Universidad del Zulia

Facultad de Ingeniería
División de Posgrado
Diseño de Reactores

Diseño de reactores
ideales
Catalyst Deactivation

Prof. Douglas R. Rodríguez O.

2023-2
133

How is affected the reactor modeling?

Do we need to make adjustments for The adjustment is usually made by on the
the decay of the catalysts in the kinetic by quantitative specification of the
design of catalytic reactors? catalyst’s activity, a(t)

REACTION KINETICS
RIGOROUS PRODUCT
MATHEMATICAL DISTRIBUTION WITH
MODELS OF THE RESPECT TO
REACTORS DEACTIVATION CONVERSION TIME
KINETIC EQUATION
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 How is affected the reactor modeling?
Do we need to make adjustments for The adjustment is usually made by on the
the decay of the catalysts in the kinetic by quantitative specification of the
design of catalytic reactors? catalyst’s activity, a(t)

Existence of a nonideal surface or the

deactivation is described by a
mechanism composed of several
elementary steps.
When the kinetics and activity are
separable, it is possible to study catalyst
decay and reaction kinetics
independently.

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𝑎(t) catalytic activity, time-dependent;
k(T) specific reaction rate, temperature-
dependent; Ci gas-phase concentration
of reactants, products, or contaminant.

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Catalyst deactivation
TYPES MECHANISMS Description
Physical deposition of fluid on the catalyst surface blocks the
sites and pores, and leads to activity loss. It may destroy
Fouling
catalyst particles and blockage of the reactor cavity. Rapid
and reversible.
Strong absorption of a chemical compound on the catalyst
Poisoning
surface blocks its active site. Slow and irreversible.
The crystallite growth in the catalytic phase reduces the
catalytic surface or buffer area and destroys the pore in the
Thermal Thermal degradation active phase crystallites (sintering). In general, sintering
CATALYST takes place at high reaction temperatures and is
Mechanical
DEACTIVATION deteriorated by the presence of moisture.
Chemical
Vapor formation
The stacking process destructs monolithic catalysts. The
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turbulent flow results in erosion due to particle collisions.

Attrition/crushing
The catalyst debris accumulates at the reactor bed,
increasing the pressure drop.
Vapor– solid reaction The vapor phase and the catalyst surface react and produce
a set of inactive phases generated by sintering the
Solid–solid reactions. adsorbate interaction.
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 Catalyst deactivation models
According to the The components of the reaction
mechanism of loss of Selective models mixture are affected individually by
Catalyst the active sites the rate of consumption/generation
deactivation of the active site
models The rate of active sites
Non-selective models consumption depends on the
Catalyst deactivation models time-on-stream (TOS) only
are either algebraic or
differential expressions that
correlate changes in the
catalyst activity with the
reaction.  Time dependent catalyst deactivation model
 Temperature dependent catalyst deactivation model
 Coke formation dependent catalyst deactivation model

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 Reactant dependent catalyst deactivation model
 Deactivation model with residual activity

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Time dependent Catalyst activity decays with time, resulting in

the reduction of active sites on the catalyst
catalyst surface.
deactivation For systems with fast catalyst deactivation
model

where “r”, “a” and “n” are constants, subscripts 1 and 2 are the rapid and
slow deactivation species respectively and “t” is time on a stream
Temperature Catalyst deactivation increases with time and Generalized power-law model:
temperature during catalytic reactions.
dependent Increasing the severity of the reaction system
catalyst leads to faster coke deposition and catalyst
deactivation deactivation, in which temperature has the
model strongest effect on the reaction rate and
consequently catalyst deactivation.

Generalized power-law expression (GPLE) with residual activity:

Residual activity “aeq” is achieved when a balance is established between

the rate of deactivation and the rate of selfgeneration for active site.
Coke formation Catalyst deactivation by coke formation, occurs
through a reversible or an irreversible
dependent mechanism.
catalyst .
deactivation
model
Reactant The selective catalyst deactivation was model site.
attributed to an individual effects of the
dependent reaction mixture composition, temperature
catalyst and time
deactivation
model
Deactivation Depending on the mechanism, catalyst
deactivation can be reversible or irreversible
model with under various condition.
residual activity
Catalyst deactivation by coke is a reversible
process while catalys poisoning by heavy
metals (Ni and V) is irreversible.

Time dependent catalyst deactivation model

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 Temperature dependent catalyst deactivation model

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Catalyst deactivation dependent on coke formation

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 Reactant dependent catalyst deactivation model

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Catalyst deactivation dependent with residual activity

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 How to estimated a model
Deterministic Involve solving a system of nonlinear Examples:
model simultaneous equations (algebraic, differential • Runge–Kutta
and sometimes partial) in multiple dependent • Genetic Algorithm (GA)
variables (product concentrations, coke content,
temperature and pressure).
Empirical model Mathematical expression generalized to fit with • Optimization methods applied an articial
chemical reaction data of one or more variables neural network (ANN)

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