaction mechanism of isoparaffin alkylation (Figure 10), the Ipatieff Prize has been given in recognition of a wide variety of catalytic pursuits and remains the top honor in catalysis for early-career researchers.

enough to be named Research Professor, a designation that came with space for a laboratory. Ipatieff funded the equipment for the laboratory himself, putting $26,000 ($450,000 in 2018 dollars) into a space in the basement of the original building on campus, University Hall. In 1942, Technological Institute opened and the High Pressure Catalysis Laboratory moved to a better equipped spot. In 1947, the space was christened the Ipatieff Teaching Laboratory so that future generations of chemists/engineers could be taught and a dedication ceremony held (Figure 8). By this point, Ipatieff had personally committed $56,000 (almost $1M in 2018 dollars) to the laboratory over the course of time, with additional gifts from, among others, UOP and its CEO Hiram Halle, Victor Manufacturing (toll manufacturer of SPA), and Standard Oil.81 Since the inception of the Ipatieff Teaching Laboratory, Ipatieff has continued to have an impact on catalysis at Northwestern by way of spaces dedicated for catalysis research to teach generations of students the techniques and research methods of the field of catalysis. As described, in the beginning, it was a single laboratory. As the laboratory moved and expanded, Ipatieff continued to come to the office until his sudden death on November 29, 1952 at the age of 85.82 In 1983, to honor Ipatieff’s legacy and expand the range of catalysis activities possible, an entire building was constructed (Figure 9). The Northwestern Catalysis Center opened in 1986 at a cost of just over $6M ($13.6M in 2018 dollars).83 The building is dedicated to Ipatieff (Figure 8E), and a charcoal portrait of him hangs in the first-floor entrance. Today, 27 faculty members from multiple academic departments at Northwestern are affiliated with the Catalysis Center and continue to educate students while producing high quality catalytic research from the approximately $1.5M/yr in annual sponsored research associated with the Center.

Figure 10. Ipatieff awarding Louis Schmerling the plaque for the first Ipatieff Prize.

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CONCLUSIONS Over the course of over 50 years of scientific work, almost 350 papers, and over 200 patents, Vladimir Ipatieff contributed numerous concepts to catalysis including high pressure, dispersion of metals on supports, and the use of promoters. He also discovered many catalysts and reactions, several of which are still in use today, some 80 years later. His efforts continue to inspire the catalysis community in many ways, including through the Ipatieff Prize administered by the ACS, processes offered by industry, and the teaching of students at Northwestern University.

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ASSOCIATED CONTENT

* Supporting Information S

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acscatal.8b02310. Further discussion of attacks on Allied shipping and refining in the Caribbean (PDF)

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Figure 9. Northwestern Catalysis Center (center) is dedicated to V.N. Ipatieff. It is connected by skybridge both to the Technological Institute (right), where the teaching lab was originally situated, and the newer Patrick G. and Shirley W. Ryan Hall Center for Nanofabrication and Molecular Self-Assembly (left).

AUTHOR INFORMATION

Corresponding Author

*E-mail: [email protected]. ORCID

The Ipatieff Professorship. Following the sudden death of Ipatieff in 1952 after 20 years of teaching catalysis in Chicago,84 donations were obtained to found an eponymously named professorship in catalysis chemistry at Northwestern.81 Ipatieff’s original laboratory assistant, Herman Pines, was appointed the first Ipatieff Professor in 1953 upon leaving his position at UOP. Robert Burwell followed in 1970, and Wolfgang Sachtler in 1983. The current Ipatieff professor, Tobin J. Marks, was appointed in 2000.

Christopher P. Nicholas: 0000-0003-1461-3791 Notes

The author declares no competing financial interest.

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ACKNOWLEDGMENTS C.P.N. gratefully acknowledges the help of the Honeywell UOP organization and Northwestern University Catalysis Center personnel including, in particular Christina Krawczyk 8537


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ACS Catalysis

(29) Ipatiew, W. Zur Frage Ü ber die Zersetzung des Ä thylalkohols in Gegenwart verschiedener Katalysatoren. J. Prakt. Chem. 1903, 67, 420. (30) http://www.ethanolproducer.com/articles/8617/feeding-thechemical-market (written March 5, 2012 and accessed July 12, 2018). (31) Steward, M. W.; Clark, H. W.; Coffey, D. P.; Luo, L.; Schweizer, A. E. U.S. Patent 9242919, to Dow Global Technologies, January 26, 2016. (32) Liu, Y.; Malek, A. M.; Coffey, D. P.; Stangland, E. E.; Schweizer, A. E. U.S. Patent 9180430, to Dow Global Technologies, November 10, 2015. (33) Activities between the Revolution in 1917 and 1920 were infrequent and arranged around converting a wartime chemical industry to peacetime industry. After 1920, this activity came together as the Central Chemical Laboratory. (34) Wang, Z. Comprehensive Organic Name Reactions and Reagents; John Wiley & Sons, 2010. (35) Vladimir, N. Ipatieff: A Testimonial in Honor of Three Milestones in His Career; American Institute of Chemists, 1942. Transcription of a symposium held at the Adventurers Club, Chicago, IL, November 20, 1942. (36) Toussaint, W. J.; Dunn, J. T.; Jachson, D. R. Production of Butadiene from Alcohol. Ind. Eng. Chem. 1947, 39, 120−125. (37) Bhattacharyya, S. K.; Avasthi, B. N. One-Step Catalytic Conversion of Ethanol to Butadiene in a Fluidized Bed. Ind. Eng. Chem. Process Des. Dev. 1963, 2, 45−51. (38) Angelici, C.; Weckhuysen, B. M.; Bruijnincx, P. C. A. Chemocatalytic Conversion of Ethanol into Butadiene and Other Bulk Chemicals. ChemSusChem 2013, 6, 1595−1614. (39) Ipatieff, V. N. Catalytic Reactions at High Pressures and Temperatures; Macmillan Publishing Co., Inc.: New York, 1936. (40) Ipatieff, V. N.; Freitag, C. Oxidation of Phosphorus with Water at Elevated Pressures and Temperatures. Z. Anorg. allgem. Chem. 1933, 215, 388. (41) Ipatieff, V. N.; Usachev, P. V. Oxidation of Phosphorus with Water at High Temperature and Pressure in the Presence of Alkali. The Production of Phosphorous acid. J. Am. Chem. Soc. 1935, 57, 300−302. (42) Buchel, K. H.; Moretto, H.-H.; Woditsch, P. Industrial Inorganic Chemistry, 2nd ed.; Wiley-VCH: Weinheim, 2000; Chapter 1.5. (43) Ipatieff, V. N. Early Work on the Displacement of Metals and Metal Oxides. J. Chem. Educ. 1953, 30, 110−115. (44) Ipatieff, V. N. My Life in the United States: The Memoirs of a Chemist; Translated and edited from his memoirs written in a mixture of languages; Northwestern University: 1959. (45) Arthur Eddington and Albert Einstein gave keynote lectures at the conference. It’s now known as the World Energy Congress and held every 3 years. https://www.worldenergy.org (accessed July 12, 2018). (46) Remsberg, C.; Higdon, H. Ideas for Rent: The UOP Story; UOP, 1994. (47) von Grosse, A. Zur Herstellung von Proactinium. Ber. Dtsch. Chem. Ges. B 1935, 68, 307. (48) Ipatieff, V. N. Aviation Gasoline by Polymerization and Alkylation of Cracking Gases. Chem. Eng. News 1942, 20, 1367−1368. (49) Ipatieff, V. N.; Pines, H. Propylene Polymerization. Under High Pressure and Temperature with and without Phosphoric Acid. Ind. Eng. Chem. 1936, 28, 684−686. (50) Ipatieff, V. N.; Schaad, R. E. Catalysts Suitable for Use in Effecting the Polymerization of Gaseous Olefins from Oil Cracking. U.S. Patent 2273320, to Universal Oil Products, Mar 3, 1942. (51) Ipatieff, V. N.; Corson, B. B.; Egloff, G. Polymerization, a New Source of Gasoline. Ind. Eng. Chem. 1935, 27, 1077−1081. (52) Schmerling, L.; Ipatieff, V. N. The Mechanism of the Polymerization of Alkenes. Adv. Catal. 1950, 2, 21−80. (53) Nicholas, C. P. Applications of Light Olefin Oligomerization to the Production of Fuels and Chemicals. Appl. Catal., A 2017, 543, 82−97. (54) Innovation and Development of Flight; Launius, R. D. Ed.; Texas A&M Press, 1999.

and Jim Puricelli, in obtaining many of the primary sources utilized here.

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REFERENCES

(1) Schmerling, L. Biographical Memoirs; National Academies of Science Press: Washington, DC, 1975; Vol. 47, Chapter 4, Vladimir Nikolaevich Ipatief f, pp 83−142. (2) Mendeleev, D. I. The Principles of Chemistry: 1868; published in the United States in 1902 by P.F. Collier & Son. (3) Menshutkin, N. I. Analytical Chemistry; University of Michigan Library, 1895. (4) Ipatieff, V. N. The Life of a Chemist: Memoirs of V.N. Ipatieff; Translated by Haensel, V.; Lusher, R.; Edited by Eudin, X. J., Fisher, H. D., Fisher, H. H., from his memoirs written in Russian; Stanford University Press: 1946. (5) Shakhnazarov, K. Y. Chernov’s Iron−Carbon Diagram, the Structure and Properties of Steel. Met. Sci. Heat Treat. 2009, 51, 3−6. (6) Ipatyev, V. N. Opyt Khimicheskogo Issledovaniia Struktury Stali. Artilleriiskii zhurnal 1892, No. part I, 937−954. (7) Ipatiew, W. Ü ber die Einwirkung von Brom auf Tertiäre Alkohole der Reihe CnH2n+2O. J. Prakt. Chem. 1896, 53, 257. (8) Huisgen, R. Richard Willstätter. J. Chem. Educ. 1961, 38, 10−15. (9) Igarashi, K. The Koenigs-Knorr Reaction. Adv. Carbohydr. Chem. Biochem. 1977, 34, 243−83. (10) Gomberg, M. Tetraphenylmethan. Ber. Dtsch. Chem. Ges. 1897, 30, 2043−2047. (11) Gomberg, M. An Instance of Trivalent Carbon: Triphenylmethyl. J. Am. Chem. Soc. 1900, 22, 757−771. ( 12 ) h t tps:// ww w. ac s. or g/ con ten t/ ac s/ en/edu cation / whatischemistry/landmarks/freeradicals.html (accessed July 31, 2018). (13) Armstead, D. E. F. A Centenary Synthesis of Carone and Dicarvelone. J. Chem. Educ. 1995, 72, 550−551. (14) Baeyer, A. Ortsbestimmungen in der Terpenreihe. Ber. Dtsch. Chem. Ges. 1895, 28, 639−640. (15) Perkin, W. H.; Thorpe, J. F. J. Chem. Soc., Trans. 1899, 75, 48− 61. (16) Baeyer, A.; Ipatiew, W. Ortsbestimmungen in der Terpenreihe: Ü ber die Caronsäure. Ber. Dtsch. Chem. Ges. 1896, 29, 2796−2802. (17) Ipatiew, W.; Wittorf, N. Zur Constitution von Isopren. J. Prakt. Chem. 1897, 55, 1−4. (18) Ipatiew, W. Ü ber die Constitution und Synthese von Isopren. J. Prakt. Chem. 1897, 55, 4−13. (19) Ipatiew, W. Eine neue Synthese von Methylheptenon. Ber. Dtsch. Chem. Ges. 1901, 34, 594−596. (20) Ipatiew, W.; Leontowitsch, W. Pyrogenetische Contactreactionen Organischer Verbindungen. Ber. Dtsch. Chem. Ges. 1903, 36, 2016−2019 and preceding pages containing 4 additional papers.. (21) Sabatier, P. Hydrogénations et Déshydrogénations par Catalyse. Ber. Dtsch. Chem. Ges. 1911, 44, 1984. (22) Zecchina, A.; Califano, S. The Development of Catalysis: A History of Key Processes and Personas in Catalytic Technology; John Wiley & Sons, 2017. (23) https://www.nobelprize.org/nobel_prizes/chemistry/ laureates/1912/sabatier-lecture.html (accessed July 12, 2018). (24) Ipatiew, W. Pyrogenetische Contactreactionen Organischer Verbindungen. Ber. Dtsch. Chem. Ges. 1902, 35, 1047−1057. (25) Boudart, M. Catalysis by Supported Metals, Chapter XX, Advances in Catalysis, Vol. 20; Frankenberg, W. G. Ed.; Academic Press, 1969. (26) Ipatieff, V. N.; Corson, B. B. U.S. Patent 2275181, to Universal Oil Products, March 3, 1942. (27) Ipatiew, W. Katalytische Reaktionen bei Hohen Temperaturen und Drucken.  Reduktionskatalyse. Ber. Dtsch. Chem. Ges. 1907, 40, 1270−1281. (28) Ipatiew, W. Katalytische Reaktionen bei Hohen Temperaturen und Drucken. Reduktionskatalyse in Gegenwart von Metalloxyden. Ber. Dtsch. Chem. Ges. 1907, 40, 1281−1290. 8538


Account

ACS Catalysis

(83) Pines, H. Genesis and Evolution of the Ipatieff Catalytic Laboratory at Northwestern University 1930−1970. Department of Chemistry, Northwestern University, 1992. (84) Burwell, R. L. Prof. V. N. Ipatieff. Nature 1953, 171, 151. (85) https://www.acs.org/content/acs/en/funding-and-awards/ awards/national/bytopic/ipatieff-prize.html (accessed July 12, 2018).

(55) http://www.refineriaisla.com/main/company-information/ (accessed July 12, 2018). (56) Ipatiew, W. Pyrogenetische Contactreactionen Organischer Verbindungen. Ber. Dtsch. Chem. Ges. 1901, 34, 3579. (57) Sabatier, P.; Mailhe, A. Bull. Soc. Chim. 1907, 4, 733 and earlier publications that year in Bull. Soc. Chim.. (58) Grosse, A. V.; Ipatieff, V. N. Catalytic Dehydrogenation of Gaseous Paraffins. Ind. Eng. Chem. 1940, 32, 268−272. (59) Varey, P. 100 octane: The story behind the fuel; Peter Varey Associates, 2017; Chapter 27. (60) Stratton, M.; Trinder, B. Twentieth Century Industrial Archaeology; Taylor & Francis, 2010; Chapter 6, The Age of Science. (61) Beesley, E.; Whipp, B. Butane Dehydrogenation at Billingham, Chem. Ind. 1953, August 10th, S50−S56. (62) Kletz, T. A. By Accident: A Life Preventing Them in Industry; PFV Publications: London, 2000. (63) Houdry Process for Catalytic Cracking, a National Historic Chemical Landmark. https://www.acs.org/content/acs/en/ education/whatischemistry/landmarks/houdry.html (accessed July 12, 2018). (64) Houdry, E. J. Process for Producing Diolefins, U.S. Patent 2423029, to Houdry Process Corporation, June 24, 1947. (65) Jackson, S. D.; Stair, P. C.; Gladden, L. F.; McGregor, J. Alkane Dehydrogenation over Vanadium and Chromium Oxides; Jackson, S. D., Hargreaves, J. S. J., Eds.; Wiley-VCH, 2009; Chapter 15, Metal Oxide Catalysis, Vol. 1. (66) Ipatieff, V. N.; Schaad, R. E. U.S. Patent 2120702 to Universal Oil Products, June 1938. (67) Do, P. T. M.; Crossley, S.; Santikunaporn, M.; Resasco, D. E. Catalytic Strategies for Improving Specific Fuel Properties. Properties J. Catal. 2007, 20, 33−64. (68) Ipatieff, V. N.; Schmerling, L. Ethylation of Benzene in Presence of Solid Phosphoric Acid. Ind. Eng. Chem. 1946, 38, 400− 402. (69) Tanabe, K.; Hölderich, W. F. Industrial Application of Solid Acid−Base Catalysts. Appl. Catal., A 1999, 181, 399−434. (70) Schmidt, R. J. Industrial Catalytic ProcessesPhenol Production. Appl. Catal., A 2005, 280, 89−103. (71) Pines, H.; LaZerte, J. D.; Ipatieff, V. N. Isomerization Accompanying Alkylation. VI. Reaction of Isobutylene and 2-Butene with Benzene. J. Am. Chem. Soc. 1950, 72, 2850−2853. (72) Pines, H.; Huntsman, W. D.; Ipatieff, V. N. Isomerization Accompanying Alkylation. VIII. Reaction of Benzene with 2- and 3Pentanol. J. Am. Chem. Soc. 1951, 73, 4483. (73) Pines, H.; Grosse, A. V.; Ipatieff, V. N. Alkylation of Paraffins at Low Temperatures in the Presence of Aluminum Chloride. J. Am. Chem. Soc. 1942, 64, 33−36. (74) Ipatieff, V. N.; Pines, H. U.S. Patent 2112846 to Universal Oil Products, April 1938. (75) Ipatieff, V. N.; Schmerling, L. Alkylation of Isoparaffins. Adv. Catal. 1948, 1, 27−64. (76) Ipatieff, V. N.; Pines, H. Hydrocarbon Synthesis, as in the Production of a Motor Fuel from Isobutane and Propene, U.S. Patent 2318781 to Universal Oil Products, May 11, 1943. (77) Edgerton, D. Britain’s War Machine: Machines, Resources, and Experts in the Second World War; Oxford University Press, 2011. (78) Bercuson, D. J.; Herwig, H. H. Long Night of the Tankers: Hitler’s War Against Caribbean Oil; University of Calgary Press, 2014. (79) Samovar on the Table: A Family Memoir. Words and thoughts of Nikolai Dimitch Matov as told to his granddaughter Lana der Partough; AuthorHouse UK, 2016. (80) Pines, H. My Mentor, Ipatieff. Chemtech 1981, 78−81. (81) Chem. Eng. News 1952, 30, p 5276. DOI: 10.1021/cenv030n050.p5276 (82) Hampson, P. The Road to Success: A Sketch of Vladimir Ipatieff, Famed Oil Scientist. Chicago Tribune, September 27, 1952 p 35. 8539


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