CATALYSIS – AN OVERVIEW

1. CATALYSIS – AN OVERVIEW NATIONAL CENTRE FOR CATALYSIS RESEARCH INDIAN INSTITUTE OF TECHNOLOGY MADRAS CHENNAI 600 036 DATED 30TH NOVEMBER 2014

2. MOTIVATION FOR THIS PRESENTATION • ONLY ONE GENERAL PRESENTATION- ALL OTHERS WILL BE DEALING WITH SPECIFIC ASPECTS OF THIS FIELD. • TO OUTLINE THE EVOLUTION AND CONCEPTUAL FRAMEWORK OF THIS FIELD • TO PROMOTE MOTIVATION AND TO APPRECIATE THE EFFORTS IN THIS FIELD • THE METHODOLOGY FOR CONCEPTS

3. OUTLINE OF THE PRESENTATION • INTRODUCTION • BRIEF HISTORICAL OUTLINE • CONCEPTUAL EVOLUTION • Questions, Enigmas, Illusions, challenges, realities, and emergent strategies of designof catalysts • Descriptors and data mining – how it will be useful • Theory - has it relevance in this field? • Perception and Assimilation? • Questions – This should evolve as the habit!

4. QUESTIONS? What areas of fundamental research are most helpful to support commercial catalyst/catalysis activity in industry? Should the dispersal of federal research grants to academic researchers be based on demonstrated excellence in science or focused to support the national laboratories? What type of linkage with academia/national laboratories is most useful to, and supportable by, industry? What elements in science or technology provided the edge to your commercial business in catalyst/catalytic processes? What novel catalytic processes do you expect to be developed in the next 10 to 15 years? What will be the nature of the exploratory and basic research that leads to these developments? Is academic and industrial catalytic research well positioned to play a leadership role in creating this new technology and, if not, what needs to be done?

5. Iidentify areas of catalyst science and technology is (1)behind competitors, (2) even with competitors, and (3) ahead of competitors. Identify problems that have long- term payoff. What areas are ''mature'' or "dead"? Has too much emphasis been placed on one area in the past? What would be the ideal mix of industrial and academic research in catalysis? What are the major unsolved problems in catalysis, and what would the solution to these problems provide in economic and technical terms? Are there new areas where catalysis could be used?

6. Some benchmark discoveries in the science and technology of catalysis. 100 years ago: Paul Sabatier (Nobel Prize 1912) at the University of Toulouse started work on his method of hydrogenating organic molecules in the presence of metallic powders. 70 years ago: Irving Langmuir (Nobel Prize 1932) at General Electric laid down the scientific foundations for the oxidation of carbon monoxide on palladium. 50 years ago: Vladimir Ipatieff and Herman Pines at UOP developed a process to make high-octane gasoline that was shipped just in time to secure the victory of the Royal Air Force in the Battle of Britain. 30 years ago: Karl Ziegler and Giulio Natta (Nobel Prize 1963) invented processes to make new plastic and fiber materials. 17 years ago: W. S. Knowles at Monsanto Company obtained a patent for a better way to make the drug L-Dopa to treat Parkinson's disease. 16 years ago: General Motors Corporation and Ford Motor Company introduced new devices in cars to clean automotive exhaust. These devices found worldwide acceptance. 10 years ago: Tennessee Eastman Corporation started a new process for converting coal into chemicals used for the production of photographic film. Yesterday: Procter and Gamble Company manufactured a new environmentally safe bleach mixed with laundry soap. Today: Thomas Cech (Nobel Prize 1989) at the University of Colorado received U.S. patent 4,987,071 to make ribozymes, a genetic material that might, one day, be used to deactivate deadly virus

8. The Central point in Catalysis Research is the identification and optimization of active sites- variety of active sites inherent in the solid surface itself Sites that are generated at the call of the molecules and sites which are not active by themselves but becomes active as a result of species generation at the adjacent sites so called spill over effect and thus it is a dynamic concept today from the original static concept NCCR

9. The Concept of Active Centres in Material ScienceHow are they relevant?What are the factors that contribute to material science?Why the dynamics of processes in Material science different from conventional dynamics?How the processes are initiated in material science and how are they different from conventional chemical processes?And many more

10. Why revisit this Concept Now?1925 first H S Taylor brought this concept to catalysis at that time it was only at molecular level and on reactivity and not selectivity

11. Materials Science • Ages have been only based on materials- stone age, iron age, bronze age • Every decade has been throwing up at least one material • Advances in sciences have largely dependent on materials • Comforts arising out of scientific discoveries dependent on materials.

12. Surface to Volume Ratio • Surface to volume ratio is important in devices • Many such systems have been performing with greater efficiency • These systems are brain, leaf, chips and so on • Why are they so special? • What make them so special?

13. Why surfaces are important? • Surface free energy decides which species is responsible • Opposing properties can be induced like hydrophilic or hydrophobic character • Area modulation, functional modulation, and a variety of other modifications are possible • Sensing behaviour increases and hence response time is decreased

14. Changes • Materials science departments have been opened all over the institutions. • Metallurgical departments have taken new avatar in the form of materials department • Material science is evolving a new branch of science • Materials science research is focussing on devices • Synthesis, fabrication and design appear to merge • Scales appear to shrink • Morphologies appear to be no barrier • Fabrication has a new meaning now

15. Catalysis 1949 to 1999

16. 1 st DECADE: 1949 - 1958 • Late 1940s- Robert M. Milton and Donald W. Breck, Union Carbide, develop • Early 1950s: commercial synthesis for zeolites - A, X, and Y types. • Late 1940s- Eugene Houdry develops monolithic platinum catalyst system for • Early 1950s: Treating exhaust gases from internal combustion engines, founds — and begins commercial operations at Yardley, Pennsylvania. Houdry is later inducted into the Inventor's Hall of Fame. • June 11, 1949: First meeting of organization that became the Catalysis Club of Philadelphia was held at the University of Pennsylvania. Paper were presented by R. C. Hansford (Mobil), A. G. Oblad (Houdry), A. V. Grosse (Temple U), T. I. Taylor (Columbia U.) and K. A. Krieger (U. Pennsylvania). A. Farkas, organizer of this symposium, was selected chairman of a committee to form a permanent organization.

17. 1 st DECADE: 1949 - 1958 • December 1949: Prof. Paul Emmett presented a lecture at Temple University and afterwards the Catalysis Club of Philadelphia was officially formed, electing A. Farkas chairman and A. Oblad as Secretary-Treasurer. Almost one hundred signed up as members. • 1949: First commercial operation of UOP's Platforming Process for naphtha reforming, Old Dutch Refining, Muskegon, Michigan; patents for Pt-Cl-Al2O3 catalysts to Vladimir Haensel. • 1949: P. W. Selwood published his first paper on nuclear induction and begins a series of classic publications on the application of magnetic techniques in catalysis. The results are summarized in his book [P. W. Selwood, "Adsorption and Collective Paramagnetism," Academic Press, 1962.] • March 2, 1950: The Bylaws of the Catalysis Club of Philadelphia, as written by Grace Kennedy (wife of Robert Kennedy, prominent catalysisscientist at Sun Oil), were adopted and still serve as the model for later formed clubs/societies.

18. 1 st DECADE: 1949 - 1958 • 1950: MILESTONE MEETING: The Discussions of the Faraday Society, Heterogeneous Catalysis, No. 8, 1950. Topics included: O. Beeck, Relates % d-character of metal and catalytic activity for ethylene hydrogenation. • D. D. Eley, Calculates the heat of adsorption of hydrogen on metals. • G. M. Schwab, Alloy catalysts for dehydrogenation. • D. D. Dowden and P. W. Reynolds, Electronic effects in catalysis by metal alloys. • P. W. Selwood and L. Lyon, Magnetic susceptibility and catalyst structure. • M. W. Tamele, Surface chemistry and catalytic activity of silica-alumina catalysts. • John Turkevich, H. H. Hubbell and James Hillier, Electron microscopy and small angle X-ray scattering. • 1950: Linear relationship between quinoline chemisorption and catalytic activity for gasoil cracking - G. A. Mills, E. R. Boedeker and A. G. Oblad, JACS, 72, 1554 (1950). • 1950: Hydroformylation catalytic species identified as HCo(CO)4 - I. Wender, M. Orchin and H. H. Storch, JACS, 72, 4842 (1950). • 1951: A. Wheeler defines role of diffusion in determining reaction rates and catalytic selectivity - Advan. Catal., 3, 250-326 (1951).

19. 1 st DECADE: 1949 - 1958 • 1951: Paul Emmett utilizes 14C radioisotope in Fischer-Tropsch mechanism studies - New York Times reports that "Gulf Oil scientist makes radioactive gasoline." • 1953: Naphtha reforming involves dual functional catalysts - mechanism for reforming with these catalysts - G. A. Mills, H. Heinemann, T. H. Milliken and A. G. Oblad, Ind. Eng. Chem, 45, 124 (1953). • 1953: Karl Ziegler discovers a catalyst system for polymerizing ethylene at low temperature and pressure to produce linear, crystalline polyethylene- Nobel Prize awarded to Ziegler in 1963. • 1954: Guelio Natta invents stereospecific polymerization of propylene to produce crystalline polypropylene- Nobel Prize awarded to Natta in 1963. • 1954: "Beginning" of catalyst characterizations using instruments with i.r. spectra for CO adsorption on copper (R. P. Eischens, W. A. Pliskin and S. A. Francis, J. Chem. Phys, 22, 1786 (1954)). This pioneering work soon included approaches to characterize active sites for adsorption on metal, metal oxide and acidic sites as well as distinguishing Brønsted and Lewis acid sites. • 1954: John P. Hogan and R. L. Banks, Phillips Petroleum, discovers chromia catalyst for polyethylene production.

20. 1 st DECADE: 1949 - 1958 • 1955: Sasol begins commercial operation of Fischer-Tropsch circulating fluid bed reactors. • 1956: Phillips Process - high pressure (500 psi) in hot solvent with supported chromia catalyst did not, on the surface, look attractive compared to Ziegler-Natta; however, engineering advances, cheap and high activity catalyst, and ever increasing scale made the Phillips Process the world's leading source of polyethylene. • 1956: First International Congress on Catalysis held in Philadelphia - more than 600 attendees. This has become an independent organization and the 11th ICC will be held during 2000 in Granada, Spain. • 1957: On June 18, Hercules opens the first Zigler catalyst based plant in the U.S. • 1958: MeroxMercaptan Oxidation Process _ UOP • 1953 -1959: Patents granted in these years led to the commercial production of three significant linear polyolefins: high-density polyethylene (1955- 56 by Hoechst, W.R. Grace, Hercules and Phillips), polypropylene (1957-8 by Hercules, Montecantini and Hoechst) and stereo-specific rubbers (1958-9 by Goodrich-Gulf, Phillips and Shell).

21. 2nd DECADE: 1959 - 1968 • 1960's: Major advances in heterogeneous photocatalysis • 1960's: Catalytic advances to allow low-temperature water-gas shift • 1960s: Scientific Design developed processes to make chlorinated solvents and maleic anhydride. A major breakthrough was the development of a catalyst to oxidize p-xylene into purified terphthalic acid. • 1960s: Development of the concepts of demanding and facile metal catalyzed reactions - introduced by Boudart and coworkers. M. Boudart, Adv. Catal., 20, 153 (1969) • 1959: Observation of olefin metathesis at Phillips Petroleum - R. L. Banks and G. C. Bailey, Ind. Eng. Chem. Prod. Res. Dev., 3, 170 (1964); R. L. Banks, "Discovery and Development of Olefin Disproportionation (Metathesis)" in "Heterogeneous Catalysis: Selected American Histories," (B. H. Davis and W. P. Hettinger, Jr., Eds.), ACS Symp. Series, 222, 403 (1983)). • 1959:Dabco (trimethylenediamine) was introduced by Houdry Corp. as a catalyst for the production of urethane foams from isocyanates and alcohols.

22. 2nd DECADE: 1959 - 1968 • 1959: Nalco introduces 1/16", and later 1/32," extrudateCoMo- alumina hydrotreating catalysts and introduced in Exxon Baytown refinery. • 1960: Ethylene to acetaldehyde - Wacker Chemistry • 1960: UOP introduces Hydrar Process for converting benzene to cyclohexene. • 1960: Completion of Sohio'sacrylonitrile plant at Lima, Ohio, based upon catalyst discovered by J. D. Idol. • 1961: Paring reaction in hydrocracking, R. F. Sullivan, C. J. Egan, G. E. Langlois and R. P. Sieg, JACS, 83, 1156 (1961). • 1962: Steam reforming with NiK2Al2O3 • 1962: Observation of reversible binding of H2 and C2H4 by Vaska's Complex, IrCl(CO)(PPh3)2, L. Vaska and J.W. DiLuzio, JACS, 84, 679 (1962). • 1962: Journal of Catalysis, the first scientific journal devoted solely to catalysis, begins publication with J. H. de Boer and P. W. Selwood as editors.

23. 2nd DECADE: 1959 - 1968 • 1962: Description of "Vaska's Complex," the first to show reversible bonding of hydrogen and ethene within the coordination sphere (L. Vaska and J. W. D. Luzio, JACS, 84, 679 (1962)). • 1963:Sachtler proves, using 14C-labeled propene, that a p-allyl complex is formed during propene oxidation (W. M. H. Sachtler, Rec. Trav. Chim., 82, 243 (1963)). • 1963:Ammoxidation of propene to acrylonitrile. • 1963: Theoretical model for describing elementary redox reactions for electrodes (R. A. Marcus, J. Phys. Chem., 43, 679 (1963)). • 1964: Introduction of rare earth metal stabilized X-zeolite for catalytic cracking by Mobil Oil - C. J. Plank, E. J. Rosinski and W. P. Hawthoren, 3, 165, (1964). Plank and Rosinski in the Inventors Hall of Fame. • 1964: Olah announces "Magic Acid," a mixture of HF and SbF5 reacts with hydrocarbons to produce stable carbocations that are observable using NMR. G. Olah awarded the 1994 Nobel Prize in Chemistry.

24. 2nd DECADE: 1959 - 1968 • 1964: Olefin metathesis announced [R. L. Banks and G. C. Bailey, Ind. Eng. Chem, Prod Res. Dev., 3 170 (1964)] commercialized in 1966. • 1964: Mechanism for hydrocracking - H. L. Coonradt and W. E. Garwood, Ind. Eng. Chem., Process Design Dev., 3, 38 (1964). • 1964: K. Tamaru summarizes transient catalytic studies emphasizing IR techniques (Adv. Catal., 15, 65 (1964)). • 1964: Spillover of Hydrogen from Pt/Al2O3 to WO3 (S. Khoobiar, J. Phys. Chem., 68, 411 (1964)). • 1964:Blyholder (J. Phys. Chem., 68, 2772 (1964)) suggested that CO adsorption on transition metals can be described by a molecular orbital picture of two contributions to bonding, partial donation of CO-5s charge to metal dsorbitals and back donation from metal dp to CO 2p* antibondingorbitals. • 1964: Startup by Monsanto of the world's first biodegradable detergents plant based upon C10-C14 linear olefins obtained by selective catalytic dehydrogenation of n-paraffins. • 1965: Wilkinson's homogeneous hydrogenation catalyst, J.F. Young, J.A. Osborn, F.H. Jardine and G. Wilkinson, Chem. Commun., (1965) 131. G. Wilkinson is the 1973 Nobel Laureate in Chemistry. • 1966: ICI developed a moderate-pressure, low-temperature methanol synthesis process employing a Cu-ZnO/Al2O3 catalyst in a gas-recycle reactor. • 1966: Introduction of concept of hard and soft acids and bases to catalysis (R. G. Pearson, Science, 151, 172 (1966)). • 1966: Development of a method to calculate the coordination numbers of surface atoms in the stable forms of small metal particles (R. van Hardeveld and A. van Montfoort, Surface Sci., 4, 396 (1966)). • 1967: Introduction of first bimetallic naphtha reforming catalyst - Pt-Re-Al2O3 - need for presulfidation of a naphtha reforming catalyst. • 1967: Catalysis Reviews begins publication with H. Heinemann as editor. • 1967: Atlantic Richfield and Halcon (formerly Scientific Design) formed a joint venture, Oxirane, to produce styrene, propylene oxide and tert-butyl alcohol. • 1967: Summaries of Linear Free Energy Relationships (LFER) in Heterogeneous Catalysis (M. Kraus, Adv. Catal., 17, 75 (1967); I. Mochida and Y. Yoneda, J. Catal., 7, 386 (1967)). • 1968: Shape selective catalysis - Selectoforming with erionite

25. 3rd DECADE: 1969 - 1979 • 1970's:Rh-catalyzed hydroformylation of propene. • 1970's: Improved selectivity for oxidation of ethene to ethylene oxide using Cs (or Cl) promoted Ag catalysts. • 1970's: Introduction of use of controlled atmospheric transmission electron microscopy for catalyst characterization and kinetics of catalysis. • 1972: Extensive studies of metal alloy catalysts by Sinfelt and coworkers results in demonstration of different activity patterns as alloy composition changes for the hydrogenolysis of ethane to methane and dehydrogenation of cyclohexane to benzene (J. H. Sinfelt, J. L. Carter and D. J. C. Yates, J. Catal., 24, 283 (1972)). • 1974: UOP Purzaust Auto Exhaust Treatment system accepted by Chrysler and is installed on 1975 models. • 1974: F. Sherwood Roland and M. Molina discover chlorine-catalyzed ozone depletion in the atmosphere. • 1975: B. Delmon organizes the first meeting for the Scientific Basis for the Preparation of Heterogneous Catalysts. • 1975: State of dispersion of small Pt and Pd metal particles in zeolites (P. Galleyot et. al., J.Catal., 39, 334 (1975)). • 1975: Demonstration that poisons of metallic catalysts are selective, decreasing rates of structure-sensitive and structure-insensitive reactions differently (R. Maurel, G. Leclercq and J. Barbier, J. Catal., 37, 324 (1975)). • 1976: Mobil Oil management announces the discovery

26. 3rd DECADE: 1969 - 1979 • 1976: Mobil Oil management announces the discovery of methanol-to-gasoline conversion using their ZSM-5 zeolite catalyst (Chemtech, 6, 86-9 (1976)). • 1978: Discovery of the strong metal support interaction (SMSI) and its role in altering the adsorptive properties of the metal function. (S. J. Tauster, S. C. Fung and R. L. Garten, JACS, 100, 170 (1978)). • 1979: Tennessee Eastman selects rhodium as catalyst for producing acetic anhydride from coal.

27. 4th DECADE: 1979 - 1988 • 1980's: Introduction of SCR (Selective Catalytic Reduction) for NOx control on stationary power generators. • 1980's: New catalytic technology commercialized in the U.S. during the 1980's (J. Armor, Appl. Catal., 78, 141 (1991)). • 1980's: Union Carbide and Shell develop the UNIPOL process for linear low-density polyethylene, which allows precise control over the product's material properties. The process was extended to polypropylene in 1985. • 1980's: Demonstration that strongly electronegative elements relative to nickel modify chemisorptive behavior far more strongly than a simple site- blocking mechanism would allow, supporting an electronic effect (D. W. Goodman, "Chem. Phys. Solid Surf," Springer-Verlag, 1986, pp. 169-195. • 1980's: Experimental evidence demonstrating the restructuring of surfaces during catalytic reactions - e.g., the conversion of ethylene to ethylidyne with expansion of the metal atoms around the carbon atom (R.J. Koestner, M. A. Van Hove and G. A. Somorjai, Surf. Sci., 121, 321 (1982) and showing the parallel restructuring of Pt and oscillation in CO oxidation (G. Ertl, Ber. Buns. Phys. Chem., 90, 284 (1986)). • 1980: Very rapid ethene polymerization by homogeneous catalyst (CP2Zr (CH3)2 activated with cocatalystaluminoxane) (H Sinn et. al., Angew. Chem., 92, 396 (1980)). • 1981: Applied Catalysis begins publication with B. Delmon as Editor-in-Chief. • 1981:Adsorbate induced restructuring of surface (M.A. van Hore et.al., Surf. Sci., 103, 190, 218 (1981)) • 1981: Introduction of constraint index as a diagnostic test for shape selectivity using cracking rate constants for n-hexane and 3-methylpentane (V. J. Frilette, W. O. Haag and R. M. Lago, J. Catal., 67, 218 (1981)).

28. 4th DECADE: 1979 - 1988 • 1982: Definition of Energy Profile for Ammonia Synthesis (G. Ertl in "Solid State and Material Sci.", CRC Press, 1982, 349). • 1982: The first of a series of silicaaluminophosphate molecular sieves prepared by Union Carbide (now part of UOP) • 1982: The concept of transition state selectivity for zeolite catalysis introduced (W. O. Haag, R. M. Lago and P. B. Weisz, J. Chem. Soc., Farad. Disc, 72, 317 (1982)). • 1983: Ashland Petroleum introduces RCC (Reduced Crude Cracking) with 40,000 blb/day plant. • 1983:Enichen scientists report the use of titanium silicalite (TS-1) as a catalyst for selective oxidations with aqueous hydrogen peroxide, including olefin epoxidation (M. Taramasso, G. Pereyo and B. Natari, U.S. 4,410,501).

29. 5th DECADE: 1989 - 1999 • 1990's: Fischer-Tropsch as a source of alpha-olefins. • 1990's: Combinatorial approaches to catalyst screening and new catalyst discovery (e.g., K. D. Shimizu et al., Chem. Eur. J., 4, 1885 (1998)). • 1990's: Selective oxidation of benzene to phenol using (Fe) ZSM-5 catalysts. • 1992: Commercial use of non-iron catalyst for ammonia synthesis. • 1992: Synthesis of MCM-41, the first uniformly structured mesoporousaluminosilicate, announced by Mobil Oil (J. S. Beck, et al., JACS, 114, 10834 (1992). • 1994: Topics in Catalysis begins publication with Gabor Somorjai and Sir John Thomas as Co-Editors. • 1995: Introduction of oxone catalytic converter for airplane air purification. • 1996: Catalytic converter selected by Fellows of the Society of Automotive Engineers as one of the top ten achievements in the auto industry during the past 100 years. • 1996: Global Overview of Catalysis - A Series of Reports for many countries begins to appear in Applied Catalysis A: General. • 1996: MagnaCat Process for separation and removing

30. 5th DECADE: 1989 - 1999 • 1996: MagnaCat Process for separation and removing aged FCC catalyst operates at a commercial scale. • 1996: Members of original acrylonitrile research team (l to r; J. L. Callahan, G. C. Cross, E. C. Milberger, E. C. Hughes and J. D. Idol (F. Veatch, deceased)) at dedication of plant site as National Historical Landmark by the ACS. • 1999: UOP Cyclar Process for the production of aromatics for LPG. • All these are reproduced from the site http://crtc.caer.uky.edu/text.htm

31. Alex Mills: the catalyst chemist

32. Eric Derouane- a visonary with high intellectual mobility (1944-2008) • 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 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,. 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.

33. Eric Derouane- a visonary with high intellectual mobility (1944-2008) • 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, Eurocatzeolite, 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. RamôaRibeiro 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 AdolpheWetrems 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 FondationUniversitaire de Belgique” (1980), the Ciapetta Lectureship of the North American Catalysis Society (1981), the Catalysis Lectureship of the SociétéChimique de France (1993) and the prestigious Francqui Prize, B (1994), the highest honor for all Sciences in Belgium. He was made “Officier de l’OrdreLéopold” in Belgium (1990), corresponding Member of the “Académie Royale des Sciences, des Lettres et des Beaux Arts de Belgique” (1991), member of the

34. Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline(1892-1962)

35. Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline (1892-1962) • 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.

36. Eugene Houdry: Catalytic Cracking of low-grade fuel into gasoline(1892-1962 • 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.

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

38. 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 TechnischeHochschule 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.

39. Heinz Heinemann: One of the accomplished founders of the Catalysis Society • 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

40. Herman Pines: he revolutionized the general understanding of catalysis

41. Herman Pines: he revolutionized the general understanding of catalysis • Herman Pines was born in Lodz, Poland, in 1902. After earning his degree at the ÉcoleSupérieure 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.

42. Herman Pines: revolutionized the general understandingof catalysis • 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, "parumaffinis," 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 -35ºC, 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.

43. Herman Pines: he revolutionized the general understanding of catalysis • 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

44. Herman Pines: revolutionized the general understanding of catalysis • 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.

45. John Sinfelt: Removal of lead from gasoline with bimetallics

46. John Sinfelt: Removal of lead from gasoline with bimetallics • 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.

47. John Sinfelt: Removal of lead from gasoline with bimetallics • 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.

48. John Sinfelt: Removal of lead from gasoline with bimetallics • 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."

49. 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.

50. Robert L. Burwell, Jr., - helped established catalysis concepts