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