CHE625

Lecturer: Pn. Sharmeela bt Matali

Office

Advanced
Chemical
Reaction
Engineering

: PA-11-8C (level 11,

Tower 2)

Contact:
03-5543 6328 (O)
013-299 0609
sharmeela@salam.uitm.edu.my
Credit to: Cik Nor Faeqah
Pn Norhasyimi

CPE624

Course Learning Outcome:

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

Explain the steps in catalytic reactions; write the mechanism and

chemical kinetics.

Able to describe rate limiting step.

Able to describe Langmuir-Hinshelwood Kinetic Mechanism.

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

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INTRODUCTION

IDEAL REACTORS REVISION

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Design Equation for Ideal

Homogeneous Reactors
Ideal

Batch Reactor

Mass

Balance
Constant density system

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Design Equation for Ideal

Homogeneous Reactors
Ideal

Plug Flow Tubular Reactor (PFTR/PFR)

Ideal

Constant Stirred Tank Reactor (CSTR)

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TO TEST your BASICS of CRE

The elementary of liquid phase reaction A ->B + 2C is
carried out isothermally in a flow reactor with no
pressure drop. The rate constant at 50oC is 10-4min-1 and
the activation energy is 85 kJ/mol. Pure A enters at 10
atm and 127oC, and molar flow rate is 2.5 mol/min.
Calculate the space time and reactor volume for 90%
conversion in CSTR and PFR.

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CHAPTER 1
CATALYTIC REACTORS AND
MASS TRANSFER

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1.1 Catalytic Reactions

What is Catalyst and Catalysis?

A catalyst is a substance that affects the rate of

a reaction but does not enter into the
stoichiometry of the reaction.

Catalysis is the change in rate of a

chemical reaction due to the participation of a

substance called a catalyst.

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

processes.
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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Lets watch a video on catalysis:

http://www.youtube.com/watch?
v=A_PhvIktMOw&feature=endscreen

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Example of Catalysis
Gaseous H2 and O2 are inert at room temperature.
They react rapidly when exposed to Pt catalyst.

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Catalysts and Catalysis

Different shapes and sizes of catalyst.

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Catalysts and Catalysis

Catalytic packed-bed reactor, schematic.

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Theory of Catalysis
Activated complex formation theory:
Catalysts generally react with one or more reactants
to form intermediates that subsequently give the
final reaction product, in the process regenerating
the catalyst. The following is a typical reaction
scheme, where C represents the catalyst, X and Y
are reactants, and Z is the product of the reaction of
X and Y:

X + C XC (1)
Y + XC XYC (2)
XYC CZ (3)
CZ C + Z (4)
X+YZ

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Theory of Catalysis
Adsorption theory (Old): The reactants in gaseous state or in
solu0ons, are adsorbed on the surface of the solid catalyst. The increase
in concentra0on of the reactants on the surface increases the rate of
reac0on. Adsorp0on being an exothermic process, the heat of
adsorp0on is u0lised in enhancing the rate of the reac0on.
Adsorption theory (Modern): The modern adsorp0on theory is the
combina0on of intermediate compound forma0on theory and the old
adsorp0on theory. The mechanism involves ve steps:

(1) Diusion of reactants to the surface of the catalyst.
(2) Adsorp0on of reactant molecules on the surface of the catalyst.
(3) Occurrence of chemical reac0on on the catalysts surface through
forma0on of an intermediate (Figure depicted below).
(4) Desorp0on of reac0on products from the catalyst surface, and thereby,
OF CHEMICAL
ENGINEERING
making the surface available again for more FACULTY
reac0on
to occur.

(5) Diusion of reac0on products away from the catalysts surface.

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Theory of Catalysis
Adsorption theory

H
Pt

H
Pt

Pt

Pt

Pt

O
Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

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A Mechanism for the oxidation of carbon

monoxide

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What is adsorp1on?
Adsorption is a physical or chemical phenomenon by which
the molecules present in a liquid or a gas attach to the
surface of a solid.
Surface means both external and internal surface.

The substance on which surface adsorp1on occurs is termed as the

adsorbent, and the substance which adsorbed from the bulk phase is
known as the adsorbate.
Depending on the force of aBrac1on, adsorp1on is mainly two types: (1)
Physical adsorp1on (Physisorp1on) and (2) Chemical adsorp1on
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(Chemisorp1on).

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Physical Adsorp1on
Physical adsorp1on (Physisorp1on)
Physical adsorp1on is a phenomenon which takes place purely due to
the van der Waals forces of aBrac1on.
- It is a reversible phenomenon.
- Because of very week force of aBrac1on, the physical adsorp1on can
not bring to any change of chemical structure of the adsorbent and
adsorbate.
- It can be compared with the condensa1on of vapour of liquids.

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Chemical Adsorp1on
Chemical adsorp1on (Chemisorp1on)

Chemical adsorp1on is adsorp1on which results from chemical bond
forma1on (strong interac1on) between the adsorbent and the adsorbate
in a monolayer on the surface.
Example: Organic compound get adsorbed on the solid surface with
chemical bond forma1on.

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Why does solid substance adsorb?

The adsorption phenomenon comes
from the existence of non-compensated
forces of a physical nature on the
surface of the solid.

Adsorbate
Adsorbent
Adsorbate

All the bonding requirements of the

constituent atoms of the material are
filled by other atoms in the material.
However, atoms on the surface of the
adsorbent are not wholly surrounded by
other adsorbent atoms and therefore can
attract adsorbates.
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Heterogeneous Reactor and

Voidage,
Reactor

volume, V = Volume of fluid plus

volume of catalyst

V = V fluid + V catalyst
Void

fraction or the fraction of the reactor

volume occupied by fluid
V fluid
Volume of fluid
=
=
Volume of reactor
V
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Different types of Rates in

Heterogeneous Catalytic Reactions
Homogeneous

reactions:
r=

Heterogeneous

moles
volume time

reactions:

moles
r =
area time
''

moles
r =
mass time
'

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Pseudo-homogeneous rate
r

x (volume ) = r x (area of catalyst)

Surface

area of catalyst

surface area of catalyst

sg =
mass of catalyst

r = s g c (1 )r"
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Space time,
volume of fluid in a reactor
=
volumetric flow rate passes through the reactor
Homogeneous

Reactors:

Heterogeneous

V fluid = V

volume of reactor
inlet volumetric flow rate

Reactors
=

V
0

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What are the criteria of the catalyst?

The following criteria dene a good quality catalyst
for a reac1on:
1. Only small quan1ty is needed for a
reac1on.
2. They are specic. One catalyst is needed for specic
reac1on only.
3. Physical proper1es may change during a reac1on
but it
does not take part in the reac1on.
4. No catalyst can change an equilibrium state of a
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reac1on.

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What are the proper1es of the catalysts?

Porous catalyst catalyst that has a large area
Molecular sieves small pore that will admit small

molecule
Monolithic catalyst can be either porous
or non-porous
Supported catalyst - consist of par1cles of an
ac1ve material dispersed over a less ac1ve
substance.
Unsupported catalyst
Promoters small amount of ac1ve

ingredients

Deac1va1on of catalyst
- Aging
- Poisoning
- Fouling or coking

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Catalyst Properties
Porous

catalyst catalyst that has a large area

Molecular sieves small pore that will admit small
molecule
Monolithic catalyst can be either porous or nonporous
Supported catalyst - consist of particles of an
active material dispersed over a less active
substance.
Unsupported catalyst
Promoters small amount of active ingredients
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Catalyst Properties
Deactivation

of catalyst

Aging
Poisoning
Fouling

Catalytic

or coking

reaction involved:

Physical

adsorption
Chemical adsorption

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Porous catalyst
Why

we need porous catalyst???

A few major catalyst:
Amorphous

silica
High area aluminas
Zeolites/aluminosilicates
Carbon
Supported noble metal catalysts (Pt, Pd, Ag,
Rh, Ni etc)
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Explanation of Catalytic Cracking through Zeolites- video

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Catalytic Reactors
Packed

Bed Reactor
Slurry reactor
Fluidized bed reactor
Riser reactor

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Catalytic Reactors
Packed

bed Reactor

Assume

no mixing
Mass balance:

dC j
dz

= jr

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Catalytic Reactors
Slurry

and Fludized Bed Reactor

Assume

well mixed
Mass Balance:

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The image cannot be displayed. Your computer may not have enough memory to open the
image, or the image may have been corrupted. Restart your computer, and then open the
file again. If the red x still appears, you may have to delete the image and then insert it
again.

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Example and Exercise in

Class
QUESTION

1 Tutorial 1
Example 7-1 (Schmidt) page 277
Problem 7-2 pg 318

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