Part 1: The Nature of Catalysts

Reactors and catalysis:

heterogeneous catalysis
importance of catalysis how
catalysts work adsorption
quantifying adsorption BET and
Langmuir isotherms
heterogeneous reaction kinetics
use of Langmuir isotherms
unimolecular and bimolecular
With thanks to Robert Fishwick forreactions
use of the notes adsorption and reaction

Part 1: The Nature of Catalysts

syllabus
heterogeneous catalysis
the nature of catalysts (with examples)
and how they work
adsorption (chemisorption, physisorption)
surface area and the BET equation
the Langmuir isotherm
kinetic modelling of unimolecular and
bimolecular reactions for systems
controlled by adsorption, surface reaction
or desorption
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Part 1: The Nature of Catalysts

learning outcomes
By the end of the module the student
should be able to understand and
describe the fundamentals of catalysis
and catalytic reactors

additional reading

RPF

Reactor Design for Chemical Engineers,

J.M. Winterbottom and M.B. King
Chemical Reaction Engineering, O. Levenspiel
3

Part 1: The Nature of Catalysts

a brief history of catalysis

Catalysis coined by Jns Berzelius in 1836

RPF

first real industrial catalysis in 1875: large-scale

production of sulphuric acid on platinum, invented
by Peregrine Philips

Ostwald develops ammonia oxidation on Pt

gauze to produce nitric acid in 1903

Bosch and Haber develop the ammonia

synthesis process around 1908 to 1914 to
allow manufacture of fertilizers

Part 1: The Nature of Catalysts

a brief history of catalysis

1897: Paul Sabatier discovers the use of finely divided nickel to

hydrogenate hydrocarbon double bonds

1905: Wilhelm Normann started

large scale production of
hydrogenated oils in Warrington
on nickel catalyst, currently
4MMtpa of hardened fats are
produced worldwide

1920s: further developments in hydrogenation catalysts provide

new routes to fine chemicals and pharmaceuticals

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Part 1: The Nature of Catalysts

a brief history of catalysis

1930: conversion of H2 and CO to CH4 and higher
hydrocarbons on Fe and Ru in the Fischer-Tropsch
process, used to produce fuel in wartime Germany
1937: partial oxidation of ethene to ethylene oxide on
Ag/Al2O3 catalyst
1938-1946: development of the Oxo process for the
production of aldehydes from alkenes, H2 and CO
1955: stereospecific polymerisation for the synthesis
of polyethylene on Ziegler-Natta complexes of titanium
1960: production of acetaldehyde by the oxidation of
ethene in the Wacker process using PdCl2-.Cu2+
catalyst
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Part 1: The Nature of Catalysts

a brief history of catalysis

Late 1930s: catalytic cracking
developed for the production of
branched hydrocarbons from
longer chains on aluminosilicate
catalysts

1942: Friedel-Craft alkylation for the production C7, C8

hydrocarbons from C3, C4 using acids, AlCl3

1950: catalytic naphtha reforming using Pt/Al2O3

1960s: zeolitic catalytic cracking developed

1960s: hydrodesulphurisation for the removal of sulphur from

diesel fuel developed on CoMo/Al2O3 catalyst
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Part
Part1:1:The
TheNature
Nature of
of Catalysts
Catalysts

a brief history of catalysis

1970s: development of three-way
catalytic converter for car emission-control
using
Pt/Pd/Rh
aHC
+ bO
cCO catalyst
+ dH O
2

2CO + O2 2CO2
2NO + 2CO N2 + 2CO2

monolith
enclosure

steel
housing

monolith
RPF

ceramic monolith
lambda probe
measure oxygen content
in the exhaust gas

support for catalytic metals

Part 1: The Nature of Catalysts

and in the future?

development trends
milder reaction conditions
improved activity and selectivity
innovations in contacting and reactor design

RPF

emerging catalytic technology

energy, fuels and chemicals from natural gas, coal and biomass
environmental engineering
enzymatic and homogeneous catalysis, immobilization of
homogeneous catalysts to aid separation

9
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Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

what is a catalyst?

a catalyst is a substance which increases

the rate at which a chemical reaction
approaches equilibrium, without itself
becoming permanently changed by the
reaction or altering the equilibrium
conditions

i.e. catalysts affect equally the forward

and reverse reaction rates

RPF

zirconium
on
10
alumina

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Catalysis & Catalysts

Facts and Figures about Catalysts

Life cycle on the earth
Catalysts (enzyme) participates most part of life cycle
e.g. forming, growing, decaying
Catalysis contributes great part in the processes of converting sun
energy to various other forms of energies
e.g. photosynthesis by plant CO2 + H2O=HC + O2
Catalysis plays a key role in maintaining our environment

Chemical Industry
90% of chemical industry has catalysis-related processes
Catalysts contributes 2% of total investment in a chemical process

11

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

What is Catalysis

Catalysis
Catalysis is an action by catalyst which takes part in a chemical
reaction process and can alter the rate of reactions, and yet itself will
return to its original form without being consumed or destroyed at the
end of the reactions
(This is one of many definitions)
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
12

CH4003 Lecture Notes 11 (Erzeng Xue)

Action of Catalysts
Catalysis action - Reaction kinetics and
mechanism
Catalyst action leads to the rate of a reaction to change.
This is realised by changing the course of reaction (compared to noncatalytic reaction)
uncatalytic
Forming complex with reactants/products, controlling the
rate of
elementary steps in the process. This is evidenced by the facts that
The reaction activation energy is altered

catalytic

energy

Part 1: The Nature of Catalysts

Catalysis & Catalysts

reactant

The intermediates formed are different from

those formed in non-catalytic reaction

produc
reaction processt

The rates of reactions are altered (both

desired and undesired ones)

Reactions proceed under less demanding conditions

Allow reactions occur under a milder conditions, e.g. at lower
temperatures for those heat sensitive materials
13

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Action of Catalysts

It is important to remember that the use of catalyst DOES NOT

vary G & Keq values of the reaction concerned, it merely
change the PACE of the process
Whether a reaction can proceed or not and to what extent a
reaction can proceed is solely determined by the reaction
thermodynamics, which is governed by the values of G & Keq,
NOT by the presence of catalysts.
In another word, the reaction thermodynamics provide the driving
force for a rxn; the presence of catalysts changes the way how
driving force acts on that process.
e.g CH4(g) + CO2(g)
2CO(g) + 2H2(g)
(100 C)
G973 =-16 kJ/mol (700 C)

G373=151 kJ/mol

At 100C, G373=151 kJ/mol > 0. There is no thermodynamic driving force, the

reaction wont proceed with or without a catalyst
At 700C, G373= -16 kJ/mol < 0. The thermodynamic driving force is there.
However, simply putting CH4 and CO2 together in a reactor does not mean they
will react. Without a proper catalyst heating the mixture in reactor results no
14
conversion of CH4 and CO2 at all. When Pt/ZrO2 or Ni/Al
2O3 is present in the

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Types of Catalysts & Catalytic

The types of catalysts Reactions
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.
15

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Applications of Catalysis

Industrial applications

Almost all chemical industries have one or more

steps employing catalysts
Petroleum, energy sector, fertiliser, pharmaceutical, fine chemicals

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
16

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Applications of Catalysis

Environmental applications
Pollution controls in combination with industrial processes
Pre-treatment - reduce the amount waste/change the composition of
emissions
Post-treatments - once formed, reduce and convert emissions
Using alternative materials

Pollution reduction
gas - converting harmful gases to non-harmful ones
liquid - de-pollution, de-odder, de-colour etc
solid - landfill, factory wastes

And many more

Other applications
Catalysis and catalysts play one of the key roles in new
technology development.
17

CH4003 Lecture Notes 11 (Erzeng Xue)

Part 1: The Nature of Catalysts

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, microkinetics, 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

18

CH4003 Lecture Notes 12 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Catalytic Reaction Processes

Understanding catalytic reaction processes

A catalytic reaction can be operated in a batch manner

Reactants and catalysts are loaded together in reactor and
catalytic reactions (homo- or heterogeneous) take place in predetermined temperature and pressure for a desired time /
desired conversion
Type of reactor is usually simple, basic requirements
Withstand required temperature & pressure
Some stirring to encourage mass and heat transfers
Provide sufficient heating or cooling
Catalytic reactions are commonly operated in a continuous
manner
Reactants, which are usually in gas or liquid phase, are fed to
reactor in steady rate (e.g. mol/h, kg/h, m3/h)
Usually a target conversion is set for the reaction, based on this
target
required quantities of catalyst is added
required heating or cooling is provided
required reactor dimension and characteristics are designed
19
accordingly.

CH4003 Lecture Notes 12 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Catalytic Reaction Processes

Catalytic reactions in a continuous operation (contd)

Reactants in continuous operation are mostly in gas phase or liquid
phase
easy transportation
The heat & mass transfer rates in gas phase is much faster than
those in liquid
Catalysts are pre-loaded, when using a solid catalyst, or fed together
with reactants when catalyst & reactants are in the same phase and
pre-mixed
It is common to use solid catalyst because of its easiness to
separate catalyst from unreacted reactants and products
Note: In a chemical process separation usually accounts for
~80% of cost. That is why engineers always try to put a liquid
catalyst on to a solid carrier.
With pre-loaded solid catalyst, there is no need to transport
catalyst which is then more economic and less attrition of solid
catalyst (Catalysts do not change before and after a reaction
and can be used for number cycles, months or years),
In some cases catalysts has to be transported because of need
of regeneration
In most cases, catalytic reactions are carried out with catalyst in a fixedbed reactor (fluidised-bed in case of regeneration20being needed), with

CH4003 Lecture Notes 12 (Erzeng Xue)

Part 1: The Nature of Catalysts

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 by

a good catalyst should resist to deactivation, caused

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.
21

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

catalyst selectivity
a second property of a catalyst is its ability
to selectively catalyse a reaction
producing a desired product among a
number of other reactions
Cu

C2H4O + H2

C2H5OH
Al2O3

C2H4 + H2O

both reactions favoured thermodynamically

RPF

22

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

how does it increase

reaction rate?
provides a lower energy reaction path
(A*) homo

E homo
A* hetero
E hetero
A

RPF

activation
energy

}H

24

enthalpy
of reaction

S(s) + O2(g) SO2(g) + energy

Reaction Coordinate

Reaction Coordinate

Potential Energy

Potential Energy

Potential Energy

Potential Energy

Which diagram best represents the potential

energy changes for this reaction?

Potential Energy

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

example of potential energy

change
Given the reaction:

activation energy
enthalpy of reaction
Reaction Coordinate

Reaction Coordinate

Reaction Coordinate
RPF

25

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

elements with catalytic applications

H He
Li Be

F Ne

Na Mg

Al

Si

Cl Ar

K Ca Sc Ti
Rb Sr

Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te

Cs Ba La Hf Ta W Re Os Ir

Xe

Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac
Lanthanides Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
Actinides

RPF

Th Pa

U Np Pu Am Cm Bk Cf Es Fm Md No Lr

catalytic elements
poisons

supports
promoters
26

CH4003 Lecture Notes 12 (Erzeng Xue)

Part 1: The Nature of Catalysts

Catalysis & Catalysts

Solid Catalysts
Catalyst composition

Catalys
t

Active phase

Support

Where the reaction occurs

(mostly metal/metal oxide)

Promoter
Textual promoter (e.g. Al - Fe for NH 3 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
27

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

active components

metals
hydrogenation, dehydrogenation,
hydrogenolysis, oxidation
Fe, Ni, Co, Pt, Pd, Rh, Ru, Ir, Cu, Au
metal oxides (semi-conductors)

oxidation, reduction, dehydrogenation, cyclization

NiO, ZnO, CuO, Cr2O3

metal oxides (insulators)

RPF

dehydration, isomerisation
Al2O3, SiO2, MgO

28
TEM of Pd/Al2O3 catalyst

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

active components

metal sulphides (from oxide precursor)

hydrodesulphurisation
copper molybdate, Ni3S2
acids
polymerisation, isomerisation, cracking, alkylation
H3PO4, H2SO4, Al2O3-SiO2 (zeolites), clays

homogeneous catalysts

RPF

hydrogenation, carbonylation, oxo reactions

various metal complexes e.g. Rh(PPh3)Cl
can be heterogenised or used in biphasic solvents for
separation from products
29

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

unsupported metals
not common as a large metal surface area
is desirable
examples include wires, gauzes and
powders
one notable example are skeletal (Raney)
species, for example, Raney Nickel
produced by leaching the aluminium from
AlNi alloys with sodium hydroxide

RPF

31

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

supported metals
the aim is to improve dispersion of the
metal species and thereby increase the
activity of the catalyst
this may be in order to best utilise
expensive metals such as platinum and
palladium or to stabilise metals such as
nickel
the most common supports are Al2O3, SiO2,
zeolites and activated carbons

RPF

32

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

precipitated catalysts
formed from a liquid solution of the metal
and support components, for example:

RPF

2Ni(NO3)2 + 2NaOH + Na2CO3 Ni2(OH)2CO3 + 4NaNO3

the key is to control the crystallite size

during precipitation and ensure adequate
mixing
the support may be added a finely divided
powder or prepared in the same solution
from soluble salts e.g. aluminium salts
converted to alumina
33

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

impregnated catalysts
more commonly used is the impregnation
of the porous support with a solution of
the active component
the support is either dipped in the solution
or the solution sprayed onto the support
this is followed by drying to remove water
and then calcination in air to form
insoluble oxides on the support surface
this may then be followed by reduction to
form crystallites of the metal
RPF

34

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

egg-shell catalysts
in the case of precious metal catalysts it is
desirable to deposit only a low weight
percentage on the support
in order to minimise diffusional effects
through the porous support the metal is
often only deposited near the outside of
the support to form a so-called egg-shell
catalyst
this is done by dipping in a strongly
adsorbing for a short time followed by
immediate drying
35
the dispersion of the metal in the
support
RPF

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

influence of catalyst
distribution

e.g. chloroplatinic acid

active component
catalyst
support
added
as solution

fully disperse

egg-shell
low internal diffusion
active component
driven into catalyst
e.g.
with citric acid
RPF

egg-white

egg-yolk
good selectivity
36

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

calcination
calcination is a heat treatment carried out
in air at a temperature slightly above the
projected operating temperature of the
catalyst
the aim is to stabilize physical, chemical
and catalytic properties
thermally unstable compounds are
decomposed during the process (e.g.
carbonates and nitrates)
the crystalline and pore structures are
modified
RPF

37

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

reduction
metal oxides may be decomposed to form
crystallites of the metal on the support
this is usually done by reacting the
catalyst with hydrogen at elevated
temperatures

RPF

38

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

catalyst pellets
pelleting: the powder is
compressed to produce pellets
of precise dimensions
extrusion: the powder is made
into a paste and pushed through
a small hole called a die
granulation: agglomeration of
powder to form small spheres

RPF

1.0
0.9
0.9
0.8
39
relative pressure drop for various pellets

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

the catalyst surface

Fischer-Tropsch catalyst

Ni-Au surface

planar
corner
edge
terrace adatom
edge adatom
RPF

40

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

the catalyst surface

platinum catalyst for the oxidation of carbon monoxide

CO

CO
O2
step

RPF

Department of Physical Chemistry, Fritz-Haber-Institut, Berlin

41

CH4003 Lecture Notes 12 (Erzeng Xue)

Part 1: The Nature of Catalysts

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

gas phase
reactant molecule

j
k
l

gas phase

mn
o

porous
solid

liquid
phase /
stagnant
layer

pore

pq r

42

Part 1: The Nature of Catalysts

Part 1: The Nature of Catalysts

steps in a heterogeneous
reaction
gas bubble (A)

CAg

CAb

12

reaction
4
site
5

pore
bulk liquid (B)

A(g) + B(l) R(l)

CA

RPF

catalyst particle

CAg

CAi
CAb

CAs

43

Part1:1:The
TheNature
Nature of
of Catalysts
Catalysts
Part

steps in a heterogeneous
reaction
1.
2.
3.

4.
5.
6.
7.
8.
9.
RPF

adsorption of A from the gas phase into the liquid interface

diffusion of A into the bulk liquid phase from the liquid side
of the gas/liquid interface
diffusional transport of reactant A from the bulk phase to
the external catalyst surface. Applies to B as well, but in
this case bulk and surface concentration may be equal
except if there is also a solvent present
pore diffusion of reactant by molecular and Knudsen
diffusion to the internal active surface site
adsorption of reactant at active site
chemical reaction at active site
desorption of product(s) from active site
pore diffusion of product(s) to the exterior surface
diffusional transport of product(s) to the bulk phase across
the surface boundary layer
44

Part
2: Adsorption
Part
2: Adsorption

physical vs. chemical

adsorption
parameter

physisorption

chemisorption

heat of adsorption

low
(<20 kJ/mol)

high
(40-650 kJ/mol

energy of
activation for
adsorption

none

none in some
case but can be
40 kJ/mol or more

number of layers
formed

>1

one only

temperature at
which effects are
significant

low
(< room
temperature)

sub-ambient to
temperatures of
800 K and above

RPF

45

Part2:2:Adsorption
Adsorption
Part

adsorption: hydrogen on nickel

adsorption
(a)
H2

Ni
Ni

RPF

(b)

(c)

(d)

Ni

Ni

Ni

Ni

Ni

Ni

1.5

2.5

idealised representation of stages in transition from molecular

hydrogen to chemisorbed atomic hydrogen
(a) approaching surface
(b) physisorbed state
(c) at transition stage
(d) in chemisorbed state
46

chemisorption
curve

potential energy

Part
2: Adsorption
Part
2: Adsorption

adsorption: hydrogen on nickel

potential energy curves for
the chemical and physical
adsorption of hydrogen on
nickel, and a diagrammatical
representation of the
adsorbed states

In this case activation energy,

EA, is positive so there is an
energy barrier to
chemisorption which will have
a major influence on kinetics

physisorption
EA curve

-HP distance from

surface

-HC

Ni

Ni
RPF

H
H

47

Part
2: Adsorption
Part
2: Adsorption

adsorption : CO oxidation
CO
O2

CO2

+
catalyst
adsorption
RPF

reaction

desorption
48

Part
2: Adsorption
Part
2: Adsorption

quantitative aspects of
adsorption
a number of isotherms can be used
to describe adsorption
the Brunauer, Emmett and Teller (BET)
isotherm
the Langmuir isotherm
the Gibbs isotherm
the Henry isotherm, etc.

RPF

49