CRE II: Heterogeneous Catalytic

Reaction
L1/2
Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
[email protected]
2

CRE-II 3 1 0
Prerequisite CHL-122
Course Outline


Introduction to Catalysis, Classification, Catalyst preparation,
evaluation of Catalyst properties. 5

Physical and Chemical adsorption, Different types of
adsorption isotherms, determination of surface area and pore
volume of the Catalyst 6

Kinetics of solid catalyzed gas phase reaction, Reaction
mechanism, Laboratory reactors for catalytic gas solid
reactions. 8-9

Mass transfer, Diffusion and Chemical reactions in catalysts.
Effects of external mass transfer and heat transfer,
Effectiveness factors. 8-9
3
Course outline , contd..
Fixed bed catalytic reactors, reactor models, concept of
heterogeneous models. 4

Non-catalytic gas-solid reactions, different model for gas-solid
reaction, 4

Gas liquid reactions, film and penetration theories, enhance
factor in gas-liquid reactions, Concept of Reactor Design 4

Reactor systems for gas-liquid reactions. Laboratory / design
activity (time permitting). 2-3

Grading: QUIZ : 10 (ONE ONLY), TERM Paper 4, Assignments/
Tut. : 2+4, Minors 2( 40), Major (40)
NO MAKE UP EXAMS, One grade will be lowered for attendance
below 65%. Pass grade 30 Marks, Relative grading.
Use of mobile in L/T class is Strictly Prohibited

4
Books:
Fogler H.S, Elements of chemical reaction engineering IV
th
Ed .
( Text Book: MUST be BRING during TUTORIAL SESSIONs)
Smith J.M., Chemical engineering kinetics, Mcgraw Hill,
Chemical Rexn Engg :beyond fundamentals by Doraiswamy
Carberry, J Chemical and catalytic reaction engineering Mcgraw
Hill
Froment G.F & Bischoff K.B., Chemical reactor analysis and
design John Wiley
C.G. Hill, An Introduction to Chemical Engineering Kinetics and
Reactor Design
Levensipiel : Chemical Rexn Engg.
5
What is a catalyst ??
Alters the rate of reaction with high selectivity
Does it participate in the reaction ?
How does it change the rate ? Offers an
alternate path with low E.
Does it affect H
R
, G
R
, and Eq. constant ?
Does it affect yield & selectivity ?
Does it initiate a reaction ?
https://groups.google.com/forum/#!forum/chl221-
sem1-2014-15
6
-What is a Catalyst ?
Allow reactions to 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 G & K
eq
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 & K
eq
, NOT by the
presence of catalysts.
The reaction thermodynamics provide the driving
force for a Rxn; the presence of catalysts changes
the way how driving force acts on that process.
Criterion for Chemical reaction equilibrium for species i,

ki

i
= 0, k= 1,2,3...r (reactions) Gibbs free energy
change for each rexn ( G)=
i
i =0

7
e.g CH
4
(g) + CO
2
(g) = 2CO(g) + 2H
2
(g)
G
373
=151 kJ/mol (100 C) & G
973

= -16 kJ/mol (700 C)
=>At 100C, G
373
=151 kJ/mol > 0.
=> There is no thermodynamic driving force,
and the reaction wont proceed with or without
a catalyst

8

At 700C, G
973
= -16 kJ/mol < 0. The
thermodynamic driving force is there. However,
simply putting CH
4
and CO
2
together in a reactor
does not mean they will react.
Without a proper catalyst heating the mixture in reactor
results no conversion of CH
4
and CO
2
at all. When
Pt/ZrO
2
or Ni/Al
2
O
3
is present in the reactor at the
same temperature, equilibrium conversion can be
achieved (<100%).
9

Assignment /Tut. 1 Due date: July 29
th


1. Give the Thermodynamic criteria for a Chemical Reaction.
2. Write down an Algorithm for calculation of product
composition in a multiple reaction from Thermodynamic
analysis (case study: Steam reforming of Ethanol
(PRODUCTS: CH
4
, CO, CO
2
, and H
2
, T= 500-800 C). State
other conditions used.
3. Different types of Reactors used in Chemical Process
Industries.
4. Reactor design equations for Batch , CSTR and plug flow
reactor and their applications in process industries.






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1. Low cost and scalable
2. Renewable starting materials
3. Environmentallyfriendly operation
4. Specialty Chemicals
5. Nontoxic byproducts

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GREEN CATALYSIS
Basic concept of green catalysis

1. 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.
Concept of Atom efficiency & E -Factor
Atom efficiency =
The molecular weight of the
desired product
The total weight of all
products.
E- Factor : Another useful indicator of
environmental acceptability is the E factor-
the weight of waste or undesirable by
product by the Weight of the desired product.
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,
Mass index (Ratio of all Raw materials [kg] to
the Product [kg]) is an input oriented indicator.
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E factor:
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For example the conventional oxidation of
a secondary alcohol
3C
6
H
5
CHOHCH
3
+ 2Cr
2
O
3
+ 3H
2
SO
4
3C
6
H
5
COCH
3
+ Cr
2
(SO
4
)
3
+ 6H
2
O
396 360

Atom efficiency of 360/864 =~ 42%.
C
6
H
5
CHOHCH
3
+ 1/2O
2

C
6
H
5
COCH
3
+ H
2
O
Atom efficiency of 120/138 = 87%, with water as the
only by product in alternate process.
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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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A catalyst accelerates a chemical reaction
without affecting the position of the equilibrium.

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.
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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20
Schematic representation of the energetic in a catalytic cycle. The uncatalyzed
reaction(a)has a higher Gibbs energy of activation G than any step in the
catalyzed reaction (b)The Gibbs energy of reaction rG

for the overall
reaction is unchanged from (a) to (b).
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)
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Action of Catalysts
22
-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 G & K
eq
values of the
reaction concerned, it merely change the PACE
of the process.


Comparison of Catalysts:

For comparative measurements, such as catalyst
screening, determination of process para-meters,
optimization of catalyst production conditions, and
deactivation studies, the following activity measures
can be used:

Conversion under constant reaction
conditions
Space velocity for a given, constant
conversion
Spacetime yield
Temperature required for a given
conversion

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Comparison of catalyst activities
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Turnover frequencies, Rates and
numbers
CATALYSIS IS A KINETIC PHENOMENON
Sequence of elementary steps at steady state:
diffusion (bulk, film, surface) - adsorption-reaction-
desorption- diffusion
TOF= number of product molecules formed per unit
area per sec(molecules.cm
-2
.sec
-1
)
TOF= number of product molecules formed per active
site per sec(molecules.sec
-1
) only if active site is
known.
TOT= 1/TOF = turnover time, time necessary
to form a product molecule(sec);
TOR = Turnover rate = TOF X Surface area
TON= TOF X total reaction time;

TON must be >100 to be industrially useful.

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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.

Mode of Action of Catalysts
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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.

In a kinetic treatment, reaction rates are measured
in the temperature and concentration ranges that
will be present in the reactor.
Rate = k(T) f(C)

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Every catalytic reaction is a sequence of
elementary steps, in which reactant molecules
bind to the catalyst, where they react, after which
the product detaches from the catalyst, liberating
the latter for the next cycle.
Steps of Catalytic Reactions
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Potential energy diagram of a heterogeneous catalytic
reaction
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Conversions, Rates and Rate
constants
Conversion = % Reactant converted;
Reaction rate = k
p
X f(P
i
) or k
c
X f(C
i
)
k = A exp(-E
#
/RT); A is temp independent.
TOFs between 0.0001 and 100 in industry; Temp
adjusted to get the desired rates.
E
#
~ 35-45 Kcal/mol for isom, cyclisation,
cracking, dehydo / hydrogenolysis; HighT needed.
E
#
~ 6-12 Kcal/mol for hydrogenation;
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Chemical Kinetics
Collision Theory
Collisions between reacting molecules are
necessary before a reaction can occur.
Only those collisions having sufficient energy are
effective in bringing about a reaction activation
energy.
Colliding molecules must be properly oriented
with respect to one another for the reaction to take
place.
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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.




np
np vA
vp
Sp= = mol/mol or %
nA,o- nA
nA,o- nA vp
vA
Selectivity
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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.

36
Presently the efficient use of raw materials and
energy is of major importance, and it is prefer-
able 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 in the Chemical Industry
Hydrogen Industry (coal, NH
3
, methanol, FT,
hydrogenations / HDT, fuel cell).
Natural gas processing (SR,ATR,WGS,POX)
Petroleum refining (FCC, Hydrotreating,
Hydrocracking, Reforming, Alkylation etc.
etc.)
Petrochemicals(monomers, bulk chemicals).
Fine Chem.(pharma, agrochem, fragrance,
textile, coating, surfactants,laundry etc)
Environmental Catalysis (auto exhaust,
deNOx, )

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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.)
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
43
Comparison between Homogeneous
and heterogeneous catalysts