Introduction

Catalyst loss of activity with time-, i.e. deactivation.

Catalyst have only limited lifetime
Also known as Ageing
catalyst activity is defined as

Catalyst deactivation is the result of number of unwanted chemical

and physical changes
Decline in activity is due to
Blocking of the catalytically active sites
Loss of catalytically active sites due to chemical, thermal or
mechanical processes

Types of Catalyst Deactivation

Catalysts frequently lose an important fraction of their activity while in
operation.
Three causes for deactivation:
a. Structural changes in the catalyst itself. These changes may result
from a migration of components under the influence of prolonged
operation at high temperatures, for example, so that originally finely
dispersed crystallites tend
to grow in size.
Important temperature fluctuations may cause stresses in the catalyst
particle, which may then disintegrate into powder with a possible
destruction of its fine structure.
b. Essentially irreversible chemisorption of some impurity in the feed
stream,
which is termed poisoning.
c. Deposition of carbonaceous residues from a reactant, product or some
intermediate, which is termed coking.

Time-Scale of Deactivation
10 -1

10 0

10 1

10 2

10 3

10 4

10 5

10 6

10 7

10 8

Hydrocracking
HDS
Catalytic reforming

FCC

Most bulk
processes
0.1-10 year

EO
MA
Formaldehyde
Aldehydes
Hydrogenations
Acetylene
Oxychlorination

C3 dehydrogenation

Fat hardening
NH 3 oxidation

Time / seconds
10

-1

10

TWC
10

10

10

10

10

1 hour 1 day

10

SCR

10

10

1 year

Batch
processes
hrs-days

Tailored Reactor and Process Design

Relation between time-scale of deactivation and reactor type

Time scale

Typical reactor/process type

years

fixed-bed reactor;
no regeneration

months

fixed-bed reactor;
regeneration while reactor is off-line

weeks

fixed-bed reactors in swing mode, moving-bed reactor

minutes - days

fluidised-bed reactor, slurry reactor;

continuous regeneration

seconds

entrained-flow reactor with continuous regeneration

Cause of Catalyst Deactivation

Four causes of Catalyst Deactivation
Poisoning of the catalyst
Deposits on the Catalyst Surface( Fouling, coking)
Thermal Processes and sintering
Catalyst loss via Gas Phase

Causes of Catalyst Deactivation

Poisoning of a Catalyst
Loss of activity due to strong chemisorptions on active sites of impurities
present in the feed stream.
In heterogeneous catalysis the poison molecules are absorbed more
strongly to the catalyst surface than the reactant molecules, the catalyst
becomes inactive.

A B

A B
C D
P P
P
P

Modify the nature of active sites

Poisons of Industrial Catalysts

Process

Catalyst

Poison

Ammonia Synthesis

Fe

CO, CO2, H2O, C2H2, S,P

Steam reforming

Ni/Al2O3

H2S,As,HCl

Methanol Synthesis

Cu

H2S, AsH3, HCl

Catalytic Cracking

SiO2-Al2O3, Zeolite

NH3, Na, heavy Metals

CO hydrogenation

Ni, Co, Fe

H2S, COS, As, HCl

Oxidation

V2O5

As

Ethylene to Ethylene Oxide

Ag

C2H2

Poisons Classification
Poisons can be Classified as
Selective and Non Selective

Reversible or Irreversible
Example : Reversible Poisoning is due to Oxygen
Compounds (O2,H2O,CO,CO2) and irreversible Poisoning
is connected with non metals such as S, Cl, As Ph

EXAMPLES OF POISONING OF CATALYSTS

Leaded petrol cannot be used in cars fitted with a
catalytic converter since lead strongly absorbs onto the
surface of the catalyst

Cannot use copper or nickel in a catalytic converter

on a car instead of the expensive platinum or
Rhodium. REASON :- Any SO2 present in the
exhaust fumes (trace amounts ) would poison the
catalyst
Once the catalytic converter has become inactive it
cannot be regenerated

Preventing Poisoning
Decrease poison Content in feed
E.g. hydrodesulphurization followed by H2S adsorption
to remove sulphur Compounds
Catalyst Formulations and Design
e.g. Cu-Based Methanol Synthesis are strongly
poisoned by Sulphur

KINETICS
The adjustment for the decay of the catalysts:
The reactions are divided into two categories
separable kinetics
rA' a ( past history ) rA' ( fresh catalyst )
non separable kinetics

rA' rA' ( past history , fresh catalyst )

Rate of Catalyst decay, rd

da
rd
p[a(t )]
dt

a (t)

1.0

First Order Decay , p(a)=a

Second Order Decay, p(a) = a2

Poisoning

Impurity P in feed Stream

A S A. S

Main Re action A . S B . S C g
B.S B S

r ' A a (t )

Poisoning Re action P S P.S

kC A
1 K AC A K B C B

da
rd
dt
k d' C pm a q

Assume rate of removal of gas stream onto catalyst sites is proportional to the Number
of sites that are unpoisoned and conc of poison in gas phase (Ct 0 C P.S )
(C )

rP.S k (C to C P.S )C P
dC P.S
rP.S k d (C t 0 C P.S )C P
dt

Typical Stability Profiles in Hydrotreating

Initially high rate of deactivation
mainly due to coke deposition
Subsequently coke in equilibrium
metal deposition continues
II
activity

coke

metals
Time-on-Stream

III
Amount of poisoning

Catalytic activity

Fouling of Catalyst
Physical (mechanical) deposition of species from fluid phase onto
the catalyst surface which results in activity loss due to blocking
of sites and/or pores
Common to reactions involving hydrocarbons
A carbonaceous (coke) material being deposited on the surface of
a catalyst
Coke Deposited can be measured
TGA or DTA
Monitoring the evolution of CO2 and H2O
Position of Deposited Coke

Preventing of Coking
Optimum catalyst composition
Equilibrium must be in between rate of coke production and rate of coke
removal
Coking can be reduced by running at elevated pressure and hydrogen-rich
streams.
E.g in catalytic reforming processes
Catalyst deactivated by coking can usually be regenerated by burning off the
carbon.

Sintering of Catalyst
A loss of active surface area resulting from the prolonged exposure to high
gas-phase temperatures
Occurs in both supported and unsupported metal catalyst
Two models for crystallite growth due to sintering
Atomic Migration
Crystallite Migration

vapour

particles migrate

coalesce

migrating
metastable

stable

surface

Sintering of Alumina upon Heating

SBET (m2/g)

Sintering

Reduction of surface area

Tcalc (K)

Catalyst Deactivation
Separable kinetics
rA' freshcatalyst

rA" a catalyst
history
a t rA' t rA' t0

rA' k T f Ci

Commercial reactors maintain constant production rate by

increasing T (reaction rate constant increases), as catalyst
decays (catalyst activity a decreases).

Experimental analysis of the decay rate is as:

da
rd
p a kd T h Ci
dt

Catalyst Deactivation
Sintering (aging)
Activity loss by loss of active surface caused by prolonged
exposure to elevated gas-phase reaction temperatures.
Mechanistically
Crystal agglomeration/growth, reducing internal surface area
accompanied by narrowing/blocking of pore cross section.
Change in surface structure through recrystallization or other modes of
defect elimination (active site loss).

Typically a 2nd order process;

da
rd kda2
dt

a
1

da kd dt
0

a t

1
1 kdt

Catalyst Deactivation
Fouling/Coking
Deposition of carbonaceous material on catalyst surface
Catalyst activity level is a function of the amount of carbon
deposited on the catalyst surface (Cc):
1
1

at

p
p np
a
1 Cc 1 A t
1 2 Cc
Cc At n

where A and n are fouling parameters dependent on the type of

gas being processed.
Activity is expressed as f(Cc) by one of the following:
a e 1Cc

Kinetics of Uniform Poisoning

Fundamental to his development, is the assumption that the catalytic site that has
adsorbed poison on it is completely inactive. If C,, is the concentration of sites
covered with poison the fraction of sites remaining active, called the deactivation or
activity function, is represented by

This deactivation function is based on the presumed chemical events occurring

on the active sites, and can be related to various chemisorption theories. The
overall observed activity changes of a catalyst pellet can also be influenced by
diffusional effects, etc., but the deactivation function utilized here will refer only to
the deactivation chemistry, to which these other effects can then be added.
Since C,, is not normally measured, it must be expressed in terms of the poison
concentration, Cp, in the gas phase inside the catalyst.
Wheeler used a linear relation