CATALYST DEACTIVATION

Catalyst deactivation occurs when there is reduction in catalyst activity. This often occurs as the
catalyst is being used. Sometimes this drop is very rapid, in the order of seconds and sometimes
it is so slow that regeneration or replacement is needed only after months of use. In any case,
with deactivating catalyst, 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, the
process is called fouling.
The definition of effectiveness factor, Equation (1), can be expanded to account for deactivation
Actual reactionrate
ɳ= intrinsic kinetics ¿ (1)
Rate predicted ¿
processes that decrease the activity of a catalyst as a function of time. In this context, the
intrinsic kinetics in Equation (1) should be determined using a new, freshly prepared catalytic
surface. The activity of the surface, and thus the actual rate of reaction, will change with time so
that ɳ=ɳ ( ϴ ) where 𝛳 is the time the catalyst has been on stream. It is necessary to consider
deactivation processes in reactor designs since they can have a marked effect on process
economics and even operability. Deactivation is usually classified as being either physical or
chemical in nature, but this classification is somewhat arbitrary. Physical deactivation includes
blocking of pores by entrained solids (fouling), loss of active sites due to agglomeration (site
sintering), closure of pores by internal collapse (support sintering), and the reversible loss of
active sites by physical adsorption of impurities. Chemical deactivation includes the irreversible
loss of active sites through chemisorption of impurities (Permanent poisoning), loss of sites due
to coking, and pore blockage due to coking. Some deactivation processes are reversible.
Deactivation by physical adsorption occurs whenever there is a gas-phase impurity that is below
its critical point. It can be reversed by eliminating the impurity from the feed stream. This form
of deactivation is better modeled using a site-competition model that includes the impurities
rather than using the effectiveness factor. Water may be included in the reaction mixture so that
the water–gas shift reaction will minimize the formation of coke. Off-line decoking can be done
by high-temperature oxidation. Deactivation by chemisorption requires a chemical treatment to
remove the chemically bonded poison from the catalytic surface and it can be modeled using a
time-dependent effective factor. Except for physical adsorption, catalytic activity can never be
restored completely. Even with continuous reactivation, the catalyst will gradually decline in
activity and have a finite life that must be considered in the overall process economics. A change
of catalyst for a large reactor can cost millions of dollars. The catalyst used in fluidized-bed
catalytic crackers is deactivated by the coking that occurs during one pass through the reactor—a
matter of seconds. More stable catalysts can last for years, with the gradual decline in activity
being accommodated by a gradual increase in reaction temperature. The effectiveness factor may
decrease by a factor of 5 before the catalyst is changed. The selectivity of the reaction will
usually drop during the course of the run.
The decision to change the catalyst is usually based on this loss of selectivity, but it can be based
on a temperature limitation imposed by materials of construction. Some deactivation processes
lower the number of active sites S0. Others add mass transfer resistances. In either case, they
cause a reduction in the reaction rate that is reflected in a time-dependent effectiveness factor:
[ Actual rate ] =ɳ ( ϴ ) [ Intrinsic rate of freshcatalyst ] (2)
Some progress has been made in developing theoretical expressions for ɳ(𝛳) for deactivation
processes such as coking. Deactivation by loss of active sites can be modeled as a chemical
reaction proceeding in parallel with the main reaction. It may be substantially independent of the
main reaction. Site sintering, for example, will depend mainly on the reaction temperature. It is
normally modeled as a second-order reaction:
dS o 2
=−K s S o (3)
dt
The number of active sites is a multiplicative factor in the rate of the main reaction. Thus, the
decline in reaction rate can be modeled using a time-dependent effectiveness. A reasonable
functional form for the time-dependent effectiveness factor is
ɳ fresh ɳ fresh
ɳ ( ϴ )= = (4)
1+S o K s ϴ 1+ K D ϴ

which results from the second-order model of site sintering. An alternative to Equation (4) is a
first-order model:
ɳ ( ϴ )=ɳ fresh exp (−K D ϴ ) (5)

It is necessary to determine ɳ(𝛳) under reaction conditions, and a life test should be included in
any catalyst development effort. The data from this test will allow ɳ to be fitted as a function of
time on stream, 𝛳. Equations (4) and (5) can obviously be used to model deactivation processes
other than site sintering, and k D can be regarded as an empirical constant with units of reciprocal
time.
The packed-bed reactor will operate at an approximate steady state that will track the slowly
changing catalyst activity. The rate at which this slow change occurs dictates the process design.
If the catalyst deactivates in minutes, continuous regeneration is necessary and fixed-bed reactors
are infeasible. Fluidized-bed and other moving-solids reactors are used to continuously circulate
the catalyst between reaction and regeneration zones. If the catalyst degenerates in days, fixed-
bed reactors are usually regenerated in situ. Typically, several packed beds in parallel are
operated in a swing-cycle between reaction and regeneration modes. If the catalyst degenerates
in years, the spent catalyst is usually returned to the vendor for regeneration or recovery of
valuable components such as precious metals.
Do not infer from the above discussion that all the catalyst in a fixed bed ages at the same rate.
This is not usually true. Instead, the time-dependent effectiveness factor will vary from point to
point in the reactor. The deactivation rate constant k D will be a function of temperature. It is
usually fit to an Arrhenius temperature dependence. For chemical deactivation by chemisorption
or coking, deactivation will normally be much higher at the inlet to the bed. In extreme cases, a
sharp deactivation front will travel down the bed. Behind the front, the catalyst is deactivated so
that there is little or no conversion. At the front, the conversion rises sharply and becomes nearly
complete over a short distance. The catalyst ahead of the front does nothing, but remains active,
until the front advances to it. When the front reaches the end of the bed, the entire
catalyst charge is regenerated or replaced.