Chapter 1

Introduction to Catalysis
Dr. Leong Loong Kong

Catalysis in Industry
Catalysts are the workhorses of chemical transformations in the industry. ~ 85²90% of the 85² products of chemical industry are made in catalytic processes. Catalysts are indispensable in: of transportation fuels in one of the ~ 440 oil refineries all over the world. Production of bulk and fine chemicals in all branches of chemical industry 

of pollution by avoiding formation of waste (unwanted byproducts) Abatement of pollution in end-of-pipe solutions end-of(automotive and industrial exhaust) 

A catalyst offers an alternative, energetically favorable mechanism to the non-catalytic nonreaction, thus enabling processes to be carried out under industrially feasible conditions of pressure and temperature.

What is Catalysis?
A catalyst alters the rate of a chemical reaction. reaction. It does so by forming bonds with the reacting molecules, and by allowing these to react to a product, which detaches from the catalyst, and leaves it unaltered such that it is available for the next reaction.


in which reactant molecules bind to the catalyst. where they react. liberating the latter for the next cycle. after which the product detaches from the catalyst.Every catalytic reaction is a sequence of elementary steps. 5 .

 Potential energy diagram of a heterogeneous catalytic reaction. .  Note that the uncatalyzed reaction has to overcome a substantial energy barrier. whereas the barriers in the 6 catalytic route are much lower. with gaseous reactants and products and a solid catalyst.

hence.Several important points:  The catalyst offers an alternative path for the reaction. which is obviously more complex. the rate of the catalytic reaction is much larger. reaction. 7  . The activation energy of the catalytic reaction is significantly smaller than that of the uncatalyzed reaction. but energetically much more favorable.

Hence. a catalyst cannot change this situation. The catalyst accelerates both the forward and the reverse reaction to the same extent. B. if a catalyst accelerates the formation of B. the product P from A and B. the catalyst does not affect the equilibrium constant for the overall reaction of A + B to P. A catalyst changes the kinetics but not the thermodynamics. In other words. The overall change in free energy for the catalytic reaction equals that of the uncatalyzed reaction. it will do the same for the decomposition of P into A and B. 8  . if a reaction is thermodynamically unfavorable. Thus.

If the bonding between reactants and catalyst is too weak. Conversely if the bond between the catalyst and one of the reactants. and B is not available to form the product. 9 . the catalyst will be mostly occupied with species A. 2. there will be hardly any conversion of A and B into products. is too strong. say A.Combination of catalyst with reactants or products will not be successful: 1.

10 .If A and B both form strong bonds with the catalyst. the intermediate situation with A or B on the catalyst may be so stable that reaction becomes unlikely. The second level lies so deep that the activation energy to form P on the catalyst becomes too high. In this case the product poisons the catalyst. The catalyst is said to be poisoned by (one of) the reactants. 3. In the same way. the product P may be too strongly bound to the catalyst for separation to occur.

Activation Energy 11 .

Preparing a catalyst in the optimum form and studying its precise composition and shape are an important specialism. solids. May be employed in various surroundings: in liquids. 12   . Enzymes and Solid Surfaces  Vary from atoms and molecules to large structures such as zeolites or enzymes.Catalysts Can Be Atoms. gases or at the surface of solids. Molecules.

Type of Catalysis 1. Example Ozone in the atmosphere decomposes via a reaction with chlorine atoms 13 . Homogeneous Catalysis Both the catalyst and the reactants are in the same phase. phase.

and also under the influence of light.Cl + O3 p ClO3 ClO3 p ClO + O2 ClO + O p Cl + O2 or overall O3+ O p O2 Ozone can decompose spontaneously. catalyst. As it leaves the reaction cycle unaltered. but a Cl atom accelerates the reaction tremendously. 14 . the Cl atom is a catalyst.

Catalytic carbonylation of methanol to acetic acid CH3OH + CO p CH3COOH Catalyst : [Rh(CO)2I2]± complexes in solution 15 .

enzymes are highly specific and efficient catalysts.2. 16 . Biocatalysis Enzymes are nature·s catalysts : A large protein The structure of which results in a very shape-specific shapeactive site . Having shapes that are optimally suited to guide reactant molecules (usually referred to as substrates) in the optimum configuration for reaction.

Enzyme catalase catalyzes the decomposition of hydrogen peroxide into water and oxygen 2H2O2 p H2O + O2 at an incredibly high rate of up to 107 hydrogen peroxide molecules per second 17 .

Breakdown of alcohol to acetaldehyde inside the body by the enzyme alcohol dehydrogenase. The acetaldehyde in turn is converted into acetate by aldehyde hydrogenase. Some people cannot tolerate alcohol (as revealed by facial flushing after drinking a small amount) because they lack the form of the enzyme that breaks down acetaldehyde. 18 .

catalysts are usually nanometer-sized nanometerparticles. supported on an inert. To use the often expensive materials (e. catalytic reactions occur at the surface. Heterogeneous Catalysis Solids catalyze reactions of molecules in gas or solution As solids ² unless they are porous ² are commonly impenetrable. porous structure. 19 .3. platinum) in an economical way.g.

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21 .Cleaning of automotive exhaust Catalytic oxidation of CO on the surface of noble metals such as platinum. palladium and rhodium.

concentration. time. but the reactors in which such conditions can be safely maintained become progressively more expensive and difficult to make.Why is Catalysis Important?  Reactions can in general be controlled on the basis of temperature. Raising the temperature and pressure will enable stoichiometric reactions to proceed at a reasonable rate of production. pressure and contact time. 22  .

the conversion of N2 and H2 into ammonia is practically impossible above 600 ºC. Without catalysts. e. higher temperatures are needed to break the very strong N N bond in N2.g. 23  . many reactions that are common in the chemical industry would not be possible. Nevertheless. and many other processes would not be economical. There are thermodynamic limitations to the conditions under which products can be formed.

enabling them to be carried out under the most favorable thermodynamic regime. and at much lower temperatures and pressures. 24  . Efficient catalysts in combination with optimized reactor and total plant design. Catalysts accelerate reactions by orders of magnitude. are the key factor in reducing both the investment and operation costs of a chemical processes.

an important intermediate towards ethylene glycol (antifreeze) and various polyethers and polyurethanes 25 . such that the use of toxic and hazardous reagents and solvents can be avoided while formation of waste or undesirable by-products is minimized.Catalysis and Green Chemistry Technology is called ´greenµ if it uses raw materials efficiently. byExample: Selective oxidation of ethylene to ethylene epoxide.

non-catalytic route (called the epichlorohydrine process) follows a three-step synthesis: Cl2 + NaOH p HOCl + NaCl (1) C2H4 + HOCl p CH2Cl±CH2OH (epichlorohydrine) (2) CH2Cl±CH2OH + 1/2Ca(OH)2 1/2CaCl2 + C2H4O +H2O (3) 26 . The old. important intermediate in the chemical industry.Ethylene epoxide an epoxide.

27 .or in total: Cl2 + NaOH + 1/2Ca(OH)2 + C2H4 q C2H4O + 1/2CaCl2 + NaCl + H2O Every molecule of ethylene oxide. 1 molecule of salt is formed. creating a waste problem that was traditionally solved by dumping it in a river.

Catalytic Route: Simple and clean. with about 10% of the ethylene ending up as CO2. 28 . ethylene oxide is formed directly from C2H4 and O2 at a selectivity of around 90 %. as the catalyst. although it does produce a small amount of CO2. promoted by small amounts of chlorine. Using silver.

E Factors and Environmental Friendliness 1. 29 . Atom Efficiency is the molecular weight of the desired product divided by the total molecular weight of all products.Atom Efficiency. Example: Conventional oxidation of a secondary alcohol 3C6H5²CHOH²CH3 + 2CrO3 + 3H2SO4 CHOH² q 3C6H5²CO²CH3 + Cr2(SO4)3 + 6H2O CO² has an atom efficiency of 360/860 = 42%.

the catalytic route C6H5²CHOH²CH3 + 1/2O2 CHOH² q C6H5²CO²CH3 + H2O CO² offers an atom efficiency of 120/138 = 87%. 30 . with water as the only byproduct.By contrast.

E factor (environmental acceptability) ² the weight of waste or undesirable byproduct divided by the weight of the desired product.2. The production of fine chemicals and pharmaceuticals generate the highest amounts of waste per unit weight of product 31 .

Q. NaCl Q = 100²1000 for toxic compounds 100² 32 . which can be assigned a value to indicate how undesirable a byproduct is. Q = 0 for clean water Q = 1 for a benign salt. Environmental quotient EQ as the E factor multiplied by an unfriendliness quotient.3.

Largest processes based on heterogeneous catalysis 33 .

Organic chemical production in the USA (2001) along with average annual change over the ten years 1991² 1991²2001 34 .

Inorganic chemical production in the USA (2001) along with average annual change over the ten years 1991² 1991²2001 35 .

Polymers and plastics produced in the USA (2001) along with average annual change over the ten years 1991² 1991²2001 36 .

World Top 50 of Chemical Producers (Source: Chemical & Engineering News. 2002) 37 . July 29.

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Relevant length scales in catalysis range from the subnanometre domain of the atomic and molecular level to the macroscopic domain of an industrial reactor 42 .

Energy processing Petroleum refining makes intensive use of catalysis for alkylation. naphtha reforming and steam reforming (conversion of hydrocarbons into synthesis gas). catalytic cracking (breaking long-chain longhydrocarbons into smaller pieces). alkylation. composed of platinum and rhodium. Even the exhaust from the burning of fossil fuels is treated via catalysis: Catalytic converters.Significance of catalysis 1. typically converters. the more harmful byproducts of automobile exhaust. gas). 43 . break down some of rhodium.

Biodiesel and related biofuels require processing via both inorganic and biocatalysts. processed via . which itself is gas. 44 . Fuel cells rely on catalysts for both the anodic and cathodic reactions.2 CO + 2 NO 2 CO2 + N2 With regards to synthetic fuels. an old but still important process is the Fischer-Tropsch synthesis Fischerof hydrocarbons from synthesis gas. catalysed by iron.

terephthalic acid from p-xylene. process). example is ammonia. 45 . Bulk chemicals Some of the largest-scale chemicals are produced via largestoxygen. Many other chemical products are generated by large-scale largereduction. sulfuric acid (from sulfur dioxide to sulfur trioxide by the chamber process). often using oxygen. monoxide. monoxide. Examples include nitric acid (from ammonia).2. largestammonia. which is prepared via the Haber process from nitrogen. The largest-scale hydrogenation. often via hydrogenation. catalytic oxidation. Methanol is prepared from carbon nitrogen. and acrylonitrile from ppropane and ammonia.

Bulk polymers derived from ethylene and propylene are often prepared via Ziegler-Natta Zieglercatalysis. examples include the Monsanto acetic acid process and hydroformylation. acidcatalysis. Most carbonylation processes require metal catalysts. Polyesters. catalysis. 46 . and isocyanates are derived via acid-base catalysis. hydroformylation. polyamides.

and Friedel-Crafts reactions. Examples include olefin metathesis using Grubbs' catalyst. Friedelreactions. reaction. 47 . Fine chemicals Many fine chemicals are prepared via catalysis. chiral. many pharmaceuticals are produced by enantioselective catalysis. Because most bioactive compounds are chiral.3. catalyst. methods include those of heavy industry as well as more specialized processes that would be prohibitively expensive on a large scale. the Heck reaction.

of fats using nickel catalyst to produce margarine. Many other foodstuffs are prepared via biocatalysis 48 . Food processing One of the most obvious applications of catalysis is the hydrogenation (reaction with hydrogen gas) margarine.4.

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