Professional Documents
Culture Documents
Heterogeneous Catalytic Chemistry by Example of IndustrialApplications
Heterogeneous Catalytic Chemistry by Example of IndustrialApplications
pubs.acs.org/jchemeduc
ABSTRACT: Worldwide, more than 85% of all chemical products are manufactured with the
help of catalysts. Virtually all transition metals of the periodic table are active as catalysts or
catalyst promoters. Catalysts are divided into homogeneous catalysts, which are soluble in the
reaction medium, and heterogeneous catalysts, which remain in the solid state. A heterogeneous
metal catalyst typically consists of the active metal component, promoters, and a support
material. In some cases, the metallic state itself forms the active ingredient. However, this
situation is largely restricted to precious metal catalysts and to some base metals used under
reducing conditions. In most cases and especially in homogeneous catalysis, it is a metal
compound or a complex that forms the active catalyst. Catalysis can be rather puzzling as a given
metal can catalyze a variety of different chemical transformations, while the same substrate,
passed over different catalysts, can give different products. It is therefore helpful to be familiar
with the fundamentals of catalytic science before being exposed to the uncountable applications,
which form the backbone of industrial chemistry. Examples of practical importance are used in
this paper to highlight important principles of catalysis.
KEYWORDS: General Public, Public Understanding, Upper-Division Undergraduate, Curriculum, Inorganic Chemistry, Catalysis,
Green Chemistry, Industrial Chemistry
■
reaction, the hydrolysis of esters. In the equation below
(Scheme 1), the acid shows above the reaction arrow to INDUSTRIAL CATALYTIC CONVERTERS
indicate that this reaction is acid catalyzed.
Various reactor types have been designed to facilitate catalytic
Scheme 1. Acid-Catalyzed Esterification conversions on an industrial scale. Four examples are given in
Figure 1.4 Reactor A is a stirred tank reactor operated
batchwise. The catalyst is dissolved in the liquid phase, and it
could be an acid or a base, a metal salt, or a metal−organic
complex. Shown is a ruthenium alkylidene complex, which is
active for the olefin metathesis reaction.5 Catalysis in solution is
■
referred to as homogeneous catalysis. Homogeneous catalysts are
usually more active and selective than heterogeneous catalysts.
ECONOMIC BACKGROUND They are also easier to tailor for specific purposes, as the
The economic importance of catalysis reflects in the following reaction mechanism is often well understood. The major
numbers: disadvantage of homogeneous catalysis lies in the fact that it is
• More than 85% of all chemical products are manufac- difficult to separate the products from the catalyst, as the
tured with the help of catalysts.1 catalyst is present in the same phase. Also, homogeneous
• 15−20% of the economic activities in industrialized catalysts do not lend themselves easily for continuous
countries depend directly on catalysis.2 operations. However, these problems can be overcome by
• The commercial value of the catalysts produced annually
amounts to ∼14 billion US$.2 Published: October 9, 2012
© 2012 American Chemical Society and
Division of Chemical Education, Inc. 1530 dx.doi.org/10.1021/ed200816g | J. Chem. Educ. 2012, 89, 1530−1536
Journal of Chemical Education Article
mainly π-bonded ethylene that, in the following step, strike the correct balance and provide the optimum strength of
reacts further to the ethyl intermediate. bonding between the reactant and the catalyst surface for the
• Formation of the ethyl intermediate. This step must be reaction to occur.
reversible, as the complete range of deuterated ethanes For ethylene hydrogenation the situation translates into the
(and not only DH2C−CH2D) is observed in case D2 is picture shown in Figure 6.23,24 First-row transition metals and
used instead of H2.20
• Formation of the second C−H bond.
• Desorption of the product.
The key step is the activation of the reactants by chemisorption
to the platinum surface. This facilitates the catalytic route of
lower activation energy for the formation of the products.
Sabatier postulated that a good catalyst provides an optimum
strength of bonding between the reactants and the catalyst
surface (Sabatier’s principle).21 Both too weak and too strong
bonds will slow down or prevent the reaction. This principle
was convincingly demonstrated by Rootsaert and Sachtler,22 as
illustrated in Figure 5. The model reaction is the decomposition
■
temperatures required to achieve the preset reaction rate. To
the left (Au and Ag), bond formation between the catalyst
surface and the formate is too weak, as indicated by the CONVERSIONS BY METALLIC-STATE CATALYSIS
corresponding ΔfH⊖ values; to the right (W, Fe, Co, Ni, and It is necessary to clearly distinguish between catalysis by metals
Cu), the enthalpy of formation is highly negative and bond and catalysis in the metallic state. The general term “metal
formation is too strong. In the first case, the intermediate does catalysis” is usually understood to include catalysis by metal
not form at a sufficiently high rate; in the second case, the compounds, such as metal oxides, salts, and organometallic
intermediate is too stable and does not decompose at a complexes. Homogeneous transition-metal catalysis is always
sufficiently high rate. The platinum group metals in the middle facilitated by metal compounds. A border case between
1533 dx.doi.org/10.1021/ed200816g | J. Chem. Educ. 2012, 89, 1530−1536
Journal of Chemical Education Article
homogeneous and heterogeneous catalysis would be the synthesis. As indicated in Figure 7, a line drawn across the
catalysis induced by colloidal nanoparticles kept in suspen- periodic table separates copper and nickel, separates the base
sion.26 Only groups VIII and IB of the periodic table (all the metals from the PGMs up to ruthenium, divides ruthenium
metals shown in Figure 7) display catalytic activity of practical from rhodium and osmium, and finally crosses down between
osmium and rhenium. Under normal catalytic reaction
conditions, metals to the left of this line dissociatively
chemisorb carbon monoxide, whereas metals to the right will
chemisorb CO molecularly (without breaking the carbon−
oxygen bond).29 In other words, on iron, cobalt, and nickel CO
dissociates, whereas it remains undissociated on the coinage
metals (Cu, Ag, and Au) and the PGMs (except Ru).
Regardless of the detailed mechanisms involved,29 the full
hydrogenation of undissociated CO over a copper catalyst leads
to methanol, whereas the hydrogenation over the base metals
iron, cobalt, and nickel leads to hydrocarbons and water. The
fact that commercial nickel catalysts can produce methane with
a selectivity of up to 96% is explained by the high abundance of
chemisorbed hydrogen relative to chemisorbed carbon
(carbidic surface carbon) on a nickel surface. As a result,
almost all the surface carbon is rapidly hydrogenated to
methane.29 This is in contrast to the situation found on iron
Figure 7. Synthesis gas (CO/H2) products obtained over various (and cobalt). The coverage by carbidic carbon is extensive and
metals depending on the mode of CO chemisorption (associative or the reduced availability of hydrogen favors hydrocarbon chain
dissociative; chemisorption of hydrogen not shown).
growth to give alkanes, and unsaturated compounds (olefins)
form as byproducts. In terms of Sabatier’s principle iron and
significance in the metallic state, especially for hydrogenation cobalt provide the optimum bond strength for the chemisorbed
and oxidation reactions. Other transition elements are too species to form Fischer−Tropsch products, whereas nickel
difficult to reduce and to maintain in the metallic state.24 In the provides the optimum bond strength for the formation of
metallic state, iron, cobalt, nickel, copper, and ruthenium methane.
catalyze hydrogenation reactions, including the hydrogenation The reverse reaction of methanation (double arrow in Figure
or hydrogenolysis of carbon monoxide. (Hydrogenolysis, in 7) is known as steam reforming and is of even greater industrial
contrast to hydrogenation, involves the cleavage of an importance. Most of the synthesis gas used for processes such
interatomic connection in the substrate.) Iron and ruthenium as methanol synthesis, Fischer−Tropsch synthesis, and hydro-
are unique in their capability of converting nitrogen to formylation (the conversion of olefins into aldehydes) is
ammonia, a reaction that can be regarded as the hydrogenolysis produced by nickel-catalyzed steam reforming.
■
of N2. Silver is used for some large-scale selective oxidation
reactions, such as the conversion of ethylene to ethylene oxide AUTOMOTIVE EXHAUST CATALYSIS
and the oxidation of methanol and ethanol to the
corresponding aldehydes. In contrast, oxidations over Rh, Pd, As indicated above, oxidations over Rh, Pd, Ir, and Pt are prone
Ir, and Pt are prone to result in deep oxidation, which is the to result in deep oxidation. Environmental abatement catalysts
total oxidation to CO2 and water. These four metals are also make use of this. The most important single application is
extremely useful for many conversions involving hydrogen, probably automotive exhaust catalysis. It is a remarkable
such as hydrogenations, dehydrogenations, hydrogenolyses, and achievement that the deep oxidation of hydrocarbons and
naphtha reforming. The catalytic activity of gold appears to be carbon monoxide and the reduction of nitrous oxides can be
restricted to the nanostate,27 as confirmed by numerous more done in a single catalytic converter.30 This is possible by the use
recent reports.28 of platinum or palladium or both combined with rhodium. A
Metallic-state catalysis over group VIII and IB elements schematic presentation is given in Figure 8. Rhodium is able to
includes many important large-scale processes. Examples are dissociatively adsorb NO in preference to O2, whereas
ammonia synthesis (Fe), ammonia oxidation (Pt−Rh), palladium and platinum are responsible for the splitting of
Fischer−Tropsch synthesis (Fe, Co), methanol synthesis oxygen.31 The chemisorbed nitrogen atoms combine to N2, and
(Cu), and refinery processes such as platforming. the chemisorbed oxygen atoms oxidize carbon monoxide and
■
hydrocarbons (HC) to CO2 and water.
METAL-DEPENDENT PRODUCT FORMATION
FROM SYNTHESIS GAS
The conversion of synthesis gas (mixtures of CO/H2 in
different ratios) provides an interesting case concerning the
change in product selectivity depending on the catalytic
element used. This is demonstrated in Figure 7. The product
selectivity changes along the first transition-metal series from
left to right. Iron and cobalt (and also ruthenium) convert
synthesis gas into a mixture of hydrocarbons by a process Figure 8. Schematic presentation of the key aspects of an automotive
known as Fischer−Tropsch synthesis. Nickel is a selective catalytic converter (HC = hydrocarbons; adsorption of CO and HC
methanation catalyst, and copper is used for methanol not explicitly shown).
The introduction of the automotive exhaust catalyst shows Scheme 5. Selective Oxidation of Hydroxymethylimidazoles
that legislative pressure can trigger innovative solutions and to Formylimidazoles
create business opportunities on a large scale (even for metal
brokers and speculators). To understand some of the price
fluctuation seen for rhodium over the last four decades,32 it has
to be kept in mind that the annual mining output of rhodium is
only about 25 tons. This constitutes ca. 1% of the annual gold
production. The annual production of platinum amounts to
approximately 130 tons. In 2008, more than 75% of the total
rhodium output was used for the manufacturing of
autocatalysts.33 ■ PEDAGOGICAL ASPECTS
■ CONCLUSION
Catalysis, and heterogeneous catalysis in particular, is a mature
field of science. Catalysis grows and diversifies further as the
world economy grows and diversifies. It contributes signifi-
According to this proposal, dehydrogenation of the alcohol cantly to value creation in the real economy. From an
to the aldehyde takes place on the noble metal surface. The environmental point of view, it impacts positively on the
chemisorbed hydrogen reacts with a higher-oxidation-state viability of many human activities, not only those of a pure
bismuth oxide species, giving water and a lower-oxidation-state chemical nature. To continue educating the catalysis experts of
bismuth species. The lower-oxidation-state bismuth is re- tomorrow at schools and universities and to raise public
oxidized by the oxidizing agent used for the overall reaction. awareness for the importance of catalysis is therefore of great
The addition of bismuth keeps the platinum surface free of significance. To the lay person and to many undergraduate
excess oxygen, thus preventing over oxidation of the substrate. students, catalysis appears as a rather complex field, not the
The left part of the catalytic cycle exemplifies the action of a least because of the huge number of different catalytic materials
common base-metal oxidation catalyst: bismuth switches and the many different catalytic processes that go with them.
between two oxidation states and (in the case of Scheme 4) Often students are exposed to specific applications of catalysis
oxidizes hydrogen to water. Depending on the substrate, Pt−Bi (e.g., descriptive heterogeneous catalysis) before they have
catalysts allow for very high selectivities under mild reaction been exposed to the basic principles of the relevant surface
conditions. Instead of air, hydrogen peroxide can also be used chemistry. This often contributes to the perception that
as the oxidizing agent. Examples for the oxidation of catalysis is a “magic” art, rather than a science. Teaching
hydroxymethylimidazoles to formylimidazoles are shown in important fundamentals of catalysis at an early stage can be
Scheme 5.35,36 Formylimidazoles are important intermediates in expected to contribute to a deeper understanding. This, in turn,
the synthesis of pharmaceuticals. Further examples for the will allow the student to put forthcoming information into
successful application of Pt−Bi oxidation catalysts were perspective. In the paper at hand, an attempt was made to
reported by Anderson et al.37 explain some important concepts of catalysis in a brief, but
1535 dx.doi.org/10.1021/ed200816g | J. Chem. Educ. 2012, 89, 1530−1536
Journal of Chemical Education Article
understandable manner. Applications of industrial and general (28) Bond, G. C.; Louis, C.; Thompson, D. T. Catalysis by Gold;
importance were used for demonstration purposes. Imperial College Press: London, 2006.
■
(29) Campbell, I. M. Catalysis at Surfaces; Chapman and Hall:
London, 1988; pp 132−142, 205−215.
AUTHOR INFORMATION (30) Gandhi, H. S.; Graham, G. W.; McCabe, R. W. J. Catal. 2003,
Corresponding Author 216, 433−442. Twigg, M. V. Platinum Met. Rev. 2011, 55, 43−53.
(31) Thomas, J. M.; Thomas, W. J. Principles and Practice of
*E-mail: hevelingj@tut.ac.za. Heterogeneous Catalysis; VCH: Weinheim, 1997; pp 576−590.
Notes (32) Sharelynx Gold. http://www.sharelynx.com/gold/RareMetals.
php#rhodium, accessed May 22, 2012.
The author declares no competing financial interest. (33) http://www.platinum.matthey.com./publications/pgm-market-
■ REFERENCES
(1) German Catalysis Society. Roadmap der deutschen Katalysefor-
reviews/archive/platinum-2009/Pt2009.html (Supply and Demand),
accessed Sept. 28, 2012.
(34) Besson, M.; Lahmer, F.; Gallezot, P.; Fuertes, P.; Flèche, G. J.
Catal. 1995, 152, 116−121.
schung; Katalyse, eine Schlüsseltechnologie für nachhaltiges Wirtschafts- (35) Bessard, Y.; Heveling, J. US Pat. US6’469’178, 2002.
wachstum, 3rd ed.; Dechema: Frankfurt, 2010; p 3. (36) Heveling, J.; Wellig, A. Eur. Pat. EP916’659, 2002; Eur. Pat.
(2) Behr, A. Angewandte Homogene Katalyse; Wiley-VCH: Weinheim, EP913’394, 2005.
2008; p 26. (English ed.: Behr, A.; Neubert, P. Applied Homogeneous (37) Anderson, R.; Griffin, K.; Johnston, P.; Alsters, P. L. Adv. Synth.
Catalysis; Wiley-VCH: Weinheim, 2012.) Catal. 2003, 345, 517−523.
(3) U.S. Climate Change Technology Program − Technology (38) Wittcoff, H. A.; Reuben, B. G.; Plotkin, J. S. Industrial Organic
Options for the Near and Long Term. http://www.climatetechnology. Chemicals, 2nd ed.; Wiley-Interscience: Hoboken, NJ, 2004.
gov/library/2005/tech-options/tor2005-143.pdf, accessed May 16,
2012.
(4) Henkel, K.-D. Ullmann’s Encyclopedia of Industrial Chemistry, 6th
ed.; Wiley-VCH: Weinheim, 2003, Vol. 31; pp 125−157.
(5) Grubbs, R. H. Tetrahedron 2004, 60, 7117−7140.
(6) Heveling, J. J. Chem. Soc., Chem. Commun. 1987, 1152−1153.
Heveling, J. J. Mol. Catal. 1990, 58, 1−19.
(7) Sheldon, R. A. Green Chem. 2007, 9, 1273−1283.
(8) Trost, B. M. Angew. Chem., Int. Ed. Engl. 1995, 34, 259−281.
(9) Tschitschibabin, A. E. J. Prakt. Chem. 1924, 107, 122−128.
(10) Ullmann’s Encyclopedia of Industrial Chemistry, 6th ed.; Wiley-
VCH: Weinheim, 2003, Vol. 30; pp 481−484.
(11) Heveling, J.; Armbruster, E.; Siegrist, W. Eur. Pat. EP691’955,
1997.
(12) Heveling, J.; Armbruster, E.; Utiker, L.; Rohner, M.; Dettwiler,
H.-R.; Chuck, R. J. Eur. Pat. EP770’687, 2002.
(13) Atkins, P.; Overton, T.; Rourke, J.; Weller, M.; Armstrong, F.
Shriver & Atkins’ Inorganic Chemistry, 5th ed.; Oxford University Press:
Oxford, 2010; pp 690−721.
(14) Sabatier, P.; Senderens, J. B. C. R. Acad. Sci. 1897, 124, 1358−
1361.
(15) Ger. Pat. 141029, 1903 (to Leprince & Siveke). Normann, W.
Brit. Pat. 1515, 1903.
(16) Knothe, G. The AOCS Lipid Library, updated Jan. 6, 2010;
http://lipidlibrary.aocs.org/history/Normann/index.htm (accessed
Aug 2012).
(17) Fiedler, M. Deutsche Gesellschaft für Fettwissenschaft, 2001;
http://www.dgfett.de/history/normann/nr_fiedler.htm (accessed Aug
2012).
(18) Horiuti, I.; Polanyi, M. Trans. Faraday Soc. 1934, 30, 1164−
1172.
(19) Somorjai, G. A. J. Mol. Struct.: THEOCHEM 1998, 424, 101−
117.
(20) Burwell, R. L., Jr. Acc. Chem. Res. 1969, 2, 289−296.
(21) Sabatier, P.; Senderens, J. B. C. R. Acad. Sci. 1902, 134, 514−
516.
(22) Rootsaert, W. J. M.; Sachtler, W. M. H. Z. Phys. Chem. 1960, 26,
16−26.
(23) Schuit, G. C. A.; van Reijen, L. L. Adv. Catal. 1958, 10, 242−
317.
(24) Bond, G. C. Platinum Met. Rev. 1968, 12, 100−105. Bond, G. C.
Platinum Met. Rev. 1979, 23, 46−53.
(25) van Santen, R. A.; Neurock, M. Molecular Heterogeneous
Catalysis; Wiley-VCH: Weinheim, 2006.
(26) Tabor, C.; Narayanan, R.; El-Sayed, M. A. Model Systems in
Catalysis; Rioux, R. M., Ed.; Springer: New York, 2010; pp 395−414.
(27) Bond, G. C.; Sermon, P. A.; Webb, G.; Buchanan, D. A; Wells,
P. B. J. Chem. Soc., Chem. Commun. 1973, 444−445.