Introduction to Catalysis

Catalyst
A substance that alters the reaction rate of a particular chemical reaction is
called a catalyst.
Chemically unchanged at the end of the reaction.
Positive Catalyst (catalyst): Increases the rate of reaction
Negative Catalyst (Inhibitors): Decreases the rate of reaction
How does a catalyst change rate of reaction???
By providing alternative pathway or mechanism to lower/higher activation energy

k(T) = k0e-Ea/RT
Ea < Ea
k0 > k0
k > k

Ea

Ea

G = G
A+B

A+B+
catalyst

G
C

uncatalyzed

G
C + catalyst

catalyzed
2

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)

Three Scales of Knowledge Application

Types of Catalysts
(1) Homogeneous Catalysts
(2) Heterogeneous Catalysts
(3) Auto-Catalysts
(1) Homogeneous Catalysts:
Catalyst with the same phase as reactants.
Usually in aqueous phase or gaseous phase.
Ex: Oxidation of I- with S2O82- with Fe3+ ion as a catalyst
2I- + S2O82- ==> I2 + 2SO42-----------------------------------------2I- + 2Fe3+ ==> 2Fe2+ + I2
2Fe2+ + S2O82- ==> 2Fe3+ + 2SO42-

(2) Heterogeneous Catalysts

Catalyst with different phase as reactants.
Usually Catalyst in solid form and reactants in aqueous or gaseous form.
Ex: SRM, POX , CDM, Hydrogenation of ethane (Ni as catalyst), CNT

CNT

Hydrogenation of ethane

(3) Auto-Catalysts
The product in the reaction acts as a catalyst of the reaction.
This product is called auto-catalyst.
Ex: 2MnO4- + 16H+ + 5C2O42-==> 2Mn2+ + 8H2O + 10CO2

Applications of catalysts:
(1) Chemical Industries
(2) Catalytic converters in automobile exhaust
(3) Biological catalysts as enzymes (fermentation, baking)

(2) Catalytic converters in automobile exhaust

Heterogeneous Catalytic Reactors

Packed Bed
(single or multi-tube)

Fluidized
Bed

Slurry
Reactor

Design goals

rapid and intimate contact be

tween catalyst and reactants
ease of separation of product
s from catalyst

Catalyst
Recycle
Reactor

Rates of Catalytic Reactions

Pseudo-homogeneous reaction rate

Mass-based rate

r = moles / masscat time

r = r / cat

Heterogeneous reactions happen at surfaces

Area-based rate

r = moles / volume time

r = moles / areacat time

r = r / SA,

SA = area / mass

Heterogeneous reactions happen at active sites

Active site-based rate

Turn-over frequency TOF = moles / site time

TOF = r / site

TOF (s1)

Hetero. cats. ~101

Enzymes ~106

Adsorption and Reaction at Solid Surfaces

Physisorption: weak van der Waals attraction of

a fluid (like N2 gas) for any surface

Eads ~10 40 kJ/mol

Low temperature phenomenon
Exploited in measuring gross surface area

Chemisorption: chemical bond formation

between a fluid molecule (like CO or ethylene)
and a surface site

Eads ~ 100 500 kJ/mol

Essential element of catalytic activity
Exploited in measuring catalytically active sites

Measuring Concentrations in Heterogeneous

Reactions Kinetics

Fluid concentrations

Traditionally reported as pressures (torr, atm, bar)

Surface concentrations

Coverage per unit area

Maximum coverage called monolayer

nj = molesj / area

Metal particle surface

1 ML: nj,max = ~ 1015 molecules / cm2

Fractional coverage

j = nj / nj,max
0 j 1

j = 1/6

Catalysts Characterization
Characteristics

Methods

Surface area, pore volume &

size

N2 Adsorption-Desorption Surface area

analyzer (BET and Langmuir)

Pore size distribution

BJH (Barret, Joyner and Halenda)

Elemental composition of
catalysts

Metal Trace Analyzer / Atomic

Absorption Spectroscopy

Phases present & Crystallinity

X-ray Powder Diffraction

TG-DTA (for precursors)

Morphology

Scanning Electron Microscopy

Catalyst reducibility

Temperature Programmed Reduction

Dispersion, SA and particle

size of active metal

CO Chemisorption, TEM

Acidic/Basic site strength

NH3-TPD, CO2 TPD

Surface & Bulk Composition

XPS

Coke measurement

Thermo Gravimetric Analysis, TPO

Catalyst Activity Testing

Activity to be expressed as:

- Rate constants from kinetics
- Rates/weight
- Rates/volume
- Conversions at constant P,T and SV.
- Temp required for a given conversion at
constant partial & total pressures
- Space velocity required for a given conversion
at constant pressure and temp

Flowsheet
Synthesis

2D & 3D C
AD Solids Micro-scale
Modeling
Design Modules
Multiscale Tran
sport

Process
Engineering
Control
Systems

Flow
Patterns

Simulation &
Optimization

Tools, Fabrication
& Assembly
Micro-process
Components

Materials of
Construction
Micro Systems
Engineering

Component Integr
ation
Multi-scale Transp
ort

Micro Process Plant

Integrated
Sensors

Raw Materials &

Feedstocks
Chemistry &
Catalysis
Reaction
Kinetics

Catalyst
Characterization
Reaction Pathways &
Mechanisms

Sampling
Sensors

Micro Analyzers
(GC, LC, MS, TOF)
Micro Process
Analytical

Data handling & Micro PAT Systems

Chemometrics Integration

Heterogeneous Reactions

The complications of rate equations:

More than one phase is present: Movement of material from phase to phase
For rate expression: Apart form chemical kinetics term mass transfer is
also incorporated

To get the overall rate expression, write the individual steps on the same basis
In terms of Volume
(Or)
In terms of Weight
(Or)
In terms of Surface

17

Rearrange the mass transfer and reaction steps into same rate form

(Or)

If the steps are in series,

If the steps are in parallel,

18

Complications :
Consider reaction steps in series:
If all the steps are linear in concentration then it is easy to combine them.
If any of the steps is non-linear in concentration then it will be difficult to
get a overall rate expression.
In such cases, approximate the rate equation (vs.) concentration curve by a
first-order expression.
It is hard to know the concentration of materials at intermediate steps.
So, these concentrations are eliminated during combining the rates.

19

Overall reaction rate for a linear process:

Dilute A diffuses through a stagnant liquid film onto a plane
surface consisting of B, reacts to produce R which diffuses back
into the mainstream.
Develop the overall rate expression for this first order L/S
reaction.
A (l) + B(s) R(l)

20

By diffusion, the flux of A to the surface is,

(1)
Since this reaction is first-order w.r.t A, based on unit surface,
(2)
At steady state, the flow rate to the surface is equal to the reaction at
surface (steps in series)

21

from which the intermediate (CAs )can be determined as,

(3)
Replacing eq. (3) into either eq. (1) or eq. (2), gives

22

Contacting patterns for two-phase systems

Ideal contacting patterns for two flowing fluids

23

Pore diffusion resistance combined with

surface kinetics

Consider a single cylindrical pore of length (L),

with reactant A diffusing into the pore, and
reacting on the surface by a 1st order reaction.
The reaction is taking place at the walls of the
pore and the product is diffusing out of the
pore.

Representation of a single
cylindrical pore

24

Now, check with flow of materials into and out of any section
of the pore can be shown as:

25

At study state a material balance for reactant A for this elementary section :
Output Input + Disappearance by reaction = 0
By Substituting the output, input and disappearance by reaction terms
we get:

For our convenience divide the above equation by (-r2 D (x))

26

Now apply limit as x approaches Zero the obtained equation changes to:

The 1st order chemical reaction is expressed in terms of unit surface area
of the wall of the catalyst pore
Therefore, K will have the unit of length per time
In general the interrelation b/w rate constants on different basis is given by:

Hence for cylindrical catalyst pore:

27

Thus in terms of volumetric units the final equation takes the form:

The above eq. is a linear differential eq. whose general solution is:

Where,
M1 & M2 are constants and
we need two boundary conditions
to evaluate them.
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First boundary condition (x=0), (Pore entrance)

Second boundary condition (x=L), (Pore exit)

According to the given model,
there is no pore exit and there is no flux or movement of the material
through the interior end of pore.

With the appropriate mathematical manipulations of CA and boundary

Conditions:

29

Hence the concentration of reactant (CA/CAs) with in the pore is :

There is a progressive drop in concentration on moving into the pore.

And this dependent on the dimensionless quantity mL (or) MT called
as Thiele modulus.

Effectiveness factor () is introduced to measure how much the

reaction rate is decreased because of the resistance to pore diffusion.

30

Distribution and Avg. value of reactant concentration within a catalyst

pore as a function of the parameter mL = L (k/D)

31

The effectiveness factor (Vs)Thiele Modulus

For small mL (<0.4), ~ 1,

the conc. Of the reactant does not

drop within the pore pore diffusion offers
negligible resistance

For large mL (> 4), ~ 1/mL,

the conc. Of the reactant drops rapidly

within the pore pore diffusion

Strongly influences the reaction rate.

(Strong pore resistance)

This graph can easily show the effectiveness Pore diffusion on modification
of the rate of reaction and it depends on whether mL is large or small
32

Porous Catalyst Particles

Main steps involved in heterogeneous catalytic reactions

1. Transport of the reactants from the bulk of a mixture to a catalyst particle

2. Transport of the reactants in the pores of the catalyst particles to an active site
3. Adsorption of the reactants to the active site
4. Reaction of reactants to form an adsorbed product
5. Desorption of the product from the active site
6. Transport of the products in the pores of the catalytic particle out of the particle
7. Transport of the products from the particle to the bulk of the mixture
33

The results of a single pore can approximate the behavior of particles of

various shapes (spheres, cylinders, flat plates etc.) for these systems,
1. Use of proper diffusion coefficient
Replace the molecular diffusion coefficient D by the effective diffusion
coefficient of the fluid in the porous structure.
2. Proper measure of particle size
To find the effective distance penetrated by the gas to get all the interior
surfaces we should define a characteristic size of particle.

34

3. Measures of reaction rates

The rate of reaction can be expressed in many equivalent ways.

35

4. Finding pore resistance effects from experiment

Define a modulus which only includes observable and measurable quantities.
This is known as Wagner-Weisz-Wheeler Modulus (Wagner Modulus).

5. Pore resistance limits

MT < 0.4 or MW < 1.15

MT > 4 or M W> 4

Reactant fully penetrates the particle and

reaches all its surface.
Then the particle is in the diffusion free regime.
Center of the particle is starved for reactant and
is unused.
Then the particle is in strong pore resistance
regime.
36

Shows the limits for negligible and for strong pore diffusion resistances
7. Particles of different sizes
Comparing the behavior of two particle sizes R1 and R2, we find,
Diffusion free regime
Strong diffusion resistance
37

Heat effects during the reaction

Non-Isothermal Effects
When the reaction is so fast that the heat released (or absorbed) in the
pellet cannot be removed rapidly to keep the pellet close to the
temperature of the fluid, then the non-isothermal effects intrude.
Two different kinds of temperature effects may be encountered:
1. Within- particle T

2. Film T

Temperature variation within the pellet

The pellet may be hotter (or colder)
than the surrounding fluid.
38

Exothermic reactions
Heat is released and particles are hotter than the surrounding fluid.
Therefore the non-isothermal rate > isothermal rate as measured by bulk
conditions.
Endothermic reactions
Heat is absorbed and particles are colder than the surrounding fluid.
non-isothermal rate < isothermal rate
If the harmful effects of thermal shock, or sintering of the catalyst
Particles, or drop in selectivity do not occur than one can
encourage exothermic reaction.

39

Non-isothermal effectiveness factor curve for temp. variation

with in the particle
40

The differential form of Eq. (1) is,

(2)
Integrating over the whole reactor gives,
(3)

Weight-time and volume-time terms,

41

Performance equations for reactors containing

Porous catalyst particles
For Plug Flow

Elementary slice of solid catalyzed plug flow reactor

At steady state a material balance for reactant A gives,
Input = output + accumulation
(1)
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For First-order catalytic reactions,

Plug flow reactor
Mixed flow reactor

CAin = CAo and A 0 ( first order reactions)

43

Experimental Methods for finding rates

The experimental strategy in studying catalytic kinetics usually measuring
the extent of conversion of gas passing in steady flow through a batch of
Solids.
Any flow pattern can be used, as long as the pattern selected is known.
If it is not known then the kinetics cannot be found.
We will discuss on the following experimental devices.
1.
2.
3.
4.

Differential flow reactor

Integral (plug flow) reactor
Mixed flow reactor
Batch reactor for both gas and solid

44

1. Differential (flow) reactor

If we choose to consider the reaction rate to be constant at all points
within the reactor then we can have a differential reactor.
Since reaction rates are concentration-dependent this assumption is usually
reasonable for small conversions or for small reactors.
For each run in a differential reactor the plug flow performance equation
becomes:

Thus each run gives directly a value for rate at avg. conc., a series of runs
gives a set of rate-conc. Data.
45

2. Integral (plug flow) reactor

If the variations in the reaction rate within a reactor is so large then to
account such variations in the method of analysis, then we have an integral
Reactor.
Since the reaction rates are conc. dependent, such large variations in rate
may be expected to occur when the composition of the reactant fluid
changes significantly in passing through the reactor.
We may follow two procedures in searching for a rate equation.
Integral analysis

Differential analysis

46

3. Mixed Flow Reactor

A mixed flow reactor requires a
uniform composition of fluid through out.
For a mixed flow reactor the performance
Equation is given by:

Carberry basket-type experimental mixed

flow reactor

47

Recycle reactor

4. Batch reactor

In this system,
we follow the changing composition
with time & Interpret the results
with batch reactor performance.
When the recycle is large enough
mixed flow is approximated
A recycle reactor without through
Flow becomes a batch reactor.
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The Packed Bed Catalytic Reactors

CATALYST DEACTIVATION DIAGRAM
Pd Sites
Vent
Flow
Controller
Pre-heater

Al2O3

Reactor
Gas
Chromatograp
h

A
Fresh Catalyst (high dispersion; high surface area)

Pore cintering
Cintered Pd

Integrator
He
O2

He

CH4

Al2O3

R.P.
T

Temperature
Controller

EXPERIMENT SETUP

-Al2O3

B
Old Catalyst
Low dispersion (low activity)

C
Old catalyst
Low surface area (low activity)

49

The reactant gas can be made to contact solid catalyst in many ways, and
each has its specific advantages and disadvantages.
Reactors cab be divided into two broad types.
1. Fixed Bed Reactor
2. Fluidized Bed Reactor

Fixed Bed Reactors

50

Fluidized Bed Reactors

Moving-Bed Reactor is an intermediate case which incorporates some of
the advantages and disadvantages of fixed-bed and fluidized-bed reactors
51

Merits and demerits of fixed bed and fluidized bed reactors

Characteristic
Feature
1. Gas Flow

Fixed-Bed Reactor

Fluidized-Bed Reactor

Plug Flow ()

Complex Flow &

by passing (X)
High Catalyst content (X)

Efficient contact ()

Fixed bed favored ()

2. Temperature
control

Large Fixed beds (X) (low cond.)

Exothermic Rxn. (X) (Hot Spot)

Good Control of Temp.

Explosive nature of Rxn.
can also performed

3. Particle Size
(small)

Plugging & High-Pressure drop (X) Effective use of catalyst

Pore and diffusion rxn.
high

4. Catalyst
Regeneration

Regeneration is difficult(X)

Liquid-like fluidized state

Can be pumped easily

52

The two main difficulties in catalytic reactor design

1. How to overcome non-isothermal behavior in packed beds.
2. How to overcome non-ideal flow of gas in fluidized beds.

Moving-Bed Reactor
53

The temperature field in a packed bed reactor for an

exothermic reaction creates a radial movement of heat and matter
The stage adiabatic packed bed reactor presents different situation.
(Since no heat transfer in the zone of reaction. The temperature and
conversions are related in much simple way.
54

Staged Adiabatic Packed Bed Reactors

With proper interchange of heat and proper gas flow,

staged adiabatic packed bed reactors became
versatile system
Staged Packed Beds (Plug flow) with intercooling
Staged Mixed Flow Reactors
Cold Shot Cooling

55

Staged Packed Beds (Plug flow) with intercooling

Sketch showing how staged packed beds can closely approach the
optimal temperature
Optimization of operations reduces to minimize the total amount
of catalyst needed to achieve a given conversion.
56

Reversible Exothermic Reactions

Three variables to optimize the amount of catalyst

1. Incoming Temp. (Ta)
2. Amount of catalyst used in 1st stage ( b along with the adiabatic)
3. Amount of intercooling (c along the bc line)

57

How to find exact (Ta)

1.Guess (Ta)
2. Move along the adiabatic line until the
following condition is satisfied.

This gives point b (amount of catalyst needed and outlet temperature

from that stage
3. Cool to point c which has same rate as b:
Rxn rate leaving the reactor = Rxn rate entering next reactor (or stage)
4. Moving along the adiabatic from point c to d until point 2 is satisfied (d).
5. If point d is the desired final conversion then our Guess is correct.
58

Staged Mixed Flow Reactors

Staged Packed bed with recycle

Choose the distribution of the catalyst

So as to maximize the KLMN area which
Then Minimizes the shaded area

59