Lectures 16-18 S.S.

Itkulova

INDUSTRIAL CATALYTIC PROCESSES

 INDUSTRIAL CATALYTIC PROCESSES
 In the chemical industry and industrial research, catalysis play an
important role. Different catalysts are in constant development to
fulfil economic, political and environmental demands. When using
a catalyst, it is possible to replace a polluting chemical reaction with
a more environmentally friendly alternative.

 Catalysis is used to produce the most important chemical products:

sulfuric and nitric acids, ammonia, and methanol.
 Catalysis has especially great importance in organic synthesis:
- oxidation,
- hydrogenation,
- dehydrogenation,
- hydration, etc.
 Catalysis is a base of many methods of oil refinery:
- catalytic cracking,
- reforming,
- aromatization,
- etc.
History of the catalysis of industrial
processes
History of the catalysis of industrial
processes
 The essence of the accelerating action of
the catalysts
consists in lowering the activation energy of a chemical reaction:
1. as a result of changes in the reaction path due to the participation of
the catalyst or
2. due to the implementation of the reaction by a chain mechanism
with the initiating action of the catalyst.
In the first case, the reaction proceeds through a series of
elementary stages, which together require less activation energy than
a direct reaction without a catalyst.

A decrease in activation energy is not the only reason for a sharp

increase in the rate of catalytic reactions compared to non-catalytic
ones.
During a new reaction path, the catalyst is an active process
participant, and this participation is in the formation of unstable
intermediate compounds - reactive complexes between a catalyst and
reacting substances, after the decomposition of which the catalyst is
regenerated.
Due to the regeneration of the catalyst after each cycle of intermediate
interactions, it remains theoretically unchanged.
 Three principles of catalysis

1) The catalyst does not shift the chemical

equilibrium, but only accelerates its reaching.
2) The catalyst always forms unstable intermediate
chemical compounds with the starting materials.
3) In catalytic reactions, the potential barrier is always
lower than in the same reaction without a catalyst.
The main technological characteristics of
the catalysts
The practical behavior of industrial catalysts is associated with
their main technological characteristics:
 activity
 performance
 activation temperature
 selectivity (selective action),
 wear resistance
 poisoning,
 etc.

The more active the catalyst, the process can be conducted at a

relatively lower temperature, which gives significant
advantages, both economic and technological.
The activity of solid catalysts depends on their activation
temperature, i.e. the minimum temperature of the reacting
substances at which the catalyst “works”, i.e. increases the
reaction rate in a measure sufficient for practice.
 Activity
 The main characteristic of the catalysts is their activity, i.e. a measure
of the accelerating effect of the catalyst in relation to a given reaction.
 The more active the catalyst, the process can be conducted at a
relatively lower temperature, which gives significant advantages, both
economic and technological. P= m /V *τ [kg/L*h]
p cat
P - productivity
 Activity
In practice, readily determined measures of activity are
often sufficient. For comparitive measurements, such
as catalyst screening, determination of process
parameters, 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
– Space–time yield
– Temperature required for a given conversion
 Space Velocity, Conversion
 Catalysts are often investigated in continuously operated test reactors, in which the
conversions attained at constant space velocity are compared. The space velocity is the
volume flow rate,V0, relative to the catalyst mass, mcat:
 Vs = Vf /(Vcat * τ) [L/(L*h) = h-1]
 Vo = Vc /(Vкат * τ) [h-1]
 The conversion X(A) is the ratio of the amount of reactant A that has reacted to the
amount that was introduced into the reactor. For a batch reactor:

 If we replace the catalyst mass in last Equation with the catalyst volume, then we see that
the space velocity is proportional to the reciprocal of the residence time.
τ – contact time , τ = 1/ S.V.
 Often the performance of a reactor is given relative to the catalyst mass or volume, so
that reactors of different size or construction can be compared with one another. This
quantity is known as the space–time yield STY:
 Comparison of the catalysts activity
 Figure compares two catalysts of differing activity with one another, and shows that
for a given space velocity, catalyst A is better than catalyst B. Of course, such
measurements must be made under constant conditions of starting material ratio,
temperature, and pressure.

 Determination of the temperature required for a given conversion is another method of

comparing catalysts.
 The best catalyst is the one that gives the desired conversion at a lower temperature.
This method can not, however, be recommended since the kinetics are often
different at higher temperature, making misinterpretations likely. This method is
better suited to carrying out deactivation measurements on catalysts in pilot plants.
Catalytic cycle
Selectivity
 Selective catalysis
Selective catalysis is catalysis in which catalysts can
accelerate only one of several possible target
reactions. It is important for industry, especially in
the production of organic products.
In some cases, various products can be obtained
from the same starting materials in view of several
parallel reactions. The selectivity of some catalysts
allows to greatly accelerate only one reaction from a
number of possible ones, and to carry out the
process at a low temperature, thus inhibiting other
reactions.
Using various selective catalysts, it is possible to
obtain various desired products from the same
starting materials.
 Examples of selective action CT
1. Dehydrogenation of isopropyl alcohol in the presence of silver
metal gives acetone
С3Н7ОН = (СН3)2СО + Н2,
and dehydration with aluminum oxide produces propylene
С3Н7ОН = С3Н6 + Н2О
2. Dehydrogenation of ethyl alcohol with zinc oxide or copper
leads to the formation of acetaldehyde
С2Н5ОН = СН3СНО + Н2
Dehydration of ethyl alcohol in the vapor phase using a solid
aluminosilicate catalyst leads to the formation of ethylene
С2Н5ОН = С2Н4 + Н2О
 Selective Catalysis: Action
The use of selective catalysis allows to carry out the
target process with obtaining intermediate product,
which subsequently turns into the target product.

For the preferential production of formaldehyde, tin

oxides or aluminosilicates are used as a selective
heterogeneous catalyst, and nitrogen oxides are used
for homogeneous gas-phase catalysis.
 Selectivity (selective conversion)
 used to characterize the complex processes, in which with the target
reaction the side reactions occur. Selectivity shows which part of the
converted reagent enters the target reaction, and is calculated by the
formula:

 where - Nпрев.-в-цел.прод. - the amount of reagent spent for the

formation of the target product;
 Nобщ. прев. – total amount of converted reagent.
 These values can be represented in units of the quantity of substance
(mol, kmol) or in units of mass (g, kg, etc.).
 Selectivity is the proportion of the target product in the total number of all
products produced.
 Selectivity
 Selectivity is expressed in fractions or percent; in the latter case, the
obtained value is multiplied by 100. The selectivity calculated in this
way is called full or integral selectivity.
S= (Ypr/Ytheor) 100%
Selectivity can be defined as the ratio of the rate of the target reaction
(rate of formation of the target product) to the total rate of the
process (rate of reagent consumption). The selectivity thus calculated
is called instantaneous or differential.

 where rцел.р. – reagent consumption rate for the target reaction; rобщ. –
total reagent consumption rate.
 Selectivity
 If during the chemical reaction the volume of the reaction
mixture does not change (V = const), then the selectivity can be
calculated using the concentration of the reagent and the target
product in the reaction mixture.
For example, for the reaction
aA + bB → rR +sS ,
 Where R – target product

 where M (A), M (R) are the molar masses, and C A0 and CA are
the initial and current concentration of the reagent, CR is the
concentration of the target product.
Stability
Industrial homogeneous vs heterogeneous catalysts
Parameters affecting the catalyst
activity and selectivity

➢ pressure
Catalyst Evaluation