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4th Year Stage Catalyst Science and Technology Lecture: 05

Duhok Polytechnique University-Petrochemical Department


2018 / 2019
Catalyst Activity
Lecturer: Dr Farhad M. Ali

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

The suitability of a catalyst

The suitability of a catalyst for an industrial process depends mainly on the following

three properties:

– Activity
– Selectivity
– Stability (deactivation behaviour)
The question which of these functions is the most important is generally difficult to answer
because the demands made on the catalyst are different for each process.

i. Activity: The activity of a catalyst depends upon the strength of chemisorption to a


large extent. The adsorption should be reasonably strong but not so strong that they
become immobile and no space is available for other reactants to get adsorbed.

ii. Selectivity: The selectivity of a catalyst is its ability to direct a reaction to yield a
particular product, e.g., starting with H2 and CO using different catalysts, we get different
products.

Reactants Products Catalyst used


CO (g) + 3 H2 (g) → CH4 (g) + H2O (g) Ni
CO (g) + 2 H2 (g) → CH3-OH (l) Cu, ZnO-Cr2O3
CO (g) + H2 (g) → HCHO (g) Cu
 As seen from these examples, different catalysts might give different products for
the same reactants

There are various kinds of product selectivity:

• Chemical selectivity, or chemo-selectivity, denotes a situation where two different


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chemical reactions can occur, giving two different products.

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

• Similarly, regio-selectivity occurs when the same chemical reaction in different regions
of the molecule leads to different products. When a reaction gives two (or more)
diastereomers, the selectivity to each of these is called diastereo-selectivity.

In the special case when two products are mirror-image diastereomers, or enantiomers,
we talk about enantio-selectivity

One enantiomer is an optical stereoisomer of another enantiomer. The two molecules are mirror
images of each other, which are not superimposable - much like your left and right hand.

A diastereomer is a stereoisomer with two or more stereocenters and the isomers are not
mirror images of each other.

• Shape–selective catalysis: The catalytic reaction that depends upon the pore
structure of the catalyst and the size of the reactant and product molecules is called
shape-selective catalysis.
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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

Cracking Isomerization of hydrocarbons in the presence of zeolites is an example of


shape-selective catalysis.

An important zeolite catalyst used in the petroleum industry is ZSM-S. lt converts


alcohols directly into gasoline.

III. Catalytic activity


Is usually denoted by the symbol (z) and measured in mol s-1, a unit which was
called katal and defined the SI unit for catalytic activity. Catalytic activity is not a kind of
reaction rate, but a property of the catalyst under certain conditions, in relation to a
specific chemical reaction.

Catalytic activity of one katal (Symbol 1 kat = 1 mol s-1) of a catalyst means an amount
of that catalyst (substance, in mol) that leads to a net reaction of one mol per second of
the reactants to the resulting reagents or other outcome which was intended for this
chemical reaction. A catalyst may and usually will have different catalytic activity for
distinct reactions.
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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

Types of catalyst deactivation:

The activity and selectivity of heterogeneous catalysts may change during the course of
reaction. Causes of solid (heterogeneous) catalyst deactivation are basically threefold:
(1) chemical, (2) mechanical, and (3) thermal.

Mechanisms of heterogeneous catalyst deactivation can be classified into five general


areas:

(1) chemical degradation including volatilization (to change or cause to change from
a solid or liquid to a vapour) and leaching (the process of extracting substances from a
solid by dissolving them in a liquid) (rarely reversible)

(2) fouling (can lead to rapid catalyst failure, many forms of fouling are reversible)

(3) mechanical degradation (can lead to rapid catalyst failure) (rarely reversible).

(4) poisoning (generally slow processes, some forms of poisoning and are reversible)

(5) thermal degradation (generally slow processes) (rarely reversible).

• Poisoning: Poisoning occurs when there is a strong chemical interaction of


reactants, products, or impurities with active sites on the catalyst surface. Sulfur Poisoning
being the most widely cited example. 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. 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. In addition to physically blocking adsorption sites, adsorbed poisons
may induce changes in the electronic or geometric structure of the surface. Catalyst can
be poisoned by reactants, products, and impurities.
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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

If impurities are present then they may become adsorbed into the active sites. The
impurity blocks the active site preventing reactant particles being adsorbed. This lowers
the effectiveness of the catalyst.

In some cases the catalyst can be regenerated by burning off the impurity but this is not
always possible and the catalyst has to be renewed. This can be very expensive and
therefore is very important that any impurities are removed before they reach the catalyst.

There are three main categories of catalyst poisoning which need to be distinguished:

(1) poison adsorption,

(2) poison-induced surface reconstruction, and

(3) compound formation between the poison and the catalyst.

Selective poisoning
A chemical directly reacts with the active site or the carrier, rendering it less or completely
inactive.

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

Nonselective poisoning
Deposition of fouling agents onto or into the catalyst carrier, masking sites and pores,
resulting in a loss in performance.

• Fouling: (very common for reactions involving hydrocarbons). The deposit of


unwanted materials on a surface is defined as fouling, and affects how a chemical
process proceeds. Fouling adds a layer of organic, inorganic or even living organisms to
the surface which affects the properties of the catalyst and the mechanism of the process.

Coke formation is one of the most prominent types of catalytic fouling and is chiefly
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involved in the deactivation of a catalyst. This coke formation forms a fouled layer on the
surface of a catalyst which reduces how much of the surface area of the catalyst is available

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

to the surroundings. With less surface area exposed, a catalyst is less effective. secondary
reactions of reactants or products, coke formation.

 Coking can be reduced by running at high pressure & hydrogen-rich feeds


 Catalyst deactivated by coking is often regenerated by burning off the carbon

• Thermal degradation: For a catalyst to be effective it must have an effective


interface with the reactants, thus heterogeneous catalysts are prepared with high surface
areas. Large surface areas are thermodynamically unstable, thus given suitable conditions
such as high temperatures the catalysts will rearrange to form the most favourable lower
surface area agglomerates. These rearrangements are often accelerated by particular
chemical environments. For example, moist atmospheres accelerate structural changes in
oxide catalyst supports. This agglomeration of catalysts is known as sintering, which
causes a decrease in the availability of active sites on a catalyst.

Rate of sintering is
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critically dependent on temperature. Therefore the hotter the catalyst the faster the rate
of deactivation. Operation at low temperatures reduces activity loss due to sintering

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

• Mechanical damage: (Attrition/crushing) Loss of catalytic material due to


abrasion; loss of internal surface area due to mechanical-induced crushing of the catalyst
particle. Mechanical failure of catalysts is observed in several different forms that depend
on the type of reactor, including (1) crushing of granular, pellet, or monolithic catalyst forms
due to a load in fixed beds; (2) attrition, the size reduction, and/or breakup of catalyst
granules or pellets to produce fines, especially in fluid or slurry beds; and (3) erosion of
catalyst particles or monolith coatings at high fluid velocities in any reactor design.

The main consequence of attrition is the generation of fines and the resulting loss of
valuable material.

Attrition is evident by a reduction in the particle size or a rounding or smoothing of the


catalyst particle easily observed under an optical or electron microscope

• Corrosion / leaching: The active sites of a catalyst may become inactive by the
adsorption of impurities in the feed stream.

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

Why transition metals are good catalysts?

Transition metals are good catalysts for two reasons:

1. They show variable oxidation states. This allows them to act as intermediates in the
exchange of electrons between reacting species.

2. They provide a surface for reactions to occur. The metal forms weak bonds to the
reacting species holding them in place.

Turnover Number (TON)

In catalysis, the term turnover number, TON, has two meanings:

• the number of moles of substrate that a mole of catalyst can convert before
becoming inactivated ( mol of substrate / 1 mol of catalyst) and

• is the amount of substrate converted per the amount of catalyst used.

In other words, the turnover number is defined as the absolute number of passes through
the catalytic cycle before the catalyst becomes deactivated. (TON has no unit)

In theory, the Ideal catalyst would have an infinite turnover number and would never be
consumed. In practice, turnover numbers begin at 100 and can go up to a million, more
so in some cases.

The lifetime of the catalyst, and therefore its stability, are measured in terms of its TON

In general, industrial chemists are interested in both TON and turnover frequency (TOF)
(see the next section). A large TON (e.g., 106–1010) indicates a stable, very long-lived
catalyst. The TON can be calculated by dividing the amount of reactant (moles) by the
amount of catalyst (moles):
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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

This assumes a yield of the product of 100%, which is most often not the case. To
calculate the true number of turnovers, the yield obtained needs to be considered.

For example, if 10 mol of reactant and 2.5 mol of catalyst are used, then the TON

becomes

If the yield of the product is 94%, then the actual number of turnovers is

TON = (%conv) x (mol (substrate)) / mol (catalyst)

Actual TON = 0.94 * 10 / 2.5 = 3.76

Authors often report mole % of catalyst used. This refers to the fraction of catalyst used
relative to the amount of limiting reactant present.

Turnover Frequency (TOF)

Turnover frequency is defined as the number of passes through the catalytic cycle per
unit time (typically seconds, minutes or hours). This number is usually determined by
dividing the TON by the time required to produce the given amount of product.

However, as with the TON, the actual yield of the product also needs to be considered.
Continuing the example above, if the reaction in question was run for 7 h to obtain the
94% yield, the TOF is

TOF = TON / time (h)


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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

A catalyst’s turnover frequency number, or turnover number per time unit, characterizes
its level of activity. So, the TOF is the total number of moles transformed into the desired
product by one mole of active site per hour. The larger the TOF, the more active the
catalyst.

Example: 10 mmols of substrate are converted to product using a catalyst loading of 0.2 mmols in 2
hours. .
TON = 10 / 0.2 = 50 TOF = 50 / 2 h = 25 h-1

Note that the TON is always a pure number (unitless), while the TOF has units of time–1.

Number of turnovers performed – more is better; TOF (turnover frequency) – faster is better

Q: Why technologists are interested in TOF and TON?

A: because both give idea about the activity and stability of the catalyst. Number of turnovers
performed – more is better; TOF (turnover frequency) – faster is better. The catalyst turnover number
(TON) and the turnover frequency (TOF) are two important quantities used for comparing catalyst
efficiency.

Questions and Answers:

1. Why a adsorption process is always exothermic

Ans.: Adsorption is spontaneous process, therefore change in free energy (ΔG) is negative.

ΔG = ΔH – TΔS, For the negative value of ΔG, in a system, in which randomness decreases, ΔH must
be negative. Hence, adsorption is always exothermic.

2. What are catalysts?

Catalysts are substances that reduce the activation energy of a chemical reaction, facilitating it or
making it energetically viable. The catalyst increases the speed of the chemical reaction.

3. What are the applications of Adsorption?


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Ans.: Adsorption finds extensive applications both in research laboratory and in industry. A few
applications are mentioned below:

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

• In preserving • In paint industry • In softening of hard water


vacuum • In chromatographic
• In glass masks analysis
• In clarification of • In catalysis
sugar • In adsorption indicators

2. What do you mean by positive and negative adsorption?

Ans.: Positive adsorption:


In case of adsorption by solids from the solutions, mostly the solute is adsorbed on the surface of the
solid adsorbent so that the concentration of solute on the surface of the adsorbent is greater than in the
bulk. This is known as positive adsorption. Hence when the concentration of the adsorbate is more on the
surface of the adsorbent than in the bulk, it is known as positive adsorption.

Negative adsorption:
In some cases, the solvent from the solution may be adsorbed by the adsorbent so that the concentration
of the solution increases than the initial concentration. This is called negative adsorption. Hence if the
concentration of the adsorbate is less on the surface of the adsorbent than in the bulk, it is known as
negative adsorption.

3. According to adsorption theory of catalysis, the speed of the reaction increases because:

A. adsorption produces heat which increases the speed of the reaction.

B. in the process of adsorption, the activation energy of the molecules becomes large.

C. the concentration of the reactant molecules at the active centres of the catalyst becomes high due to
adsorption.

D. adsorption lowers the activation energy of the reaction

4. Which of the following characteristics is not correct for physical adsorption?

A. Adsorption on solid is reversible.

B. Adsorption is spontaneous.
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C. Adsorption increases with increase in temperature.

D. Both enthalpy and entropy of adsorption are negative.

DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019


4th Year Stage Catalyst Science and Technology Lecture: 05

5. During the adsorption of Krypton on activated charcoal at low temperature

a. ΔH < 0 and ΔS < 0

b. ΔH > 0 and ΔS < 0

c. ΔH > 0 and ΔS > 0

d. ΔH < 0 and ΔS > 0

6. Which catalyst properties can be influenced by promoters?

Ans.: Activity, selectivity, and stability.

7. Why are promoters used in catalysis?

Ans.: Promoters is an additive which has no catalytic properties of its own but enhances the activity of a
catalyst. Promoter results in increase of available surface area stabilization against crystal growth and
sintering and improvement of mechanical strength.

8. What are the carrier or support used and why they are used with catalyst?

Ans.: A catalyst support is the material, usually a solid with a high surface area, to which a catalyst is
affixed. The reactivity of heterogeneous catalysts and nanomaterial-based catalysts occurs at the surface
atoms. Catalyst support results in highly porous nature - increase of available surface area improve stability
improves the heat transfer characteristics. Some of Alumina, Asbestos, Iron oxide, Manganese, activated
carbon, Zinc oxide.

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DR FARHAD M. ALI L05- CATALYST ACTIVITY-2018-2019