Catalytic reaction Engineering

Handled By,
M.Deepika.,M.Tech
Assistant Professor,
Department of Petrochemical Engineering
 Introduction to Reaction Engineering
• https://www.slideshare.net/SyedMuhammad
UsmanSha/difference-between-batchmixed-
flow-amp-plugflow-reactor
• https://www.youtube.com/watch?
v=PvISXEwQhf4
 Introduction to catalysis

• The science and technology of catalysis is of great significance as it affects

our daily life.
• Four major sectors of the world economy; petroleum and energy
production, chemicals and polymer production, food industry and
pollution control, involve catalytic processes.
 Solid catalysts

Catalyst components
A solid catalyst consists of mainly three
components :
• 1. Catalytic agent
• 2. Support /carrier
• 3. Promoters and Inhibitors
 Catalytic agent
• These are the catalytically active component in the catalyst.
• These components generate the active sites that participate in the chemical reaction.
Activity of any catalyst is proportional to the concentration of these active sites.
• Though concentration of the active sites depends on the amount of catalytically
active component, however, it is not always directly proportional.
• Availability of active sites depends mainly on the dispersion of catalytic agent. The
dispersion is defined as ratio of total number of exposed atoms/molecules of
catalytic agent available for reaction to total number of atoms/molecules of catalytic
agent present in the catalyst sample.
Catalytic agents may be broadly divided in the following categories:
• i. Metallic conductors ( e.g Fe, Pt, Ag, etc.)
• ii. Semiconductors (e.g. NiO, ZnO,etc.)
• iii. Insulators (e.g. Al2O3, SiO2,MgO etc.)
 Metallic conductors

• The metals that have strong electronic

interaction with the adsorbates are included
in this category.
• The metals are used in various catalytic
reactions such as methanol synthesis,
oxidation , hydrogenation and
dehydrogenation processes.
 Examples of metal catalysts
• Cu for water gas shift reaction and methanol
synthesis ;
• Ag for oxidation of ethylene to ethylene oxide, Au
for oxidation of methanol to formaldehyde;
• Fe for ammonia synthesis;
• Pd and Pt for hydrogenation of olefins, dienes,
aniline or nitriles as well as dehydrogenation of
alkanes, alcohols, cyclohexanes, cyclohexanols
etc.
 Semiconductors
• The oxides and sulfides of transition metals that have catalytic activity are included in
this category.
• Similar to conducting metals, they are also capable of electronic interaction with
adsorbed species and catalyze the same type of reactions. Usually the lower valence
band electrons participate in bonding.
• The upper conduction band separated by band gap energy is empty unless electrons are
promoted by heat or radiation.
• Semiconductor characteristics may be intrinsic or induced by addition of foreign ion,
creating cationic or anionic vacancies.
• Common transition oxides and sulfides such as CuO, AgO, NiO CoO, Fe2O3 , MnO, Cr2O3,
FeS, V2O5 show conductivity.
• These materials participate in catalytic reactions and reaction occurs through
acceptation or donation of electrons between the reactant material and catalysts.
• Few applications of semiconductor catalysts are : CuO for oxidation of nitric oxides, NiO
for dehydrogenation of alkanes, MnO2 for oxidation of alcohols, and V2O5 for oxidation
of hydrocarbons.
 Insulators
• Catalytic functions of insulators are different from that of
conductor and semi conductor materials.
• Insulators have large values of band gap energy and very
low concentration of impurity levels.
• The electrons remain localized in valence bonds and redox
type reactions involving electronic interaction as observed
for metal or semiconductor catalysts does not occur.
• However, insulators have sites that generate protons,
thereby, promote carbonium ion based reactions such as
cracking, isomerization or polymerization.
• Al2O3, SiO2, SiO2-Al2O3, zeolites, MgO, CaO, MgAl2O4,
SiO-MgO are few examples of the insulators used as
catalysts.
 Support or carrier
• Support or carrier provides large surface area for dispersion of small amount
of catalytically active agent.
• This is particularly important when expensive metals, such as platinum,
ruthenium, palladium or silver are used as the active agent.
• Supports give the catalysts its physical form, texture, mechanical resistance
and certain activity particularly for bifunctional catalysts.
• Area of the support can range from 1 - 1000 m2/gm.
• Common supports are alumina, silica, silica-alumina, molecular sieves etc. The
surface area of α - alumina is in the range 1-10 m2/gm whereas the surface
area for γ or η - alumina can be in the range 100 – 300 m2/gm.
• Support may be inert or interact with the active component. This interaction
may result in change in surface structure of the active agent and thereby
affect the catalyst activity and selectivity. The support may also exhibit ability
to adsorb reactant and contribute to the reaction process.
 Promoters
• Promoters are generally defined as substances added during preparation of
catalysts that improve the activity or selectivity or stabilize the catalytic agents.
• The promoter is present in a small amount and by itself has little or no activity.
• Promoters are termed as physical or chemical promoter depending on the
manner they improve the catalyst performance.
• The additives that maintain physical integrity of the support and/or deposited
catalytic agents are termed as physical promoters.
• For example, addition of small quantities of alumina to an iron catalyst
employed in ammonia synthesis prevents sintering of the iron crystallites. Thus,
for this catalyst, alumina is a physical promoter.
• The addition of K2O to the same catalyst increases the intrinsic activity of the
iron crystallites and therefore acts as a chemical promoter.
• The promoter can be added during catalyst preparation or during reaction.
 Negative promoters or inhibitors
• Inhibitors act opposite to promoters.
• When added in small amounts, these can
reduce catalyst activity, selectivity or stability.
• Inhibitor is particularly useful for reducing the
activity of a catalyst for undesirable side
reactions.
• In oxidation of ethylene, ethylene dichloride is
added to inhibit CO2 formation thus acting as
an inhibitor.
 Industrial catalysts can be broadly
grouped into three categories:
1.Bulk catalysts

• When the entire catalyst consists of the catalytically active

substance ,then the solid catalyst is called a bulk catalyst.

• Examples include silica- alumina catalysts for catalytic cracking;

iron- molybdate for oxidation of methanol to formaldehyde; iron

doped with alumina and potassium oxide for the synthesis of

ammonia.
2. Supported catalysts
• In supported catalysts, the catalytically active materials are
dispersed over the high surface area support material.
• For example, hydrodesulphurization is carried out over
molybdenum oxide supported on alumina.
3. Mixed agglomerates
• These catalysts are agglomerated mixture of active
substance and support. These type of catalysts are
used less frequently.
 Preparation of solid catalyst

The catalyst preparation methods can broadly

categorized as follows :
1. Bulk preparation process:

• Bulk catalysts and supports are prepared by this

method. Bulk preparation is mainly done by the
following methods :
a. Precipitation process
b. Sol gel process
2. Impregnation process:
• Supports are first prepared by bulk preparation
methods and then impregnated with the
catalytically active material.
• The active materials can be deposited on the
supports by various methods.
• Most of the methods involve aqueous solutions
and liquid solid interface.
• In some cases, deposition is done from the gas
phase and involves gas- solid interface.
3. Physical mixing :
• Mixed agglomerated catalysts are prepared by this
method.
• These catalysts are prepared by physically mixing the
active substances with a powdered support or
precursors of support in ball mill.
• The final mixture is then agglomerated and activated.
 Sol gel process
• In the sol gel process, initially a stable colloidal solution called sol is
formed.
• The sol is a liquid suspension of solid particles ranging in size from 1
nm to 1 micron.
• It can be obtained by hydrolysis and partial condensation of
precursors such as an inorganic salt or a metal alkoxide.
• The further condensation of sol particles into a three dimensional
network produces a gel material.
• The gel is a diphasic material in which the solids encapsulate the
solvent.
• The molecular weight of the oxide species produced continuously
increases.
• The materials are referred to as aqua sol or aqua gels when water is
used as a solvent and aquosol or alcogel when alcohol is used.
• https://www.youtube.com/watch?v=dlCCNMt
oJvk
• https://www.youtube.com/watch?
v=YeuZPAqFn50
Precipitation and co-precipitation
• In this process, the desired component is precipitated from the
solution.
• Co precipitation is used for simultaneous precipitation of more
than one component.
• Catalysts based on more than one component can be prepared
easily by co-precipitation.
• The precipitation process is used for preparation of bulk catalysts
and support material such as Al2O3, SiO2, TiO2, ZrO2 etc.
 Process
• In general, the metal hydroxides are precipitated from their precursor salt solution
because of their low solubility.
• The precipitation of hydroxides can be performed either by starting from an alkaline
solution which is acidified or from acidic solution by raising the pH.

• However, most hydroxides for technical application are precipitated from an acidic
solution by the addition of an alkaline precipitating agent.
• Usually, ammonia or sodium bicarbonate is used as the precipitating agent.
• Highly soluble inorganic salts such as nitrates, carbonates or chlorides are generally
used as metal precursors.
• For example, preparation of alumina is done by precipitating aluminium hydroxide
from aluminium nitrate solution by addition of ammonium hydroxide.
During precipitation, several processes occur
and the major steps are :
1. liquid mixing / supersaturation
2. nucleation
3. crystal growth to form primary products
4. aggregation of the primary particles
• https://www.youtube.com/watch?
v=jIFesT0t4k0
•Initial mixing or interdispersing of components in the solution has a significant effect on the
precipitation.
•Good mixing result in a more homogeneous product particularly in case of co- precipitation.
•Rate of stirring primarily affects the nucleation whereas growth rate is much less influenced by
this factor.
•Stirring rate also affect the aggregation.
•Aggregate size can be influenced by changing the stirring rate and the manner of mixing.
•
• The nucleus is defined as the smallest solid phase aggregate of atoms, molecule or
ions which is formed during a precipitation and which is capable of spontaneous
growth.
• For nucleation to start the solution need to be super saturated.
• Only when the concentration exceeds a critical threshold value a nucleus will form
and the precipitation will begin.
• Thus nucleation depends strongly both on concentration and temperature. There
is a critical super saturation concentration below which nucleation is very slow and
above which nucleation is very fast. 
 Process
Precipitation process can be carried out
indifferent ways.
• Batch
• continuous
In a batch process, the salt solution from which
the metal hydroxide is to be precipitated is
taken in a vessel and the precipitating agent is
added.
• The continuous process involves continual
simultaneous addition of salt solution and
precipitating agent to a vessel with
simultaneous withdrawal of precipitate.
• This process has a higher demand on process
control. All the parameters (pH, temperature,
concentration, residence time) can be
controlled as desired.
• When metal solution is added to the precipitating agent, the product tends to be
homogeneous since the precipitating agent is present in large excess.
• This process is particularly important in co-precipitation as it give more homogeneous
product than the process where the precipitating agent is added to a mixed metal
solution. In the latter case, the hydroxide with lower solubility tends to precipitate first,
resulting in formation of non-homogeneous product.
• Simultaneous addition of both reagents to a buffer solution of constant pH results in
better homogeneity and process control.
• In this process, ratio of metal salt and precipitating agent can be controlled. However,
product at the start and at the end may vary due to change in concentration of other ions
that are not precipitated.
• These counter ions tend to occlude in larger extent in final products. Aging is also longer
for final products.
• Aging represent time of formation of co precipitated and its separation from solution.
• Aging results in change in structure and properties of hydroxide network. Aging leads to
more crosslinked network.
• Advantages and disadvantages: 
The main advantages of the precipitation process is the possibility of creating
pure and homogenous material.
However the major disadvantages include necessity of the product
separation after precipitation and generation of the large volume of salt
containing solutions.
There is also difficulty in maintaining a constant product quality throughout
the whole precipitation process if the precipitation is carried out
discontinuously.
Preparation of dual oxides catalysts by coprecipitation
Mixed oxide support and catalyst can be prepared by coprecipitation method. As discussed earlier,
for coprecipitation, the solubility of the two components should be in similar range for
simultaneous precipitation resulting in homogeneous product. Otherwise the precipitation will
be sequential resulting in non-homogeneous product.
Two examples are discussed below.
1.  SiO2-Al2O3
SiO2-Al2O3 is used in catalytic cracking process and is also used as support for active metals in
various applications. Preparation of dual oxides by coprecipitation is similar to precipitation of
single oxide. At pH 6 (at 500C) the precipitation of both silica and alumina sols begins and
gelation takes places.
2.  NiO-Al2O3
NiO-Al2O3 is used for hydrogenation and methanation reactions. Although this catalyst can be
produced by other route, coprecipitation method of preparation is also done to increase the
intimate interaction between active metal and support. The sodium bicarbonate can be used as
precipitating agent for formation of nickel aluminium hydroxyl carbonate with good
homogeneity of final product.
• Supported  catalysts
• Supported catalysts are prepared by deposition of the active metal on the support materials.
The main purpose of using a support is to achieve an optimal dispersion of the catalytically
active component and to stabilize it against sintering. But in many reactions the support is
not inert and the overall process consists of two catalytic functions both for active
components and support.
Supported catalysts are prepared in two main steps :
• Deposition of the precursor of the active component on the support.
• Transformation of this deposited precursors to catalytically active site.
• The final active component can be in metallic state, oxide form or reduced from depending
on the requirements.
There are various deposition methods. Most of these involve aqueous solutions and liquid
solid interface. In some cases deposition is also done from the gas phase and involve gas-
solid interface. The methods most frequently used are:
– impregnation
–  ion exchange     
 Impregnation

• Dry or incipient impregnation

• Wet / diffusional impregnation
 Parameters affecting the
impregnation process
• The pH of the solution is an important parameter in the impregnation
process.
• On liquid side pH determines the most abundant species in solution to be
deposited on to the support.
• HNO3, carboxylic acids, ammonia are usually used for adjusting the pH
because these can decompose during thermal treatment.
• On solid side, pH controls the nature of surface charge and the number of
charged sites, in other words, the zeta potential.
• During impregnation, the extent of interaction between the metal
complex and the support is controlled by parameters such as isoelectric
point of oxide support, temperature and nature of support and dopants.