CHOICE OF REACTOR - Reactor

Conditions
REACTOR CONDITIONS
• REACTION EQUILIBRIUM
• REACTOR TEMPERATURE
• REACTOR PRESSURE
• REACTOR PHASE
• REACTOR CONCENTRATION
 REACTION EQUILIBRIUM
• In the previous discussion, the choice of reactor type
was made on the basis of the most appropriate
concentration profile as the reaction progressed.

• However, there are still important effects regarding

reaction conditions to be considered.

• Before considering reaction conditions, some basic

principles of chemical equilibrium need to be
reviewed.
 REACTION EQUILIBRIUM
• Reactions can be considered to be either
reversible or essentially irreversible.
 REACTION EQUILIBRIUM
• For reversible reactions:

– For a given mixture of reactants at a given

temperature and pressure, there is a maximum
conversion (the equilibrium conversion) that cannot
be exceeded and is independent of the reactor design.

– The equilibrium conversion can be changed by

appropriate changes to the concentrations of
reactants, temperature and pressure.
 REACTION EQUILIBRIUM
• The key to understanding reaction equilibrium is the Gibbs
free energy, or free energy, defined as:

 G = H − TS

• Like enthalpy, the absolute value of G for a substance cannot

be measured, and only changes in G are meaningful.

• For a process occurring at constant temperature, the change

in free energy is:

 G =  H −T  S
 REACTION EQUILIBRIUM
• A negative value of G implies a spontaneous
reaction of reactants to products.

• A positive value of G implies the reverse

reaction is spontaneous.

• A system is in equilibrium when G = 0

REACTION EQUILIBRIUM
 REACTION EQUILIBRIUM
• The free energy can also be expressed in
differential form:
dG = −SdT + VdP
• where V is the system volume.
• At constant temperature, dT = 0 and
dG = VdP
• For N moles of an ideal gas PV = NRT; V=NRT/P
• where R is the universal gas constant.
 REACTION EQUILIBRIUM
• The concepts of fugacity and activity have no strict
physical significance but are introduced to transform
equations for ideal systems to real systems.

• However, it does help to relate them to something

that does have physical significance.

• Fugacity can be regarded as an “effective pressure”,

and activity can be regarded as an “effective
concentration” relative to a standard state.
REACTION EQUILIBRIUM
 REACTION EQUILIBRIUM
• Note that the partial molar free energy is used to
designate the molar free energy of the individual
component as it exists in the mixture.
• The free energy change for reactants and products at
standard conditions is given by:
 Homogeneous gaseous reactions
• If the fugacity is expressed as the product of
partial pressure and fugacity coefficient
• fi = φi pi
– where fi = fugacity of Component i
– φi = fugacity coefficient of Component i
– pi = partial pressure of Componenti
– Therefore Ka is given as
 Heterogeneous Liquid Reactions
• The state of all components is not uniform (eg.
Reaction between a gas and a liquid)

• This requires standard states to be defined for

each component.

• The activity of solid in the equilibrium constant

can be taken to be unity.
 Le Chatelier’s Principle
• A basic principle that allows the quantitative
prediction of the effect of changing the
reactor conditions on any chemical system in
equilibrium
• “If any change in the conditions of a system in
equilibrium causes the equilibrium to be
displaced, the displacement will be in such a
direction as to oppose the effect of the
change”
 REACTOR TEMPERATURE
Single Reactions - Endothermic Reactions
• reversible - LCP- the operation at high temperature
increases the conversion - increases the rate of the
reaction allowing reduction in reactor volume.
• The temperature should set as high as possible
consistent with safety, moc and catalyst life
• If the reactor operated adiabatically(mean molar heat
capacity of reactants and products are assumed
constant), temp. of the reaction mixture α reactor
conversion. As conversion ↑ temp↓ because of reaction
endotherm
• Equilibrium conversion - increased- operating reactor
non adiabatically-adding heat during the reaction.
 REACTOR TEMPERATURE
Exothermic Reactions
• For single exothermic irreversible reactions, the temperature
should be set as high as possible, consistent with materials
of construction, catalyst life and safety, in order to minimize
reactor volume.
• In reversible exothermic reactions, as the conversion
increases, the temperature rises because of the reaction
exotherm.
• Rather than adiabatic operation, the equilibrium conversion
could also have been increased by operating the reactor
nonadiabatically and removing heat as the reaction
proceeds so as to maximize conversion within the
constraints of feasible heat transfer, materials of
construction, catalyst life, safety, and so on.
 REACTOR TEMPERATURE
Exothermic Reactions
• Le Chatelier’s principle dictates that operation at a low
temperature increases maximum conversion. However,
operation at a low temperature decreases the rate of reaction,
thereby increasing the reactor volume. Then ideally, when far
from equilibrium, it is advantageous to use a high temperature
to increase the rate of reaction.

• As equilibrium is approached, the temperature should

be lowered to increase the maximum conversion.

• For reversible exothermic reactions, the ideal temperature is

continuously decreasing as conversion increases.
 REACTOR PRESSURE
• The selection of reactor pressure for vapor-phase
reversible reactions depends on whether there is
a decrease or an increase in the number of moles
• Increasing the pressure of vapor-phase reactions
increases the rate of reaction and hence
decreases reactor volume both by decreasing the
residence time required for a given reactor
conversion and increasing the vapor density.
• In general, pressure has little effect on the rate of
liquid-phase reactions.
 REACTOR PRESSURE
Single Reactions
(a) Decrease in the number of moles.
• A decrease in the number of moles for vapor-phase reactions
decreases the volume as reactants are converted to products.

• Increasing the reactor pressure increases the equilibrium

conversion. Increasing the pressure increases the rate of
reaction and also reduces reactor volume.

• Thus, if the reaction involves a decrease in the number of

moles, the pressure should be set as high as practicable,
bearing in mind that the high pressure might be costly to
obtain through compressor power, mechanical construction
might be expensive and high pressure brings safety problems.
 REACTOR PRESSURE
Single Reactions
(a) Increase in the number of moles
• An increase in the number of moles for vapor-phase reactions
increases the volume as reactants are converted to products.
• LeChatelier’s principle dictates that a decrease in reactor pressure
increases equilibrium conversion. However, operation at a low
pressure decreases the rate of reaction in vapor phase reactions and
increases the reactor volume.
• Thus, initially, when far from equilibrium, it is advantageous to use
high pressure to increase the rate of reaction. As equilibrium is
approached, the pressure should be lowered to increase the
conversion.
• The low pressure required can be obtained by operating the system
at reduced absolute pressure or by introducing a diluent to decrease
the partial pressure. The diluent is an inert material (e.g. steam) and
is simply used to lower the partial pressure in the vapor phase.
 Multiple reactions producing by products.
• The arguments presented for the effect of pressure on single
vapor phase reactions can be used for the primary reaction
when dealing with multiple reactions.

• Again, selectivity and reactor yield are likely to be more

important than reactor volume for a given conversion.

• If there is a significant difference between the effect of

pressure on the primary and secondary reactions, the
pressure should be chosen to reduce as much as possible the
rate of the secondary reactions relative to the primary
reaction.

• Improving the selectivity or reactor yield in this way may

require changing the system pressure or perhaps introducing a
diluent.
 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 gas–solid 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
3. Entrapment
 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
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