50 Years of Catalysis

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By. Prof. Burt Davis
University of Kentucky Center for Applied Energy Research, 2540 Research Park Drive, Lexington, KY 40511-8410

For more details and PDF files go to http://crtc.caer.uky.edu/history.htm

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1st DECADE: 1949 – 1958

• Late 1940s to Early 1950s – Robert M. Milton and Donald W. Breck, Union Carbide, develop 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.

• 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-Al2O2 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 catalysis scientist at Sun Oil), were adopted and still serve as the model for later formed clubs/societies.

• 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).

• 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.

• 1954 – B.F. Goodrich (S. E. Horne) and Gulf Oil announce use of Ziegler catalyst to polymerize isoprene to duplicate natural rubber.

• 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. Organizing the International Congress on catalysis was conceived by the Catalysis Club of Philadelphia and received endorsement from the Catalysis Club of Chicago, the University of Pennsylvania, and the National Science Foundation. [At the end of the acknowledgments it is noted the the organization of the Congress was planned by RL Burwell, Jr, A Farkas, AV Grosse, H Heineman, WR Kirner, KA Krieger, JM Mavity, AG Oblad and CL Thomas. The organizers included people from Chicago.]

• 1957 – On June 18, Hercules opens the first Zigler catalyst based plant in the U.S.

• 1958 – Merox Mercaptan Oxidation Process _ UOP.

• 1953 to 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).

 

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 (trimethylene diamine) was introduced by Houdry Corp. as a catalyst for the production of urethane foams from isocyanates and alcohols.

• 1959 – Nalco introduces 1/16″, and later 1/32,” extrudate CoMo- 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’s acrylonitrile 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.

• 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.

• 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 ds orbitals and back donation from metal dp to CO 2p* antibonding orbitals.

• 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.

 

3rd DECADE: 1979 – 1988

• 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 to 1975 – 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 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.

 

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 (CP2 Zr (CH3)2 activated with cocatalyst aluminoxane) (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)).

• 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).

 

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 catalyst.

• 1992 – Commercial use of non-iron catalyst for ammonia synthesis.

• 1992 – Synthesis of MCM-41, the first uniformly structured mesoporous aluminosilicate, 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 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.