W. Keith Hall: One of the giants in catalysis

Keith Hall

Keith Hall passed away in his farm/home at Mill Run, Pennsylvania on 3 January 2001 at the age of 82. The catalytic community has lost a major family-member and leader.

Keith was born in McComb, Ohio and graduated from Emory University in 1940. Shortly thereafter, a summer course in high explosives at Georgia Tech undoubtedly led Frank Long to hire him to work on Manhattan Project at the Bruceton Experimental Station as directed by the U.S. Bureau of Mines. Working under the direction of George Kistiakowski and Louis Hammett, Keith met and married his wife Gladys, a secretary earning money for college (“they paid better than anyone else!”) in 1945 while at Bruceton. As the war ended, Keith continued at the Bureau with H. H. Storch and Robert B. Anderson where he was introduced to catalysis, specifically to Fischer-Tropsch synthesis. Concurrently, he received his MS in 1948 from Carnegie Institute. The end of the war had generated an interest in synthetic fuels, and Sol Weller, Irving Wender and Milton Orchin joined the group. This concerted effort was finally terminated by congress in 1956. In 1951 Keith moved across town to work on his PhD at Mellon Institute under Paul Emmett. Keith received his PhD in 1956 from University of Pittsburgh. His son Burl (now a physicist at LBL) was born in 1955. Contemporaries working at the Mellon Institute with Emmett included Dick Kokes, Joe Kummer, Don McIver, Bob Anderson (?), Bob Zabor, and Bob Haldeman. When Emmett left Pittsburgh in 1954, Hall was named as his successor.

Keith continued to work at the Mellon Institute as a Senior Fellow until 1970 when he took a Senior Scientist position with Gulf Research outside Pittsburgh. Keith retired from Gulf in 1973. George Keulks convinced Keith to accept the position of Distinguished Professor of Chemistry at the University of Wisconsin-Milwaukee. Many students and postdoctoral students worked with Keith at Milwaukee. While there he coordinated the US-USSR exchange in chemical catalysis. Keith is well remembered for his mandatory Saturday research meetings to keep the troops in order. These meetings developed an international reputation themselves and were known to last well into the afternoon by visitors world wide. Keith retired from this position in 1985 to return to his farm in Mill Run. But his retirement was short lived, as once again he was convinced to become a Distinguished Professor, this time at the University of Pittsburgh, his PhD alma mater. Keith finally retired, for the third and final time, from this position in 1998.

Keith started his catalysis research on Fischer-Tropsch synthesis with Bob Anderson and continued with Emmett [J.Am.Chem.Soc. 82, 1027 (1960)]. But he also initiated studies of hydrogenation over metals and alloys to test Dowden’s electronic theories of catalysis [J.Phys. Chem 62, 816 (1958) and 63, 1102 (1959)]. His employment of isotopic techniques was highly visible throughout his career [J.Am.Chem.Soc. 79, 2091 (1957)]. He published seven papers with Emmett. After Emmett left to again take a position at Johns Hopkins University, Keith continued his interest in hydrogen on solids, primarily metals supported on oxides. He employed a variety of techniques including ESR and NMR often coupled with isotopic studies [J.Catal. 2, 506 (1963) and 2, 518 (1963)]. Keith soon became interested in acidity of silica alumina [J.Catal. 1, 53 (1962) and 3, 512 (1964)]and eventually on zeolites, an interest that would continue throughout his research. He studied hydrocarbon isomerization over a variety surfaces (J. Catal. 13, 161 (1969), Trans. Faraday Soc. 566-66, 477 (1970)]. Keith also became involved in studies of oxidation on metals and eventually on metal oxides, most notably Mo/Al2O3 [J.Catal. 34, 41 (1974)]. Again isotopic studies and a variety of spectroscopic techniques were employed [J. Catal. 53, 135 (1978)], including infrared. In the 1980’s Keith initiated a series of studies related to auto exhaust catalysis. These started with Fe/zeolites [J.Catal. 166, 368 (1997)] and eventually Cu/zeolites [Catal. Let. 15, 311 (1992), J.Phys.Chem. 97, 1204 (1993)] where he developed considerable insight into SCR [J.Catal. 149, 229 (1994)] and NOx reactions [Appl. Catal. B-Env. 2, 303 (1993)]. In parallel, Keith’s interest in the reasons for catalytic acidity and in the role of hydrogen on metals and oxides continued well into the 1990’s.

Keith’s publications have had a profound impact on the catalytic community. Over a score of these have been cited more than a hundred times by others. These include each of those mentioned in the previous discussion as we traced Keith’s areas of research. Altogether he had more than 4,000 citations to his work.

Keith served and led the Catalytic and Chemical community in several ways. He was the editor on the Journal of Catalysis from 1967 to 1989, a period when J.Catalysis became the primary Journal in heterogeneous catalysis. Frank Stone was the European editor and they were close friends. Keith was the president of the Catalysis Society of North America from 1981-85 and founded the Catalysis Society Trust, which has given the society on a strong fiscal base. Keith gave five lectures at Gordon Conferences, was chairman of the Gordon Conference on Catalysis, and served as a Trustee of the Gordon Conferences from 1981-87. Who can forget his perennial presence in the front row of the Gordon Conferences where he would challenge and extrapolate the concepts presented as well as remind the speakers of the prior-art they may have neglected to mention? He had the same room at the conference for many years which was closest to the late night discussions in which he participated actively. In the afternoon he would sail and discuss the concepts of the catalytic science presented. Keith was also active in the ACS and served on the executive committee on the Colloid and Surface Chemistry Division.

Keith received numerous awards, including the Kendall Award, the ACS Petroleum Chemistry Award, and the Exxon Award for Excellence in Catalysis.

One of the most notable aspects of Keith Hall’s research career is the large number of people with whom he worked and to whom he graciously attributed their joint accomplishments. He learned from as he taught each of his students, postdoctoral students, and research colleagues. More than a dozen students received their graduate degrees under Keith’s supervision. These include: Suhil Abdo, L. Christner, Michel Deeba, José Goldwasser, Chuck Kibby, Dave Kreske, Y. Li, J. Larson, Edwardo Lombardo, R. Schneider and L. Wang. Keith had over two dozen postdoctoral colleagues including: John Bett, Victor Borokov, Noel Cant, W. Curt Conner, Michel Crespin, Gary Delzer, Joseph Engelhardt, Xiaobing Feng, G. Fierro, Chia-Min Fu, H. Gerberich, Joe Hightower, Marwan Houalla, V. Korchak, T. Komatsu, Sheldon Lande , K.-Y Lee, H. Leftin, Jacques Leglise, Mario Lo Jocono, Ross Madon, William Millman, Mikoto Misono, Jaun Petunchi, Ko-ichi Segawa, Henri Van Damme, Frank Witzel, Jan Uytterhoeven and Jozsef Valyon. Fifteen of these graduate and postdoctoral students hold faculty positions and continue to teach.

In addition, Keith has collaborated with over ninety other catalytic research scientists around the world. His collaborators included: Paul H. Emmett, Dick Kokes, Vladim Kazanski, Bob Anderson, Henry H. Storch, H. R. Gerberich, F. H. Van Cauwelaert, M. Missono, Frank Massoth, Kh. Minichev, George Keulks, W. Nick Delgass, Jim Dumesic, Gerhart Ertl, Helmut Knözinger, Dave Hercules, Farrell Lytle, Jose Fripiat, Bernie Gerstein and Julie d’Itri. Keith had over one hundred and twenty co-authors in his more than three hundred and fifty publications.

It is obvious that Keith Hall’s influence on catalytic research has been profound not only in what he has accomplished directly but in his vast network of interactions throughout the catalytic world. Moreover, Keith readily served as a leader in the catalytic research community through the Journal of Catalysis, the Gordon Conferences and the Catalysis Society. All scientists in catalysis have lost a family member!

Vladimir Nikolaevich Ipatieff

Vladimir Nikolaevich Ipatieff

Vladimir Nikolaevich Ipatieff was born on 21 November 1867 in Moscow, Russia. His early career was that of a military man: in 1887 he graduated from the Mikhailovskoe artilleriiskoe uchilishche, and in 1892 from the Mikhailovskaia artilleriiskaia akademiia. But his interest in chemistry diverted him from a strictly military path. Teaching the subject at the Artillery Academy, he went on to get a doctorate from St. Petersburg University in 1907, while advancing in military rank to major general in 1910. From 1906 to 1916, he taught chemistry at the University as well, and was made a member of the Imperial Academy of Sciences in 1916. As a lieutenant general during the First World War, he served as Director of the Commission for Preparation of Explosives and Chairman of the Chemical Committee.

Following the revolution, he remained in the Soviet Union, where he founded the High Pressure Institute in 1927. But in 1931, while on a trip abroad, he decided not to return and came to the United States, where he taught at Northwestern University from 1931 to 1935. In 1939 he was elected a member of the National Academy of Sciences. Ipatieff died in Chicago on 29 February 1952. Northwestern University dedicated a laboratory in his honor.

[A slightly different version about his move to the USA (from Professor Peter Stair of Northwestern Univeristy): Ipatieff had been a General under Tsar Nicholas II and Chairman of the Chemical Administration and winner of the Lenin Prize under the Soviets. Shortly after Ipatieff emigrated from the USSR to avoid the Stalin purges, he was approached by representatives of Universal Oil Products (UOP) who invited him to work in the USA in the dual capacity of Director of Chemical Research at UOP and Professor of Chemistry at Northwestern University. He worked together with Herman Pines to discover and develop the important processes of isomerization and alkylation with liquid acids based upon the reaction of paraffin molecules in petroleum reacting with an aqueous solution of sulfuric acid. In early 1940, at the beginning of World War II, the first alkylation plant came on stream in the US. The boost in aircraft fuel octane made possible by this plant played a significant role in the success of the British Royal Air Force in the Battle of Britain.]

Ipatieff authored hundreds of articles on chemistry in a number of languages, as well as textbooks, such as Kolichestvennyi analiz, which he wrote while still a student (St. Petersburg, 1891); a scientific autobiography, Catalytic Reactions at High Pressures and Temperatures (New York, 1936); and personal memoirs, Zhizn’ odnogo khimika (New York, 1945), translated into English as The Life of a Chemist (Stanford, 1946). He also held several hundred patents, marking his most significant contributions to science: the formulation of high-octane gasoline, the “cracking” method now used to refine gas, and other discoveries relating to catalytic reactions (especially under high pressures and temperatures), and the synthesis of petroleum and its distillates.
 
Contributed by Hoover Institute and Peter Stair
From the Hoover Institution’s Archives: (http://www-hoover.stanford.edu/hila/ruscollection/ipat_b.html)

Sir Eric Rideal

E. Rideal

Sir Eric Rideal

Sir Eric Rideal who was one of the founders of catalysis in Great Britain and who was the eponym of the famous Eley Rideal mechanism. Professor E. Rideal was famous for the work of the Colloid Science Laboratory which he set up in Cambridge University in the 1930s. He was born in 1890 and was first involved in surface chemistry during the First World War when, with
H.S. Taylor, he worked on catalysts for the Haber process for the production of ammonia from nitrogen and hydrogen, and for the selective oxidation of carbon monoxide in mixtures of CO and hydrogen. Later Taylor and Rideal wrote a pioneering book Catalysis in Theory and Practice. The Rideal Conference is so named in his honor; this triennial series of UK research conferences on surface chemistry and catalysis was initiated by Charles Kemball and others in the late 1960s.
 
Contributed by Jacques Vedrine
June 2002

Robert L. Burwell, Jr.: Helped established catalysis concepts

Robert L. Burwell, Jr.

Robert L. Burwell, Jr.

Robert L. Burwell, Jr., Ipatieff Professor Emeritus of Chemistry at Northwestern University, will always be remembered by his many friends, colleagues, and students as a learned gentleman of high moral standard, a dedicated educator, and a thorough and brilliant researcher in heterogeneous catalysis. He was a leading figure in guiding the development of the catalysis community in the U.S. and the world. His many contributions to the community included serving on the governing body of the (North American) Catalysis Society from 1964 to 1977 as Director, Vice President, and in 1973-77, President. From 1955-84, he served on the Board of Director, as U.S Representative to the Congress, Vice President, and President (1980-84) of the International Congress on Catalysis. He chaired the Gordon Research Conference on Catalysis in 1957, and was Associate Editor and a member of the Editorial Board of Journal of Catalysis.

Robert Burwell received his Ph.D. in 1936 from Princeton University under the guidance of Sir Hugh Taylor. After three years as a Chemistry Instructor at Trinity College, in 1939 he joined the Chemistry Department at Northwestern University. Except for the World War II period from 1942 until 1945, when, having enlisted, he worked at the Naval Research Laboratory, Dr. Burwell served at Northwestern until he retired in 1980. As Ipatieff Professor Emeritus, he continued his research and intellectual activities for another decade after retirement. During his career he published over 170 original research articles, served on National Research Council Committees, IUPAC Committees, the Petroleum Research Fund Advisory Board, the National Science Foundation Chemistry Advisory Board, and others, as well as Chairing the Chemistry Department at Northwestern University. In 1994, he moved to Virginia with Elise, his wife of over sixty years.

Professor Burwell was among the first scientists who understood the critical connection between general chemistry and catalysis. He introduced and popularized concepts that are now familiar to and even commonplace within the entire catalysis community. His research themes centered around elucidation of the reaction mechanisms, nature of surface intermediates, and characterization of active sites of solid catalysts. He was well known for the use of H-D exchange for such studies. Using this technique, he identified the importance of 1,2-diadsorbed alkane on noble metal surfaces in the exchange and the hydrogenation reaction, and the irreversibility in the adsorption of alkene during hydrogenation. He established the “rollover” mechanism for cyclic hydrocarbons in these reactions, and the term “surface organometallic zoo”. He carefully documented the importance of surface coordination unsaturation in catalysis by metal oxides, and developed new catalysts of unusual activities by deposition of organometallic complexes on alumina and silica, and by modifying silica surface.

His many scientific contributions and their industrial applications were recognized in his day, as evidenced by the many awards and honors he received. They included the ACS Kendall Award in Colloid and Surface Chemistry, the Lubrizol Award in Petroleum Chemistry, and the Humboldt Senior Scientist Award. In addition, the Robert L. Burwell Lectureship Award of the (North American) Catalysis Society was established in recognition of his outstanding contributions to the field of catalysis. Professor Burwell was also known for the first short course in heterogeneous catalysis that he taught for several years together with Michel Boudart.

To those who knew him personally, Burwell was not only an imposing intellect, but a warm, deeply caring, pleasant person, a complicated person with many facets. For instance, while wise and judicious, he nevertheless conducted himself with a great sense of humor and wit. Any who he favored soon realized he could engage in lively conversation on practically any subject. Many of his coworkers also remembered him for his numerous perceptive scientific advice and suggestions. Very often in seminars, students felt that they learned more about a subject from his probing questions than the actual seminar itself. His family remembered him also as a caretaker extraordinaire. His devotion to his wife, particularly during the last year of her life, will be remembered by all.

Dr. Burwell was a walking encyclopedia—indeed he was scientific consultant to the World Book Encyclopedia. He read extensively on virtually every subject. He particularly enjoyed a commanding knowledge of the birds, flora and fauna and could be seen bird watching in the snowy early springs in Evanston. He enjoyed cultural matters and sharing of his knowledge with his colleagues, friends, and post-doctoral and graduate students, a trait he continued even after he retired to Virginia with his wife, where he became an active member of many local Virginia museums and a variety of genealogical societies (and a founder of the Computer Club and Wine Club at the retirement community). He was often expected to be the cultural guide for his group of friends on tours around the world. He particularly enjoyed teaching American culture and the nuances of the English language to his international post-doctoral and graduate students. Dr. Burwell loved to refer to the 4th of July as “the day we celebrate English becoming a foreign language”. He also possessed a cultivated taste for wine, and was proud of his collection of antique porcelain.

Perhaps the most appropriate reference to Robert Burwell was from Marie Westbrook, the Department Secretary of Chemistry at Northwestern, who referred to him always as “Mr. Burwell”, not as “Doctor” or “Professor”. When asked why, she replied: “A lot of people can become a Professor or a Doctor, and I use Mister just for him”. On May 15, Mr. Burwell passed away at the age of 91. He was buried on June 28th, 2003 in Christ Episcopal Church in West River, Maryland next to his beloved wife, Elise.
 
Contributed by Prof. H. Kung

Pioneer of Catalytic Cracking: Almer McAfee at Gulf Oil

With the support of Gulf Refining Company, Almer McDuffie McAfee developed the petroleum industry’s first commercially viable catalytic cracking process-a method that could double or even triple the gasoline yielded from crude oil by then-standard distillation methods. Based partly on an 1877 Friedel-Crafts patent, the McAfee cracking process required anhydrous aluminum chloride, a catalyst that was prohibitively expensive. In 1923 McAfee and Gulf would solve that problem by developing a way to synthesize the catalytic reagent at low cost, on an industrial scale. Indeed, each time McAfee’s methods appeared to become obsolete, circumstances changed in his favor. Today the results of McAfee’s further work with aluminum chloride, which led to the Alchlor process, are still on the scene.

For a more complete history on McAfee’s innovations (by Paul T. Buonora), please see Chemical Heritage Magazine, 16:2 (Fall 1998). Chemical Heritage Foundation website: www.chemheritage.org/.
 
Contributed by J. Armor

John Sinfelt: Removal of lead from gasoline with bimetallics

John Sinfelt

John Sinfelt

Use of lead alkyls, primarily in the form of tetraethyllead, to enhance the octane number and performance of U.S. motor gasolines nearly doubled from 235,000 tons in 1955 to 445,000 in 1975. As the harmful health effects of tailpipe-exhausted lead compounds became increasingly apparent, legislative initiatives, beginning in 1975, mandated the complete removal of lead additives from U.S. motor fuels by year-end 1991. Dr. Sinfelt’s research on alternate petroleum conversion chemistries allowed refiners to remove lead alkyls from gasoline years before the mandated deadline. Application of novel, highly active and selective bimetallic cluster catalyst systems he invented and championed made it possible to produce high-octane motor gasoline without the use of lead additives.

Dr. Sinfelt’s distinctive research methodology emphasized entirely new concepts in the understanding and use of catalyst materials containing bimetallic clusters. Earlier work on metal alloys emphasized the relation between catalytic performance of a metal and its electron band structure. However, little attention had been paid to the possibility of catalytically influencing the selectivity of chemical transformations (product selectivities). One of Dr. Sinfelt’s most important discoveries, achieved through in-depth studies on bimetallic catalysts, concerns control of chemical reaction selectivity. He discovered that it is, in fact, possible to catalyze one type of chemical reaction in preference to other reactions that are themselves thermodynamically favorable. He clearly showed that bimetallic catalysts could be tailored to effectively reduce undesirable competing reactions, and thus control the kinetic specificity of surface reactions. This made possible the economical conversion of low octane number molecules to ones with high octane numbers. The public benefited greatly from the environmental improvements due to lead-free gasoline, and motorists did not pay a hugh price for it.

While Dr. Sinfelt’s research has made far-reaching contributions to our understanding of hydrocarbon conversion processes, the practical benefits of his research are equally profound. The application of bimetallic catalysts in petroleum refining was crucial to making high-octane “lead-free” motor fuels widely available. Today, bimetallic catalysts have replaced traditional catalysts in catalytic reforming (the major commercial process used in increasing the octane rating of motor fuels) allowing thereby elimination of lead-based, octane improving additives. Dr. Sinfelt is the inventor both of a Pt-Ir catalyst that has been widely used in catalytic reforming and of a staged reforming process that has also found wide application. The latter uses two different bimetallic catalysts in separate reactors to optimize performance. The classic work of Sinfelt on the kinetics of catalytic reforming reactions in the late 1950’s and early 1960’s provided the foundation for these important industrial advances.

In addition to eliminating the hazard of lead in gasoline, Sinfelt’s work enabled the development and application of multi-metallic catalysts for the exhaust systems of automobiles to decrease the emission of pollutants such as carbon monoxide, unburned hydrocarbons and nitrogen oxides. The catalysts commonly used today contain a combination of metals; i.e., they are bi-metallic or tri-metallic. These catalysts, like reforming catalysts, perform better when more than one metallic element is present. Current exhaust catalyst systems are based on Sinfelt’s ground breaking discoveries. Finally, since these catalysts are poisoned by lead, its removal from gasoline made the application of auto exhaust catalysts technically feasible.

The basic studies of Dr. Sinfelt on bimetallic catalysts generated much interest in the field and called attention to their importance for catalytic reforming and for the production of lead-free gasoline. The discovery was first reported in two U. S. Patents to Sinfelt et al. (3,442,973, which issued in 1969 and 3,617,518, which issued in 1971) and in two papers in the Journal of Catalysis 24, 283 (1972) and 29, 308 (1973). These early publications stimulated much interest in bimetallic catalysts as a major area of research that is still flourishing. For these contributions to the lead phase-down in the United States, Dr. Sinfelt was awarded the National Medal of Science by the President of the United States in 1979 and the prestigious Perkin Medal in 1984. His is among the most important contributions enabling the worldwide reduction of environmental lead and the elimination of the associated risks to human health.

In a tribute to John Sinfelt in I&EC, 42 (2003) 1537, Professor Michel Boudart comments, “His impact has been uniquely important because John combined the inventiveness required for scientific discovery with the ability to engineer his work to many successful applications in industry. John succeeded though repeated scientific discoveries and engineering applications, without ever preaching … John managed to become a role model to those who practice catalytic science, not only in the secretive industrial environment but also in universities worldwide … The legacy of John Sinfelt is his unshakable belief in chemical kinetics to advance catalytic science and engineering. John’s impact on the field exceeds by much the impact of his own scientific and engineering contributions.”
 
Contributed by Gary McVicker and John Armor

Herman Pines – He revolutionized the general understanding of catalysis

Her­man Pines

Her­man Pines

Herman Pines was born in Lodz, Poland, in 1902. After earning his degree at the École Supérieure de Chimie in Lyon, France, he came to the U.S. in 1928. He was the closest associate of Vladimir Nikolayevitch Ipatieff from the day they met in 1930, until Ipatieff’s death in 1952. Ipatieff, who was 35 years older than Pines, then held two jobs: he was an employee of Universal Oil Products (UOP) in Des Plaines and a research professor at Northwestern University. As a consequence of the close interaction of these two devoted scientists, Herman Pines, an employee at UOP, became involved in Ipatieff’s research at Northwestern. What started spontaneously and unofficially, was formalized in 1941, when Herman was appointed Research Assistant Professor at Northwestern, with the stipulation that he should spend his Wednesdays working here. This appointment coincided with the relocation of Ipatieff’s lab from the basement of University Hall to the newly erected Technological Institute.

One of the first actions of this new professor was to write, with Ipatieff, a memorandum to the Chemistry Department proposing the creation of a Catalysis Teaching and High Pressure Laboratory. This document was dated September 29, 1941, but it was not until 1947 that the Catalysis Lab officially opened in the Technological Institute. A special High Pressure Laboratory was built in 1952 and officially dedicated August 14, 1953, in the presence of the Presidents of Northwestern University and of UOP. Professor Sir Hugh Taylor of Princeton University gave a lecture on catalysis for the occasion. Shortly thereafter, a bronze plaque honoring Vladimir N. Ipatieff was mounted over the entrance of the High Pressure Lab; it is now located in the reception area of the Catalysis Center.

Meanwhile, Herman Pines had been promoted, in 1951, to the rank of Associate Research Professor; after Ipatieff’s death, in 1952, he became the first V.N. Ipatieff Professor of Organic Chemistry. On January 1, 1953, he left UOP and began officially as a full-time professor at Northwestern.

Only a few of the outstanding scientific achievements of Herman Pines can be mentioned here; it is not an overstatement to say that his work revolutionized the general understanding of chemistry, in particular the chemistry of hydrocarbons interacting with strong acids.

An unchallenged dogma of the chemistry of the 1930’s was that paraffins would not react with anything at low temperature; even the name of this class of compounds, “parum affinis,” was based on this assumed lack of reactivity. It must have been quite a shock to the scientists of those days, when Pines and Ipatieff showed, in 1932, that in the presence of a strong acid the paraffin iso-butane would react, even at -35 ºC, with olefins. This was the basis of the alkylation process, patented in 1938 and industrially developed soon after. Its most spectacular application is the synthesis of iso-octane from n-butene and iso-butane. Iso-octane improves the quality of gasoline and airplane fuel; it played a decisive role in the victory of the Royal Air Force during the Battle of Britain in 1941. The catalysis of converting paraffins to isoparaffins is, of course, one of the cornerstone of the petroleum industry.

The alkylation process was not discovered by accident. It was the pinnacle of research that started with an observation that puzzled Herman Pines in 1930. At that time he was working in the analytical lab of UOP; his task was to vigorously shake petroleum fractions with concentrated sulfuric acid in a calibrated glass cylinder and to determine how much of the oil dissolved in the aqueous acid phase. It was known that only unsaturated hydrocarbons would be dissolved in the acid; this experiment of shaking the petroleum and reading the meniscus was the standard procedure to determine how many unsaturated products were present in a petroleum fraction. Herman observed, however, that after a few hours the phase boundary between oil and acid had shifted again: more oil was formed-oil that would not dissolve in the aqueous phase. Apparently paraffins had been formed from olefins; Herman concluded that this process required the simultaneous formation of a highly unsaturated coproduct which remained dissolved in the aqueous phase. They called this process “conjunct polymerization,” and years later analytical methods were found which permitted identification of this unsaturated coproduct as a mixture of substituted cyclopentadienes. The step which led from this early observation to the alkylation process was later described by Herman:

“On a hunch we thought that paraffins might even react with olefins in the presence of acids; we therefore introduced a stream of ethylene and hydrogen chloride to a stirred mixture of the pentanes and AlCl3. We observed that the ethylene was absorbed and that the hydrocarbons recovered from the reaction consisted of saturated hydrocarbons only, an indication that ethylene must have reacted with the pentanes.”

On this basis, Herman Pines and Vladimir Ipatieff developed the new chemistry of acid catalyzed reactions; it formed the cornerstone of their scientific work and was brought to its present beauty by Herman in his years at Northwestern. Major discoveries led to new processes for the isomerization of paraffins and the alkylation of aromatic compounds, but also to base catalyzed organic reactions. Two hundred and fifty publications in the scientific literature, one hundred and forty-five U.S. patents and the book “The Chemistry of Catalytic Hydrocarbon Conversions” demonstrate the wealth of Herman’s scientific legacy. The forty-one graduate students and thirty-three postdoctoral fellows who performed research in his lab helped carry his scientific message to the world. As U.S. editor of Advances in Catalysis, he keenly looked for and critically evaluated new concepts of catalysis, and assured that their originators described them carefully to the scientific community. In 1957 he was chairman of the Chicago Catalysis Society, in 1960 chairman of the Gordon Conference of Catalysis. He received three awards from the ACS, an honorary degree from the University of Lyon and invitations to lecture and advise in Israel, Brazil, Venezuela, Argentina, Poland, Czechoslovakia and Spain.

The Catalysis Center remained his scientific home. He rarely missed a seminar and often asked critical questions. He could be quite sharp when speakers used catalysis only as a buzzword for the introduction of their lectures and spoke about work of rather questionable relevance to “real” catalysis. Although he could be critical, he was never insensitive; his gentle and friendly nature made it quite impossible for him to do any harm to anyone. While there is a unanimous consensus that he was one of the towering scientists of this century, he always remained very modest; when his trendsetting discoveries of the 1930’s were mentioned, he always referred them to Ipatieff. He worked assiduously his entire life, bringing his last book to completion at the age of ninety. Future generations can learn from his example how revolutionary discoveries arise from sharp observations by an investigating mind. Herman Pines passed away on April 10, 1996.
 
Contributed by Wolfgang Sachtler

Heinz Heinemann: One of the accomplished founders of the Catalysis Society

During a 60-year career in industry and academia, Heinz contributed to the invention and development of 14 commercial fossil fuel processes, received 75 patents and was the author of more than a hundred publications. Among his inventions was a process for converting methanol to gasoline. At his death, he was a distinguished scientist in the Washington office of LBNL. During the period 2001 to 2004, he served as a manager of the Washington Chemical Society (ACS) and as president of its Retired Chemists Group. After retirement from a career in industry, Heinz was a long-time lecturer in the College of Chemistry at the University of California, Berkeley, and a chemistry researcher at Lawrence Berkeley National Laboratory.

Born in Berlin, Germany, he attended the University and Technische Hochschule in Berlin. When his doctoral dissertation was rejected because he was Jewish, he made his way to Basel, Switzerland, where he received his PhD in physical chemistry from the University of Basel, before coming to the United States in 1938. He became a U.S. citizen in 1944. He worked for several petroleum companies in Louisiana and Texas and won a postdoctoral fellowship at the then-Carnegie Institute of Technology, now Carnegie-Mellon University. The fellowship was funded by the government of the Dominican Republic and involved research into ethanol, which was made from the Dominican Republic’s primary cash crop, sugar cane.

He published more than 150 papers and over 50 patents in catalysis and petroleum chemistry, mostly while working for Houdry Process Corp., the MW Kellogg Co. as director of chemical and engineering research, and the Mobil Research and Development Co. as manager of catalysis research. During those years he actively participated in the research and development of 14 commercial processes, including the process for converting methanol to gasoline.

After retiring from industry in 1978, he joined the Lawrence Berkeley National Laboratory as a researcher and became a lecturer in the Department of Chemical Engineering at UC Berkeley. His research involved coal gasification, catalytic coal liquefaction, hydrodenitrification, nitrogen oxide emission control and the development of a special catalyst that enables methane, the major component of natural gas, to be used to make petrochemicals. The research team he led invented and patented a process known as catalytic oxydehydrogenation.

He was a co-founder of the Philadelphia Catalysis Club, the Catalysis Society of North America and the International Congress of Catalysis, serving as its president from 1956 to 1960. He was the founder of Catalysis Reviews, and worked as its editor for 20 years. He also was Consulting Editor for over 90 books in the Chemical Industries Series, published by Marcel Dekker, Inc.

He received many honors, among them election to the National Academy of Engineering , the Houdry Award of the Catalysis Society, the Murphree Award of the American Chemical Society, the H.H. Lowry Award presented for research he pursued in his seventies, and a Distinguished Scientist/Engineer award of the U.S. Department of Energy. In addition, he was elected a member of the Spanish Council for Scientific Research for his support in founding its Institute of Catalysis and Petrochemistry.

Heinz Heinemann passed away on Nov. 23, 2005 of pneumonia. He was 92.
 
Contributed by http://chemistry.berkeley.edu/Publications/news/fall2005/heinz_obit.html

Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline

Eugene Houdry

Eugene Houdry

One of the first improvements in petrochemical production was the process developed by Eugene Houdry for “cracking” petroleum molecules into the shorter ones that constitute gasoline. (Earlier commercial processes for cracking petroleum relied instead on heat.)

Eugene Houdry (1892–1962) obtained a degree in mechanical engineering in his native France before joining the family metalworking business in 1911. After he served in the tank corps in World War I—for which he received honors for extraordinary heroism in battle—he pursued his interest in automobiles (especially race cars) and their engines. On a trip to the United States he visited the Ford Motor Company factory and attended the Indianapolis 500 race. His interest soon narrowed to improved fuels. Because France produced little petroleum—and the world supply was thought to have nearly run out—Houdry, like many other chemists and engineers, searched for a method to make gasoline from France’s plentiful lignite (brown coal). After testing hundreds of catalysts to effect the hoped-for molecular rearrangement, Houdry began working with silica-alumina and changed his feedstock from lignite to heavy liquid tars. By 1930 he had produced small samples of gasoline that showed promise as a motor fuel.

In the early 1930s Houdry collaborated with two American oil companies, Socony Vacuum and Sun Oil, to build pilot plants. Oil companies that did not want to resort to the new additive tetraethyl lead were eagerly looking for other means to increase octane levels in gasoline. In 1937 Sun Oil opened a full-scale Houdry unit at its refinery in Marcus Hook, Pennsylvania, to produce high-octane Nu-Blue Sunoco gasoline. By 1942, 14 Houdry fixed-bed catalytic units were bearing the unanticipated burden of producing high-octane aviation gasoline for the armed forces.

(One limitation of the process was that it deposited coke on the catalyst, which required that the unit be shut down while the coke was burned off in a regeneration cycle. Warren K. Lewis and Edwin R. Gilliland of the Massachusetts Institute of Technology, who were hired as consultants to Standard Oil Company of New Jersey [now ExxonMobil], finally solved this problem with great ingenuity and effort. They developed the “moving bed” catalytic converter, in which the catalyst was itself circulated between two enormous vessels, the reactor and the regenerator.)

Houdry continued his work with catalysts and became particularly fascinated with the catalytic role of enzymes in the human body and the changes in enzyme-assisted processes caused by cancer. About 1950, when the results of early studies of smog in Los Angeles were published, Houdry became concerned about the role of automobile exhaust in air pollution and founded a special company, Oxy-Catalyst, to develop catalytic converters for gasoline engines—an idea ahead of its time. But until lead could be eliminated from gasoline (lead was introduced in the 1920s to raise octane levels), it poisoned any catalyst.

The following taken from Chemical Heritage Foundations Othmer Library Catalog
http://othmerlib.chemheritage.org/search/dArchival+Materials./darchival+materials/-5,-1,0,B/frameset&FF=darchival+materials&5,,16.

Eugene Houdry was born on April 18, 1892 in France. In 1911 he received a degree in mechanical engineering. He worked for his family’s metal working business. In 1930, he moved to the U.S. wher he revolutionized the production of gasoline by developing a process for cracking low-grade fuel into high test gasoline. During WWII, he developed a single-step butane dehydrogenation process for producing synthetic rubber. After WWII, he founded a company entitled Oxy-Catalyst, and shifted his focus to reducing health risks associated with automobile exhaust. He patented the catalytic muffler for automobiles in 1962. He died on July 18, 1962. He was inducted into the National Inventor’s Hall of Fame in 1990.
 
Contributed by A. Mills and Chemical Heritage (http://www.chemheritage.org/classroom/chemach/petroleum/houdry.html)

Eric Derouane: A visonary with high intellectual mobility

Eric Derouane died on 17th March 2008 from a heart attack in his home in Luz, Lagos, Portugal. With him, the Catalysis Community has lost one of its strongest and brilliant scientists.

Born on 4th July 1944 at Péruwelz (Hainaut), Belgium, Eric Derouane obtained a Licence degree at the University of Liège, B (1965), a Master of Arts (MA) degree in Chemistry in Prof. J. Turkevich’s laboratory at Princeton University, USA (1966) and a Doctorat ès Sciences (PhD) at the University of Liège, B (1968), including a one year (1966-1967) in France at the “Service de Physique du Solide et de Résonance Magnétique, CEN Saclay” in Prof. A. Abragam’s laboratory. He stayed a year (1969-1970) in USA at Stanford University as visiting Scholar in Prof. M. Boudart’s laboratory. He became Research Assistant of the “Fonds National de la Recherche Scientifique” (FNRS) and Lecturer at the University of Liège, B (1969-1973). In 1973, he was appointed Professor at the “Facultés Universitaires Notre-Dame de la Paix” (FUNDP) in Namur, B, where he created the Laboratory of Catalysis, of which he remained Director until 1995. He was on sabbatical leaves in 1979 as Research Fellow with J. Sinfelt at Exxon Res. & Develop. Corp., Linden, USA, and in 1982-84 as Research Scientist, Head of Exploratory Catalysis Synthesis Group at Mobil Res. & Develop. Corp., Central Research Laboratory, Princeton, USA. In 1995, he became Full Professor at the University of Liverpool and was appointed Director of the Leverhulme Centre for Innovative Catalysis (LCIC). In 2003, he obtained the Gulbenkian Professorship at the University of Algarve in Faro, P, where he was Director of the Chemical Research Centre. He became later Invited Professor at the “Instituto Superior Tecnico” (IST) of the Technical University of Lisbon, where he had extensive cooperation with the group led by Prof. F. Ramôa Ribeiro.

His main fields of investigation dealt with catalysis over zeolites in general, supported metals, novel materials and mixed oxides in particular, and alkane upgrading and fine chemicals more specifically. One of Eric’s most striking qualities was his acute interest for every new scientific discovery and for industrial applications of his findings.

Eric Derouane had an unusual working efficiency. He had a high intellectual mobility and was always attracted by new materials and new concepts. Among them, one can mention ZSM-5/MFI new zeolite in the early 70s, leading to a 30 year collaboration with J.C. Védrine, cuprate-type superconductors, confinement effect and molecular traffic control in zeolitic materials. He also studied reaction mechanisms using isotopic labelling and in-situ MAS-NMR in the 80s, combinatorial catalysis and high throughput technology in the late 90s.

During his 20 years of dedicated service to the University of Namur, Eric Derouane developed new concepts, which had an important impact on the catalysis and zeolite communities. In 1986, he was elected Head of the Chemistry Department. He then embarked upon an impressive re-structuring programme to improve its efficiency. The model, which he initiated, is still in service today. His laboratory was recognized as an outstanding school of scientific research and education in catalysis.

Very early, Eric Derouane realized the importance of interdisciplinarity, which lead him to play a key role in the creation of the Institute for Studies in Interface Sciences (ISIS) at Namur in 1987, which gathered laboratories of physics and chemistry for 20 years. Eric Derouane also paid heed to technological transfer to industries. After his experience gained through his sabbatical positions at Exxon and at Mobil, he developed many collaborations with industrial partners and served as consultant.

At Liverpool, the aim of the LCIC was to promote creative fundamental catalytic science and often to take-up industrial challenges. Eric Derouane defined innovation as “the creation of a new or better product or process, implying creativity, usefulness, and application”. Towards this end, the LCIC had industrial affiliates as partners. Under his leadership the LCIC became the largest catalysis centre in the UK.and a centre of scientific exchanges and collaborations. Eric Derouane established links with many UK and international laboratories. Eric Derouane created in 1997 an European Associated Laboratory “Laboratory for high specificity catalysis” between LCIC/University of Liverpool and Institut de Recherches sur la Catalyse, Lyon, F/CNRS.

In 1999, he co-founded with Prof. S. Roberts the spin-off Liverpool-based company “Stylacats”, of which he became director. He provided wise suggestions and ideas, which lead the company to pioneer new technologies, in particular catalysts for asymmetric hydrogenation, microwave-induced reactions and enzyme mimetics.

At the University of Faro, Eric Derouane developed a research project, jointly with the Instituto Tecnico de Lisboa, on Friedel-Crafts reactions. He also collaborated closely on various research projects with Prof. F. Ramôa Ribeiro’s zeolite group of the Instituto Superior Tecnico of the University of Lisbon.

Eric Derouane co-authored over 400 scientific papers, 11 books and 61 patents.
Eric Derouane also contributed to the development and strengthening of the european catalysis community. He created in 1975 the European Association in Catalysis (EUROCAT), a consortium of European laboratories under the auspices of the Council of Europe and promoted standardisation of characterisation of catalysts: Euro-Pt1 to -Pt4, Euro-Ni1 & -Ni2, Eurocat zeolite, Eurocat oxides, etc. This Eurocat group paved the way to the creation of the European Federation of Catalysis Societies (EFCATS) and of the François Gault lectureship. He was elected President of EFCATS in 1995 for two years.

He became Editor-in-chief of J. Mol. Catal. in 1982 and was member of the Editorial Boards of several scientific journals and member of the scientific committees of many congresses and colloquia. He co-organized several congresses himself, in particular with F. Lemos and F. Ramôa Ribeiro in Portugal several NATO Advanced Studies Institutes on topics including “the conversion of light alkanes”, “combinatorial catalysis and high throughput catalyst design and testing”, “principles and methods for accelerated catalyst design and testing” and “sustainable strategies for the upgrading of natural gas”.

Eric Derouane’s contributions to catalysis have been recognised by many awards and academic honors, including the Wauters Prize (1964), the Mund Prize (1967) of the “Société Royale de Chimie”, the Stas-Spring Prize (1971) and the Adolphe Wetrems Prize (1975) of the “Académie Royale de Belgique”, the Rosetta Briegel-Barton Lecturership at the University of Oklahoma (1973), the Prize of the “Cercle of Alumni de la Fondation Universitaire de Belgique” (1980), the Ciapetta Lectureship of the North American Catalysis Society (1981), the Catalysis Lectureship of the Société Chimique de France (1993) and the prestigious Francqui Prize, B (1994), the highest honor for all Sciences in Belgium.

He was made “Officier de l’Ordre Léopold” in Belgium (1990), corresponding Member of the “Académie Royale des Sciences, des Lettres et des Beaux Arts de Belgique” (1991), member of the “New York Academy of Sciences” and Associate Member of the “European Academy of Arts, Sciences and Humanities”. He was conferred Doctor Honoris Causa, Technical University of Lisbon (1996) Eric Derouane attracted many students and foreign scholars to his laboratories in Namur, Liverpool and Faro. His energy, his clear mind and his broad knowledge impressed his students, researchers and colleagues. He was an outstanding and demanding professor, always ready to share his knowledge with his students. His courses were always clear, highly structured and easily understandable. Many of his former students and post-docs occupy today prominent positions in universities and industries. All of them will remember his brilliant and rigorous scientific approach, and no doubt they all will greatly miss him.
 
Contributed by
Jacques C. Védrine and Michel Che, Paris
Fernando Ramôa Ribeiro, Lisboa
Jianliang Xiao, Liverpool
Bao-Lian Su, Namur
23 April 2008