CPE624 Advanced Chemical

Reaction Engineering
PN SYAFIZA ABD HASHIB

CPE 624 Advanced Chemical Reaction

Engineering

CHAPTER 1 :
Catalytic Reactors and Mass Transfer
1.

2.
3.
4.

5.
6.
7.
8.
9.

10.

Catalytic Reactions
Catalytic Reactors
Surface and Enzyme Reaction Rates
Porous catalysts
Transport and reaction
Mass transfer coefficient
External mass transfer
Pore diffusion
Langmuir-Hinshelwood kinetics
Designing catalytic reactors
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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.
Catalysts that speed the reaction are called
positive catalysts. Substances that interact with
catalysts to 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.

Catalytic Reactions

Homogeneous catalysis

Catalyst in solution with min one reactant

Re-use the catalyst after separation
Catalyst in the same phase as the reactants
Ex : industrial Oxo process : manufacturing isobutyl-aldehyde

Heterogeneous catalysis

Involves more that one phase

Catalyst in solid form, products/reactants in liquid or gaseous

Ex : Benzene production, hydrodesulfurization

More economical, catalyst kept inside the reactor

Reaction occurs at /very near the fluid-solid interface
Other forms are gas-liquid (mass transfer limited) and gas- liquid-solid
system
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Example of Catalysis

Gaseous H2 and O2 are inert at room temperature.

They react rapidly when exposed to Pt catalyst.

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

Theory of Catalysis
Adsorption theory (Old): The reactants in gaseous state or in
solutions, are adsorbed on the surface of the solid catalyst. The
increase in concentration of the reactants on the surface increases
the rate of reaction. Adsorption being an exothermic process, the heat
of adsorption is utilised in enhancing the rate of the reaction.

Adsorption theory (Modern): The modern adsorption theory is the

combination of intermediate compound formation theory and the old
adsorption theory. The mechanism involves five steps:
(1) Diffusion of reactants to the surface of the catalyst.
(2) Adsorption of reactant molecules on the surface of the catalyst.
(3) Occurrence of chemical reaction on the catalysts surface through
formation of an intermediate (Figure depicted below).
(4) Desorption of reaction products from the catalyst surface, and thereby,
making the surface available again for more reaction to occur.
(5) Diffusion of reaction products away from the catalysts surface.

Theory of Catalysis
Adsorption theory

H
H

H
Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

What is adsorption?
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 adsorption 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 attraction, adsorption is mainly

two types: (1) Physical adsorption (Physisorption) and (2)
Chemical adsorption (Chemisorption).

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

Chemical Adsorption
Chemical adsorption (Chemisorption)
Chemical adsorption is adsorption which results from chemical
bond formation (strong interaction) between the adsorbent and the
adsorbate in a monolayer on the surface.
Example: Organic compound get adsorbed on the solid surface with
chemical bond formation.

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.

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.

Adsorbate
Adsorbent
Adsorbate

What are the criteria of the catalyst?

The following criteria define a good quality catalyst for a

reaction:
1. Only small quantity is needed for a reaction.
2. They are specific. One catalyst is needed for specific
reaction only.
3. Physical properties may change during a reaction but it
does not take part in the reaction.
4. No catalyst can change an equilibrium state of a reaction.

What are the properties 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 particles of an
active material dispersed over a less active
substance.

Deactivation of catalyst
Unsupported catalyst
- Aging
- Poisoning
Promoters small amount of active
- Fouling or coking

ingredients

Catalyst

What is catalyst?

How does the catalyst functioning?

To enhance the reaction rate

Does not consumed in the reaction
Providing lower energy barrier

Two categories of catalyst

1) Porous

2) Non-porous

Types of Catalyst
Porous catalysts

1.

1.
2.

Monolithic catalyst
Supported/Unsupported catalysts

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Engineering

Porous Catalyst
Why we need porous catalyst???
A few major catalyst support and catalysts:

Amorphous silica
Silica gels have surface areas up to ~ 500 m2/g, and they are widely
used as supports for catalysts.

High surface area aluminas

The surface area is up to ~ 200 m2/g in crystalline form.

Zeolites/aluminosilicates

Zeolites are microporous crystalline solids with well-defined

structures. Generally they contain silicon, aluminium and oxygen in
their framework

Carbon
The activated carbon is a highly porous with high surface area
(usually > 500 m2/g) carbon materials.

Porous catalysts

Catalyst that has a large area resulting from pores

Typical silica-alumina cracking catalyst

Raney nickel used in hydrogenation of vegetable and animal oils

Molecular sieves-Small pores to avoid large molecules from entering

Pores volume of 0.6cm3/g

Average pore radius of 4 nm
Surface area 300m2/g

derived from certain clays and zeolites

Totally synthetic ie crystalline aluminosilicates

Selective catalyst- pores to control residence time of various
molecules
CPE 624
Advanced Chemical Reaction Engineering

Steps in Heterogeneous Catalytic Reaction

i.

ii.

iii.

iv.
v.
vi.

vii.
19

External mass transfer (diffusion) of the reactants (e.g.,

species A) from the bulk fluid to the external surface of
the catalyst pellet.
Pore diffusion of the reactant from the pore mouth
through the catalyst pores to the immediate vicinity of the
internal catalytic surface.
Adsorption of reactant A onto the active site of catalyst
surface
Reaction on the surface of the catalyst (A B)
Desorption of the products (e.g., B) from the surface.
Pore diffusion of the products from the interior of the
pellet to the pore mouth at the external surface
External mass transfer of the products from the external
pellet surface to the bulk fluid
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Step in catalytic reaction

20

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Monolithic catalyst

Process with major considerations in pressure drop and heat

removal

ie platinum gauze reactor used in the ammonia oxidation portion of

nitric acid manufacture
catalytic converters used to oxidize pollutants

Porous (honeycomb) or nonporous (wire gauze)

CPE 624
Advanced Chemical Reaction Engineering

Supported/Unsupported catalysts

Support- particles of an active material dispersed over a

less active substance
The active material is frequently a pure metal or metal
alloy
Promoters active ingredients to increase catalyst
activity

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Engineering

Catalytic Reactors
1.

2.
3.
4.

Packed bed reactor (PBR)

Slurry reactor
Fluidized bed reactor
Riser reactor

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Packed Bed Reactor

Typical tank/tube filled with catalyst pellets

Fluid flow & void space
PBR/multitube/single tube
Fluid in PBR flows from one end to another end (no
mixing)

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Engineering

Catalytic Reactors

Packed bed Reactor

Assume no mixing
Mass balance:

25

dC j
dz

jr

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Packed Bed Reactor

dC j

v j r (Single reaction)

dz
dC j
u
vij ri (Multiple reactions)
dz
i

VR V fluid VCatalyst

V fluid VR
VCatalyst (1 )VR
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Catalytic Reactors

Slurry and Fludized Bed Reactor

Mass Balance:

C A0 C A r

27

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The slurry reactor

Fluid and catalyst are stirred

Fluid is a liquid (catalyst must be small)
The catalyst in powder/pellets form
Moving fluid is frequently well mixed hence equal to a
CSTR :

C Ao C A r

Residence time :

VR

V fluid

CPE 624 Advanced Chemical Reaction

Engineering

The fluidized bed reactor

Fluid and catalyst are stirred

Fluid is gas (catalyst must be very small)
The catalyst in powder/pellets form
Moving fluid is frequently well mixed hence equal to a
CSTR :

C Ao C A r

Residence time :

VR

V fluid

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Engineering

The riser reactor

High velocity in the reactor

Solids entrained in the flowing fluid and move with nearly
same fluid velocity
Catalyst is carried with the reactants, separated and
returned to the reactor
Completely mixed, hence no mixing and behave to a PBR
:

dC A
u
r
dz
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Engineering

Surface and enzyme reaction rates

Assumption for heterogeneous reactions:

No reaction in the fluid phase

All reaction occurs on the catalyst surface/catalyst wall
Table 7-1 : Homogeneous & Surface reaction rates

Rate

r
r"
r'

Significance

Units

Homogeneous/
Pseudohomogeneous rate

moles/vol.time

Rate per catalyst area

moles/area.time

Rate per weight of catalyst

moles/weight.time

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Psedohomogeneous Rate
determination of equivalent homogeneous rate for heterogeneous
reaction

area
r
r"
volume

surface area of catalyst

vol.of reactor

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Engineering

Psedohomogeneous Rate
Example :
PBR filled with pellets with surface area Sgc per unit/pellet
volume

Vcatalyst
area
S g c (1 )

S g c
V fluid
volume
Surface
area/weight of
catalyst

(1 )
Density of catalyst
pellet

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Fraction occupied by
the catalyst

Psedohomogeneous Rate
determination of equivalent homogeneous rate for heterogeneous
reaction

weight
r
r '
volume

weight of catalyst
vol.of reactor

CPE 624 Advanced Chemical Reaction

Engineering

Psedohomogeneous Rate
Example :
PBR filled with pellets with surface area Sgc per unit/pellet volume

weight

r ' c r '
volume

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Engineering

Space time,

Homogeneous:

vol.of reactor
inlet volumetric f / rate

Heterogeneous:
V flu id VR

VR
o

CPE 624 Advanced Chemical Reaction

Engineering

Exercise 1 : Slurry reactor design

A slurry reactor contains diameter spherical particles that
catalyze the reaction with a rate in moles/cm2.s with CA in
moles/liter. There are 105particles/cm3 and only the external
surface of the particles is catalytic. What flow rate of C AO=2
moles/liter can be processed in a 10 liter reactor if the
conversion is 90%?

CPE 624 Advanced Chemical Reaction

Engineering

Exercise 2 : Pseudo homogeneous rate

The reaction r = kCAS occurs on the external surface of
a sphere of diameter D suspended in a stagnant fluid in
which the diffusion coefficient of the reactant is DA. Find
the total rate of the reaction in terms of these quantities.
How does the rate depend on particle diameter? How
would this influence the design of a slurry reactor with
this catalyst?

CPE 624 Advanced Chemical Reaction

Engineering