CHEMICAL REACTION ENGINEERING-II

UNIT - V
Deactivating Catalysts

B.Manikandan

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Introduction

Deactivating Catalysts
Introduction - Remember the Rate Equations for Catalytic Reactions !

The previous chapters assumed that the effectiveness of catalysts in

promoting reactions remains unchanged with time.
Often this is not so, in which case the activity usually decreases as the
catalyst is used. Sometimes this drop is very rapid, in the order of
seconds;
Sometimes it is so slow that regeneration or replacement is needed only
after months of use.
In any case, with deactivating catalysts regeneration or replacement is
necessary from time to time.
If deactivation is rapid and caused by a deposition and a physical
blocking of the surface this process is often termed fouling.
Removal of this solid is termed regeneration.
Carbon deposition during catalytic cracking is a common example of
fouling
C10 H22 C5 H12 + C onCatalyst
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Introduction

Introduction

If the catalyst surface is slowly modified by chemisorption on the active

sites by materials which are not easily removed, then the process is
frequently called poisoning.
Restoration of activity, where possible, is called reactivation.
If the adsorption is reversible then a change in operating conditions may
be sufficient to reactivate the catalyst.
If the adsorption is not reversible, then we have permanent poisoning.
This may require a chemical retreatment of the surface or a complete
replacement of the spent catalyst.
Deactivation may also be uniform for all sites, or it may be selective, in
which case the more active sites, those which supply most of the catalyst
activity, are preferentially attacked and deactivated.

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Introduction

Introduction

We will use the term deactivation for all types of catalyst decay, both fast
and slow; and we will call any material which deposits on the surface to
lower its activity a poison.
This chapter is a brief introduction to operations with deactivating
catalysts.
We will consider in turn:
The mechanisms of catalyst decay
The form of rate equation for catalyst decay
How to develop a suitable rate equation from experiment
How to discover the mechanism from experiment
Some consequences for design

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Introduction

MECHANISMS OF CATALYST DEACTIVATION

The observed deactivation of a porous catalyst pellet depends on a
number of factors: the actual decay reactions, the presence or absence
of pore diffusion slowdown, the way poisons act on the surface, etc.
We consider these in turn.
Decay Reactions: Broadly speaking, decay can occur in four ways.
First, the reactant may produce a side product which deposits on and
deactivates the surface.
This is called parallel deactivation.
Second, the reaction product may decompose or react further to produce
a material which then deposits on and deactivates the surface.
This is called series deactivation.
Third, an impurity in the feed may deposit on and deactivate the surface.
This is called side-by- side deactivation.

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Introduction

MECHANISMS OF CATALYST DEACTIVATION

Decay Reactions

If we call P the material which deposits on and deactivates the surface,

we can represent these reactions as follows:
Parallel deactivation:

The key difference in these three forms of decay reactions is that the
deposition depends, respectively, on the concentration of reactant,
product, and some other substance in the feed.
Since the distribution of these substances will vary with position in the
pellet, the location of deactivation will depend on which decay reaction is
occurring.
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Introduction

MECHANISMS OF CATALYST DEACTIVATION

Decay Reactions

A fourth process for catalyst decay involves the structural modification or

sintering of the catalyst surface caused by exposure of the catalyst to
extreme conditions.
This type of decay is dependent on the time that the catalyst spends in
the high temperature environment, and since it is unaffected by the
materials in the gas stream we call it independent deactivation.

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Introduction

MECHANISMS OF CATALYST DEACTIVATION

Decay Reactions - Pore Diffusion

For a pellet, pore diffusion may strongly influence the progress of catalyst
decay.
First consider parallel deactivation. From the previous Chapter we know
that reactant may either be evenly distributed throughout the pellet
(MT <0.4 and Effectiveness Factor = 1) or may be found close to the
exterior surface (MT >4 and Effectiveness Factor <1)
Thus the poison will be deposited in a like manner-uniformly for no pore
resistance, and at the exterior for strong pore resistance.
In the extreme of very strong diffusional resistance a thin shell at the
outside of the pellet becomes poisoned.
This shell thickens with time and the deactivation front moves inward.
We call this the shell model for poisoning.

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Introduction

MECHANISMS OF CATALYST DEACTIVATION

Decay Reactions - Pore Diffusion

On the other hand, consider series deactivation. In the regime of strong

pore resistance the concentration of product R is higher within the pellet
than at the exterior.
Since R is the source of the poison, the latter deposits in higher
concentration within the pellet interior.
Hence we can have poisoning from the inside-out for series deactivation.
Finally, consider side-by-side deactivation. Whatever the concentration of
reactants and products may be, the rate at which the poison from the
feed reacts with the surface determines where it deposits.
For a small poison rate constant the poison penetrates the pellet
uniformly and deactivates all elements of the catalyst surface in the same
way.
For a large rate constant poisoning occurs at the pellet exterior, as soon
as the poison reaches the surface.
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Introduction

MECHANISMS OF CATALYST DEACTIVATION

Decay Reactions - Pore Diffusion

The above discussion shows that the progress of deactivation may occur
in different ways depending on the type of decay reaction occurring and
on the value of the pore diffusion factor.
For parallel and series poisoning, the Thiele modulus for the main
reaction is the pertinent pore diffusion parameter.
For side- by-side reactions, the Thiele modulus for the deactivation is the
prime parameter.
Nonisothermal effects within pellets may also cause variations in
deactivation with location, especially when deactivation is caused by
surface modifications due to high temperatures.

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Introduction

THE RATE AND PERFORMANCE EQUATIONS

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Introduction

THE RATE AND PERFORMANCE EQUATIONS

In terms of nth-order kinetics, Arrhenius temperature dependency, and

isothermal conditions, Eqn for the main reaction becomes,

where d is called the order of deactivation, m measures the concentration

dependency and Ed is the activation energy or temperature dependency
of the deactivation.

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Introduction

THE RATE AND PERFORMANCE EQUATIONS

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Introduction

The Rate Equation from Experiment

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Introduction

The Rate Equation from Experiment

Batch Solids:Determining the Rate for Independent Deactivation

Let us illustrate how to interpret experiments from the various

batch-solids reactors of Fig.1 and how to manipulate the basic
performance equations for these reactors by testing the fit for the simplest
of equation forms for independent deactivation.

This represents first-order reaction and first-order deactivation which, in

addition, is concentration independent.

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Introduction

The Rate Equation from Experiment

Batch Solids:Determining the Rate for Independent Deactivation

Here we need to develop an expression relating the changing gas

concentration with time. Using time as the one independent variable
throughout the run, the kinetic expressions become

This expression shows that even at infinite time the concentration of

reactant in an irreversible reaction does not drop to zero but is governed
by the rate of reaction and of deactivation, or

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Introduction

The Rate Equation from Experiment

Batch Solids:Determining the Rate for Independent Deactivation

The batch-batch reactor becomes a practical device when the

characteristic times for reaction and deactivation are of the same order of
magnitude.
If they are not and if deactivation is much slower, then CA, becomes very
low and difficult to measure accurately.
Fortunately, this ratio can be controlled by the experimenter by proper
choice
of W/V.
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Introduction

Batch-Solids, Mixed Constant Flow of Fluid

Inserting the rate of Eq. 14a into the performance expression for mixed flow
gives

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Introduction

Batch-Solids, Mixed Constant Flow of Fluid

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Introduction

Batch-Solids, Mixed Changing Flow of Fluid (to keep

CA , fixed)
For steady flow in a mixed reactor we have found

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Introduction

Batch-Solids, Plug Constant Flow of Fluid

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Introduction

Batch-Solids, Plug Changing Flow of Fluid (to keep

CA,out fixed

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Introduction

How Pore Diffusion Resistance Distorts the Kinetics of

Reactions with Deactivating Catalysts

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Introduction

How Pore Diffusion Resistance Distorts the Kinetics of

Reactions with Deactivating Catalysts

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