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Chemical Reaction Engineering- II (2170501)

Semester VII (CHEM)


Chapter Name: Catalysis (Chapter 5)

Catalysts
Catalysis is the increase in rate of reaction by addition of substance called Catalyst. Catalysts are those substances
/material that on addition will alter the path of reaction by forming temporary intermediate and thus lowering the
rate of reaction. There are two types of catalysts (i) Homogeneous catalyst (ii) Heterogeneous catalyst

(i) Homogeneous catalyst: A homogeneous catalyst is one whose molecules are dispersed in the same phase
(usually gaseous or liquid) as the reactant molecules

(ii) Heterogeneous catalysts: A heterogeneous catalyst is one whose molecules are not in the same phase as
the reactants, which are typically gases or liquids that are adsorbed onto the surface of the solid catalyst.
For e.g. Use of Vanadium Pentoxide in Habers Process, Use of Copper in conversion of Ethanol to Acetaldehyde
(Oxidation Process)

Physical Properties of Catalyst


The surface area of sold has pronounced effect on the amount of gas adsorbed and on its activity as catalyst. For
Example, if a fresh sample of fresh Raney Nickel which is highly porous and large surface area is held in hand, heat
can be felt due to oxygen adsorption which is exothermic in nature. Thus, larger surface are gives higher
adsorption rate.

The dependence of rate of adsorption and catalytic reaction on surface makes it imperative to develop reliable
method for analysis of surface area. The physical properties like surface area, Pore volume, distribution, void
volume, Solid density are important in any catalytic reaction.

(A) Determination of Surface Area:

The standard method to measure area is to conduct physical adsorption of gas on solid surface. For that, the
amount of Nitrogen gas adsorbed at equilibrium(normal boiling point) is measured over pressure range below 1 atm
The amount adsorbed when one molecular layer is attained must be identified in order to determine the area. For
this, BET i.e., Brunauer-Emmet-Teller method is used.

Determination of internal surface area is based on adsorption and condensation of N2 at liquid N2 temperature,
77K.
Initially, the sample is evaporated at 293-523 K (120-250C) followed by cooling to 77 K by liquid N2. Then
gradually the partial pressure of nitrogen above the sample is increased. Some quantity of gas will be adsorbed by
the sample and removed from the gas phase. After stabilization the equilibrated pressure is recorded and amount of
nitrogen adsorbed at each equilibrated pressure is noted. The isotherm, volume adsorbed as function of relative
pressure p/po, is plotted from the data. The pressure over the sample is gradually increased until pressure reaches
near saturation pressure, by when the complete adsorption isotherm is developed. The desorption isotherm is
measured by a step-wise reduction in pressure until a low pressure over the sample is achieved. Although the
volumes are adsorbed at different conditions, the values are reported at STP conditions.

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

The BET equation describes the relationship between volume adsorbed at given partial pressure and the volume
Adsorbed at monolayer coverage. BET equation can be written as:
1 ( 1)
=( )+
( 0) 0

Where,
P, Partial pressure of N2 P0, Saturation Pressure at experimental temperature
V, volume adsorbed Vm, Volume adsorbed at monolayer coverage

C, BET constant. The is plotted as a function of . The plot is linear in the range of relative

pressures = 0.05 - 0.3. At higher relative pressure p/po, the BET plot deviates from linearity as non-ideality
or pore condensation was not accounted for the derivation of BET equation. Slope and intercept of this linear
plot is used for determination of monolayer capacity Vm.
The intercept and slope from the plot is given as

Then the monolayer volume vm is given as,

The total number of N2 molecules adsorbed corresponding to monolayer volume vm can be calculated as

Now each adsorbed N2 molecule occupies an area of surface comparable to its cross section area 0.162 nm2.

(B) Void Volume and Solid Density:

A void volume or pore volume of catalyst can be determined by boiling a weighed sample immersed in

water. After the air in the pores is displaced, the sample is superficially dried and weighed. The increase
in weight divided by density will give pore volume.

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

The method used is Helium-Mercury method. In this method, the volume of helium displaced by sample of

catalyst is measured, then helium is removed and the volume of mercury displaced is measured. Since, mercury will
not fill the pores of most catalyst at atmospheric pressure, the difference in volume will give the pore volume of
catalyst.

Then void fraction of void volume is measured using following equation:


[() ]
=
[ ]

[]
t =
[() + (
)]

Where, Mp is mass of particle, Vg is volume of particle per gram of particle, and is density of particle
If the sample of particle is divided by the mercury volume will give density of the porous particle. Then, porosity,
[ ]
= =
[ ]
where V is void volume per gram particle.

The volume of helium displaced is measure of the occupy volume by the solid material. From this, and the

weight of the sample, the density of solid phase can be obtained.

From the helium-mercury measurements pore volume, the solid density and porosity of catalyst can be

determined. Values of are the order of 0.5, indicating that the material is half void space and half solid material.
Since overall void fractions in fixed bed are about 0.4, a rule of thumb for fixed bed catalytic reactor is that about
30% of volume is pore space, 30% solid catalyst carrier and 40% is void space between catalyst.

(C) Pore Volume Distribution:

There are two methods used for pore volume distribution measurement

(i) Mercury Penetration method: As mercury do not wet the catalyst surface because of significant
surface tension. The pressure required to force mercury into the pores depends on the pore radius. The
pressure varies inversely with 100 psi required to fill the pores of 1000 nm to 10000 psi for 10 nm.
By equating the force due to surface tension(which tends to keep mercury out of pore) to a applied force is given
by Ritter and Drake which is as follow:

2 = 2

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

Where, a is pore size, is surface tension, p is pressure, s contact angle between mercury and pore wall.
The contact angle varies with surface of catalyst but 1400 is good approximation.

8.75105
Therefore, () =
()

(ii) Nitrogen Desorption method: As the lower temperature of Nitrogen adsorption is continued to higher
pressure multilayer adsorption occurs and ultimately the adsorbed films are thick enough to bridge the pore.

Since the vapour pressure decreases as the capillary size decreases, such condensation will occur in first small

pores. Condensation will complete when the partial pressure becomes equal to total pressure and the entire region
is filled with condensed nitrogen.

Now, if the pressure is reduced slowly, amount of nitrogen will evaporate and will empty the pores.

The Kelvin equation gives relationship between vapour pressure and radius of the concave surface of the meniscus
of the liquid.
21
=
( )
0

Where, V1 is molal volume of condensed liquid, is surface tension, is contact angle between condensate and
surface. is thickness of adsorption after single layer adsorption.
For = 0 cos = 1.

By combining both methods one can evaluate pore size for any catalyst in any form accurately.

Classification and Preparation of catalyst

In 1984, Dowden and co-workers proposed that catalyst maybe classified on the basis of electron
mobility as conductors, semiconductors and insulators.
(1) 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

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

alkanes, alcohols, cyclohexanes, cyclohexanols etc.


(2) 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
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,
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.

(3) Insulators: Catalytic functions of insulators are different from that of conductor and semiconductor 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.

For example Al2O3, SiO2, SiO2-Al2O3, zeolites, MgO, CaO, MgAl2O4, SiO-MgO are form of insulator catalysts.

Catalyst Preparation:
A solid catalyst contain three components (i) Catalytic agent (ii) Support/Carrier (iii) Promoter/Inhibitor(if any)

(i) 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.

(ii) Support/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 is used as the active agent. Supports give the catalysts its physical form, texture, mechanical resistance

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

and certain activity particularly for bi-functional 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 - alumina is in

the range 1-10 m2/gm whereas the surface area for or - alumina can be in the range 100 300 m2/gm.

The catalyst preparation methods can broadly categorized as follows:

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

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
involve s gas- solid interface.

(a) Precipitation Process:


Precipitation provides method for forming porous catalyst. It consists of adding a precipitating agent to the
aqueous solution of the desired components. Washing, drying, and sometimes activation are subsequent steps
in the process.
For example, preparation of Magnesium oxide catalyst. It can be prepared by precipitating the magnesium from

the nitrate solution by adding sodium carbonate. The precipitates of MgCO3 are then washed, dried and calcined to
obtain catalyst of Magnesium Oxide. The oxidizing agent here is nitric acid and precipitating is alkali solution.
It is to be noted that molar ration of aqueous solution(metal precursor), pressure, precipitating agent, drying time

Temperature are the factors that influence the pore size distribution and void volume of final product.
For example, if the temperature is increased the void volume will increase which will be due to the fact that moisture
Trapped inside void will evaporate. But further increase in temperature will lead to shrinkage of void.

In some instance a porous material can be obtained by mixing the components with water and milling to desired
grain size, drying and calcining. After this the catalyst is impregnated over support.
The steps in preparation of catalyst impregnated over support includes (1) evacuating the carrier

(2) contacting he carrier with impregnating solution (3) removing the excess solution (4) drying (5)activation

For example, a nickel hydrogenation catalyst can be prepared on alumina by soaking the evacuated alumina
Particles with nickel nitrate solution, draining to remove excess solution and heating in oven to decompose

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

the nitrate to nickel oxide. The final step is reduction of oxide to metallic nickel is best carried out with the
particles in place in the reactor by passing the hydrogen through the equipment. Activation in situ prevents
contamination with air and other gases which might poison the reactive nickel.

(b) Sol-Gel method:


In this process initially stable colloidal solution called sol is formed. The sol is liquid suspension of solid particles

ranging in size 1 nm to 1 micron. It can be obtained by hydrolysis and partial condensation of precursor such as
inorganic salts. The further condensation of sol produces gel material. The gel is diphasic material in which the solid
encapsulates the solvent. The encapsulated liquid is removed either by drying or with supercritical extraction.
The resulting solid product is called aerogel. When gels are dried using drying it is called aerogel and when it is dried
using extraction, it is called xerogel. The aerogel retains high porosity and has high pore volume.

For example, preparation of zirconium catalyst Zirconia propoxide is used as precursor. The sol is prepared using

aqueous solution of nitric acid and n-propanol. It is stabilized for 2 hour at room temperature and dried using
supercritical CO2 at 343 K and 2.1*107 Pa. The sol is then converted to gel which is calcined in two steps. In first
step it is calcined under vacuum for 3 hour at 383 K and in second it is calcined at 773 K in flowing O2 for 2 hour.
The final product obtained is Xerogel Zirconia.

Catalyst 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.

Catalyst Inhibitors:
Inhibitors act opposite to promoters. When added in small amount it can reduce catalysts activity, selectivity or

stability. Inhibitor is particular useful to prevent or reduce the activity of a catalyst for undesirable side
reactions.

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

In oxidation of ethylene, ethylene dichloride is added to inhibit CO2 formation thus acting as an

inhibitor.

Catalyst Poison:
It is referred to the partial or total deactivation of a catalyst caused by exposure to a range of chemical

compounds. Poisoning may be desirable when it results in improved selectivity (e.g. Lindlar's catalyst) but may
be undesirable when the catalyst is rendered ineffective (e.g. Lead in catalytic converters). Poisoning refers
specifically to chemical deactivation, rather than other mechanism of catalyst degradation such as thermal
decomposition or physical damage.

Accelerators:
The material added to reactant stream to improve the performance of catalyst are called accelerators.
For e.g. Steam added to butene feed of dehydrogenation reactor appear to reduce the amount of coke formed
and increase the yield of butadiene. The catalyst in this case is Iron.

Nature and Mechanism of Catalytic reaction


A catalyst is effective in increasing the rate of chemical reaction because it makes possible route for alternative

which has lower energy than previous reaction. Consider the reaction of hydrogen and oxygen in presence of
Spongy Platinum catalyst. According to proposed concept, hydrogen combines with spongy Pt. to form
Intermediate substance, which then reacts with oxygen to provide the final product and reproduce the catalyst.

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

The general characteristics of catalyst may be summarized by:


1. A catalyst accelerates reaction by providing alternate paths to products, the activation energy of each catalytic
steps being less than that for homogeneous reaction.
2. In the reaction cycle active centres of catalyst are combined with at least one of the reactant and then freed
With the appearance of product. The reactant then again combines to reactant and cycle goes on.
3. Comparatively small active centres required to produce large product.
4. Equlibrium conversion is not altered by catalysis. A catalyst which accelerates forward reaction in equilibrium
Is a catlyst for the reverse reaction.
5. The catalyst can radically alter selctivity.

General Terminologies used in Catalysis:


1. Turnover frequency of catalyst:

The turnover frequency (TOF) quantifies the specific activiy of catalytic centre for a special reaction under
defined
conditions by the number of molecular reaction or catalytic cycles occuring at centre per unit time.
For Hetrogeneous reaction TOF is given by:

=
[
]

For most industrial applications it is in range of 0.01-100 sec-1

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

2. Selectivity of Catalyst:
The selectivity of catalyst means the ability of convert the reactant to maximum desired product. In other
words, lesser or negligible formation of side product.

3. Active Site of Catalyst:


Active site is point on the catalyst surface that can form strong chemical bonds with an adsorbed molecule
or atom. These sites are formed due to irregualr surface, dislocations etc.

4. Dispersion of Catalyst:
Dispersion is the fraction of atoms of a material that is exposed to surface. In general it is defined as ratio
of number of surface atoms to total number of atoms of the material. As the atoms exposed to surface
takes part in chemical reaction dispersion of catalyst is important parameter. Dispersion increases with
decrease in crytal size and approaches unity at crystal diameter about 1 nm.

5. Sabatiers principle:
This states that there must be an optimum of rate of catalytic reaction as function of the heat of
adsorption.
If the adsorption is too weak catalyst has little effect and will be unable to dissociate bond. If too strong
the adsorbates will be unable to desorb molecules from the surface. Both exterems result in small rate of
reaction.

Prepared By: Ms. BHATT HIRAL J. Page


Chemical Reaction Engineering- II (2170501)
Semester VII (CHEM)
Chapter Name: Catalysis (Chapter 5)

Prepared By: Ms. BHATT HIRAL J. Page

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