Catalysis Today 52 (1999) 165±181

Catalyst deactivation
Pio Forzatti*, Luca Lietti
Dipartimento di Chimica Industriale e Ingegneria Chimica ``G.Natta'', Politecnico di Milano, P.zza Leonardo da Vinci 32, 20133 Milan, Italy

Abstract

The fundamentals of catalyst deactivation are presented in this review. The chemico-physical aspects concerning the various
deactivation causes (i.e. poisoning, sintering, coking, solid-state transformation, masking, etc.) have been analyzed and
discussed, along with the mathematical description of the deactivation phenomena. # 1999 Elsevier Science B.V. All rights
reserved.

Keywords: Catalyst deactivation; Catalyst poisoning; Catalyst sintering; Catalyst coking; Kinetics of catalyst deactivation

1. Introduction tance for the design of deactivation-resistant catalysts,

the operation of industrial chemical reactors, and the
One of the major problems related to the operation study of speci®c reactivating procedures.
of heterogeneous catalysis is the catalyst loss of Deactivation can occur by a number of different
activity with time-on-stream, i.e. ``deactivation''. This mechanisms, both chemical and physical in nature.
process is both of chemical and physical nature and These are commonly divided into four classes, namely
occurs simultaneously with the main reaction. Deac- poisoning, coking or fouling, sintering and phase
tivation is inevitable, but it can be slowed or prevented transformation. Other mechanisms of deactivation
and some of its consequences can be avoided. include masking and loss of the active elements via
In the following, the causes of catalyst deactivation volatilization, erosion and attrition. In the following a
will be reviewed and the chemico-physical aspects brief description of the various deactivation mechan-
related to the various deactivation processes will be isms will be reported.
discussed, along with mathematical description of the
deactivation phenomena. 1.1.1. Poisoning
Chemical aspects of poisoning. Poisoning is the loss
1.1. Chemical, physical and kinetic aspects of of activity due to the strong chemisorption on the
catalyst deactivation active sites of impurities present in the feed stream.
The adsorption of a basic compound onto an acid
The knowledge of the chemical and physical catalyst (e.g. isomerization catalyst) is an example of
aspects of catalyst deactivation is of pivotal impor- poisoning. A poison may act simply by blocking an
*Corresponding author. Tel.: +39-02-2399-3238; active site (geometric effect), or may alter the adsorp-
fax: +39-02-7063-8173 tivity of other species essentially by an electronic
E-mail address: [email protected] (P. Forzatti) effect. Poisons can also modify the chemical nature

0920-5861/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 0 - 5 8 6 1 ( 9 9 ) 0 0 0 7 4 - 7
166 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

of the active sites or result in the formation of new ing is ``irreversible'', and irreversible damages are
compounds (reconstruction) so that the catalyst per- produced.
formance is de®nitively altered. Upon poisoning the overall catalyst activity may be
Usually, a distinction is made between poisons and decreased without affecting the selectivity, but often
inhibitors [1]. Poisons are usually substances whose the selectivity is affected, since some of the active sites
interaction with the active sites is very strong and are deactivated while others are practically unaffected.
irreversible, whereas inhibitors generally weakly and This is the case of ``multifunctional'' catalysts, which
reversibly adsorb on the catalyst surface. have active sites of different nature that promote,
Poisons can be classi®ed as ``selective'' or ``non- simultaneously, different chemical transformations.
selective''. In the latter case the catalyst surface sites The Pt/Al2O3 reforming catalysts are typical exam-
are uniform to the poison, and accordingly the poison ples: the metal participates in the hydrogenation±
chemisorption occurs in a uniform manner. As a result, dehydrogenation reactions whereas alumina acts both
the net activity of the surface is a linear function of the as support and as acid catalyst for the isomerization
amount of poison chemisorbed. In the case of ``selec- and cracking reactions. Hence basic nitrogen com-
tive'' poisoning, on the other hand, there is some pounds adsorb on the alumina acid sites and reduce
distribution of the characteristics of the active sites isomerization and cracking activity, but they have
(e.g. the acid strength), and accordingly the strongest little effect on dehydrogenation activity.
active sites will be poisoned ®rst. This may lead to ``Selective'' poisons are sometimes used intention-
various relationships between catalyst activity and ally to adjust the selectivity of a reaction: for example,
amount of poison chemisorbed. the new Pt±Re/Al2O3 reforming catalysts are pre-
Poisons can be also classi®ed as ``reversible'' or treated in the presence of low concentration of a sulfur
``irreversible''. In the ®rst case, the poison is not too compound to limit the very high hydrocracking activ-
strongly adsorbed and accordingly regeneration of the ity. Apparently, some very active sites that are respon-
catalyst usually occurs simply by poison removal from sible for hydrocracking are poisoned by S-compounds.
the feed. This is the case, for example, of oxygen- This treatment is known as ``tempering'' a catalyst [2].
containing compounds (e.g. H2O and COx) for the Table 1 reports a list of the poisons typically
ammonia synthesis catalysts. These species hinder encountered in some industrial catalytic processes.
nitrogen adsorption, thus limiting the catalyst activity, In some cases, due to the very strong interaction
but elimination of these compounds from the feed and existing between poisons and the active sites, poisons
reduction with hydrogen removes the adsorbed oxy- are effectively accumulated onto the catalytic surface
gen to leave the iron surface as it was before. However, and the number of active sites may be rapidly reduced.
gross oxidation with oxygen leads to bulk changes Hence, poisons may be effective at very low levels: for
which are not readily reversed: in this case the poison- instance, the methanation activity of Fe, Ni, Co and Ru

Table 1
Examples of poisons of industrial catalysts

Process Catalyst Poison

Ammonia synthesis Fe CO, CO2, H2O, C2H2, S, Bi, Se, Te, P

Steam reforming Ni/Al2O3 H2S, As, HCl
Methanol synthesis, low-T CO shift Cu H2S, AsH3, PH3, HCl
Catalytic cracking SiO2±Al2O3, zeolites Organic bases, NH3, Na, heavy metals
CO hydrogenation Ni, Co, Fe H2S, COS, As, HCl
Oxidation V2 O5 As
Automotive catalytic converters Pt, Pd Pb, P, Zn
(oxidation of CO and HC, NO reduction)
Methanol oxidation to formaldehyde Ag Fe, Ni, carbonyls
Ethylene to ethylene oxide Ag C2H2
Many Transition metal oxides Pb, Hg, As, Zn
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 167

``shielded'' or ``unshielded'' structures [4,5]: for

example As in the form of arsine (AsH3), having a
lone pair, is a strong poison for catalysts such as Pt in
hydrogenation reaction, whereas no effect on catalytic
activity is observed on the decomposition of H2O2,
possibly because As under oxidizing conditions is
present in the form of arsenate AsO3ÿ 4 . Along similar
lines the order of increasing poisoning activity for
sulfur species, i.e. H2S>SO2>SOÿ 4 , can be explained.
Poisoning of metal oxide-based catalysts. Metal
oxide-based catalysts are generally more resistant than
metal catalysts to deactivation by poisoning. Acid
catalysts (e.g. cracking catalysts) are poisoned by
basic materials (alkali metals or basic N-compounds)
[6]. Several studies have been reported in the literature
concerning the effects of the nature (i.e. Lewis versus
Brùnsted) and strength of the acid sites and the basic
character of the poison on the deactivation of acid
catalysts [7±9].
Oxide catalysts other than acid catalysts are also
poisoned by several compounds, and often by Pb, Hg,
Fig. 1. Effect of H2S poisoning on the methanation activity of
As, Cd. These compounds react with the catalyst
various metals (Tˆ4008C, Pˆ100 kPa, feed: 4% CO, 96% H2 for
Ni; 1% CO, 99% H2 for others) [3]. active sites usually leading to a permanent transfor-
mation of the active sites which thus become inactive.
Preventing poisoning. Poisoned catalyst can hardly
catalysts is strongly reduced by H2S in the range 15± be regenerated, and therefore the best method to
100 ppb [3] (Fig. 1). reduce poisoning is to decrease to acceptable levels
It follows that the analysis of poisoned catalysts the poison content of the feed. This is generally
may be complicated, being the content of poison of a achieved by appropriate treatments of the feed, e.g.
fully deactivated catalyst as low as 0.1% (w/w) or less. catalytic hydrodesulphurization followed by H2S
Extremely sensitive analysis is then mandatory, and adsorption or absorption to remove S-compounds,
since poisons usually accumulate on the catalyst sur- methanation for the elimination of COx from the
face, surface sensitive techniques are particularly ammonia synthesis feed, adsorption over appropriate
useful. beds of solids to remove trace amounts of poisons (e.g.
Poisoning of metal-based catalysts. Maxted [4] ZnO for H2S, sulfured activated charcoal for Hg,
reported that for metal catalysts of groups VIII B alkalinized alumina for HCl). In several processes,
(Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt) and I B (Cu, e.g. low-temperature shift, guard-beds (often consti-
Ag, Au), typical poisons are molecules containing tuted by the same catalytic material) are installed
elements of groups V A (N, P, As, Sb) and VI A before the principal catalyst bed and effectively reduce
(O, S, Se, Te). The surface metal atoms active in the the poisoning of the catalyst bed. A review of a
catalytic reactions can be depicted as involved in the number of these methods can be found in [10].
chemisorption of the reactants (and of poisons as well) Another approach to prevent poisoning is to choose
via their ``dangling orbitals''. Accordingly, any che- proper catalyst formulations and design. For example,
mical species having a ``proper electronic con®gura- both Cu-based methanol synthesis and low-tempera-
tion'' (e.g. unoccupied orbitals or unshared electron) ture shift catalysts are strongly poisoned by S-com-
or multiple bonds (e.g. CO, ole®ns, acetylenes, etc.) pounds. In these catalysts signi®cant amounts of ZnO
can be considered as potential poisons. Accordingly are present that effectively trap sulfur leading to the
several molecules have been classi®ed as having formation of ZnS. The catalyst design (e.g. surface
168 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

area, pore size distribution, pellet size) can also mod- of CnHm species at temperatures above 6008C and
ify the poison resistance: these aspects will be brie¯y deposition of carbon precursors).
discussed in the next section. The mechanism of coke formation on oxides and
Finally, it is noted that the operating conditions also sul®des is rather complex but it can be roughly
affect the poison sensitivity of several catalysts: for visualized as a kind of condensation±polymerization
example 5 ppm sulfur in the feed poison a Ni/Al2O3 on the surface resulting in macromolecules having an
steam reforming catalyst working at 8008C, less than empirical formula approaching CHx, in which x may
0.01 ppm poison a catalyst working at 5008C, due to vary between 0.5 and 1. It has been suggested that the
the increased strength of S adsorption. pathway to coke, starting from ole®ns or aromatics,
may involve: (a) dehydrogenation to ole®ns; (b) ole®n
1.1.2. Coking polymerization, (c) ole®n cyclization to form substi-
Chemical aspects of coking. For catalytic reactions tuted benzenes, and (d) formation of polynuclear
involving hydrocarbons (or even carbon oxides) side aromatics from benzene [16]. These mechanisms pro-
reactions occur on the catalyst surface leading to the ceed via carbonium ions intermediates and accord-
formation of carbonaceous residues (usually referred ingly they are catalyzed by Brùnsted acid sites. The
to as coke or carbon) which tend to physically cover details of coke-forming reactions vary with the con-
the active surface. Coke deposits may amount to 15% stituents of the reaction mixture, the operating con-
or even 20% (w/w) of the catalyst and accordingly ditions, and the catalyst used, but one can speculate
they may deactivate the catalyst either by covering of that the reactive intermediates combine, rearrange and
the active sites, and by pore blocking. Sometimes a dehydrogenate into coke-type structures via carbo-
distinction is made between coke and carbon. The nium ions-type reactions, as shown in Fig. 2. Carbo-
difference is however somewhat arbitrary: usually nium ions can also crack to form small fragments that
carbon is considered the product of CO disproportio- can further participate in the coke-forming process as
nation (2CO ! C‡CO2), whereas coke is referred to hydrogen transfer agents.
the material originated by decomposition (cracking) The chemical nature of the carbonaceous deposits
or condensation of hydrocarbons. depends very much on how they are formed, the
Mechanisms of carbon deposition and coke forma- conditions of temperature and pressure, the age of
tion on metal catalysts have been detailed in several the catalyst, the chemical nature of the feed and
reviews [11±15]; they differ signi®cantly from those products formed. Several authors pointed out a direct
on oxide or sul®de catalysts [16]. For instance, the relationship between the amount of coke deposited
mechanisms for carbon formation from carbon mon- and the aromatic and polynuclear aromatic content of
oxide over Ni catalysts have been reviewed by Bartho- the feed [19,20]. Also, it has been reported that coke
lomew [11]. The rate-determining step is presumably formation occurs more rapidly when a hydrogen
the CO dissociation leading to the formation of var- acceptor, such as an ole®n, is present [21,22], in line
ious carbon forms, including adsorbed atomic carbon with the hypothesis of a carbonium ion chemistry for
(Ca), amorphous carbon (Cb), vermicular carbon (Cn), coke formation.
bulk Ni carbide (Cg), and crystalline, graphitic carbon Various analytical techniques have been used in
(Cc) [17]. The formation of such species depends on order to characterize the nature, amount and distribu-
the operating conditions, catalyst formulation, etc. In tion of coke deposits. The chemical identity of the
the case of the steam reforming of hydrocarbons on carbonaceous deposits has been extensively investi-
Ni-based catalysts, three different kinds of carbon or gated by IR [23,24]. Other techniques are well suited
coke species were observed [18], i.e. encapsulated- for this purpose, e.g. UV±Vis, EPR, 13 C-NMR. A short
like hydrocarbons (formed by slow polymerization of review of these methods has been recently reported
CnHm on Ni surface at temperatures lower than [25]. The amounts of coke deposited into the catalyst
5008C), ®lamentous or whisker-like carbon (produced pores may be estimated by burning the coke with air
by diffusion of C into Ni crystals, detachment of Ni and recording the weight changes via TG-DTA tech-
from the support and growth of whiskers with Ni on niques and/or by monitoring the evolution of the
top), and pyrolitic-type carbon (obtained by cracking combustion products CO2 and H2O.
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 169

Fig. 2. Carbonium ion mechanism for formation of higher aromatics from benzene and naphtalene [19].
170 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

Coke deposits may not be uniformly distributed in under which carbon formation is thermodynamically
the catalyst pellets, and attempts were made to favored. Obviously this is a necessary but not suffi-
measure the coke concentration pro®les by several cient requirement in that carbon may form if the
techniques, including controlled combustion, electron carbon forming reactions are inherently faster than
microscopy, 1 H- and 129 Xe ÿ NMR, XPS, AES the carbon-removal reactions.
[25,26]. It appears that under certain conditions the The catalyst composition does also affect signi®-
coke pro®le is very non-uniform, with preferential cantly the coke deposition. Promoters or additives that
deposition of carbon in the exterior of the particle. The enhance the rate of gasi®cation of adsorbed carbon or
non-uniform coke deposition inside the catalyst pores coke precursors and/or depress the carbon-forming
may be related to the existence of intraparticle diffu- reactions minimize the content of carbon on the
sional limitation, as reported by Levinter et al. [27]. It catalyst surface. For this reason alkali metal ions,
is noted that as coke accumulates within the catalyst e.g. potassium, are incorporated in several catalysts
pores, the effective diameter of the pores decreases, (e.g. Ni-based steam reforming catalysts, Fe2O3±
leading to an increase of the resistance to the transport Cr2O3 dehydrogenating catalysts, etc.). Potassium
of reactants and products in the pores. If coke is has several effects: it neutralizes acid sites which
concentrated near the pore mouth it will be more would catalyze coke deposition via the carbonium
effective as a barrier than the same amount evenly ion mechanism previously mentioned, and catalyzes
distributed on the pore wall, and eventually pore the gasi®cation of the adsorbed carbon deposits, thus
blockage can occur [26±29]. providing an in situ route for catalyst regeneration.
Preventing coke deposition. In practice, the coke Along similar lines, bimetallic Pt±Re/Al2O3 reform-
deposition may be controlled to a certain extent by ing catalysts are superior to Pt/Al2O3 in view of their
using an optimal catalyst composition and an appro- greater resistance to deactivation by coking, which
priate combination of process conditions. During the allows long activity (up to 1 year) at relatively low H2
reaction an equilibrium is reached between the rate of pressures, without regeneration.
coke production and the rate of coke removal by
gasifying agents (e.g. H2, H2O and O2 that remove 1.1.3. Sintering
coke as CH4, CO and COx, respectively) so that Sintering usually refers to the loss of active surface
steady-state conditions, corresponding to a certain via structural modi®cation of the catalyst. This is
level of coke present on the catalyst surface, are generally a thermally activated process and is physical
eventually reached. Otherwise, if the rate of coke in nature.
deposition is higher than that of coke removal, a Sintering occurs both in supported metal catalysts
suitable regeneration procedure must be applied. and unsupported catalysts. In the former case, reduc-
For example, in hydro-desulfurization reactions the tion of the active surface area is provoked via agglom-
catalyst life is roughly proportional to the square of eration and coalescence of small metal crystallites into
hydrogen partial pressure: hence, in spite of hydrogen larger ones with lower surface-to-volume ratios. Two
cost, process equipment cost (high pressure) and different but quite general pictures have been pro-
operating costs (compression) still there remains a posed for sintering of supported metal catalysts, i.e.
substantial economic incentive for operating at high the atomic migration and the crystallite migration
H2 partial pressure. Along similar lines models. In the ®rst case, sintering occurs via escape
of metal atoms from a crystallite, transport of these
1. in the catalytic reforming processes high hydrogen
atoms across the surface of the support (or in the gas-
partial pressures are usually employed to limit the
phase), and subsequent capture of the migrating atoms
catalyst deactivation by carbonaceous deposits,
on collision with another metal crystallite. Since
and
larger crystallites are more stable (the metal±metal
2. low hydrocarbon/steam ratios are typically
bond energies are often greater than the metal±support
employed in steam reforming over Ni catalysts.
interaction), small crystallites diminish in size and the
In general, in many processes the gas mixture com- larger ones increase. The second model visualizes
position is kept as far as possible from conditions sintering to occur via migration of the crystallites
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 171

along the surface of the support, followed by collision The ®gure shows two different regimes: a rapid,
and coalescence of two crystallites. almost exponential loss of surface area during the
A number of different rate-limiting steps can poten- initial stage and, later on, a slower (almost linear)
tially be identi®ed in either model, e.g. loss. These data may be consistent with a shift from
crystalline migration at low temperatures to atomic
1. the dissociation and emission of metal atoms or
migration at high temperatures [30].
metal-containing molecules from metal crystal-
Contrasting data are available concerning the effect
lites;
of the atmosphere on sintering. For Pt-supported
2. the adsorption and trapping of metal atoms or
catalysts, several authors [31] reported that under
metal-containing molecules on the support surface;
oxidizing atmosphere the sintering is more severe
3. the diffusion of metal atoms, metal-containing
than under inert or reducing atmosphere. Bartholo-
molecules and/or metal crystallites across support
mew however observed that this is not a general case,
surfaces;
since the rate of dispersion also depends on Pt loading
4. the metal particle spreading;
(Fig. 3) [32]. These effects may be related to changes
5. the support surface wetting by metal particles;
in surface structure due to adsorbed species such as H,
6. the metal particle nucleation;
O or OH in H2, O2 or H2O-containing atmospheres,
7. the coalescence of metal particles;
respectively. This points out the role of surface energy
8. the capture of atoms or molecules by metal parti-
which depends on the gas composition and on the
cles;
kinetics of the surface reactions.
9. the metal atom vaporization and/or volatilization
Finally, the presence of strong metal±support inter-
through volatile compounds
actions (SMSI) affect the spreading, wetting and
As a matter of fact, sintering of supported metals redispersion of the supported metals: accordingly,
involves complex physical and chemical phenomena because of the strong interaction of NiO with oxide
that make the understanding of mechanistic aspects of supports, NiO/SiO2 is thermally more stable in air than
the sintering a difficult task. Ni/SiO2 in H2 [32]. Along similar lines, Pd stabilizes
Experimental observations showed that sintering Pt in O2-containing atmospheres, possibly because of
rates of supported metal catalysts are strongly affected strong interactions of PdO with the oxide supports
by the temperature and to a lower extent by the [33].
atmosphere. The effect of temperature and atmosphere Other factors affect the stability of a metal crystal-
can be easily derived from constant temperature± lite towards sintering, e.g. shape and size of the
variable time data such as those reported in Fig. 3. crystallite [34], support roughness and pore size

Fig. 3. Effects of H2 and O2 atmospheres and of metal loading on sintering rates of Pt/Al2O3 catalysts [32].
172 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

[35], impurities present in either the support or the site to sintering, i.e. redispersion [40]. This process
metal. Species such as carbon, oxygen, Ca, Ba, Ce or has been explained by either a physical splitting of the
Ge may decrease metal atom mobility, while others metal particles or to a spreading of metal monolayers
such as Pb, Bi, Cl, F or S can increase the mobility. over the surface. The redispersion is of industrial
Rare earth oxides such as CeO2 and La2O3 have been importance in catalytic reforming over Pt/Al2O3 cat-
suggested to ``®x'' noble metal atoms in automotive alysts, where it has been observed that appropriate
exhaust converters due to a strong, localized chemical chlorine treatments in the presence of oxygen during
interaction [36±38]. the catalyst regeneration procedures may be useful for
The effects of chlorides on the sintering of sup- Pt redispersion. This treatment, often termed as ``oxy-
ported noble metal catalysts has been extensively chlorination'', possibly involves the transport of metal
investigated, since in several cases catalysts are pre- oxide or oxychloride molecules through the vapor or
pared from chlorine-containing precursors (e.g. along the surface.
H2PtCl6) or are treated with chlorine-containing com- Chlorides are also well known to cause severe
pounds to maintain or enhance their acid properties. sintering of Cu in Cu-based methanol synthesis and
The presence of chlorine either in the gas-phase or on low-temperature shift catalysts (Fig. 4).
the support favors the sintering of Pt [39]. However, Metal oxide catalysts and supports are also affected
recently there has been an accumulation of convincing by sintering, that is related to the coalescence and
experimental evidences that Cl favors a process oppo- growth of the bulk oxide crystallites. The process is

Fig. 4. Temperature rise (A) and variation of catalyst activity (B, from laboratory data), Cu crystal size (C), Cl and S content (E and D,
respectively) with reactor depth for an old charge of low-temperature shift catalyst in a commercial reactor [10].
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 173

accompanied by an increase of the crystallite dimen-

sion leading to a decrease in the surface area and
porosity. Like for sintering of supported metal cata-
lysts, also in this case the mechanisms leading to
crystallites coalescence and growth are rather obscure.
In any case, the actual rate and the extent of sintering
depends on many factors, including the metal oxide
concerned, the initial crystallite size and the size
distribution, the presence of additives that favor or
promote sintering, the environment. The key variable
is temperature, so that operation at low temperatures
greatly reduces the sintering rate. Reaction atmo-
sphere also affects sintering: water vapor, in particular,
accelerates crystallization and structural change in
oxide supports. Accordingly, over high-surface area
catalysts it is desirable to minimize the water vapor
concentration at high temperatures during both opera-
tion and activation procedures as well. The presence of
speci®c additives is known to reduce the catalyst
sintering. For example BaO, CeO2, La2O3, SiO2 Fig. 5. Effects of vanadia and tungsta loading on the surface areas
and ZrO2 improve the stability of g-alumina towards of TiO2-supported V2O5-WO3 catalysts [46].
sintering [41±45], whereas Na2O enhances its sinter-
ing. In addition to a decrease in the surface area, presence of some foreign compounds in the lattice or
sintering may also lead to a decrease in the pore even on the surface. For example, V2O5 has been
openings, and eventually the pores close completely reported to favor the sintering of the TiO2-anatase
making the active species inaccessible to the reactants. support as well as the anatase-to-rutile transformation
in TiO2-supported V2O5 catalysts. On the other hand,
1.1.4. Solid-state transformation WO3 effectively contrasts this phenomenon (Fig. 5)
Solid-state transformation is a process of deactiva- [46].
tion that can be viewed as an extreme form of sintering
occurring at high temperatures and leading to the 1.1.5. Other mechanisms of deactivation
transformation of one crystalline phase into a different Other mechanisms of deactivation include masking
one. These processes may involve both metal-sup- or pore blockage, caused e.g. by the physical deposit
ported catalysts and metal oxide catalysts as well. In of substances on the outer surface of the catalyst thus
the ®rst case we can observe the incorporation of the hindering the active sites from reactants. In addition to
metal into the support, e.g. incorporation of metallic the coke deposition already discussed, masking may
Ni into the Al2O3 support (at temperatures near occur during hydrotreating processes where metals
10008C) with formation of inactive nickel aluminate, (principally Ni and V) in the feedstock deposit on the
or reaction of Rh2O3 with alumina (in automotive catalyst external surface, or in the case of automotive
exhaust catalysts) to form inactive Rh2Al2O4 during exhaust converters by deposition of P (from lubri-
high-temperature lean conditions. cants) and Si compounds.
In the case of metal oxide catalysts or supports the Certain catalysts may also suffer from loss of active
transformation of one crystalline phase into a different phase. This may occur via processes like volatiliza-
one can occur, like the conversion of g- into d-Al2O3 tion, e.g. Cu in the presence of Cl with formation of
with a step-wise decrease in the internal surface area volatile CuCl2, or Ru under oxidizing atmosphere at
from about 150 m2/g to less than 50 m2/g. elevated temperatures via the formation of volatile
Several of these transformations are limited by the RuOx, or formation of volatile carbonyls by reaction of
rate of nucleation. This process may occur due to the metals with CO [3].
174 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

Finally, loss of catalytic material due to attrition in the surface. Accordingly, if N0 is the number of active
moving or ¯uidized beds is a serious source of deac- sites on a non-deactivated catalyst and Nt is the
tivation since the catalyst is continuously abraded number of active sites at any stage of deactivation,
away. Accordingly the availability of attrition-resis- the fraction of active sites is aˆNt/N0. The goal is now
tant catalysts for ¯uid-bed catalytic cracking is ex- to relate a with a. Butt and Petersen [15] extended the
tremely important since the process operates with Langmuir±Hinshelwood±Hougen±Watson (LHHW)
regeneration and catalyst recycle. Also, washcoat loss kinetic approach to the description of systems of
on monolith honeycomb catalysts may occur, espe- changing activity, and considered the dehydrogenation
cially when the gases are ¯owing at high linear reaction of methyl-cyclohexane (A) to toluene (B)
velocities and/or when rapid changes in temperatures with formation of coke (C) according to the following
occur. Indeed differences in thermal expansion scheme:
between the washcoat and the honeycomb lead to a
loss of bonding.

2. Kinetics of catalyst deactivation

A quantitative description of deactivating systems is By considering the surface reaction A* , B* as the

essential in order to optimize the design and operation rate-determining step (kÿ2<k2<k1,kÿ1,k3,kÿ3), and
of catalytic processes, especially for fast deactivating since in most situations the rate of poisoning is small
systems. compared to the rate of reaction, i.e. k4<kÿ4<k2, the
The activity a of a deactivating catalyst is expressed following rate expression can be obtained:
according to the equation:
Rt
k2 KA CA Ct ÿ
k4 KA CA
dt
a ˆ r=r0 ; (1) rˆ e 0 1‡KA CA ‡KB CB : (4)
1 ‡ KA CA ‡ KB CB
where r0 is the initial rate of reaction (i.e., the rate of
Only in the case that the coke formation does not
reaction of a fresh catalyst sample) and r is the rate of
depend
R t on the Cconcentrations of the reacting species,
reaction measured after a determined time-on-stream).
then 0 1‡KkA4CKAA‡K
A
dt ˆ K 0
t and therefore:
r0 is generally obtained by extrapolation to zero on a C
B B

rate versus time-on-stream plot. k2 KA CA Ct 0

In general, the rate of reaction depends on the actual rˆ eÿK t : (4a)
1 ‡ KA CA ‡ KB CB
reaction conditions as well as on the activity, which is
function of the previous catalyst history: In this example the obtained rate equation clearly
satis®es the separability requirement. However, many
r ˆ r…C; T; P; . . . ; a†: (2)
situations are reported in which this criterion is not
According to the term coined by Szepe and Leven- ful®lled [15].
spiel [47], i.e. separability, possibly the rate of reaction In the case of separability of the kinetics, there are
may be separated into two terms: a reaction kinetics several mathematical forms of the deactivation func-
dependency, which is time-independent, and an activ- tion used in the literature. In all cases, a relationship is
ity dependency, which is not: searched between a and a and a population balance is
used to relate a and time, or empirical forms directly
r ˆ r0 …C; T; P; . . .†r1 …a†: (3)
relating a and time, as discussed in the following.
Usually the separable factor r1(a) is simply taken as Kinetics of deactivation by coke. Much work
a normalized variable a (0a1). has been done on coking, which is a common cause
Since the activity of a catalyst (and hence the rate of of deactivation for many petroleum re®ning and
reaction) is related to the population of the active sites petrochemical processes. In a pioneering work,
on the surface, the catalyst deactivation can be con- Voorhies [48] empirically described coke formation
sidered as the decrease of the number of active sites on as a function of time-on-stream via the following
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 175

simple equation: with 'Cˆ(CtÿCC*)/Ct. This deactivation function has

n one of the forms previously proposed for 'A, but it is
Cc ˆ At ; (5)
not necessarily identical to 'A. A rate equation similar
where Cc is the wt% of coke on the catalyst, t is the to Eq. (8) is obtained when the coke precursor is
time-on-stream, A is a constant depending on the formed from a consecutive reaction scheme.
feedstock, reactor type, reaction conditions and n is Eqs. (7) and (8) form a set of simultaneous equa-
an exponent with a value close to 0.5. In this equation tions showing that coking not only depends on the
the amount of coke formed on the catalyst is assumed reaction mechanism, but also on the composition of
to be independent of the hydrocarbon feed rate, an the reaction mixture. This approach differs from that
hypothesis that has not been con®rmed by all authors. proposed by Wojchiechowsky [51] and Szepe and
In spite of this, the Voorhies correlation has been Levenspiel [47]. The point of divergence is that these
widely accepted and probably used beyond the origi- authors relate the activity or deactivation functions
nal purposes. directly to time with several empirical functions, e.g.
A different approach has been developed by Fro- 'ˆ1ÿt, 'ˆexp(ÿt), 'ˆ(1‡t)ÿ1, 'ˆtÿ0.5 or
ment and Bishoff [49,50]. These authors relate the rate 'ˆ(1‡t)ÿN. Using 'ˆf(t) instead of 'ˆf(Cc) pre-
of coke formation to the composition of the reacting sents the obvious advantage that the rate equation is
mixture, catalyst temperature and catalyst activity. It directly expressed in terms of time and therefore it is
has been assumed that coke (C) formation could occur self-suf®cient to predict the deactivation rate at any
either by a reaction parallel or consecutive to the main process time. However, this approach is valid only
reaction: when the coke formation does not depend on the
reactants concentration, that looks like unusual.
Furthermore, the constant  appearing in 'ˆf(t)
depends on the operating conditions determining
In order to derive a rate expression for the deacti- the coke deposition, so that its application is strictly
vating catalysts, the common A$B reaction step limited to the conditions prevailing during its deter-
has been considered ®rst. According to the LHHW mination. On the other hand, Bartholomew [11]
approach, by writing the site balance equation in the argued that the approach followed by Froment and
form: Bishoff may be questionable when several forms of
carbon are present, some of which may not contribute
Ct ÿ CC ˆ C1
…1 ‡ KA CA ‡ KB CB † (6) to deactivation.
Several cases have been reported in the literature
and by assuming that the rate of the surface reaction is
concerning the non-adequacy of the separability
the rate-determining step, the following expression for
approach [52]. However, in spite of these major criti-
the rate of reaction r is obtained:
cisms, several deactivation kinetics have been accu-
kr Ct KA 'A …CA ÿ CKB † rately described by means of kinetic models involving
rˆ ; (7) the separability concept. In some cases this may be
1 ‡ KA CA ‡ KB CB
related to the number of parameters employed in the
where 'A ˆ …Ct ÿCCt
C †
remaining active (deactivation or kinetic equations leading to a good ¯exibility of the
activity function). Froment and Bishoff [49,50] model and allowing for a nice ®t of the experimental
empirically related 'A to the coke content of the data. Accordingly, a certain degree of correlation
catalyst Cc, i.e. 'Aˆexp(ÿCc) or 'Aˆ(1‡Cc)ÿ1. among the various parameters might be expected,
Accordingly, the problem is now to determine how Cc and caution must be considered when gaining physical
varies with time. When the coke formation is parallel meaning from the obtained parameters.
to the main reaction path, the following equation can The above treatments have been developed for
be easily obtained: reactions occurring under chemically controlled
regime. In real situations the picture is more compli-
kc Ct KA 'C CA cated since the presence of diffusional limitations may
rC ˆ ; (8)
1 ‡ KA CA ‡ KB CB signi®cantly affect the results. Furthermore, in the
176 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

case of fouling, coke may grow up to block the pore.

Beekman and Froment [53,54] used a probabilistic
approach to deal with this problem.
Effects of poison or coke non-uniform distribution
in the catalyst pellets. Since the 1950s, Wheeler [55]
showed that a homogeneous catalyst surface could
produce a non-linear curve in a plot of the reaction rate
versus fraction of unpoisoned surface even for a non-
selective poison. Wheeler assumed that poisons, being
strongly adsorbed, tend to collect at the exterior of
porous catalyst pellets with a very sharp front pro-
ceeding inward as the quantity of poison adsorbed by
the catalyst increases. This is the so-called pore mouth
poisoning model, and is consistent with the fact that
the deposition of several poisons is strongly diffusion
limited (Fig. 6). According to this model, the pore can
be seen as divided into two zones:
1. a catalytically inactive zone that has already Fig. 7. Decrease in pellet activity with amount of poison for
different types of poisoning. (a) All type of poisoning,  (Thiele
adsorbed its saturation amounts of poison, and modulus)2; (b) uniform poisoning, 2; (c) core poisoning,
2. an unpoisoned zone. ˆ3; (d) core poisoning, ˆ5; (e) core poisoning, 5; (f) pore
mouth poisoning, ˆ10; (g) pore mouth poisoning, ˆ100 [15].
On the opposite side, poisons with very low sticking
coef®cients tend to uniformly distribute throughout
the porous catalyst pellet (uniform poisoning). called core poisoning model that will be discussed
A schematic picture representing these two differ- below.
ent situations is shown in Fig. 6, along with the so- In the presence of a ``non-selective'' poison and
under kinetic regime, the activity of the catalyst (in
terms of r/r0) is linear in the amounts of adsorbed
poison in both the ``pore mouth poisoned'' and ``uni-
formly poisoned'' model (Fig. 7, curve a). Indeed in
these cases the net result of the poisoning is to reduce
the number of the catalyst active sites. A different
situation holds under internal controlled diffusional
regime. In this case, the catalyst with ``pore mouth
poisoning'' will show a more rapid decline in activity
with the amounts of adsorbed poison with respect to
the case of kinetic regime (Fig. 7, curves f and g).
Indeed the reactants must cross the inactive part of the
catalyst moving towards the interior unpoisoned zone
of the catalyst particle in order to react. This slows
down the process much faster than would be expected
on the basis of the fraction of the active sites actually
removed, since the outer poisoned zone offers an
additional resistance to the diffusion of the reactants
inside the catalyst pellet.
On the other hand, the activity of a catalyst uni-
formly poisoned declines less rapidly under diffu-
Fig. 6. Three limiting cases of poisoning and/or fouling. sional controlled regime than under chemical
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 177

regime (Fig. 7, curve b). Indeed the poisoning of the intrinsic kinetics of carbon burning were reported by
catalyst decreases the effective or intrinsic rate of Bondi et al. [63] to be ®rst-order in the carbon content
reaction and accordingly the reactants are able to Cc and in the oxygen partial pressure PO2 , i.e.
penetrate more deeply into the pores of the catalyst. roxˆkPO2 Cc. The validity of this assumption is cer-
Therefore they can utilize more surface area than they tainly dependent on the amount of coke present:
could initially. The net result is that the activity of the indeed in the presence of thick coke deposits, oxida-
catalyst pellet decreases less rapidly than linearly with tion would initially remove an outer coke layer so that
the amount of poison in the catalyst. It should be the rate of reaction must be zero-order in coke.
mentioned however that similar behaviors have not Much of the work devoted to the coke burning
been observed in real cases, since poisons usually tend kinetics is related to the regeneration of catalysts used
to be adsorbed at the pore inlet. in catalytic cracking. In this case, a typical amount of
A third case should be mentioned, not actually coke on deactivated catalysts is near 5% (w/w), and
common for poisons but representative e.g. for coking accordingly a sub-monolayer coverage is reasonable.
processes. This is the core poisoning model (Fig. 6), Typical examples of coke rate plots versus  are
and represents the deactivation of the pores from the reported in Fig. 8 for a SiO2±Al2O3 catalyst; the initial
inside, possibly with a sharp front. This is for example ¯atten portion of curve B in the ®gure may be ascribed
the case of a coking process in which the foulant to the fact that initially not all the surface carbon is
precursor is a reaction product that therefore may be accessible to oxygen and kinetically it represents the
formed in the center of the catalyst particle. In this transition from zero-order to ®rst-order kinetics in Cc.
case, in the presence of strong diffusional limitations, Kinetics of sintering of supported metal catalysts. A
no decrease in the catalyst activity is observed, since number of workers have attempted to correlate sinter-
the reaction takes place in the catalyst outer portion, ing kinetics via power±law expressions (PLE):
whereas the foulant accumulate in the catalyst inner
d…D=D0 †
portion. ˆ ÿk…D=D0 †n ; (9)
dt
A mathematical analysis of the cases discussed
above has been reviewed in [15,56,57]. An interesting where D is the metal dispersion and k the activated
practical conclusion deriving from the previous dis- kinetic rate constant for sintering. Alternative forms of
cussion is that a proper catalyst design may improve correlation may involve the metal surface area instead
the pellet ef®ciency upon poisoning. Indeed since of dispersion. In several cases it has been found that
poisoning usually occurs on the outer shell of the application of Eq. (9) leads to values of k varying with
catalyst pellet, the use of particularly shaped catalysts sintering time, and hence with dispersion. In particu-
or of non-uniform distribution of the catalytic material
in the pellet ± e.g. eggshell ± may favor, in principle,
the desired reaction with respect to the poisoning.
Several studies have been reported on this subject [58±
60]. For example a study of different Pt/Pd distribu-
tions in automotive exhaust catalysts and on the use of
an outer layer as scavenger for impurity poisons was
developed by Hegedus et al. [61,62]. As expected, not
a single rule does exist, but the most effective dis-
tribution of the catalytic material depends on the
manner in which the poisoning (or fouling) process
occurs.
Regeneration of coked catalysts and kinetics of coke
removal. In general, the oxidation of coke is a very
Fig. 8. Typical examples of rate plots of carbon remaining versus
rapid reaction, and in many practical applications it is burning time; SiO2±Al2O3 in air, 5388C. (*) Normal sample, 3%
diffusion limited. On the other hand, intrinsic oxida- carbon (A); (*) initial flattening due to partial inaccessibility, mix
tion kinetics are of interest for several purposes. The 7±20% carbon (B) [15].
178 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

lar, the values of k at short times are greater than those

measured at long times [32]. Thus it is not possible to
quantitatively compare kinetic parameters from this
rate expression because they are function of time, and
this indicates that a simple correlation like Eq. (9) is
inadequate to cope with the complexities of sintering
kinetics. However some trend may be identi®ed when
comparing deactivation rates of different catalysts or
of the same catalyst under different environments.
A slightly different expression has been proposed
by Fuentes et al. [64]:
d…D=D0 †
ˆ ÿk…D=D0 ÿ Deq =D0 †n ; (10)
dt
which adds the term ÿDeq/D0 to account for the
asymptotic approach observed in the typical disper-
sion versus time curves (Fig. 3). Eq. (10) is known as Fig. 9. Fluid catalytic cracking unit.
generalized power law expression, viz. GPLE. It has
been found that the various parameters appearing in these studies have been reported by Weekman et al.
the equation are modest function of time: accordingly, [65±70].
by the use of this equation it was possible to perform a Due to the complexity of the reacting system (hun-
direct quantitative comparison regarding the effect of dreds of individual reactions are involved) a suitable
temperature, time, atmosphere, metal, support and lumped model has been developed, in which a generic
promoters on the rate of sintering of supported metal class of compounds are treated as a kinetic entity with
catalysts [32]. respect to both the cracking reactions and the deac-
tivation behavior. In this respect, a very simple model
has been considered in which the gas oil charge (O) is
3. Example of deactivation in catalytic chemical cracked to a gasoline fraction (G) together with low
processes: the catalytic cracking molecular weight products and coke (X):

Fluid catalytic cracking (FCC) is used in re®neries

to produce gasoline and middle distillates from gas
oils. The process (Fig. 9) consists of a cracking unit in
which a gas oil feed is cracked into lighter components The reaction scheme reported above shows that
(gasoline) in the presence of a catalyst. During the some undesired products X are formed not only from
cracking reactions, very rapid catalyst deactivation gasoline G, but also directly from gas oil O. Accord-
occurs (with characteristic times in the order of sec- ingly, an analysis of the operation of FCC processes
onds) by coke deposition. Accordingly the spent requires the development of models for the cracker
catalyst is continuously moved to a regenerator vessel (riser) reactor and the regenerator.
where coke is burned with air. Therefore the FCC The cracker reactor can be modeled as a riser-tube
process is a representative example of how process reactor, where gas oil O and dispersing steam carry the
solutions and catalyst design have been developed in freshly regenerated catalyst upwards in two-phase
order to cope with such an unavoidable very rapid (gas±solid) ¯ow. The cracking and coke-forming reac-
decay. tions take place in the riser-tube reactor. Data obtained
Several reports are available in the literature con- with representative feedstocks and operating condi-
cerning the development and application of suitable tions in a ®xed bed reactor [65] showed that, disre-
models describing the interaction of reaction kinetics garding the very rapid initial decay, the net catalyst
and deactivation applied to the FCC process. Most of activity is described in terms of an exponential func-
 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181 179

tion of the time-on-stream, i.e.  ˆ eÿtm where  is (i.e. the product of the decay velocity  and the total
the remaining fraction of the initial activity,  the time of decay, tm), Eq. (12) is obtained:
decay velocity and tm is the time-on-stream. This dy
exponential model is consistent with a Voorhies-type ˆ ÿAy2 eÿ ; (12)
dZ
dependence of the coke content with residence time
[67]. with A ˆ 1" 0 k0 K0

LHSV ˆ LHSV ;where K0 is the rate constant
Weekman and Nace [65,67,68] developed a simple for gas oil cracking (K0ˆK1‡K3),  (ˆt/tm) is the
model for catalytic cracking for ®xed, moving and dimensionless time variable and 0 the initial vapor
¯uid beds. In the case of an isothermal ®xed bed, by density. The reaction velocity group A is the reaction
assuming rate multiplied by the vapor phase residence time and
represents the ``length'' of reaction. Integration of
1. idealized piston ¯ow; Eq. (12) yields the conversion :
2. absence of diffusional limitations; and
3. quasi-steady-state approximation. A
eÿ
ˆ1ÿyˆ : (13)
1 ‡ A
eÿ
(i.e. the decay of the catalyst is slow relative to the
vapor residence time), the unconverted weight fraction The value of gas oil conversion represented by
y of gas oil is given by: Eq. (13) is an instantaneous one.
R 1 The time-averaged
h i
value of the conversion,   ˆ 0  d ˆ 1 ln 1‡Ae1‡A
ÿ ,
dy 
v
ˆ …ÿr†; (11) is reported in Fig. 10 as a function of the decay and
dZ 1 LHSV reaction groups [65].
where Z is the axial dimensionless coordinate (Zˆz/L), Under actual reaction conditions, the reactor is best
 the bed void fraction, v the vapor density, 1 represented by a moving bed reactor. Accordingly, the
the liquid reactant density, and r is the rate of gas residence time of the catalyst in the riser (typically 5±
oil consumption and LHSV the liquid hourly space 7 s) is the characteristic time for deactivation. The
velocity. catalyst activity pro®le is invariant with time, and by
Weekman observed that the pseudo-component gas assuming plug ¯ow for both the solid and the gas
oil O cracks according to second-order kinetics, i.e. phases basically the same equations employed for
ÿr ˆ k0 y2 eÿtm . Introducing the characteristic decay ®xed beds can be adopted also for moving beds.
time ˆtm, which represents the ``length'' of decay However, the position in the catalyst bed now replaces

Fig. 10. Time-averaged conversion for fixed beds [65].

180 P. Forzatti, L. Lietti / Catalysis Today 52 (1999) 165±181

the time-on-stream, so that Z will replace  in the Eq. (15) can be integrated under isothermal condi-
argument of the exponential in the decay function. tions and plots can be obtained relating the gasoline
This means that the ``length'' of decay  is now the yield as a function of gas oil conversion for various K1/
decay velocity, , multiplied by the total residence K0 and K2/K0 values (Fig. 11) [67,68,71]. It appears
time of the catalyst in the moving bed tc, i.e. ˆtc. that the overcracking ratio K2/K0 must be very low in
The calculated conversion at the bed exit is: order to obtain good gasoline yields. The maximum
ÿ
gasoline yield is sensitive to conversion, and therefore
A
1 ÿ eÿ
ˆ : (14) the extent of conversion should be limited in the riser.
 ‡ A
…1 ÿ eÿ † Voltz et al. [70] observed that K1 is a fraction of K0,
Similar models have also been obtained for ¯uid and that these parameters (along with , the decay
beds [65]. velocity) depend primarily upon the aromatics-to-
Weekman and Nace [65,67,68] demonstrated the naphthalene ratio of the gas oil.
validity of the kinetic-deactivation model by applica- The detailed reaction engineering of the riser reac-
tion over a wide range of experimental conditions. An tor is of course more complex than it has been pre-
interesting application of the Weekman±Nace model sented here, although these results are not bad
is the maximization of the gasoline yield. In this case, approximations of industrial cracking reactors. In
by considering the reaction scheme reported above, particular, two major complications should be con-
the gasoline mass±balance equation can be written as: sidered:
dyG K1 K2
ˆ 
y2 ÿ 
yG ; (15) 1. the reactor is not isothermal;
dZ LHSV LHSV 2. the presence of gas-phase axial dispersion lowers
where yG is the mass fraction of gasoline, K1 is the rate the conversion and the yields.
constant for gasoline formation and K2 is the rate
constant for gasoline cracking. Eq. (15) shows that
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