CHE505

REACTION ENGINEERING II

TOPIC 1
Chemical Catalytic
Reaction

Credit to: Dr Siti Wahidah, Dr Norhidayah,

Pn. Norhasyimi, Pn. Sharmeela,
Cik Siti Khatijah & Cik Faeqah
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 1.1 Catalysts

1.2 Steps in Heterogeneous

Catalytic Reactions

1.3 Rate Limiting Steps

1.4 Temperature Dependence

of Catalytic Reaction Rates

1.5 Langmuir-Hinshelwood
Kinetic

1.6 Designing Catalytic

Reactors

1.7 Deactivation of Catalyst

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 By the end of this topic,
you should be able to:

1 Explain the steps in catalytic reactions;

write the mechanism and chemical
kinetics.

2 Able to describe rate limiting step.

3 Able to describe Langmuir-Hinshelwood

Kinetic Mechanism.

** Ref : The Eng. Of Chemical Reactions ( Schmidt) –Chapter 7 (pg 269).

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A catalyst is a substance that affects the rate of a
reaction but emerges from the process unchanged.

A catalyst usually changes a reaction rate by promoting

a different molecular path ("mechanism") for the
reaction.

Catalyst affect yield and selectivity.

Changes only the rate of reaction; it does not affect

the equilibrium.

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Catalysts that speed the reaction are called positive
catalysts WHILE slow the reaction are called inhibitors
(or negative catalysts).

Substances that increase the

activity of catalysts are
called promoters, and
substances that deactivate
catalysts are called catalytic
poisons.

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Gaseous H2 and O2 are inert at room temperature

They react rapidly when exposed to Platinum as

catalyst.

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Three key aspects of catalyst action :
1 Taking part in the reaction
It will change itself during the process by interacting with
other reactant/product molecules.

2 Altering the rates of reactions

In most cases the rates of reactions are increased by the
action of catalysts; however, in some situations the rates of
undesired reactions are selectively suppressed.
3 Returning to its original form
After reaction cycles a catalyst
with exactly the same nature is
‘reborn’.
In practice a catalyst
has its lifespan - it
deactivates gradually
during use.
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DIFFERENT SIZES AND SHAPES OF CATALYST

Source: http://www.arabianoilandgas.com/article-9496-top-10-catalysts-companies/

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CATALYTIC PACKED-BED REACTOR-SCHEMATIC

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WHAT IS CATALYSIS……

Catalysis is the change in rate of a chemical

reaction due to the participation of an additional
substance called a catalyst.

Also…

 Catalysis is the occurrence, study, and use of catalysts

and catalytic processes

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TYPE OF CATALYSTS
&
CATALYTIC
REACTION

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The Types Of Catalysts

Classification based on the its physical state, a catalyst

can be:
Gas Liquid Solid

Classification based on the substances from which a

catalyst is made
Inorganic (gases, metals, metal oxides, inorganic acids, bases etc.)

Organic (organic acids, enzymes etc.)

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Classification based on the ways catalysts work

Homogeneous  both catalyst and all reactants/products are in

the same phase (gas or liq)

Heterogeneous  reaction system involves multi-phase

(catalysts + reactants/products)

Classification based on the catalysts’ action

Acid-base catalysts

Enzymatic

Photocatalysis

Electrocatalysis, etc.

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Role of Catalysis in a National
Economy

24% of GDP from Products made using catalysts (Food,

Fuels, Clothes, Polymers, Drug, Agro-chemicals).

>90 % of petro refining & petrochemicals processes use

catalysts.

90 % of processes & 60 % of products in the chemical

industry.

> 95% of pollution control technologies.

Catalysis in the production/use of alternate fuels (NG,DME,

H2, Fuel Cells, biofuels…) .

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Advantages of Catalytic
Processes

Achieving better process economics and productivity

Increase reaction rates  fast

Simplify the reaction steps  low investment cost

Carry out reaction under mild conditions (e.g. low T, P)

 low energy consumption

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 Reducing wastes
Improving selectivity toward desired products  less raw
materials required, less unwanted wastes

Replacing harmful/toxic materials with readily available ones

Producing certain products that may not be possible

without catalysts

Having better control of process (safety, flexible etc.)

Encouraging application and advancement of new

technologies and materials

And many more …

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RESEARCH IN CATAYSIS
(multidisciplinary approach)

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Reaction kinetics and mechanism
Reaction paths, intermediate formation & action, interpretation
of results obtained under various conditions, generalising reaction
types & schemes, predict catalyst performance…

Catalyst development
Material synthesis, structure properties, catalyst stability,
compatibility…

Analysis techniques
Detection limits in terms of dimension of time & size and under
extreme conditions (T, P) and accuracy of measurements,
microscopic techniques, sample preparation techniques…

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Reaction modelling
Elementary reactions and rates, quantum mechanics/chemistry,
physical chemistry …

Reactor modelling
Mathematical interpretation and representation, the numerical
method, micro-kinetics, structure and efficiency of heat and
mass transfer in relation to reactor design …

Catalytic process
Heat and mass transfers, energy balance and efficiency of process

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Some Developments in Industrial Catalysis-1
1900- 1920s

Industrial Process Catalyst
1900s: CO + 3H2  CH4 + H2O                         Ni

Vegetable Oil + H2  butter/margarine        Ni

1910s: Coal Liquefaction                                    Ni

N2 + 3H2  2NH3 Fe/K

NH3 NO NO2 HNO3 Pt

1920s:  CO + 2H2  CH3OH (HP)              (ZnCr)oxide

Fischer‐Tropsch synthesis                   Co,Fe

SO2  SO3 H2SO4 V2O5

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 Industrial Catalysis-3
1950s

C2H4  Polyethylene(Z‐N)                     Ti
C2H4  Polyethylene(Phillips)            Cr‐SiO2
Polyprop & Polybutadiene(Z‐N)              Ti
Steam reforming                                 Ni‐K‐ Al2O3
HDS, HDT of naphtha                       (Co‐Mo)/Al2O3
C10H8  Phthalic anhydride             (V,Mo)oxide
C6H6  C6H12  (Ni)
C6H11OH C6H10O                                    (Cu) 
C7H8+ H2 C6H6 +CH4 (Ni‐SiAl)  

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 Industrial Catalysis-5
1970s

Xylene Isom( for p‐xylene)                      H‐ZSM‐5
Methanol (low press)                               Cu‐Zn/Al2O3
Toluene to benzene and xylenes           H‐ZSM‐5
Catalytic dewaxing                                   H‐ZSM‐5 
Autoexhaust catalyst                          Pt‐Pd‐Rh on oxide
Hydroisomerisation Pt‐zeolite
SCR of NO(NH3)                                        V/ Ti
MTBE                                          acidic ion exchange resin
C7H8+C9H12 C6H6 +C8H10 Pt‐Mordenite

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 Industrial Catalysis-8
2000+

• Solid catalysts for biodiesel

- solid acids, Hydroisom catalysts
• Catalysts for carbon nanotubes
- Fe (Ni)-Mo-SiO2

For Developed Catalysts MAINLY

IMPROVEMENT IN PERFORMANCE by New
Synthesis Methods & use of PROMOTERS

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 PROMOTERS

Substances which themselves are not catalysts, but

when mixed in small quantities with the catalysts
increase their efficiency are called
as promoters or activators

For example, in Haber’s process for the synthesis of

ammonia, traces of molybdenum increases the
activity of finely divided iron which acts as a
catalyst

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

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 CATALYTIC POISONS

A substance which destroys the activity of the

catalyst to accelerate a reaction, is called a poison
and the process is called Catalytic Poisoning.

For example, the presence of traces of arsenious

oxide in the reacting gases reduces the activity of
platinized asbestos which is used as catalyst in
contact process for the manufacture of sulphuric
acid.

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The activity of iron catalyst is destroyed by the
presence of H2S or CO in the synthesis of ammonia
by Haber’s process.

The platinum catalyst used in the oxidation of

hydrogen is poisoned by CO.

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Explanation of Catalytic Poisoning

The poison is adsorbed on the catalyst surface in

preference to the reactants.

The catalyst may combine chemically with the

impurity.

Fe + H2S  FeS + H2

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 AUTO CATALYSIS

When one of the products of a reaction itself acts as

a catalyst for that reaction the phenomenon is
called autocatalysis.

Examples of autocatalysis:

Hydrolysis of an ester.

Here CH3COOH is acting as a catalyst.

CH3COC2H5 + H2O  CH3COOH + C2H5OH

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 NEGATIVE CATALYSIS/ INHIBITORS

When a catalyst reduces the rate of reaction, it is

called a Negative catalyst or Inhibitor.

A negative catalyst is
used to slow down or
stop altogether an
unwanted reaction.

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Inhibition should be distinguished from catalyst
poisoning.

An inhibitor only hinders the working of a catalyst

without changing it, whilst in catalyst poisoning the
catalyst undergoes a chemical reaction that is
irreversible in the environment in question (the
active catalyst may only be regained by a separate
process).

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 CLASSIFICATION OF CATALYTIC PROCESSES

There are two types of catalytic processes:

Homogeneous catalysis

Heterogeneous catalysis

These two processes have industrial importance.

There is another mechanism involving catalysis i.e.

enzyme catalysis which possess biological importance.

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 CATALYST TYPE

HOMOGENEOUS HETEROGENEOUS

Insolution with at least  more than one phase

one of the reactants – typical solid
Example;
catalyst in
liquid/gaseous
0xo process for
reactants
manufacturing normal
 Example;
isobutylaldehyde
The dehydrogenation of
cyclohexane

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 HOMOGENEOUS CATALYSIS

Catalyst and reactants are in the same phase

The catalyst is evenly distributed throughout

Reaction proceeds through an intermediate species of lower

energy
There is usually more than one reaction step

Transition metal ions are often involved - oxidation state

changes

Example: Acid  Esterification

Conc. H2SO4 catalyses the reaction between acids and alcohols

CH3COOH + C2H5OH CH3COOC2H5 + H2O

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 HETEROGENEOUS CATALYSIS

Catalyst is in different physical phase from the

reactants

It is also called Contact catalysis

It possesses great industrial importance.

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37
http://www.chemistryexplained.com/Bo-Ce/Catalysis-and-Catalysts.html

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 What are the properties
of the catalysts…..
1. Porous  2. Molecular  3. Monolithic  4. Supported  5. Unsupported 
catalyst  sieves  catalyst  catalyst  catalyst
• Catalyst that  • Materials with  • Can be either  • Consists of  • Mainly 
has a large  small pores  porous or  minute  promoters
area resulting  (admit small  nonporous,  particles of an  that increase 
from pores molecule but  encountered in  active material  activity
prevent large  processes  dispersed over 
ones from  where  a less active 
entering) pressure drop  substance.
& heat 
removal are 
major 
consideration.

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 SOLID CATALYST
Catalyst composition

Active phase
Where the reaction occurs (mostly metal/metal oxide)

Promoter
Textual promoter (e.g. Al - Fe for NH3 production)

Electric or Structural modifier

Poison resistant promoters

Support / carrier
Increase mechanical strength

Increase surface area (98% surface area is supplied within

the porous structure)
May or may not be catalytically active 40
Some common solid support / carrier materials

Alumina Other supports

Inexpensive Active carbon (S.A. up to
Surface area: 1~700 m2/g 1000 m2/g)
Acidic Titania (S.A. 10~50 m2/g)
Zirconia (S.A. 10~100 m2/g)
Silica
Magnesia (S.A. 10 m2/g)
Inexpensive
Lanthana (S.A. 10 m2/g)
Surface area: 100~800 m2/g
Acidic

Zeolite
mixture of alumina and silica
often exchanged metal ion present
shape selective
Acidic 41
What are the criteria of
the catalyst…..

They are specific. One

Only small quantity is catalyst is needed for
needed for a reaction specific
reaction only

Physical properties may

change during a reaction No catalyst can change
BUT it an equilibrium state of a
does not take part in the reaction
reaction

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 CATALYTIC REACTION PROCESSES

General requirements for a good catalyst

Activity  being able to promote the rate of desired

reactions

Selective  being to promote only the rate of

desired reaction and also retard the undesired
reactions
Note:
The selectivity is sometime considered to be more important than
the activity and sometime it is more difficult to achieve
(e.g. selective oxidation of NO to NO2 in the presence of SO2)

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General requirements for a good catalyst

Stability  being able to promote the rate of

desired reactions

Selective  a good catalyst should resist to

deactivation, caused by:
The presence of impurities in feed (e.g. lead in petrol poison TWC).
Thermal deterioration, volatility and hydrolysis of active
components.
Attrition due to mechanical movement or pressure shock.

A solid catalyst should have reasonably large surface

area needed for reaction (active sites). This is usually
achieved by making the solid into a porous structure.
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