Catalysis & Catalysts

Hikmat S. Al Salim

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 6CO + 6H O (+ light energy) C H O + 6O .
Catalysis plays a key role in maintaining our environment
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Chemical Industry

ca. $2 bn annual sale of catalysts

ca. $200 bn annual sale of the chemicals that are related products
90% of chemical industry has catalysis-related processes
Catalysts contributes ca. 2% of total investment in a chemical process
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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

altering the rates of reactions

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

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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 non-catalytic reaction)
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

The intermediates formed are different from

those formed in non-catalytic reaction

The rates of reactions are altered (both

desired and undesired ones)

uncatalytic
catalytic

energy

reactant
product
reaction process

Reactions proceed under less demanding conditions

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

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)

G373=151 kJ/mol (100 C)

G973 =-16 kJ/mol (700 C)

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 conversion of CH4 and CO2 at
all. When Pt/ZrO2 or Ni/Al2O3 is present in the reactor at the same temperature,
equilibrium conversion can be achieved (<100%).

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.
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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

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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.
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Research in Catalysis

Research in catalysis involve a multi-discipline approach

Reaction kinetics and mechanism

Catalyst development

Elementary reactions and rates, quantum mechanics/chemistry, physical chemistry

Reactor modelling

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

Material synthesis, structure properties, catalyst stability, compatibility

Analysis techniques

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

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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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 pre-determined
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 accordingly.
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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

fixed-bed reactor (fluidised-bed in case of regeneration being needed),
with the reactant being gases or liquids
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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)

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.
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Example Heterogeneous Catalytic Reaction Process

The long journey for reactant molecules to
. travel within gas phase
. cross gas-liquid phase boundary
. travel within liquid phase/stagnant layer
. cross liquid-solid phase boundary
. reach outer surface of solid
. diffuse within pore
. arrive at reaction site
. be adsorbed on the site and activated
. 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

gas phase

liquid phase /
stagnant layer

porous
solid

pore

Heat transfer follows similar track

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Solid Catalysts

Catalyst composition

Active phase

What makes a
catalyst?

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

Catalyst
Support

Increase mechanical strength

Increase surface area (98% surface area is supplied within the porous structure)
may or may not be catalytically active

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Solid Catalysts
Some

common solid support / carrier materials

Alumina

Inexpensive
Surface area: 1 ~ 700 m2/g
Acidic

Silica

Inexpensive
Surface area: 100 ~ 800 m2/g
Acidic

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)
Active site

Zeolite

mixture of alumina and silica,

often exchanged metal ion present
shape selective
acidic

porous
solid

pore

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Solid Catalysts
Preparation

of catalysts

Precipitation
To form non-soluble precipitate by desired
reactions at certain pH and temperature

Adsorption & ion-exchange

Cationic: S-OH+ + C+ SOC+ + H+

Drying
& firing
precursor add acid/base
solution with pH control
Support

Anionic: S-OH- + A- SA- + OHI-exch.

S-Na+ + Ni 2+ S-Ni 2+ + Na+

Impregnation

precipitate
or deposit
precipitation

Dry mixing

Drying
& firing

Concentration
Support

Fill the pores of support with a metal salt

solution of sufficient concentration to give
the correct loading.

filter & wash

the resulting
precipitate

Amount
adsorbed

Support

Drying
& firing
Soln. of metal
precursor

Pore saturated
pellets

Physically mixed, grind, and fired

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Solid Catalysts

Preparation of catalysts
Catalysts

Commonly used Pre-treatments

Reduction

if elemental metal is the active phase

Sulphidation

50
25
0
500

600

700

800 900

0
0

Time / hours

10

if a metal sulphide is the active phase

Activation

75

Temperature C

Some catalysts require certain activation steps in order to receive the best performance.
Even when the oxide itself is the active phase it may be necessary to pre-treat the
catalyst prior to the reaction
Induction period

Typical catalyst life span

Can

be many years or a few mins.

Activity

100

BET S.A.

BET S.A. m2/g

need to be calcined (fired) in order to decompose the precursor and to

received desired thermal stability. The effects of calcination temperature and time
are shown in the figures on the right.
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Normal use

Time

dead

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Mechanism of Surface Catalysed Reaction

Langmuir-Hinshelwood

mechanism

This mechanism deals with the surface-catalysed reaction in which

that 2 or more reactants adsorb on surface without dissociation
A(g) + B(g) A(ads) + B(ads) P
The rate of reaction

ri=k[A][B]=kAB

From Langmuir adsorption isotherm (the case III) we know

(the desorption of P is not rate-determining

step r.d.s.)

B0 ,A PA

=
A 1+ B P + B P

0 ,A A
0 ,B B

B0 ,B PB
B =
1 + B0 ,A PA + B0 ,B PB

We then have

B0 ,A PA
B0 ,B PB
kB0 ,A B0 ,B PA PB

=
ri = k

1 + B0 ,A PA + B0 ,B PB 1 + B0 ,A PA + B0 ,B PB 1 + B0 ,A PA + B0 ,B PB

When both A & B are weakly adsorbed (B0,APA<<1, B0,BPB<<1),

ri = kB0 ,A B0 ,B PA PB = k' PA PB
2nd order reaction

When A is strongly adsorbed (B0,APA>>1) & B weakly adsorbed (B0,BPB<<1 <<B0,APA)

kB B P P
ri = 0 ,A 0 ,B A B = kB0 ,B PB = k' ' PB
1st order w.r.t. B
B0 ,A PA

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Mechanism of Surface Catalysed Reaction

Eley-Rideal

mechanism

This mechanism deals with the surface-catalysed reaction in which

P
that one reactant, A, adsorb on surface without dissociation and
other reactant, B, approaching from gas to react with A
+ B(g)
A(g) A(ads)
P (the desorption of P is not rate-determining step r.d.s.)

The rate of reaction

ri=k[A][B]=kAPB

From Langmuir adsorption isotherm (the case I) we know

We then have

B P
kB P P
ri = k 0 ,A A PB = 0 ,A A B
1 + B0 ,A PA
1 + B0 ,A PA

B0 ,A PA
1+ B0 ,A PA

When both A is weakly adsorbed or the partial pressure of A is very low (B0,APA<<1),

ri = kB0 ,A PA PB = k' PA PB

A =

2nd order reaction

When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)

ri =

kB0 ,A PA PB
= kPB
B0 ,A PA

1st order w.r.t. B

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Mechanism of Surface Catalysed Reaction

Mechanism of surface-catalysed reaction with dissociative adsorption

The mechanism of the surface-catalysed reaction in which one

reactant, AD, dissociatively adsorbed on one surface site
+ B(g)
P
AD(g) A(ads) + D(ads)

B
A

(the des. of P is not r.d.s.)

ri=k[A][B]=kADPB

The rate of reaction

From Langmuir adsorption isotherm (the case I) we know

We then have

1/ 2
1/ 2
(
B0 ,AD PAD )
k (B0 ,AD PAD ) PB
ri = k
P =
1/ 2 B
1/ 2
1 + (B0 ,AD PAD )
1 + (B0 ,AD PAD )

When both AD is weakly adsorbed or the partial pressure of AD is very low (B0,ADPAD<<1),
1/ 2
ri = k (B0 ,AD PAD ) PB = k' PAD
PB
1/ 2

1/ 2
(
B0 ,AD PAD )
AD =
1/ 2
1 + (B0 ,AD PAD )

The reaction orders, 0.5 w.r.t. AD and 1 w.r.t. B

When A is strongly adsorbed or the partial pressure of A is very high (B0,APA>>1)

k (B0 ,AD PAD ) PB

1/ 2

ri =

(B0 ,AD PAD )

1/ 2

= kPB

1st order w.r.t. B

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Mechanism of Surface Catalysed Reaction

Mechanisms of surface-catalysed reaction involving dissociative adsorption

In a similar way one can derive mechanisms of other surface-catalysed reactions, in

which

dissociatively adsorbed one reactant, AD, (on one surface site) reacts with another
associatively adsorbed reactant B on a separate surface site

dissociatively adsorbed one reactant, AD, (on one surface site) reacts with another
dissociatively adsorbed reactant BC on a separate site

The use of these mechanism equations

Determining which mechanism applies by fitting experimental data to each.

Helping in analysing complex reaction network

Providing a guideline for catalyst development (formulation, structure,).

Designing / running experiments under extreme conditions for a better control

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Solids and Solid Surface

Bulk and surface

The composition & structure of a solid in bulk and on surface

can differ due to
Surface

Bombardment by foreign molecules when exposed to an environment

Surface

contamination
enrichment

Some elements or compounds tend to be enriched (driving by thermodynamic

properties of the bulk and surface component) on surface than in bulk

Deliberately

Coating (conductivity, hardness, corrosion-resistant etc)

Doping the surface of solid with specific active components in order perform certain
function such as catalysis

made different in order for solid to have specific properties

To processes that occur on surfaces, such as corrosion, solid sensors and

catalysts, the composition and structure of (usually number of layers of)
surface are of critical importance
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Solids and Solid Surface

Morphology

of a solid and its surface

A solid, so as its surface, can be well-structured crystalline (e.g. diamond C,

carbon nano-tubes, NaCl, sugar etc) or amorphous (non-crystallised, e.g.
glass)

Mixture of different crystalline of the same substance can co-exist on

surface (e.g. monoclinic, tetragonal, cubic ZrO2)

Well-structured crystalline and amorphous can co-exist on surface

Both well-structured crystalline and amorphous are capable of being used

adsorbent and/or catalyst

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Solids and Solid Surface

Defects

and dislocation on surface crystalline structure

A perfect crystal can be made in a controlled way

Surface defects
Terrace

terrace

step

kink

adatom / vacancy

Dislocation

Step

screw dislocation

Defects and dislocation can be desirable for certain catalytic reactions

as these may provide the required surface geometry for molecules to be
adsorbed, beside the fact that these sites are generally highly energised.
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Pores of Porous Solids

Pore

sizes

micro pores dp <20-50 nm

meso-pores 20nm <dp<200nm

macro pores dp >200 nm

Pores can be uniform (e.g. polymers) or non-uniform (most metal oxides)

Pore

size distribution

Typical curves to characterise pore size:

Cumulative curve

Frequency curve

Uniform size distribution (a) &

non-uniform size distribution (b)

dw
dd

wt
wt

b
d

Cumulative curve

Frequency curve
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