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Title: HETEROGENEOUS CATALYSIS CHALLENGES - SOCIETAL NEEDS - DEVELOPING THE BASIC UNDERSTANDING OPPORTUNITIES - DESIGNING AT THE NANO SCALE


1
HETEROGENEOUS CATALYSISCHALLENGES - SOCIETAL
NEEDS - DEVELOPING THE BASIC
UNDERSTANDINGOPPORTUNITIES- DESIGNING AT THE
NANO SCALE
2
Challenges I
Dream reactions waiting for a catalyst
Jens Rostrup-Nielsen XVII Sympósio
Iberoamericano de Catálisis, July 16-21, 2000
3
Challenges II
  • Dreaming on .
  • Heterogeneous catalysts for assymmetric synthesis
  • Photolytic water splitting (hydrogen economy)
  • Biomimetics, synthetic enzymes
  • Non-thermal processes in general
  • (e.g. electro- and photocatalysis)

See E. Derouane, CATTECH 5, 226 (2001)
4
Challenges III
  • The science of heterogeneous catalysis
  • A comprehensive scientific basis
  • Much has been done
  • Much more is needed (oxides, size effects,
    photocatalysis, electrocatalysis, relation to
    homogeneous and enzyme catalysis )
  • Making the insight useful!
  • The ultimate test

5
Opportunities- design at the nano-scale
  • Rational catalyst design
  • Discovery on the basis of insight
  • Data-driven methods
  • - Accelerated discovery by access to
  • large amounts of data
  • Bio-inspired catalysis

6
Rational catalyst design
  • What determines the catalytic
  • activity/selectivity/lifetime ?
  • How can we affect it?
  • - We have tremendous new possibilities

7
Ammonia synthesisN23H2? 2NH3
Ozaki and Aika, Catalysis 1 (Anderson and
Boudart, Ed.)
8
Ammonia synthesis over Ru
Ru(0001)
step
Logadottir, Nørskov
9
Steps do everything
Au decorates steps Hwang, Schroder, Gunther,
Behm, Phys. Rev. Lett. 67, 3279 (1991)  
Dahl, Logadottir, Egeberg, Larsen, Chorkendorff,
Törnqvist, Nørskov, Phys.Rev.Lett. 83, 1814
(1999)
10
The Brønsted-Evans-Polanyi relation
Logatottir, Rod, Nørskov, Hammer, Dahl, Jacobsen,
J. Catal. 197, 229 (2001)
11
Calculated ammonia synthesis rates400 C, 50 bar,
H2N231, 5 NH3
Logatottir, Rod, Nørskov, Hammer, Dahl, Jacobsen,
J. Catal. 197, 229 (2001)
12
Interpolation in the periodic table
Jacobsen, Dahl, Clausen, Bahn, Logadottir,
Nørskov, JACS 123 (2001) 8404.
13
Interpolation in the periodic table
Jacobsen, Dahl, Clausen, Bahn, Logadottir,
Nørskov, JACS 123 (2001) 8404.
14
Measured ammonia synthesis rates 400 C, 50 bar,
H2N231
Jacobsen, Dahl, Clausen, Bahn, Logadottir,
Nørskov, JACS 123 (2001) 8404.
15
Data driven methods
  • High throughput screening
  • Direct testing of many catalysts, fast,
    efficiently
  • Data mining
  • Correlating catalytic activity/selectivity/
    durability to descriptors that can be tabulated

16
H. Toulhoat and P. Raybaud Workshop Catalysis
from First Principles Vienna 02/02
Using DFT calculations in the search of
prospective catalysts
  • The object of the game
  • Find sets of descriptors Dik of solid materials
    Mi , and a mathematical model F such that Aij
    being the Turn Over Frequency of Mi as catalyst
    for the reaction j at operationg conditions Cj
    one has
  • Identify ranges of Dik that maximize F
  • Screen Databases of Materials Properties before
    screening real materials
  • Better if one descriptor is sufficient, but do
    not take it for granted
  • Much better if F has a sound physical basis
  • Adsorbate/substrate bond strengths should provide
    good descriptors according to the Sabatier
    principle

17
H. Toulhoat and P. Raybaud Workshop Catalysis
from First Principles Vienna 02/02
Using DFT calculations in the search of
prospective catalysts
18
H. Toulhoat and P. Raybaud Workshop Catalysis
from First Principles Vienna 02/02
Using DFT calculations in the search of
prospective catalysts
  • E MC _at_ Fm-3m carbides is rather consistent with
    simple chemisorption models
  • Onset of dissociative chemisorption as MC bond
    strength increases

19
H. Toulhoat and P. Raybaud Workshop Catalysis
from First Principles Vienna 02/02
Using DFT calculations in the search of
prospective catalysts
  • The experimental Alloying effects is correctly
    predicted

20
Getting data/descriptors
  • Structure (in situ)
  • Spectroscopy (in situ)
  • Surface thermochemistry
  • Calculations
  • There is a large need for systematic data
  • - and for good descriptors

21
Structure-activity Correlation Hydrodesulfurizatio
n of thiophene
Topsøe, Clausen, Massoth Hydrotreating Catalysis,
Science and Technology (Anderson and Boudart
(Eds.), Springer (1996).
22
Descriptors from spectroscopy
23
Single crystal microcalorimerty
Larsen, Starr, Campbell, Chem.Thermodyn. 33, 333
(2001) Brown, Kose, King, Chem. Rev. 98, 797
(1998).
24
Descriptors from DFT
Correlation between adsorption energies and
activation barriers and the d-band center
Mavrikakis , Hammer, Nørskov Phys. Rev. Lett. 81,
2819 (1998)
25
CO tolerance of Pt alloy anodes for PEM fuel
cells
Pt
M
S. Gottesfeld et al., J. Electrochem. Soc. 148
(2001) A11.
   Christoffersen, Liu, Ruban, Skriver, Nørskov,
J.Catal. 199, 123 (2001)
26
How can the d-band center be changed?
Calculated d band shifts
Overlayer
Host
Ruban, Hammer, Stoltze, Skriver, Nørskov,
J.Mol.Catal. A 115, 421 (1997)
27
Methane activation
Transition state for CH4 dissociation on Ni(211)
b
Bengaard, Rostrup-Nielsen, Nørskov
28
Methane activation on Ni/Ru
Egeberg, Chorkendorff, Catal. Lett. 77, 207
(2001)
29
Lessons from biology
  • Catalysis at ambient temperature and pressure
  • Extreme selectivity
  • Direct coupling of energy into the important
    reaction coordinate (non-thermal catalysis)

30
Nitrogenase
nitrogenase
ATP
complex formation
Fe protein

4Fe-4S cluster
MoFe protein
P-cluster
nucleotide replacement
ATP cleavage electron transfer
FeMo cofactor
Fe protein
reduction

complex dissociation
Burgess, Lowe, Chem. Rev. 96, 2983
(1996) Schindelin, Kisker, Schlessman, Howard,
Rees, Nature 387, 370 (1997)
31
N2 hydrogenation on FeMoco
Rod, Nørskov JACS 122, 12751 (2000)
32
The Fe Protein cycle
E
MoFe protein
Fe protein
ATP
1)
4Fe-4S cluster
FeMoco
P-cluster
2)
E
3)
ADP
E
4)
See also Spee, Arendsen, Wassnik, Marrit, Hagen,
Haaker, FEBS Lett. 432, 55 (1998)
33
Comparing the FeMoco and Ru(0001)
Rod, Logadottir, Nørskov J.Chem.Phys.
112, 5343 (2000)
34
Status
  • Well developed basic understanding
    theory-experiment
  • Beginning to be able to use it directly in
    catalyst design
  • Some activity-descriptor correlations
  • Host of new in situ methods for catalyst
    characterization
  • New very powerful screening methods
  • We have a starting point which is radically
    different from the situation 5 or 10 years ago!

35
Moving forward
  • More basic understanding theory-experiment
  • Integration of the conceptual framework for
    heterogeneous, homogeneous and enzyme catalysis
  • More systematic data (descriptors)
  • Better synthesis methods
  • Better coupling of catalyst design and process
    engineering
  • INTEGRATION

36
Promoting development
An integrated approach
Experiments, models
Synthesis testing characterization
Theory
37
atom-economy, environmental issues, enantiomeric
purity
38
Molecular and Supramolecular Chemistry in
catalysis 1.Surface-tailored molecular
precursors for nano-structured catalysts.2.
Self-assembly and recognition mechanisms in
supramolecular chemistry as tools to prepare new
catalysts.
39
Molecular insight in Homogeneous and
Heterogeneous Catalysts Mechanistic
comprehension of catalytic processes.
40
Catalytic reaction engineering. kinetics of
molecularly defined heterogeneous
catalysts Scale up issues of industrially-relevan
t processes
41
Atom-scale understanding of model and real
catalysts Atom scale description and control of
complex surface structuresMolecular mechanics
and ab-initio simulation methods applied to the
understanding of molecular properties in nano
structured catalysts.Structural and
spectroscopic characterization of
Nano-structured catalysts with focus on
controlled atmosphere and time-resolved
experiments.
42
Current challenges in catalysis range from the
efficient exploitation of energy resources to the
creative use of natural and artificial
enzymes. Our strategic goal is to unify concepts
in catalysis by bridging the gaps between
homogeneous and heterogeneous catalysis, between
elementary gas-phase reactions and complex
processes in highly organized biological systems,
as well as between fundamental and applied
catalysis research. Our initiative focuses on
analyzing catalytic mechanisms, designing novel
catalytic materials and strategies, and
developing new catalytic processes on laboratory
and mini-plant scales. We want to integrate the
expertise in chemistry, biology, physics, and
engineering into an innovative research program.
We aim at creating a centres of catalytic
research and generating new synergisms in this
central field of science and technology.
43
Interesting Catalysis Articles George
ParshallJournal Pure Appl. Chem., 74
(2002)2259Title Trends in processing and
manufacturing that will affect implementation of
the Chemical Weapons ConventionCommentsDiscusse
s the task of implementing the Chemical Weapons
Convention. Today's wide use of versatile,
multipurpose production facilities in making fine
chemicals complicates the task of discerning
whether a particular facility is used only for
nonprohibited purposes. Tiny microreactors
operated continuously under computer control can
produce significant quantitites of toxic
chemicals with a very small "footprint" within a
larger production facility. These with the
dispersal of chemical production facilities and
skills may seriously complicate the tasks of the
OPCW inspectors. Improvements in analytical
instrumentation and methodology should facilitate
detection of illicit production of chemical
warfare agents. Chunshan SongJournal
Catalysis Today 77 (2002) 17-49Title Fuel
Processing for low-temperature and high
temperature fuel cells, Challenges and
opportunities for sustainable development in the
21st centuryCommentsThis review discusses the
needs for fundamental changes in the energy
system for major efficiency improvements in terms
of global resource limitation and sustainable
development. The strategies and optins of fuel
processors depend on the type of fuel cells and
applications.
44
Colin GentJournal Chemical Communications
(2002) issue 24.Title Changes in the Chemical
Industry the perspective of a catalyst
supplierCommentsColin, as the former head of
catalysis for ICI, discusses changes going
through the chemical industry and relates these
to industrial catalysis while discussing the
underlying business cycles and the interactions
between society and industry. R. Berger, J.
Perez-Ramirez, F. Kapteijn, and J.
MoulijnJournal Chem. Engn. Sci., 57 (2002)
4921-4932Title Catalyst Performance Testing
bed dilution revisitedCommentsAn investigation
of the systematic (negative) deviation of the
conversion of N2O caused by excessive dilution of
the catalyst bed with inert particles in
gas-solid reaction systems. The combination of
both high dilution and high conversion should be
avoided in kinetic studies. S. Born, D. Lupton,
M. Grehl, and H. MeyerJournal Precious Metals,
2001, 25th, 206-214Title Rhenium- on the way to
becoming a precious metal?CommentsA historical
review of the chemistry, applications and cost of
Rhenium. In 2001 Re was 1600./Kg .
45
A. Frennet, V. Chitry, and N. KruseJournal
Applied Catalysis A 229 (2002) 273-281Title In
situ measurement of the surface area during
catalyst prepartion development of a new
methodsCommentsA new volumetric method working
in the dynamic regime using physisorption of
Argon at 77 K in the same microreactor where
other characterization experiments are
performed. G. Centi, P. Ciambelli, S.
Perathoner, and P. RussoJournal Catalysis Today
75 (2002) 3-15Title Environmental Catalysis
Trends and OutlookCommentsAn overview of the
subject based on material coming from a recent
international workshop. Yu. Matatov-Maytal and
M. SheintuchJournal Applied Catalysis A 231
(2002) 1-16Title Catalytic fibers and
clothsCommentsA review which summarizes the
results on preparation, properties, and
applications of fibrous catalysts. Fibrous
catalysts are flexible and versatile and find
applications due to their excellent mass transfer
characteristics, low pressure drop, and ease of
handling.
46
. A. Hagemeyer R. Borade P. Desrosiers S.
Guan D.M. Lowe D.M. Poojary H. Turner H.
Weinberg X. Zhou R. Armbrust G. Fengler U.
NotheisJournal Applied Catalysis A General,
227 (2002) 43-61Title Application of
combinatorial catalysis for the direct amination
of benzene to anilineCommentsCombinatorial
study of the direct amination of benzene to
aniline using solid cataloreactants as oxidants
hundreds of samples in the primary screen arrays
of 24 catalysts in the secondary screen 25,000
samples were screened in about a year. Novel
cataloreactant systems consisting primarily of a
noble metal and a reducible metal oxide one
optimized forumulation was Rh/Ni-Mn/K-TiO2. Some
of best activities 10 benzene conversion and
gt95 selectivity to aniline at 300C and 300 bar
for a reaction time of about 2 hr. Catalyst was
regenerated repeatedly by reoxidation in
air. Bert M. WeckhuysenJournal Chem. Commun.,
2002, 97-110Title Snapshots of a working
catalyst possibilities and limitations of is
situ spectroscopy in the field of heterogeneous
catalysisCommentsAn overview of the
possibilities of different spectroscopic
techniques for probing catalytic events under
reaction conditions. Several case studies are
provided in this review. The author concludes
that the main challenges remaining include, 1-
further development of time-resolved
spectroscopy 2- the need for more advanced
theoretical tools for spectroscopic
interpretation 3- the combination of
spectroscopy and microscopy 4- the further
development of site-selective spectroscopic
techniques and, 5- the development of expert
systems for on line control of catalytic systems
in a reactor.
47
. John N. ArmorJournal Applied Catalysis A
General 2001, 2221-2407-426Title New
Catalytic Technology Commercialized in the USA in
the 1990sCommentsThis article extends an
earlier summary on the same subject done for the
1980s. It summarizes catalytic chemical,
petroleum, biochemical, and environmental
technology that was successfully commercialized
during the decade of the 1990s within the USA.
The tables were assembled from the feedback of
technical representatives of companies that
commercialized, catalytic technology in the
1990s, and the tables provide over 130 examples
of new catalysts or catalyst improvements for
operating processes (both in some advanced stage
of scale up or commercialized). This review
demonstrates that catalytic technology clearly
continues to play a major role in enhancing a
number of businesses on a worldwide basis.
48
R. PenningJournal February 2001 issue of
Hydrocarbon Processing, pp. 4546Title
Petroleum refining a look at the
futureCommentsIn the long term, the refinery
wont just produce fuels, but also chemicals and
energy. In the near term, most of the refinery
investments will be committed to resolving
environmental concerns. Beyond refinery
emissions, more effort will be focused on
developing lower sulfur fuels, replacing MBTE in
gasoline, and lowering the levels of benzene in
gasoline. Sulfur removal can be approached by
post or pre-treatment. Efforts will be made to
improve hydroprocessing methods in an attempt to
upgrade difficult, refractory, distillate-range
products, such as the upgrade of FCC light cycle
oil to high quality diesel with lower sulfur and
aromatics. H2 availability will continue to be a
concern for refiners struggling to meet lower
sulfur levels in both gasoline and diesel fuel.
Petroleum refining in the future will address
changing product slates, cogeneration, and fuel
cells. If diesels do become more popular,
refineries will need to reconfigure to make more
diesel and less gasoline, while producing high
demand petrochemicals.
49
C. Mehnert, R. Cook, N. Dispenziere, and M.
AfeworkiJournal J. Am. Chem. Soc. 124 (2002)
12932-12933Title Supported Ionic Liquids- A new
concept for homogeneous hydroformylation
catalysisCommentsThe surface of a support
material is modified with a monolayer of
covalently attached ionic liquid fragments. The
active catalyst dissolves in the ionic liquid
phase and performs as a homogeneous catalyst O.
Busch, C. Hoffman, T. Johann, H-W. Schmidt, W.
Strehlau, and F. SchüthJournal J. Am. Chem.
Soc., 124 (2002) 13527-13532Title Application
of New Color Detection Based Method for the Fast
Parallel Screening of DeNOx CatalytstsCommentsA
new fast, parallel detection method for stage 1
HTS screening of solid catalysts was developed
based on the color change of organic dyes in the
presence of reaction products. It was
demonstrated that this method could be extended
toward more massive parallelization to speed up
preevaluation of catalysts. Several active
compositions were identified, some of which were
more extensively tested in a stage II screening
system. Results of stage I screening were
confirmed, and a promising new NOx storage
catalyst was discovered.
50
Brief history of oil industry Oil majors are
founded in the last quarter of 19th Century Most
important product originally was lamp
oil Combustion engines were invented in late 19th
Century Switch of British navy from coal to
bunker oil and mass production of
automobiles Hydrogen may again recreate the
energy industry Pathways have to be invented that
enable to move to sustainable hydrogen at a
minimum societal cost Natural gas plays an
important intermediate role
51
Simplified Generalised Energy Chains
today Source storage
conversion distribution
use Oil Tanks
Refining Trucks, Ships
ICE Gas Pipe line LNG
Conditioning pipeline
ICE,Turbine Wind Grid, Batteries
Generation Grid Ele.
Motor Biomass dry biomass
Processing Trucks, ships ICE
Turbine Hydro- Grid ,batteries
Conditioning Grid Ele
Motor Electric Solar Grid,
Batteries conditioning Grid
Ele.Motor
52
  • WHY HYDROGEN?
  • Electric power most versatile and clean energy
    carrier
  • Electric motors have close to 100 efficiency
  • Electric motors have the highest power density
  • Electric motors are simple and cheap
  • Electric motors are responsive and easy to
    control
  • However
  • Electrons are difficult to store
  • Weight
  • Cost
  • Charge/discharge efficiencies

53
  • The basic assumptions for hydrogen
  • Hydrogen can be
  • Stored better than electrons ( true at least a
    factor 3 at the present day
  • Technology, but not good enough)
  • Transported over long distances ( True)
  • Manufactured from virtually all energy sources
    ( true with inevitable
  • Energy losses)
  • Easily transformed into electric power ( true
    with inevitable energy loss)
  • Used safely

54
Key challenges for hydrogen Efficient
production Efficient storage Efficient
use Societal acceptance
55
Example Production Catal
ytic partial oxidation based fuel reformer CPO
SGC HTS LTS SELOX Air
Hydrogen Steam
carbon dioxide Fuel
Nitrogen
water
56
  • Challenges for catalysis and process technology
  • Scalability Catalyst
    coating
  • Dynamics technology
  • Start up / shut down Cost
  • Interplay of process steps Maintainability
  • responsiveness Transition of economy from
  • Process intensity scale to numbers
  • Size
  • heat capacity
  • Robustness Steps
    changes required in

  • catalysis

  • Process technology

  • Material science

  • colloid science

  • Manufacturing methods

57
The ultimate goal of chemical reaction
engineering is to predict the performance of a
reactor, most often containing a catalyst, based
upon the minimum amount of experimental
information. If this goal could be satisfied,
then it would be possible, in principle, to
design a chemical reactor knowing only the size
and internal configuration of the reactor, the
size, shape, and chemical composition of the
catalyst, and the overall stoichiometries of the
desired chemical reactions. The past 50 years
have been witnessed impressive progress towards
this ultimate objective, particularly concerning
the design of the chemical reactor once the
kinetics of the various chemical reactions
occurring in the reactor have been specified.
While progress has also been made towards
understanding the mechanism and kinetics of
catalyzed process from a fundamental level, the
advances in this domain are still insufficient to
allow for the prediction of catalyst performance
(viz., activity, selectivity, and stability)
based on first principles, or even empirical
based design principles. This talk will attempt
to identify some of the challenges for making
progress towards the goal of being able to
design catalysts.
58
1st 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. 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.
59
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).
60
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.
61
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
Merox Mercaptan 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).
             
62
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
63
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.
64
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.
65
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.
66
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 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.
67
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).
68
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 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
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