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Chapter 1
1.1. Introduction
Most processes in life and industry would not practically be possible without
catalysis, which makes particularly essential the thorough understanding of
all the factors which determine the catalytic properties.
A catalyst is dened as a substance (gas, liquid or solid) that increases
the rate and selectivity of a chemical reaction without being consumed.
One might therefore believe that this substance will keep eternally the
same catalytic properties. It is not so: in practice, all the catalysts undergo
mechanical, physical and/or chemical alterations with, as a consequence, a
more or less fast loss in activity and often in selectivity. This alteration of
the catalytic properties, called deactivation, occurs both in homogeneous
catalysis and heterogeneous catalysis even though this theme of crucial
industrial importance is the subject of more attention in heterogeneous
catalysis, partly because of a larger number of factors aecting the stability
of solid catalysts.
Catalyst deactivation is a problem of great technical, economic and
ecologic concern in the practice of industrial chemical processes [14].
In petrochemicals and bulk chemicals production which mainly occurs
through heterogeneous catalysis, the importance of deactivation phenomena
have been acknowledged for a long time and a relevant section of
literature deals with methods to minimize them by an appropriate design
of catalysts and processes. On the contrary, in the ne and specialty
chemicals industry, which uses less solid catalysts, the importance of
their lifetime remains underestimated [5]. Actually, as the production
of these high added-value chemicals requires the use of valuable and
3
DEACTIVATION AND REGENERATION OF ZEOLITE CATALYSTS
Imperial College Press
http://www.worldscibooks.com/chemistry/p747.html
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with the solid catalyst. Leaching (v) which occurs essentially during the
liquid-phase synthesis of functionalized organic molecules results from the
presence in the reaction medium of highly polar species, often bearing
complexing and/or solvolytic moieties which favour the dissolution of the
active components of the catalyst (this is typically the case with metal
sites).
It should however be underscored that in addition to chemical steps,
physical processes often occur in catalyst deactivation. In particular,
mass transport limitations can play a major role in poisoning (i),
fouling (ii), structural alterations (iii) and leaching (v). Furthermore, coke
is a non-desorbed secondary reaction product. Hence the formation of
coke molecules requires not only chemical steps, but also their retention
within the pores or on the outer surface of the catalyst. This retention
may be due to chemical factors, e.g. strong chemisorption, but more
frequently to physical ones: low volatility (gas-phase reaction) or solubility
(liquid-phase reaction), steric blockage (trapping) within micropores, etc.
(Chapter 7).
Deactivation can be reversible or irreversible under the process
conditions. A reversible deactivation caused by leaching of active
components from the catalyst in a continuous process (e.g. loss of Cl
from alkane isomerization or reforming chlorinated alumina catalysts) can
be coped with by adding the leached compound (generally precursors)
to the feed. An irreversibly deactivated catalyst has to be either
recycled or disposed of or to be subjected to a reactivation treatment:
rejuvenation or regeneration. Rejuvenation corresponds to a reactivation
treatment which can be carried out in the reactor used for the
catalytic process under conditions similar or not very dierent from the
operating conditions. A typical example is the removal of non-polyaromatic
carbonaceous compounds deposited under mild conditions (e.g. relatively
low temperatures) on hydroprocessing catalysts which are still reactive
to be hydrocracked under more severe conditions, e.g. slightly higher
temperature and/or hydrogen ow rate [3]. When rejuvenation treatments
are not ecient enough to restore the catalytic performances, the catalyst
is regenerated, this reactivation treatment being carried out either ex situ
(often by a specialized company) or in situ [4]. Coking and sintering of
metals are typical examples of deactivation processes which are irreversible
under the process conditions. Indeed, coke removal as well as metal
redispersion has to be carried out in an oxidative atmosphere which is
incompatible with the catalytic transformation.
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Origin
Mechanism
Examples
Poisoning
Fouling and
coking
Chemical and
structural
alterations
Metals: sintering
Acid oxides: e.g. dealumination
then collapse of the zeolite
framework under hydrothermal
conditions
Mechanical
alteration
Leaching
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1
2
B
D. To simplify the presentation, rst-order
transformations: A
reactions and uniform coke distribution through the catalyst bed were
assumed and the rate constants k were expressed as a function of CC ,
the catalyst coke content:
k1 = k10 exp(1 CC )
k2 = k20 exp(2 CC )
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(D = aromatics + parans) are quite identical with the fresh and coked
catalysts. On the contrary, large dierences were found between these curves
in methanol transformation over a SAPO-34 catalyst which occurs through
the following scheme:
1
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11
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framework. One solution to this problem is to use basic traps such as La2 O3
that react with vanadic acid to form stable vanadates [21, 22]. Note that to
limit these structural alterations, promoters in small amount (e.g. Pt) are
generally added to the catalysts so as to facilitate complete coke combustion
at lower temperatures.
As it was shown with Pt-KLTL aromatization catalysts, sulphur
compounds can signicantly increase Pt sintering. One strategy that was
attempted to limit this process was to introduce promoters which might
stabilize crystal growth, e.g. Ni cations that act as anchoring sites for Pt
particles (Chapter 16).
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14
Fig. 1.1.
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15
adopted is to use the rst part as a guard bed to trap the feed contaminants,
the rest of the bed being thus protected.
Deactivation being highly dependent on the operating conditions, their
optimization determines for a large part the catalyst lifetime in commercial
processes. Thus, aromatic transalkylation, e.g. toluene disproportionation,
toluene-C+
9 aromatics transalkylation, which however occurs through acidcatalysed reactions have to be carried out under high hydrogen pressure
over acid zeolites doped with metals so as to limit coke formation, hence
deactivation [24]. In many liquid-phase syntheses of functionalized organic
compounds over acid zeolite catalysts, deactivation is essentially due to
the strong chemisorption of molecules of desired products within the
micropores, owing to their high polarity and their bulkiness; the resulting
long contact time of these molecules with the inner acid sites leads to their
transformation into carbonaceous compounds (coke). An appropriate
selection of the operating conditions (as well as the judicious selection
of the zeolite and of the type of reactor) favours desorption of the
desired products, limiting signicantly the catalyst deactivation. Thus in
acetylation of aromatic substrates with acetic anhydride, the following
operating conditions have to be chosen: high substrate/acetic anhydride
molar ratio, eventual use of a suitable solvent, temperature high enough
to favour the desorption but low enough to avoid extensive secondary
reactions, and high space velocity values to enhance the sweeping of the
products out of the zeolite catalyst [5].
Operating conditions of regeneration by coke combustion also have to
be chosen so as to limit the structural alterations of zeolite catalysts related
to the severe hydrothermal conditions. On the basis of the scheme of coke
oxidation, a two-stage regeneration system has been developed and it is
used in FCC units devoted to the treatment of residues. The rst stage
operates at a temperature just sucient to allow the combustion of most
of the H atoms and only part of the C atoms, the second stage at a higher
temperature completing the combustion. Therefore, owing to the relatively
low temperature in the rst stage and to the low partial water pressure in
the second, structural alterations of the catalysts are signicantly limited
(Chapter 12).
It should be underscored that in commercial processes in which catalyst
deactivation is relatively slow, the operating conditions in xed-bed reactors
have to be adapted as a function of time-on-stream so as to maintain a
pseudo stationary level of activity. For that, the operating temperature is
gradually increased up to a value generally imposed by the product quality.
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Note that, very often, this increase in temperature not only compensates
for the decrease in activity but also causes a decrease in selectivity and
accelerates deactivation [1, 3].
1.5. Conclusion
Although the deactivation of solid catalysts is a general phenomenon,
it has long been neglected by most of the academic researchers, who
concentrated their eorts on catalytic activity and selectivity. Fortunately,
such situation has signicantly changed, in particular, thanks to the
periodic organization, since 1980, of international symposiums on the topic
(Catalyst Deactivation 1980, 1987, 1992, etc., the last of the series being
held in October 2009 in Delft) and to the publication of various review
papers. Therefore, in most academic laboratories involved in heterogeneous
catalysis, mastering catalyst stability has now become nearly as important
as controlling activity and selectivity. However, progress in this way has
still to be realized in the eld of heterogeneously catalysed syntheses of ne
chemicals in which the catalyst is very often simply considered, at least by
academic researchers, as a consumable reagent (Chapter 17).
Very signicant progress has been made in the understanding of
deactivation phenomena that is essential to develop optimal ways to
prevent, to limit and to cure catalyst deactivation. In particular, an
ever-increasing care was placed on the choice of operating conditions
to mimic the conditions of industrial applications for investigating
catalyst deactivation (Chapter 3). Ecient techniques were developed
to characterize the deactivating species such as coke, their mode of
formation and their eects as well as the physical and chemical alterations
of zeolite catalysts (Chapters 4, 5). The general tendency is to use
mainly spectroscopic techniques often carried out in situ and even in
operando mode. That is why it does not seem superuous to remind that
to understand the complex deactivation phenomena, a multi-technique
approach, coupling them to simpler and often more laborious chemical
methods, remains indispensable.
The signicant advances in the understanding of the deactivation
mechanisms are shown in Chapters 69. The three main causes of zeolite
catalyst deactivation poisoning, coking and structural alterations are
successively considered. In the modelling of deactivation by coking, kinetic
models were recently developed that considered the chemical steps involved
in both the formation of coke and of desorbed products, then including
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the interactions between coke and product precursors. These models which
provide a wealth of information on the eects of operating conditions on
catalyst activity, selectivity and stability are powerful tools for optimizing
the behaviour of industrial reactors.
The characteristics of deactivation, in particular its rate, play
an important part in the selection of the reactor-regenerator system
(Chapter 10). Various measures can be taken to prevent or limit
deactivation (Part IV). The tuning of the catalyst features, the optimization
of operating conditions and the pretreatment of the feed to eliminate
contaminants are the easier factors to be set up. Rules for selecting
and optimizing zeolite catalysts and operating conditions in hydrocarbon
processing in order to limit the rate of coking and the deactivating eect
of coke are proposed in Chapter 11. The mode of regeneration depends
naturally on the cause(s) and on the rate of deactivation. As coke formation
is the main cause of deactivation during most zeolite-catalysed reactions,
the mechanism of coke removal by oxidation at high temperatures is
presented in Chapter 12 as well as the detrimental eect of this regeneration
treatment on the zeolite characteristics.
The last chapters (1317) are devoted to the description of deactivation
and regeneration of zeolite catalysts during commercial processes of
rening, petrochemical and ne chemical industries. Another criterion for
the process selection deals with the type of catalysis, i.e. monofunctional
catalysis over acid, noble metal and oxidation sites and bifunctional
associating metal and acid sites. These examples oer the opportunity to
underscore the complexity and the interdependence of the modes of catalyst
deactivation.
References
[1]
[2]
[3]
[4]
[5]
[6]
[7]
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[8]
[9]
[10]
[11]
[12]
[13]
[14]
[15]
[16]
[17]
[18]
[19]
[20]
[21]
[22]
[23]
[24]
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