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CHAPTER 1

(Lecture Note Part 1)

CATALYTIC REACTION
AND
MASS TRANSFER

Subtopic covered in Chapter 1

Catalytic Reactions and Reactors


Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Catalytic Wall Reaction
Langmuir-Hinshelwood Kinetic Mechanism
Temperature Dependence of Catalytic Reaction Rates
Application of Reaction Engineering in Microelectronic
Fabrication
Catalyst Deactivation

CATALYST-DEFINITION
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 equlibrium.

CATALYST-EXAMPLE
Example- H2 and O2 to form water; with
Platinum as catalyst

Basis of Catalysis
A catalyst lower the activation barrier for a transformation, by
introducing a new reaction pathway

WITHOUT A CATALYST

WITH A CATALYST

Three key aspects of catalyst action

taking part in the reaction


it will change itself during the process by interacting with
other reactant/product molecules

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
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
CH4003 Lecture Notes 11 (Erzeng Xue)

What is Catalysis

Catalysis is the increase in the 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.

CH4003 Lecture Notes 11 (Erzeng Xue)

Types of Catalysts & Catalytic Reactions


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.)
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.

CH4003 Lecture Notes 11 (Erzeng Xue)

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)

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
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

CH4003 Lecture Notes 11 (Erzeng Xue)

CH4003 Lecture Notes 11 (Erzeng Xue)

Catalysis & Catalysts

Research in Catalysis
Research in catalysis involve a multi-discipline approach
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

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
11

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
NH3 NO NO2 HNO3
1920s: CO + 2H2 CH3OH (HP)

Fischer-Tropsch synthesis
SO2 SO3 H2SO4

Fe/K
Pt
(ZnCr)oxide

Co,Fe
V2O5

Industrial catalysis-3
1950s
C2H4 Polyethylene(Z-N)
C2H4 Polyethylene(Phillips)
Polyprop &Polybutadiene(Z-N)
Steam reforming
HDS, HDT of naphtha
C10H8 Phthalic anhydride
C6H6 C6H12
C6H11OH C6H10O
C7H8+ H2 C6H6 +CH4

Ti
Cr-SiO2
Ti
Ni-K- Al2O3
(Co-Mo)/Al2O3
(V,Mo)oxide
(Ni)
(Cu)
(Ni-SiAl)

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
C7H8+C9H12 C6H6 +C8H10

acidic ion exchange resin


Pt-Mordenite

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

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.
(i) For example, in Habers process for the synthesis of
ammonia, traces of molybdenum increases the activity of
finely divided iron which acts as a catalyst.
(ii) In the manufacture of methyl alcohol from water gas ,
chromic oxide is used as a promoter with the catalyst zinc
oxide .

http://www.emedicalprep.com

Explanation of Promotion Action


1. Change of Lattice Space: The lattice spacing of the
catalyst is changed thus enhancing the spacing
between the catalyst particles. The adsorbed
molecules of the reactant are further weakened and
cleaved. This makes the reaction go faster.
2. Increase in peaks and cracks: Promoters increase the
peaks and cracks on the surface of the catalyst
thereby increasing the concentration of reactant
molecules and hence the rate of reaction.

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.
(i)

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.

(ii) The activity of iron catalyst is destroyed by the presence of H2S or CO in


the synthesis of ammonia by Habers process.
(iii) The platinum catalyst used in the oxidation of hydrogen is poisoned
by CO.

Explanation of Catalytic Poisoning


1. The poison is adsorbed on the catalyst surface in
preference to the reactants.
2. The catalyst may combine chemically with the
impurity.
Fe + H2S

FeS + H2

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: (a) Hydrolysis of an ester
CH3COC2H5 + H2O

CH3COOH + C2H5OH

Here CH3COOH is acting as a catalyst.

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.
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).

Classification of catalytic processes


There are two types of catalytic processes: 1. Homogeneous catalysis
2. Heterogeneous catalysis
These two processes have industrial importance.
There is another mechanism involving catalysis i.e.
enzyme catalysis which possess biological
importance.

CATALYST-TYPE
HOMOGENEOUS

HETEROGENEOUS

In solution with at
least one of the
reactants
Example;
0xo process for
manufacturing
normal
isobutylaldehyde

more than one


phase typical solid
catalyst in
liquid/gaseous
reactants
Example;
The dehydrogenation
of cyclohexane

Homogeneous Catalysis
Action 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
Acids

Esterificaton
Conc. H2SO4 catalyses the reaction between acids and alcohols

CH3COOH + C2H5OH

CH3COOC2H5 + H2O

Heterogeneous Catalysis
Catalyst is in different physical phase from the
reactants.
It is also called Contact catalysis.
It possesses great industrial importance.

Theory of Heterogeneous 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 Heterogeneous Catalysis (cont.)


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.

Adsorption theory

H
Pt

H
Pt

Pt

Pt

Pt

O
Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Steps in Catalytic Reaction


External
diffusion
Internal
diffusion
Adsorption
Surface
reaction

External
diffusion

Internal
diffusion
Desorption

CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Example Heterogeneous Catalytic Reaction Process

The long journey for reactant molecules to


j. travel within gas phase
k. cross gas-liquid phase boundary
l. travel within liquid phase/stagnant layer
m. cross liquid-solid phase boundary
n. reach outer surface of solid
o. diffuse within pore
p. arrive at reaction site
q. be adsorbed on the site and activated
r. react with other reactant molecules, either
being adsorbed on the same/neighbour
sites or approaching from surface above

Product molecules must follow the same


track in the reverse direction to return to gas
phase

Heat transfer follows similar track

gas phase
reactant molecule

j
k
l

gas phase

liquid phase /
stagnant layer

mn
o

porous
solid

pore

pq r

porous
carrier
(catalyst
support)

bed of
catalyst
particles

reactants

substrate

reactor

product
reactiondesorption

adsorption
products

catalyst support
active
site

CATALYST-PROPERTIES

Porous-Catalyst a catalyst that has a very large area


resulting from pores
Molecular sieve Materials with small pores (admit
small molecule but prevent large ones from entering
Monolithic- can be either porous or nonporous,
encountered in processes where pressure drop and heat
removal are major consideration.
Supported-consists of minute particles of an active
material dispersed over a less active substance.
Unsupported- mainly promoters that increase activity

catalyst that
has a large
area

small pore
that will
admit small
molecule

can be either
porous or
non-porous

4.Supported catalyst
consist of particles of an active
material dispersed over a less
active substance

5.Unsupported catalyst
Promoters small amount of
active ingredients

CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Solid Catalysts
Catalyst composition
Active phase
Where the reaction occurs (mostly metal/metal oxide)

Promoter
Textual promoter (e.g. Al - Fe for NH3 production)
Catalyst
Electric or Structural modifier
Support
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

CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

Solid Catalysts
Some common solid support / carrier
materials
Alumina
Inexpensive
Surface area: 1 ~ 700 m2/g
Acidic

Silica

Other supports

Active carbon (S.A. up to 1000 m2/g)


Titania (S.A. 10 ~ 50 m2/g)
Zirconia (S.A. 10 ~ 100 m2/g)
Magnesia (S.A. 10 m2/g)
Lanthana (S.A. 10 m2/g)

Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic

Zeolite

41

mixture of alumina and silica,


often exchanged metal ion present
shape selective
acidic

Active site

porous
solid

pore

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 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 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.

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

The following criteria define a good quality catalyst for a reaction:

Only small quantity is


needed for a reaction

They are specific. One


catalyst is needed for
specific
reaction only

Physical properties may


change during a reaction
but it
does not take part in the
reaction

No catalyst can change


an equilibrium state of a
reaction

CH4003 Lecture Notes 12 (Erzeng Xue)

Catalysis & Catalysts

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)
Stability - 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.
47

END OF CLASS QUESTION:


EXPLAIN EACH PROCESS INVOLVE IN CATALYSIS
STEPS REACTIONS. ILLUSTRATE EACH STEP IN A
CATALYTIC REACTION BY DIAGRAMS.

Subtopic covered in Chapter 1

Catalytic Reactions and Reactors


Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Catalytic Wall Reaction
Langmuir-Hinshelwood Kinetic Mechanism
Temperature Dependence of Catalytic Reaction Rates
Application of Reaction Engineering in Microelectronic
Fabrication
Catalyst Deactivation

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

Homogeneous Reactors:
volume of fluid in a reactor
=
volumetricflow rate passes through the reactor

Heterogeneous Reactors

V fluid = V

volume of reactor
inlet volumetric flow rate

V
0

Packed bed Reactor


Assume no mixing
Mass balance:

dC j
dz

jr

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Slurry and Fluidized Bed Reactor


- Reactants are well mixed as CSTR
Mass Balance:

C A0 C A r
Reactor Residence Time

V
= fluid =
v

V R
v

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Riser Reactor
In riser reactor, no mixing at all, PFTR

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Surface and Enzyme Reaction Rates

Assumption to be made: catalyst in solid phase


All reaction on the surface of the catalyst
(there is no reaction in the fluid phase).
Surface reaction has unit of moles per unit area
of catalyst per unit time, r
Homogeneous

reaction rate:
r

moles
volume time

Heterogeneous (surface) reaction

moles
r
area time
''

rate:

Surface area of catalyst

surface area of catalyst


sg
mass of catalyst

r s g c (1 )r"

Summary of Reaction Rates

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Answer: 2x105

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Topic 1
Catalytic Reaction and Mass Transfer
Catalytic reactions and reactors
Surface and Enzyme Reaction Rates
Introduction of Porous Catalyst
Transport and Reaction
External Mass Transfer
Pore Diffusion
Catalytic wall reaction
Langmuir-Hinshelwood Kinetic Mechanism
Temperature dependence of catalytic reaction rates
Application of reaction engineering in microelectronic
fabrication
Catalyst deactivation

Why we need porous catalyst???


A few major catalyst support and catalysts:

Silica gels have surface areas up to ~ 500 m2/g, and they are widely
used as supports for catalysts.
The surface area is up to ~ 200 m2/g in crystalline form.
Zeolites are microporous crystalline solids with well-defined
structures. Generally they contain silicon, aluminium and oxygen in
their framework
The activated carbon is a highly porous with high surface area
(usually > 500 m2/g) carbon materials.

Depositing noble metals on high-surface area oxide support (Al2O3,


SiO2, Zeolites) disperses the metal over the surface so that nearly
every metal atom is on the surface.

Transport and Reaction

Different size scales in a catalytic reactor...

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Steps in Heterogeneous Catalytic Reaction


i.

ii.

iii.

iv.
v.
vi.

vii.

CPE624

FACULTY OF CHEMICAL ENGINEERING

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

Concentration Gradient in Catalytic Reactor

CAb = ??

CAs = ??
CA(x) = ??

Copyright 1998 by Oxford University Press, Inc.

Concentration Gradient in Catalytic Reactor (cont.)

Copyright 1998 by Oxford University Press, Inc.

How do we know whether the reaction


rate is reaction limited (reaction
control) or external mass transfer
limited (external mass transfer
control)??

First, lets recall on mass transfer


coefficient

Mass Transfer Coefficients (for gasses)


If there is a concentration difference of A
between two locations 1 and 2, then

JA = kmA (CA1 CA2)


JA is the mass transfer flux, [mol/s.m2]
km is the mass transfer coefficient,
[mol/(sm2)/(mol/m3), or m/s]
CA1-CA2, concentration difference [mol/m3].
JA
k mA =
(CA1 - CA2 )

Then KmA can be defined as:

k mA

Mass transfer coefficient (kmA) can be defined


through the Sherwood number:
[convective mass transfer rate]
k mA l
=
Shl =
[diffusive mass transfer rate]
DA
where l is length and DA is the diffusion coefficient of A

Shl D A

Mass Transfer Coefficients : Sherwood Numbers (Shl) ...


Sherwood Numbers (Shl) several simple geometries..
1) Flow over flat plate (of
length L):

2) Flow over a sphere:

For laminar flow (ReL < 105):


1

ShL 0.66 Re L2 Sc

For turbulent flow (ReL > 105):

ShL

0.036 Re0L.8

Sc

4) Flow over a cylinder:

For ReD <4 :

3) Flow through a tube


For laminar flow (ReD < 2100):

8
ShD
3
For turbulent flow:

ShD

0.023 Re0D.8

ShD 2.0 0.4 Re D 0.06 Re D3 Sc 0.4


2

Sc

Sh D = 0.98 ReD

External Mass Transfer


At steady state:
[rate of transport to surface] = [rate of reaction at surface]
For first order reaction;

4R 2 k mA (C Ab C As ) 4R 2 r" 4R 2 k"C As

By rearranging
C As

C Ab

1 k "
k mA

Eliminating CAs

k " C Ab
"
r"
k eff
C Ab
1 k"
k mA

nonporou
s catalyst
pellet

Reaction limited

k << kmA

CAb

k=kmA

CAs
CA

Mass transfer limited


k >> kmA

(d)

Copyright 1998 by Oxford University Press, Inc.

External Mass Transfer

We now examine the limiting cases:


If k" << kmA then,

r" k" CAb

Reaction limited (reaction control)

If kmA << k" then,

r" kmA CAb

External mass transfer limited (external


mass transfer control)

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press

Schmidt, L.D. (1998). The Engineering of Chemical Reactions, New York: Oxford University Press