4th Year Stage Catalyst Science and Technology Lecture: 04

Duhok Polytechnique University-Petrochemical Department

2019 / 2020

Heterogeneous Catalysis

Lecturer: Dr Farhad M. Ali

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

What is a phase?

If you look at a mixture and can see a boundary between two of the components, those
substances are in different phases. A mixture containing a solid and a liquid consists of
two phases. A mixture of various chemicals in a single solution consists of only one
phase, because you can't see any boundary between them.

Types of Catalysis:

(a) Heterogeneous catalysis:

catalyst is present in a different phase than that of reactants.

▪ A heterogeneous catalyst exists in a different phase from the reactant molecules -

often as a solid in contact with either a gaseous or liquid reactant

▪ Many important industrial reactions are catalyzed by the surfaces of special solid
materials

▪ Heterogeneous catalysts are often composed of metals or metal oxides

▪ The greater the surface area of a heterogeneous catalyst, the more reactions can
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take place. Thus, in manufacturing heterogeneous catalysts techniques are used to

maximize the surface area (e.g. using highly porous structures)

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

▪ The initial step in heterogeneous catalysis is the adsorption of reactants onto the
surface of a catalyst

▪ The surface of metal catalysts is highly reactive in comparison to interior atoms

The reaction occurs on the catalyst surface which may be the transition metal or one of
its compounds. The reactants must be adsorbed onto the catalyst surface at the 'active
sites'.

This can be physical adsorbed or 'weakly' chemically bonded to the catalyst surface.
Either way, it has the effect of concentrating the reactants close to each other and
weakening the original intra–molecular bonds within the reactant molecules and so allows
a greater chance of successful collision.

The diagram below illustrates a typical heterogeneous catalysis e.g. hydrogenation of

alkenes with hydrogen and a nickel catalyst.
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DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

Strength of adsorption / catalyst:

The strength of adsorption is crucial to having a productive catalyst surface it helps to

determine the effectiveness of catalyst activity:

The bonding to the catalyst surface (chemisorption/adsorption) must be strong enough

to weaken reactant molecule bonds but weak enough to allow new bonds to form and the
products to 'escape' from the catalyst surface (desorption).
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Typical examples to illustrate this idea ....

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

 If the catalyst–reactant bonding is too strong, most reactant-product molecules

will be too strongly 'chemisorped' inhibiting reaction progress e.g. tungsten (W)
have too strong adsorption and so products cannot be released,
 If the catalyst–reactant bonding is too weak, many reactants are not
chemisorbed strongly enough to allow the initial bond breaking processes to
happen.

(Au) and (Ag) tend to be more limited catalysts, but even silver, can act as a catalyst for
some reactions. Ag have too week adsorption, and the reactants do not adsorb in high
enough concentration.

Just right strength: (Cu), (Ni), (Pt), (Rh), (Pd) catalyse many reactions such as
hydrogenation, redox reactions involving CO and NO etc. Palladium can catalyse the
spontaneous combustion/combination of hydrogen and oxygen at room temperature!

Examples:
1: Potassium chlorate decomposition:

When solid potassium chlorate is heated, potassium chloride and oxygen are
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produced. The reaction is not particularly fast.

2 KClO3 (s) → 2 KCl (s) + 3 O2 (g) catalyst MnO2 (s), faster and lower temperature

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

2: Hydrogen peroxide decomposition

2H2O2(aq) → 2H2O(l) + O2(g) MnO2(s) as catalyst

3: Iron, Fe(s), catalyses the combination of nitrogen and hydrogen gases in the
important industrial Haber synthesis of ammonia, important in the manufacture of
nitric acid and artificial fertiliser salts.

The manufacture of ammonia (The Haber Process)

Fe used as catalyst. The catalyst is actually slightly more complicated than

pure iron. small amount of potassium hydroxide was effective as a
promoter
4: Platinum: Manufacture of Nitric acid: (Ostwald Process)

Nitric acid production involves two stages:

a) oxidation of ammonia (over a hot platinum catalyst)
b) absorption of the resulting nitrogen oxides
(a) Oxidation of ammonia

over a hot platinum catalyst

Most plants operate with: an alloy of platinum and rhodium as catalyst: a series of
90% platinum/10% rhodium catalyst gauzes in parallel at 975-1225 K
(b) Absorption of the nitrogen oxides
Air is added and the gases compressed again (7-12 atm typically).
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DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

The gases (NO2 & N2O4) are then passed through one or more towers to meet a stream
of water with the formation of nitric acid:

Rhodium is added to the platinum to give the gauze strength and to reduce the loss of platinum

5: Platinum/rhodium/palladium metals, Pt(s)/Rh(s)/Pd(s), (three way catalyst) on a

ceramic support, catalyse the following reactions in car exhausts inside the catalytic
converter.

2NO(g) + 2CO(g) → N2(g) + 2CO2(g)

catalytic converter is a component of your exhaust that converts harmful gases such as carbon
monoxide into safer compounds

The NO and CO are adsorbed onto the catalyst surface, bonds broken and reformed prior
to the products nitrogen and carbon dioxide leaving the catalyst surface in a similar way to
the hydrogenation illustrated above. The CO is from the inefficient combustion of the
hydrocarbon fuel,

CxHy + (x/2 + y/4)O2 → xCO + y/2H2O

and the nitrogen(II) oxide is 'naturally' formed at high temperature in the engine

N2(g) + O2(g) → 2NO(g)

These transition metal catalysts can also oxidise unburned hydrocarbons from inefficient
combustion.

CxHy + (x + y/4) O2 → x CO2 + y/2 H2O

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DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

Note: Pt, Rh and Pd are very expensive metals and copper and nickel are cheaper

alternatives but they are vulnerable to catalytic poisoning by traces of sulphur dioxide in
the exhaust gases. Once poisoned, the catalyst in a converter cannot be regenerated, so,
it’s a new costly converter!

6: Nickel, Ni(s), catalyses the addition of hydrogen to an alkene double bond, e.g. in

the hydrogenation of unsaturated vegetable oils to make more saturated margarine with
a slightly higher softening point making it more spreadable.

CH=CH– + H2 → Ni catalyst → –CH2–CH2–

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7: Solid heterogeneous catalysts are really important in the petrochemical industry:

Examples:

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

i. Isomerisation: These reactions convert linear alkane vapours into branched alkanes
of the same carbon number over a platinum–aluminium oxide (Pt/Al2O3) catalyst at
150 oC. Branched alkanes have a higher-octane rating than linear alkanes, so a
better petrol fuel component.
e.g. hexane → methylpentanes or dimethylbutanes

ii. Reforming: Converting straight chain alkane vapour into cyclic alkanes and
aromatic hydrocarbons can be achieved by using a Pt/Al2O3 catalyst at 500 oC.
Aromatic hydrocarbons are important chemical feedstock to make many useful
aromatic compounds.
Example:

iii. Cracking: Catalytic cracking of vaporised hydrocarbons at e.g. 500 oC using

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zeolites to make more lower alkanes for petrol or alkenes. Alkenes are important
intermediates in making many useful compounds from anti–freeze to plastics. Is

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

one of the most important conversion processes used in petroleum refineries. It is

widely used to convert the high-boiling, high-molecular weight hydrocarbon
fractions of petroleum crude oils into more valuable gasoline, olefinic gases, and
other products.
e.g. higher alkanes → lower alkanes and alkenes

Note: Zeolites tend to become 'poisoned' with carbon–soot deposits in the high
temperature cracking reactions and this blocks the adsorption of the hydrocarbons.
However, in this case, the catalyst can be regenerated in a separate container through
which very hot air is passed to burn off the carbon–soot deposits.

8: Vanadium(V) oxide, V2O5, is used as a catalyst in the 'Contact Process' in the

production of sulphur trioxide for the manufacture of sulphuric acid.
The catalysing of the conversion of sulphur dioxide into sulphur trioxide:

2SO2(g) + O2(g) → 2SO3(g)

The mechanism, somewhat simplified, it goes via the catalytic cycle ...
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(i) SO2 + V2O5 → SO3 + V2O4, then

(ii) V2O4 + 1/2O2 → V2O5

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

The vanadium changes oxidation state from +5 to +4 and back to +5 in the cycle

Advantages Disadvantages
 Catalyst needs to be
separated after reaction
Homoge
 Good contact with  Catalyst recovery may be
neous
reactants difficult because the
catalysis
temperature for the
distillation can destroy the
catalyst
 There is a lower effective
 There is little difficulty in concentration of catalyst
Heteroge
separating and recycling since the reaction occurs
neous
the catalyst. only on the exposed active
catalysis
surface.

Reaction Rate and catalyst:

If a catalyst is to increase the reaction rate, k, it would appear to be able to do so by
one of two ways:

1) Increase the frequency factor, A, ( )

The Arrhenius equation states that the rate constant, k, of a reaction is
i. directly proportional to the frequency factor (A),
ii. inversely proportional to the activation energy Ea, and
iii. directly proportional to the temperature). (i.e. in some way increase the rate
of successful molecular collisions

2) Decrease the activation energy, Ea

Generally speaking, a catalysts typically increases reaction rates by lowering the
activation energy, Ea. This is related to the energy required to stretch and break a bond,
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thus, catalysts must facilitate this process in some way.

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

Also, a catalyst often lowers the overall activation energy for a reaction by providing a
completely different reaction mechanism for the reaction. In other words, a different set
of underlying elementary reaction steps.

Autocatalysis:
When one of the products of a reaction acts as catalyst, the process is called
autocatalysis.

Examples of autocatalysis include:

1. The reaction of permanganate with oxalic acid,

The reaction is very slow at room temperature, it is quite slow to start with. The reaction

is catalysed by manganese(II) ions. if you look at the equation, you will find manganese(II)
ions amongst the products. More and more catalyst is produced as the reaction proceeds
and so the reaction speeds up.

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DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

2. Spontaneous degradation of aspirin into salicylic and ethanoic acid (causing old
aspirin containers to smell mildly of vinegar).

The ethanoic acid released from the aspirin will cause some accelerated degradation of
our ibuprofen (act as auto catalyst)

Promoters and Poisons:

Promoters are chemical substances that enhance the activity of a catalyst.

Substances which themselves are not catalysts, but when mixed in small quantities with
the catalysts increase the catalyst efficiency are called as promoters or activators.

Examples,

1. In Haber’s process for the synthesis of ammonia, traces of molybdenum (act as

Promoters) increases the activity of finely divided iron which acts as a catalyst.

N2 (g) + 3 H2 (g) → 2 NH3 (g) Fe as catalyst with Mo as promoter

2. In the manufacture of methyl alcohol from water gas, chromic oxide is used as a
promoter with the catalyst zinc oxide.

CO (g) + 2 H2 (g) → CH3-OH (l) ZnO as catalyst with Cr2O3 as promoter

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Catalytic poisons: decreases the activity of a catalyst. Substances which destroy the
activity of the catalyst by their presence are known as catalytic poisons.

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020
4th Year Stage Catalyst Science and Technology Lecture: 04

For example:

i- The presence of traces of arsenic(III) oxide (As2O3) in the reacting gases reduces
the activity of platinized asbestos which is used as catalyst in contact process for
the manufacture of sulphuric acid.
ii- The activity of iron catalyst is destroyed by the presence of hydrogen sulphide,
H2S, or carbon monoxide, CO, in the synthesis of ammonia, NH3 by Haber’s
process.
iii- The platinum catalyst used in the oxidation of hydrogen is poisoned by carbon
monoxide, CO.

Effect of temperature on catalyst activity:

Change of temperature alters the rate of catalytic reaction as it does for the same
reaction in absence of catalyst. By increasing the temperature, there is an increase in
the catalytic power of a catalyst but after a certain temperature its power begins to
decrease. A catalyst has thus, a particular temperature at which its catalytic activity is
maximum. This temperature is termed as optimum temperature.

A catalyst may be positive (i.e., increases rate of reaction) or negative (i.e., decreases
rate of reaction).

Mechanism of Heterogeneous Catalysis

1. Diffusion of reactants to the surface of the catalyst.

2. Adsorption of reactant molecules on the surface of the catalyst.

3. Chemical reaction on the surface through the formation of the intermediate.

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4. Desorption of the products from the catalyst surface.

5. Diffusion of the products away from the catalyst's surface.

DR FARHAD M. ALI
L04- TYPES OF CATALYSIS-HETEROGENEOUS CATALYSIS-2019-2020