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CATALYSTS

Catalysts
Most processes are catalyzed where catalysts for the reaction
are known.
The choice of catalyst is crucially important.
Catalysts increase the rate of reaction but are ideally unchanged
in quantity and chemical composition at the end of the reaction.
If the catalyst is used to accelerate a reversible reaction, it does
not by itself alter the position of the equilibrium.
However, it should be noted if a porous solid catalyst is used,
then different rates of diffusion of different species within a
catalyst influence the equilibrium indirectly.

Catalysts
When systems of multiple reactions are involved, the
catalyst may have different effects on the rates of the
different reactions.
This allows catalysts to be developed that increase the rate
of the desired reactions relative to the undesired reactions.
Hence the choice of catalyst can have a major influence on
selectivity.
The catalytic process can be homogeneous, heterogeneous
or biochemical.

Catalysts
In general, heterogeneous catalysts are
preferred to homogeneous catalysts.
Because the separation and recycling of
homogeneous catalysts often can be very
difficult.
Loss of homogeneous catalyst not only creates
a direct expense through loss of material but
also creates an environmental problem.

Solid Catalysts
The solid catalyst can be either of the following.
Bulk catalytic materials, in which the gross
composition does not change significantly
through the material, such as platinum wire
mesh.
Supported catalysts, in which the active
catalytic material is dispersed over the surface
of a porous solid.

Solid Catalysts
The overall rate of a heterogeneous gassolid reaction on a
supported catalyst is made up of a series of physical steps
as well as the chemical reaction. The steps are:
Mass transfer of reactant from the bulk gas phase to the
external solid surface.
Diffusion from the solid surface to the internal active sites.
Adsorption on solid surface.
Activation of the adsorbed reactants.
Chemical reaction.
Desorption of products.
Internal diffusion of products to the external solid surface.
Mass transfer to the bulk gas phase.

Solid Catalysts
Generally, the solid catalyzed reactions
performance is analyzed by the
effectiveness factor.
Higher the effectiveness factor, the higher
the rate of reaction.
The effectiveness factor depends
size and shape of the catalyst pellet
Distribution of active material within the pellet

Catalysts
Heterogeneous catalysts can thus have a major
influence on selectivity.
Changing the catalyst can change the relative
influence on the primary and by product
reactions.
This might result directly from the reaction
mechanisms at the active sites or the relative
rates of diffusion in the support material or a
combination of both.

BIOCHEMICAL CATALYSTS
Enzymes Enormous rate
enhancement can be achieved than
micro organisms.
Disadvantage: (1)Use of isolated
enzyme is more expensive
(2)removal of enzyme from the
product requires an expensive
separation
These difficulties are overcome by;
1. Adsorption
2. Covalent bonding

TEMPERATURE CONTROL
In the first instance, adiabatic operation of the
reactor should be considered since this leads
to the simplest and cheapest reactor design.
If adiabatic operation produces
an unacceptable rise in temperature for
exothermic reactions (or)
an unacceptable fall in temperature for
endothermic reactions,
this can be dealt with in a number of ways:

Cold shot and hot shot


The injection of cold fresh feed directly into the
reactor at intermediate points, known as cold shot.
This can be extremely effective for control of
temperature in exothermic reactions. This not only
controls
The temperature by direct contact heat transfer
through mixing with cold material but also controls
the rate of reaction by controlling the
concentration of feed material.

Cold shot and hot shot


If the reaction is endothermic, then
fresh feed that has been preheated
can be injected at intermediate
points, known as hot shot.
Again the temperature control is
through a combination of direct
contact heat transfer and control of
the concentration.

Indirect heat transfer with the


reactor
Indirect heating or cooling can also be considered.
This might be by a heat transfer surface inside
the reactor, such as carrying out the reaction
inside a tube and providing a heating or cooling
medium outside of the tube.
Alternatively, material could be taken outside of
the reactor at an intermediate point to a heat
transfer device to provide the heating or cooling
and then returned to the reactor.

Heat carrier
An inert material can be introduced with the reactor feed to
increase its heat capacity flowrate (i.e. the product of mass
flowrate and specific heat capacity)
To reduce the temperature rise for exothermic reactions or
reduce temperature fall for endothermic reactions.
Where possible, one of the existing process fluids should be
used as heat carrier.
For example, an excess of feed material could be used to
limit the temperature change, effectively decreasing the
conversion, but for temperature control purposes.

Heat carrier
Product or by product could be recycled to
the reactor to limit the temperature change.
But care must be taken to ensure that this
does not have a detrimental effect on the
selectivity or reactor yield.
Alternatively, an extraneous inert material
such as steam can be used to limit the
temperature rise or fall.

Direct heat transfer-Reasons


In fact, cooling of the reactor effluent by direct heat
transfer can be used for a variety of reasons:
The reaction is very rapid and must be stopped quickly to
prevent excessive byproduct formation.
The reactor products are so hot or corrosive that if passed
directly to a heat exchanger, special materials of
construction or an expensive mechanical design would be
required.
The reactor product cooling would cause excessive fouling
in a conventional exchanger.

Direct Heat Transfer


The liquid used for the direct heat transfer should be
chosen such that it can be separated easily from the
reactor product and hence recycled with the
minimum expense.
Use of extraneous materials, that is, materials that do
not already exist in the process, should be avoided if
possible because of the following reasons:
Extraneous material can create additional separation
problems, requiring new separations that do not exist
inherently within the process.

Direct Heat Transfer


The introduction of extraneous material can create new
problems in achieving product purity specifications.
It is often difficult to separate and recycle extraneous
material with high efficiency.
Any material not recycled can become an environmental
problem.
As shall be discussed later, the best way to deal with
effluent problems is not to create them in the first place.

Catalyst profiles
For packed-bed reactors, the size and shape of
the pellets and the distribution of active
material within the pellets can be varied
through the length of the reactor to control the
rate of heat release.
For example, suppose the temperature of a
highly exothermic reaction needs to be
controlled by packing the catalyst inside the
tubes and passing a cooling medium outside of
the tubes.

Catalyst profiles
If a uniform distribution of catalyst is used, a
high heat release would be expected close to
the reactor inlet, where the concentration of
feed material is high.
The heat release would then gradually
decrease through the reactor.
Cooling medium does not remove completely
the heat released in the early stages.

Catalyst profiles
Temperature reaches a peak and then decreases towards
the reactor exit as the rate of heat release decreases.
Using catalyst of low effectiveness at the inlet and zones
with increasing effectiveness through the reactor would
control the rate of reaction to a more even profile through
the reactor, allowing better temperature control.
Alternatively, rather than using a different design of pellet
in different zones through the reactor, a mixture of catalyst
pellets and inert pellets can be used to effectively dilute
the catalyst

Reactor Designs

Reactor Designs

CATALYST DEGRADATION
Performance of the catalyst
deteriorates with time

Loss of catalyst performance can


occur in number of ways:
1.Physical Loss - homogeneous catalyst,
catalytic fluidized bed reactors.
2.Surface deposits- physical barrier to
reacting species - insoluble and
nonvolatile(carbon deposits-coke in
hydrocarbon reactions.
3. Sintering -molecular rearrangement of
support or active material (high
temperature gas phase reactions-reduction
in effective surface area of the catalyst)

4.Poisoning-materials that chemically


react or form strong bonds with
catalyst-reduce its activity (impurities
in the raw materials or products of
corrosion)
5.Chemical change- some catalysts
slowly change chemically
Catalyst degradation results in
catalysts loss, lowers rate of the
reaction, lowers the performance of
the reactor

REACTOR
CONFIGURATIONS
or
PRACTICAL
REACTORS

GAS-LIQUID REACTORS
There are many reactions involving more than
one reactant, where the reactants are fed in
different phases as gasliquid or liquidliquid
mixtures.
If the reaction is two-phase, intimate mixing is so
important, which increases the mass transfer.
The three aspects of mixing, mass transfer and
reaction can be present widely in various forms
of different configurations

CONTACTING PATTERNS

This is a counter-current
arrangement where plug-flow is
induced in both the gas and the
liquid.
Packing material or trays can be
used to create interfacial area
between the gas and the liquid.
In some cases, the packed bed
might be a heterogeneous solid
catalyst rather than an inert
material.

Figure shows a packedbed arrangement where


plug-flow is induced in
both the gas and the
liquid.
But both phases are
flowing cocurrently.
This, in general, will give
a poorer performance
than the countercurrent

Key Points
However, the cocurrent arrangement, known as a tricklebed reactor, might be necessary if the flow of gas is much
greater than the flow of liquid.
This can be the case for some gasliquid reactions
involving a heterogeneous catalyst with a large excess of
the gas phase.
A continuous gas phase and a liquid phase in the form of
films characterize the flow pattern.
Countercurrent contacting might well be preferred but a
large flow of gas makes this extremely difficult.

Another way to provide cocurrent


plug-flow for both phases is to feed
both phases to a pipe containing an
in-line static mixer.
Various designs of static mixer are
available, but mixing is usually
promoted by repeatedly changing the
direction of flow within the device as
the liquid and gas flow through.
This will give a good approximation to
plug-flow in both phases with
cocurrent flow.
Static mixers are particularly suitable
when a short residence time is
required.

This approximates mixed-flow behavior


in the gas phase and plug-flow in the
liquid phase.
The arrangement tends to induce a high
gas-film mass transfer coefficient and a
low liquid-film mass transfer coefficient.
As the liquid film will tend to be
controlling, the arrangement should be
avoided .
It gives a lower driving force than a
countercurrent packed column.
But might be necessary if, for example,
the liquid contains solids or solids are
formed in the reaction.
If the reaction has a tendency to foul a
packed bed, a spray column might be
preferred for reasons of practicality.

This approximates plug-flow in


the gas phase and mixed-flow
in the liquid phase.
The arrangement tends to
induce a low gas-film mass
transfer coefficient and a high
liquid-film mass transfer
coefficient.
As the gas film will tend to be
controlling, the arrangement
should be avoided when
reacting a gas with a high
solubility

Key Points
Bubble column will tend have a lower performance
than a countercurrent packed bed.
The arrangement has two advantages over a packed
bed.
Firstly, the liquid hold-up per unit reactor volume is
higher than a packed bed, which gives greater
residence time for a slow reaction for a given liquid
flowrate.
Secondly, if the liquid contains a dispersed solid (e.g.
a biochemical reaction using microorganisms), then a
packed bed will rapidly become clogged.
A disadvantage is that it will be ineffective if the liquid

Figure shows an agitated tank in which


the gas is sparged through the liquid.
This approximates mixed flow behavior in
both phases.
The driving force is low relative to a
countercurrent packed bed.
However, there may be practical reasons
to use a sparged agitated vessel.
If the liquid is viscous (e.g. a biochemical
reaction using microorganisms), the
agitator allows the gas to be dispersed as
small bubbles and the liquid to be
circulated to maintaingood contact
between the gas and the liquid.

Key point
Of the contacting patterns we have
seen,
countercurrent packed beds offer the
largest mass transfer driving force and
agitated tanks the lowest.

Effect of Temperature on G-L


Reactions
As the temperature increases,
rate of reaction increases,
solubility of the gas in the liquid
decreases,
rates of mass transfer increase;
volatility of the liquid phase increases,
decreasing the
partial pressure of the dissolving gas.

Key Points
Some of these effects have an
enhancing influence on the overall
rate of reaction.
Others will have a detrimental effect.
The relative magnitude of these
effects will depend on the system in
question.

Mass Transfer Aspects


The mass transfer can also influence the selectivity.
For example, consider a system of two parallel reactions
in which the second reaction produces an unwanted by
product and is slow relative to the primary reaction.
The dissolving gas species will tend to react in the liquid
film and not reach the bulk liquid in significant quantity for
further reaction to occur there to form the by product.
Thus, in this case, the selectivity would be expected to be
enhanced by the mass transfer between the phases.

Liquidliquid reactors
Examples of liquidliquid reactions are the nitration
and sulfonation of organic liquids.
In liquidliquid reactions, mass needs to be transferred
between two immiscible liquids for the reaction to take
place.
However, rather than gas and liquid-film resistance,
there are two liquid-film resistances.
The reaction may occur in one phase or both phases
simultaneously.

Liquidliquid reactors
For the mass transfer (and hence, reaction) to
take place, one liquid phase must be
dispersed in the other.
A decision must be made as to which phase
should be dispersed in a continuous phase of
the other.
In most cases, the liquid with the smaller
volume flowrate will be dispersed in the other.

Liquidliquid reactors
The overall mass transfer coefficient depends on
the physical properties of the liquids and the
interfacial area.
In turn, the size of the liquid droplets and the
volume fraction of the dispersed phase in the
reactor govern the interfacial area.
Dispersion requires the input of power either
through an agitator or by pumping of the liquids.

Liquidliquid reactors
The resulting degree of dispersion depends on
the power input, interfacial tension between
the liquids and their physical properties.
While it is generally desirable to have a high
interfacial area and, therefore, small droplets.
Too effective a dispersion might lead to the
formation of an emulsion that is difficult to
separate after the reactor.

REACTOR PATTERNS

Figure shows a packed bed


in which the two liquids
flow countercurrently.
Plates can also be used to
create the contact
between the two liquid
phases, rather than a
packed bed.
This arrangement will
approximate plug-flow in
both phases.

Figure shows a
multistage agitated
contactor.
A large number of
stages and low
backmixing will tend to
approximate plug-flow
in both phases.
However, the closeness
to plug-flow will depend

Figure shows an in-line static mixer.


Dispersion is usually promoted by
repeatedly changing the direction of
flow locally within the mixing device
as the liquids are pumped through.
This will give a good approximation
to plug-flow in both phases in
cocurrent flow.
As with gasliquid reactors, static
mixers are particularly suitable
when a short residence time is
required.

Figure shows a spray


column in which the light
liquid is dispersed.
This approximates plugflow in the light liquid
phase and mixed-flow
behavior in the heavy
liquid phase.

Figure shows a spray column in


which the heavy liquid is
dispersed.
This approximates mixed flow in
the light liquid phase and plugflow behavior in the heavy liquid
phase.
Spray columns will generally give
a lower driving force than
countercurrent packed
columns,multistage agitated
contactors and in-line static
mixers.

Figure shows an
agitated tank followed
by a settler in a mixer
settler arrangement,
which will exhibit mixedflow in both phases.
Although Figure shows a
single-stage agitated
tank and settler, a
number of agitated
tanks, each followed by
a settler, can be
connected together.

Key Points
For such a cascade of mixersettler devices, the two liquid
phases can be made to flow countercurrently through the
cascade.
Cross-flow arrangement can also be used in which one of the
phases is progressively added and removed at different points
through the cascade.
Such a flow arrangement can be useful if the reaction is limited
by chemical equilibrium.
If removal of the liquid removes the product that has formed,
the reaction can be forced to higher conversion than that of a
countercurrent arrangement.

REACTOR CONFIGURATION

Tubular reactors
Although tubular reactors often take the
actual form of a tube, they can be any
reactor in which there is steady
movement only in one direction.
If heat needs to be added or removed as
the reaction proceeds, the tubes may be
arranged in parallel, in a construction
similar to a shell-and-tube heat exchanger.

Tubular reactors
Here, the reactants are fed inside the tubes and
a cooling or heating medium is circulated around
the outside of the tubes.
careful control of residence time is important, as
is the case where there are multiple reactions in
series.
A high ratio of heat transfer surface area to
volume is possible, which is an advantage if high
rates of heat transfer are required.

Tubular reactors
One mechanical advantage tubular
devices have is when high pressure
is required.
Under high-pressure conditions, a
small-diameter cylinder requires a
thinner wall than a large-diameter
cylinder.

Stirred-tank reactors
Stirred-tank reactors consist simply of an
agitated tank and are used for reactions
involving a liquid.
Applications include:
homogeneous liquid-phase reactions
heterogeneous gasliquid reactions
heterogeneous liquidliquid reactions
heterogeneous solidliquid reactions
heterogeneous gassolidliquid reactions.

Stirred-tank reactors can be operated in batch,


semi-batch, or continuous mode.

Stirred-tank reactors
In batch or semi-batch mode:
Operation is more flexible for variable production rates
or for manufacture of a variety of similar products in the
same equipment;
Labor costs tend to be higher (although this can be
overcome to some extent by use of computer control).

In continuous operation, automatic control tends to


be more straightforward (leading to lower labor
costs and greater consistency of operation).

Stirred-tank reactors
For homogenous reactions, STRs
should be avoided for some types of
parallel reaction systems and for all
systems in which byproduct formation
is via series reactions.
Stirred-tank reactors become
unfavorable if the reaction must take
place at high pressure.

Packed Bed Reactors


Generally, temperature control in fixed beds is difficult
because heat loads vary through the bed.
The temperature inside catalyst pellets can be
significantly different from the bulk temperature of the
reactants flowing through the bed.
This is due to the diffusion of reactants through the
catalyst pores to the active sites for reaction to occur.
In exothermic reactors, the temperature in the catalyst
can become locally excessive. Such hot spots can
cause the onset of undesired reactions or catalyst
degradation.

Moving-bed catalytic
reactors
If a solid catalyst degrades in performance, the
rate of degradation in a fixed bed might be
unacceptable.
In this case, a moving-bed reactor can be used.
Here, the catalyst is kept in motion by the feed to
the reactor and the product.
This makes it possible to remove the catalyst
continuously for regeneration.

Fluidized-bed catalytic
reactors
In fluidized-bed reactors, solid material in the
form of fine particles is held in suspension by
the upward flow of the reacting fluid.
The effect of the rapid motion of the particles
is good heat transfer and temperature
uniformity.
This prevents the formation of the hot spots
that can occur with fixed-bed reactors.

Fluidized-bed catalytic
reactors
The performance of fluidized-bed reactors is not
approximated by either the mixed-flow or plug-flow
idealized models.
The solid phase tends to be in mixed-flow, but the bubbles
lead to the gas phase behaving more like plug flow.
Overall, the performance of a fluidized-bed reactor often
lies somewhere between the mixed-flow and plugflow
models.
Fluidized beds are also useful in situations where catalyst
particles need frequent regeneration.

Fluidized-bed catalytic
reactors
One disadvantage of fluidized beds, is that attrition of
the catalyst can cause the generation of catalyst fines.
Such fines are then carried over from the bed and lost
from the system.
This carryover of catalyst fines sometimes necessitates
cooling the reactor effluent through direct contact heat
transfer by mixing with a cold fluid.
Fines tend to foul conventional heat exchangers.

KILNS
Reactions involving free-flowing solid, paste and slurry
materials can be carried out in kilns.
In a rotary kiln, a cylindrical shell is mounted with its axis
making a small angle to the horizontal and rotated slowly.
The solid material to be reacted is fed to the elevated
end of the kiln and it tumbles down the kiln as a result of
the rotation.
The behavior of the reactor usually approximates plugflow.