UNIT - 3

Catalyst Deactivation
 Introduction

• When a catalyst is used for a long period of time then there is

a chance that the catalyst can be deactivated .
• The drop is sometimes very slow and some times rapid.

• Fouling: If deactivation is rapid and caused by a deposition

and a physical blocking of the surface.

• Regeneration: Removal of the blocking material or the

deposited solid material from the surface of the catalyst is
known as regeneration.
 Introduction (Contd…)
• Poisoning: 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.

• Reactivation: 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.
 Mechanisms of Catalyst Deactivation

• The catalyst deactivation depends on a number of factors.

They might be due to
– The actual decay reactions
– The presence or absence of pore diffusion slow down
– The way poisons act on the surface and so on.
 Decay Reactions

• They are of four types.

– Parallel deactivation
– Series deactivation
– Side by side deactivation
– Independent deactivation

• Parallel deactivation – the reactant may produce a side product

which deposits on and deactivates the surface

• Series deactivation - the reaction product may decompose or

react further to produce a material which then deposits on and
deactivates the surface.
 Decay Reactions (Contd…)

• Side-by-side deactivation - an impurity in the feed may

deposits on and deactivate the surface
 Decay Reactions (Contd…)

• Independent deactivation – 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.
 Pore Diffusion
• The pore diffusion strongly influence the catalyst decay in a
pellet.

• In parallel deactivation -
– For MT<0.4 and ε=1, the poison will be deposited uniformly on the
surface of the interior pore.
– For MT>4 and ε<1, the poison is deposited on the exterior surface. This
is the case for strong pore diffusion.
– An external thin shell of poison is formed on the surface and this
thickens with time and the deactivation front moves inward. This is
known as shell model poisoning.
 Pore Diffusion (Contd…)

• In 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.
 Pore Diffusion (Contd…)

• 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.
 Additional Factors Influencing Decay
• There are various factors may influence the observed change
in activity of catalyst. These include:
– pore mouth blocking by deposited solid,
– equilibrium, or reversible poisoning where some activity
always remains,
– and the action of regeneration (this often leaves catalyst with an active
exterior but inactive core).

• Most important of all, the observed deactivation may result

from a number of processes at work simultaneously;
– for example, the speedy immobilization of the most active sites by
poison P1 and then the slower attack of the remainder of the sites by
P2.
 The rate and Performance Equations

• The activity of a catalyst pellet at any time is defined as

and in terms of the fluid bathing the pellet the rate of

reaction of A should be of the following form:
 The rate and Performance Equations (Contd…)

• Similarly, the rate at which the catalyst pellet deactivates may

be written as

• In terms of nth-order kinetics, Arrhenius temperature

dependency, and isothermal conditions, the reaction rate
becomes, for the main reaction:
 The rate and Performance Equations (Contd…)

• and for deactivation which in general is dependent on the

concentration of gas phase species, the deactivation 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.
 The rate and Performance Equations (Contd…)

• For different decay reactions we may expect different forms

for the above equations. Thus
• In certain reactions, such as isomerizations and cracking,
deactivation may be caused both by reactant and product, or
 The Rate Equation from Experiment

• Experimental devices for studying deactivating catalysts fall

into two classes:
 The Rate Equation from Experiment (Contd…)

• Because of the ease of experimentation, batch-solids devices

are much preferred; however, they can only be used when
deactivation is slow enough (in the order of minutes or longer)
so that sufficient data on the changing fluid composition can be
obtained before exhaustion of the catalyst.

• When deactivation is very rapid (in the order of seconds or less)

then a flowing-solids system must be used.

• Cracking catalysts whose activity half-lives can be as short as 0.1

second fall into this class
 The Rate Equation from Experiment (Contd…)

• Now the type of batch-solids flowing-fluid reactor that we find

convenient to use depends on whether the deactivation
expression daldt is concentration independent or not.

• When it is concentration independent, any type of batch

solids system may be used and can be analyzed simply, but
when it is concentration dependent, then unless one
particular type of reactor is used (that in which CA is forced to
stay unchanged with time) the analysis of the experimental
results becomes horrendously awkward and difficult.
Batch-Solids: Determining the Rate for
Independent Deactivation
 Batch-Solids, Batch-Fluid

• Using time as the one independent variable throughout the run

the kinetic expressions of Eq. 14 become

• Integrating the above equation gives

• For unit initial activity, or a0=1, the equation becomes

• Replacing Eq.18 in Eq. 15 we then find

• On separation and integration
 How Pore Diffusion Resistance Distorts the Kinetics of
Reactions with Deactivating Catalysts

Consider the following rate scheme for reactions on spherical particles:

For no deactivation but with or without pore diffusion

resistance these rate expressions become

where
How Pore Diffusion Resistance Distorts the Kinetics of
Reactions with Deactivating Catalysts
With deactivation

where
These expressions show that in the regime of strong pore
diffusion resistance a decreases, causing MTd to also decrease.
This means that effectiveness factor rises with time, as shown
in the figure. However a decreases faster than ξ rises so the
reaction rate decreases with time.
Performance Equations in the Regime of Strong
Diffusional Resistance
Performance equations for plug flow G/batch S, with
the simple first order system