LESSON 3

HETEROGENEOUS CATALYSIS AND SOLID CATALYSTS

1- INTRODUCTION

Catalysis is very important in industry:

- 60% of the chemicals are synthesized by catalytic processes.
- 70% of chemical manufacturing processes are catalytic.
- Over 99% of world gasoline production occurs through the catalytic cracking
of petroleum fractions and other catalytic reactions.
- Over 90% of new industrial processes are catalytic.

Heterogeneous catalytic reactions:

- Very important from the industrial point of view
- The catalyst is a solid and reagents are gasses or liquids
- Occur in multiphase reaction systems
- The reaction occurs at the interphase
- The structure and surface composition of solids is of critical importance to their
performance as catalysts.

The following picture shows some examples of the importance of heterogeneous catalytic processes for industry.

Picture 1. Industrial processes using heterogeneous catalysts.

There are a few differences between homogeneous and heterogeneous catalytic processes.

Homogeneous (liquid phase) Heterogeneous

Low activity, since the number of active High activity, since the number of active
centers per unit of reactor volume is sites that may be exposed to the reagents
relatively low per unit of reactor volume is higher

Operate at medium temperatures to Operating temperature is not limited by the

preserve the function of the catalyst characteristics of the solvent, allowing the
reaction rate increase

Difficulties in separating the catalyst from Easy separation of product and catalyst
the reaction medium (the same because phases are different.
phase).
An example of the stepwise processes that occur in heterogeneous catalysis is the oxidation of carbon monoxide
to carbon dioxide over palladium. This is a very important process in everyday life. Motor vehicles are fitted with
catalytic converters. The picture explains how this happens.

Figure 2. Oxidation of carbon monoxide to carbon dioxide over palladium.

The synthesis of ammonia is an heterogeneous catalyst process’s result too. Iron catalyses the dissociation of
the nitrogen molecules and hydrogen molecules leading to the formation of ammonia. This is the process.

The third figure shows how the activation energy barriers are much lower than the estimated activation energy
barrier for the unanalyzed synthesis of ammonia.

Figure 3. How catalysts affect to the activation energy in ammonia synthesis.

The previous examples show:

- The great importance of the adsorption and desorption of species on active sites, and of the kinetics of
these stages.
- The number of molecules of reactant converted to product in a time interval (reaction rate) depends on
the number of active sites available.
- It should be maximized the number of active sites available to the reactants by dispersing the active
species (small crystallites on a substrate with a high surface area).

To be successful the catalyst:

- Must allow the reaction to proceed at a suitable rate under conditions that are economically desirable.
- At as low a temperature and pressure as possible.
- It must also be long lasting.

2- CATALYTIC MATERIALS

A solid catalyst usually have 3 components

- An active phase
- A promoter
- A carrier or support

Active phase: The active phase is a point on the surface of the catalyst that can form strong chemical bonds
with an atom or molecule (chemisorption). Its function is to catalyze a particular chemical reaction. The active
phases may be metals, metal oxides, metal sulfides or metal carbides. In figure 4 there are some examples.

Figure 4. Materials of active phases.

Figure 5. The way particles have to do to reach to the active phase.

3- PROPERTIES OF SOLID CATALYSTS

The design of the catalyst requires the optimization of the physical properties, chemical properties and catalytic
properties, we have to see what property is interesting for us.

Figure 6. Optimization triangle.

Physical properties:

- MECHANICAL STRENGTH OF PARTICLE (kg cm-2)

It is the force needed to break a particle in the axial or radial direction.

- ATTRITION

Percent loss of material due to friction between the particles.

- PARTICLE SIZE (mm)

It is the diameter and / or length of the catalyst pellets.

Physico-mechanical properties:

- DENSITY (kg m-3)

Density of solid or true density: relationship between mass and volume corresponding to the pure solid:

Particle density or apparent density: relationship between mass and volume corresponding to the particle
(including pores)

Bed density or packed density: relationship between mass and volume corresponding to the particle in a catalytic
packed bed

- PORE SIZE (nm)

Macropores (dp> 50 nm)

Mesopores (dp = 3-50 nm)
Micropores (dp <3 nm)

- SPECIFIC SURFACE AREA (m2 g-1)

It is the total area (including the surface inside the pores) comprised in one gram of solid:
Microporous surface
Meso-macroporous surface

- PORE VOLUME (cm3 g-1)

Is the volume of pores of one gram of solid catalyst.

Macropore volume
Mesopore volume
Micropore volume

4- DENSITY, SPECIFIC VOLUME AND POROSITY

Experimentally, the volume of a solid is measured by the displacement of He gas. He penetrates into the pores of
the material, so the volume displaced corresponds to the actual volume of the solid. Its density is:

On the other hand, since mercury does not penetrate the pores of a solid immersed in it, the volume of the
particles, including the pores, is measured by Hg displacement. Then, the particles or pellets density is:

For a simple cubic packing, the number of atoms per unit cell is one. The side of the unit cell has a length of 2 r ,
3 3 3
where r is the radius of the atom. The cell volume is 𝑉 = 𝑎 = (2𝑟) = 8𝑟 .

Solid real density:

Real specific volume:

The atomic packing factor (APF) is defined as:

For a simple cubic packing:

 - Face centered cubic (fcc) packing. - Body centered cubic (bcc) packing.
- The number of atoms per unit cell = 4. - The number of atoms per unit cell = 2.

Pellets

- Apparent Pellet Density:

- Apparent Pellet Specific Volume:

- Specific Pore Volume:

- Pellet Porosity:

- ɛ𝑝(%):

Mean pore diameter:

In general, in porous solids the external surface area can be considered negligible compared to the internal
(pore) surface area.

On the other hand, considering a model of rigid and homogeneous in diameter cylindrical pores, the total pore
volume can be calculated as:

d: the mean pore diameter

l: the total length of the pores

Specific surface area (normally BET):

d:

5- CATALYTIC BED POROSITY

In a catalytic bed there are voids between the particles.

- Bed Density:

- Empty Bed Volume:

- Bed Porosity:

- ɛl %:
6- PROPERTIES OF SOLID CATALYSTS

Chemical properties

Composition: Weight percentage of different elements in the catalyst.

Concentration of active centers: Number of active sites per gram of catalyst.

Surface Area covered by active sites per gram of solid.

The concentration of active sites is a function of the metal charge of active phase dispersed or exposed to
reactive fraction which is.

Dispersion degree: Dm = Ns / Nt

Ns = number of surface atoms or molecules.

Nt = total number of atoms or molecules of the phase catalytically active. The dispersion can vary between 0 and
1 and is inversely proportional to the size of crystallite.

Acidity: Brønsted centers: capacity to donate protons Lewis centers: capacity to accept electrons. The acidity
plays an important role in many catalytic processes (cracking, isomerization, polymerization).

Oxidation state: Chemical or valence state of the active species.

Chemical structure: Geometric grouping of atoms. It depends on the atoms properties, the number of valence
electrons and the chemical bond.

Catalytic properties

Are activity, selectivity and catalyst stability. They are dynamic properties as they often change over time of use
of the catalyst.

Activity:

- Conversion
- Reaction rate: Moles converted / time including x reactor volume (in catalytic reactions reactor volume
can be substituted by catalyst weight or catalyst surface area).
- Frequency or turnover number: Is the number of molecules converted or produced by one catalytic
active site per second

Selectivity: Property that allows changing only the rate of a given reaction, not affecting others. It is evaluated as
the amount or rate of production of one product relative to the total product.

Stability: Loss of activity under certain reaction conditions due to the reduction of the number of active sites
available (deactivation phenomena).

Deactivation phenomena

Are grouped into these general categories:

- Poisoning
- Fouling
- Sintering of the active phase
- Aging
- Loss (volatilization) of the active phases

Poisoning

Poisoning occurs when there is a strong chemical interaction of reactants, products, or impurities with active sites
on the catalyst surface. Thus, poisoning has operational meaning; that is, whether a species acts as a poison
depends upon its adsorption strength relative to the other species competing for catalytic sites.In addition to
physically blocking adsorption sites, adsorbed poisons may induce changes in the electronic or geometric
structure of the surface. For example, oxygen can be a reactant in partial oxidation of ethylene to ethylene oxide
on a silver catalyst and a poison in hydrogenation of ethylene on nickel.

Fouling

Generally fouling covers all phenomena where the surface is covered with a deposit. The most widely known
form of fouling of catalysts is coke formation. There are many reactions and mechanisms of coke formation
depending on the nature of the catalyst therefore it is not clearly defined. But one can say that for the most part
coke formation arises as a result of carbonaceous residues covering the active sites of a heterogeneous catalyst
surface, subsequently decreasing the active surface area of the catalyst. In addition the deposition of rust from
elsewhere in the catalytic system is not uncommon. Coke-forming processes also involve chemisorption of
different kinds of carbons or condensed hydrocarbons that may act as catalyst poisons causing the chemical
deactivation of the catalyst. For example, the fouling of zeolite catalysts occurs in the form of coke molecules
limiting the access of the reactant to the active sites of a cavity or a pore intersection of the zeolite.

Figure 7. Fouling and poisoning.

Sintering

Deactivation due to growth or agglomeration of the metal crystals (active centers) during the reaction.

Aging

Deactivation due to processes of degradation of the structure of the catalyst in the reaction conditions (reduction
of specific surface, narrowing or closure of pores) which reduces the number of accessible active centers of the
catalyst.

Loss of active phase by volatilisation

It is due to loss of active sites of the solid catalyst due to its transformation to volatile species (gas phase) by
chemical reaction.

The main causes of deactivation are:

- High temperature (aging, sintering).

- Use of carbon-rich reagents (fouling).
- Presence of impurities that interact strongly with the active centers (poisoning or active phase loss by
volatilization).

7- SOLID CATALYSTS PREPARATION

There are 2 steps:

- Support preparation
- Active phase incorporation
1- Support preparation

Methods

Deposition by precipitation: It consists of the deposition on the support of a hydroxide by precipitation of a

soluble salt of the metal. Precipitation is mainly produced by modifying the pH of the solution.

Impregnation: It is the most used method because of its simplicity. It consists on the introduction of the support
into a solution containing the precursor of the desired active phase in the desired concentration and removing the
solvent by evaporation.

2- Active phase incorporation

- Incorporation of metals on a given support by a method of preparation (catalyst precursor).

- Transformation of the metal phase to catalytic active phase by an activation process (supported
catalyst).

It consists on obtaining the active phase

1- If the active phase is a metal oxide:

- Drying
- Calcination under air atmosphere at high temperature to obtain the metal oxide

2- If the active phase is a metal:

- Drying
- Calcination under air atmosphere at high temperature to obtain the
metal oxide.
- Calcination under reductive atmosphere (hydrogen) at high
temperature to obtain the reduced metal.