L1&2

CLL727:Heterogeneous Catalysis and

Reactor Design
Tue , Wed, Fr. 10-11:00 AM

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
Course Plan CHL 727

Topics No. of Lectures

Introduction and Basic concepts 2
Application of catalyst functionality concepts for control of 3
reaction selectivity and kinetic models

Steps in catalytic reaction(Adsorption, Kinetic models, 3

interparticulate and intraparticle transport process

Selection ,Preparation and Characterization of catalysts 6

Application of functionality concepts for control of reaction 3

selectivity and kinetic models

Acid base catalysts, Supported metal catalysts and Zeolites, their 4

Application
Catalyst deactivation, various deactivation models 4
Catalysis Reactors: Commercial Reactors( Fixed bed, fludized bed, 14
trickle bed , slurry Reactors etc.), Reactor Modeling,

Industrially important Green catalysts and processes such as 3

oxidation, processing of petroleum and hydrocarbons, synthesis
gas and related process

TOTAL 42
Grading : Minor 1 and 2 : 40 , Design work : Assignments cum Tutorial 4 /Design 2
Problem: 10, Quiz : 6 Major 40
NO MAKE UP EXAMS
 Text/References / Prerequisite: CRE UG Courses
(Kinetics and Reactor design)

(i) a. Heterogeneous catalysis: Satterfield

b. Principles and Practice on Heterogeneous Catalysis: J.M Thomas
and W.J Thomas
(ii)
I. Chorkendorff, J.W Niemantsverdriet ‘ Concept of
Modern Catalysis and Kinetics’
(iii)
R.A Sheldon, Arends, U. Hanefeld ‘ Green
Chemistry and Catalysis’
(iv)
M.A. Vennices ‘ Kinetics of catalytic reactions’
(v) Froment and Bischoff : Reactor design
Nauman : Reactor design
9. Suggested/Additional

(i)
B.W. Wojciechowski and N.M. Rice ‘ Experimental Methods
in Kinetic studies’
(ii)
J,. Regalbuto ‘ Catalyst Preparation: Sciernce and
engineering’
(iii)
B. Cornils, W.A. Herrmann, R. Schlogl, C.H. Wong Catalysis
from A to Z.
3
(iv)
Published articles from journals
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 .
-Key to Chemical Transformation in all Industrially
benign processes .(> 90% process)

4
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.

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 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.

“A catalyst accelerates a chemical reaction without

affecting the position of the equilibrium.”

6
Concept of GREEN CATALYSIS

1. Low cost and scalable

2. Renewable starting materials

3. Environmentally‐friendly operation

4. Specialty Chemicals

5. Non‐toxic by‐products

7
 What is a catalyst ??
• Alters the rate of reaction with high selective
• Does it participate in the reaction ??
• How does it change the rate ? – Offers an
alternate path with low E.
• Does it affect HR, GR, and Eq. constant ??
• Does it affect yield & selectivity ??
• Does it initiate a reaction ??

8
WHAT DOES A CATALYST LOOK LIKE

9
10
11
 Action of Catalysts
• 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)
– Reactions proceed under less demanding conditions
• Allow reactions occur under a milder conditions, e.g. at
lower temperatures for those heat sensitive materials
• It is important to remember that the use of catalyst
DOES NOT vary DG & Keq values of the reaction
concerned, it merely change the PACE of the process.

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o 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 dG & Keq, NOT by the presence of
catalysts.
o The reaction thermodynamics provide the driving
force for a rxn; the presence of catalysts changes
the way how driving force acts on that process.

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e.g CH4(g) + CO2(g) = 2CO(g) + 2H2(g)
DG°373=151 kJ/mol (100 °C) & DG°973
=-16 kJ/mol (700 °C)
=>At 100°C, DG°373=151 kJ/mol > 0. There is no
thermodynamic driving force, the reaction won’t
proceed with or without a catalyst

14
 =>At 700°C, DG°373= -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%).

15
 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.

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 ACTIVITY MEASURE FOR CATALYST:
For comparative measurements, such as catalyst screening,
determination of process para-meters, optimization of
catalyst production conditions, and deactivation studies

– Conversion under constant reaction conditions

– Space velocity for a given, constant conversion
– Space–time yield
– Temperature required for a given conversion

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Often the performance of a reactor is given relative to the catalyst mass or volume,
so that reactors of different size or construction can be compared with one another.
This quantity is known as the space–time yield STY

STY= Desired product quantity/ Catalyst vol. time

Comparison of catalyst activities 18

 Mode of Action of Catalysts

The suitability of a catalyst for an industrial process depends

mainly on the following
three properties:

– Activity
– Selectivity
– Stability (deactivation behavior)
The question which of these functions is the most important is generally difficult to
answer because the demands made on the catalyst are different for each process.

Activity
Activity is a measure of how fast one or more reactions proceed
in the presence of the catalyst. Activity can be defined in terms
of kinetics or from a more practically oriented viewpoint.
In a formal kinetic treatment, it is appropriate to measure
reaction rates in the temperature and concentration ranges that 19
 Why R& D in catalysis is important
• 90 % of chemical industry involve products made
using catalysts (food, fuels, polymers, textiles,
pharma/ agrochemicals,etc)

• For discovery/use of alternate sources of energy/fuels/

raw material for chemical industry.

• For Pollution control-Global warming.

• For preparation of new materials (organic & inorganic-

eg: Carbon Nanotubes).
 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

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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

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 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…

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 SOLID-GAS SOLID-LIQUID
Homo-hetero catalysis INTERFACES
Nanocatalysis

Solid acid Novel Dynamic Transient in situ

catalysts catalysts restructuring kinetics

In situ
Chemical
Heterogeneous techniques
engineering
Homogeneous
Surface science
Material science ACTIVATION
Molecular Techniques REGENERATION
modeling & modelling

Selective
Theory &
catalysts
modelling
DESIGN
Reaction CONTROL
Field Bio
kinetics assisted processes

ENANTIOSELECTIVE
Laser induced
catalysis
FINE AND SPECIALITY
CHEMICALS BIOMIMITIC
CATALYSIS
ELECTROCATALYSIS

Biosensors
BIOSENSORS
PHOTOCATALYSIS
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The picture of green catalysis

Practical approaches Operational tools

Green
Catalysis
chemistry

Strategic goal Green Waste

engineering management
Sustainable
development
Industrial Process
ecology intensification

Renewable
energy Monitoring tools
Life-cycle
assessment

E-factor,
atom economy
The drivers of green chemistry

Economic benefit
Lower Lower
capital investment operating costs

Societal pressure Government legislation

Improved Less
public image hazardous materials

Safer
and smaller plants
Green chemistry High fines for waste

Producer
Pollution control
responsibility
Concept of Green catalysis
Technology is called “Green” if it uses raw
materials efficiently, such that the use of toxic and
hazardous reagents and solvents can be avoided
while formation of waste or undesirable by-products
is minimized.
E factor:
• Mass balances of alternative routes in chemical processing

can be compared using measures E factor and mass index.

The E factor :Ratio of Waste [kg] to Product[kg]), is an

output orientated indicator, whereas the Mass index

(Ratio of all Raw materials [kg] to the Product [kg]) is an

input oriented indicator.

• There is a substantial increase in E factors on going
downstream from bulk chemicals (<1–5) to fine
chemicals (5 – >50) and specialties (25 – >100). 28
 Basic concept of green catalysis
1. Sheldon has introduced several indicators to
measure the efficiency and environmental impact of
a reaction.
Atom Efficiency: is the molecular weight of the desired
product divided by the total molecular weight of All
Products.
For example the conventional oxidation of a secondary
alcohol
3C6H5–CHOH–CH3 + 2Cr2O3 + 3H2SO4
3C6H5–CO–CH3 + Cr2(SO4)3 + 6H2O
120 396
Atom efficiency of 360/860 = 42%.
C6H5–CHOH–CH3 + 1/2O2 C6H5–CO–CH3 + H2O has

Atom efficiency of 120/138 = 87%, with water as the only byproduct.

Concept of Atom efficiency & E -Factor
The molecular weight of
the desired product
Atom efficiency =
The total weight of all
products
Turnover Frequency TOF
The turnover frequency TOF quantifies the specific
activity of a catalytic center for a special reaction
under defined reaction conditions by the number of
molecular reactions or catalytic cycles occurring at the
center per unit time.
For heterogeneous catalysts the number of active centers is
derived usually from sorption methods.
For most relevant industrial applications the TOF is in the range
10>>–2 to 10>>2 s–1 (enzymes 10>>3–10>>7 s–1).

TOF (time -1) = volumetric rate of reaction/number of

centers /volume
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Turnover Number TON

The turnover number specifies the maximum use that can be made of a catalyst
for a special reaction under defined conditions by a number of molecular
reactions or reaction cycles occurring at the reactive center up to the decay of
activity.
The relationship between TOF and TON , TON = TOF [time–1] . lifetime of the catalyst
[time]

For industrial applications the TON is in the range 10>>6 to 10>>7.

Selectivity
The selectivity Sp of a reaction is the fraction of the starting material that is converted
to the desired product P. It is expressed by the ratio of the amount of desired product to
the reacted quantity of a reaction A . In addition to the desired reaction, parallel and
sequential reactions can also occur

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Stability
•The chemical, thermal, and mechanical stability of a catalyst determines its
lifetime in industrial reactors.
•Catalyst stability is influenced by : decomposition, coking, and poisoning.
Catalyst deactivation can be followed by measuring activity or selectivity as a
function of time.
•Catalysts that lose activity during a process can often be regenerated before
they ultimately have to be replaced. The total catalyst lifetime is of crucial
importance for the economics of a process.
•Today the efficient use of raw materials and energy is of major importance,
and it is preferable to optimize existing processes than to develop new ones.
For various reasons, the target quantities should be given the following order
of priority:
Selectivity >Stability> Activity
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 Catalysis is multidisciplinary
( physics, chemistry & chem. Engg. )

• The catalyst is an inorganic solid; Catalysis is a

surface phenomenon; solid state and surface
structures play important roles.

• Adsorption, desorption and reaction are subject to

thermodynamic, transport and kinetic controls (chem
engg);

• Adsorbate-substrate and adsorbate - adsorbate interactions

are both electrostatic and chemical (physical chemistry).

• The chemical reaction is organic chemistry. 34

 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

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 • Inorganic (gases, metals, metal oxides,
inorganic acids, bases etc.)
• Organic (organic acids, enzymes etc.)
• The types of catalysts
– 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)

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Classification of Catalysts

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