4.

Catalyst deactivation

The activity of catalysts is typically not constant as a function of time on line in the
catalytic process. An increase in the catalytic activity can be viewed as the formation of
the catalytically active phase under reaction conditions, whereas a decrease in the
catalytic activity is typically assigned to catalyst deactivation1. The latter is typically
associated with a reduction of the number of available catalytically active sites for the
catalyzed chemical transformation. The rate of catalyst deactivation varies significantly
for the various processes resulting in a significant decrease in catalyst activity in a time
span ranging from a few seconds to several years [1,2].
Time on line
1s 1 min 1 hr 1 day 1 year
FCC
Hydrocracking
HDS
Catalytic reforming
Hydrogenation aldehydes
acetylene
fat hardening
CO (Fischer-Tropsch)
N2 (NH3-synthesis)
C3 dehydrogenation
Ethylene oxidation (EO)
n-Butane oxidation (MA)
NH3 oxidation (NO)

0.1
1.E-01 10
1.E+01 103
1.E+03 105
1.E+05 107
1.E+07 109
1.E+09

Time on line, s
Figure 4.1: Typical time scale for catalyst deactivation for various processes (redrawn
from [2] with inclusion of data on the Fischer-Tropsch process)

Catalyst deactivation is an important problem in operation of catalytic processes, since a

reduced catalyst activity may result in loss of production. Various strategies have been
designed to cope with deactivation catalysts with the prime target to keep the
productivity of the catalytic process constant. For example, in the catalytic reformer [3],
the conversion of straight run heavy naphtha (hydrocarbons with a boiling point in the
range of ca. 140-200oC) into aromatics over Pt-Re/-Al2O3, the reaction temperature is
continuously increased to counter the decreasing catalytic activity. The design of the
fluid catalytic cracker (FCC) [2,3], where atmospheric gas oil and light vacuum gas oil
(hydrocarbons with a boiling point between ca. 315 and 430oC) is cracked to gasoline in
the presence of a zeolite (Faujasite – Y with additions of H-ZSM-5), is tailored to
accommodate a rapid deactivating catalyst. The design of the reactor for the low
temperature Fischer-Tropsch synthesis (conversion of CO and hydrogen to long chain
hydrocarbons over iron- or cobalt-based catalysts) accommodates on-line catalyst
removal and addition [4].

The process of catalyst deactivation is highly dependent on the type of catalyst

employed and the type of catalytic reaction, viz. a catalyst may show negligible
deactivation in a certain catalytic reaction, but severe catalyst deactivation in another
type of reaction under otherwise similar conditions. Catalyst deactivation can be
classified in various ways, e.g. in terms of inherent deactivation and operational

1
A detailed overview on catalyst deactivation is also given by Bartholomew [1]

98
deactivation [5]. Inherent deactivation occurs by exposing the catalyst to realistic, but
clean reaction conditions. Operational deactivation results in additional decline in
catalytic activity due to exposure of the catalyst to industrial conditions. An example of
the latter is the exposure of the catalyst to trace amounts of other components, which
e.g. may lead to poisoning of the catalytically active sites. Furthermore, the loss of
catalyst particles due to mechanical disintegration of the catalyst particles can attribute
to an observed loss in catalyst activity in a particular reactor environment.

Typical forms of catalyst deactivation include sintering, collapse of pore structure, creep
of the support material, phase transformation of catalytically active material, removal of
active sites from the catalyst/reactor, coking, poisoning and fouling. Often various
deactivation mechanisms may operate simultaneously in a catalyst making it difficult to
ascertain the dominant deactivation mechanism.

4.1 Inherent catalyst deactivation

Inherent catalyst deactivation implies that the change in the catalyst activity with time
can only be mitigated by a change in the catalyst formulation. Catalysts suffering from
inherent catalyst deactivation will require a priori strategies to deal with this type of
deactivation for prolonged industrial application of this type of catalysts. Typical inherent
catalyst deactivation mechanisms may originate from the operation of the catalyst at
particular reaction conditions or from a side reaction of the feed. The operation of a
catalyst under specific reaction conditions (using a clean feed) may result in the loss in
the catalytically active surface area of the catalyst with time (e.g. via volatilization,
sintering, creep of the support material, and phase transformation). A typical side
reaction occurring with organic products as a feed or product is the formation of coke.

4.1.1 Volatilization
The catalytically active phase may volatilize under typical reaction conditions.
Volatilization will result in the transport of the catalytically active material out of the
reactor (or reaction zone), and will not longer contribute to the overall catalytic activity.

Calculating the loss of the catalytically active phase through volatilization

The maximum rate of loss of the catalytic active phase can be estimated by assuming equilibrium
between the solid, catalytically active phase and the gas phase. Thus, the maximum rate of loss
of the catalytically active phase will depend on the vapour pressure of the catalytically active
component under the applied reaction conditions, and the pressure and the flow rate of the gas
through the catalyst bed. The partial pressure of the catalytically active phase in the vapour
phase is at equilibrium equal to the vapour pressure of this compound. The mole fraction of the
compound in the gas phase is then equal:
*
p catalytica lly.active .compound
y catalytica lly.active .compound 
p total
The rate of transport out of the reactor (or reaction zone) will be equal to:
*
p catalytica
ncatalytica lly.active .compound  y catalytica lly.active .compound  ntotal   ntotal
lly.active .compound
p total
and assuming that the catalytically active component will not change the total molar flow rate
significantly, the change in the mass of the catalytically active component can be expressed as

99
 
d m catalytica lly.active .compound  *
p catalytica lly.active .compound

V
   total
dt p total  Mcatalytica lly.active .compound V
*
p catalytica lly.active .compound

V
mcatalytica lly.active .compound  mcatalytica lly.active .compound ,t 0   total
t
p total  Mcatalytica lly.active .compound V

Hence, the maximum rate of loss of catalytically active material with time is proportional to the
vapour pressure of the catalytically active material and the gas flow rate and proportional to the
reciprocal value of the absolute pressure. For example, the time required to lose 10% of the
catalytic active material can now be computed:

p total  Mcatalytica lly.active .compound V

t   0.9  m catalytica lly.active .compound ,t 0
*
p catalytica 
Vtotal
lly.active .compound
Taking, a catalyst containing 10 wt.-% of the catalytically active phase in a reaction conducted at
.
10 bar with a space velocity of 100 ml(STP)/(min g) under conditions at which the vapour
-2
pressure of the catalytically active component is 10 bar, would yield a minimum time required to
lose 10% of its catalytically active phase through volatilization between 2 and 7 years (depending
on the molar mass of the catalytically active component). The calculated time for the loss of the
catalytically active material is a minimum time, since equilibrium between the solid catalyst and
the vapour phase is assumed.

In principle volatilization must be expected for all catalytic materials, but the contribution
of volatilization to the catalyst deactivation will be negligible if the vapour pressure of the
catalytically active material is low. For instance, metals have typically a low vapour
pressure (see Figure 4.2) and thus deactivation through volatilization of the metal will be
negligible. Metals are typically present as nano-sized crystallites within a catalyst, which
will have a higher vapour pressure than bulk components (as can be seen from the
Kelvin equation:
 p sub limation d  4   M
ln 
p
 sub limation d     
 particle  RT  dparticle
)
resulting in an increase in the sublimation pressure by up to a factor of 1000 for
crystallites of a size of 1 nm, if the surface energy of the crystal is independent of size
(an increase in the surface energy with decreasing particle size [6,7] would result in a
stronger increase of the sublimation pressure with decreasing crystallite size). The
sublimation pressure of nano-sized materials rapidly approaches that of bulk materials.

100
 1.E+00
Ni(CO)4

Vapour pressure, bar

Fe(CO)5 Re2O7
VOCl3 Cu2Cl2 NiCl AgCl Sn
1.E-04

Au
1.E-08

Pd
Pt Ru
1.E-12
100 400 700 1000 1300 1600
Temperature, K
Figure 4.2: Vapour pressure of some inorganic compounds with relevance to catalytic
processes

The interaction of the catalytically active phase with the reactants may result in a phase
transformation, which may subsequently lead to the loss of the required components to
form the catalytically active phase. For example, the ammonia oxidation yielding NO is
catalyzed by Pt-Rh gauze and the platinum loss is attributed to the formation of volatile
platinum oxide, since the rate of weight loss was proportional to the oxygen content in
the gas [8]. Volatilization does not only occur at high temperatures. For instance the
formation of volatile carbonyl compounds due to the interaction of the catalytically active
phase with CO in the reaction mixture [9,10] may result in the loss of the catalytically
active materials from the reactor (reaction zone). The formation of metal carbonyls from
the metals and carbon monoxide is an exothermic reaction and thus the vapour pressure
of these carbonyls in equilibrium with carbon monoxide in the vapour phase and the
metal will decrease with increasing temperature. For instance, the Gibbs free energy for
the formation of Fe(CO)5 from -Fe increases from -2 kJ/mol at 300K to 112 kJ/mol at
500 K and for the formation of Ni(CO)4 from Ni increases from -9 kJ/mol at 300 K to 41
kJ/mol at 500 K [11] (the latter corresponds to an equilibrium pressure of Ni(CO)4 in the
presence of 10 bar of carbon monoxide at 500 K of 0.46 bar). It should however be
noted that the volatilization through the formation of metal carbonyls is likely to be
kinetically inhibited due to the strong adsorption of these carbonyls on metal surfaces
[12]. Other inorganic compounds with a high vapour pressure at low temperature, which
may result in volatilization of the catalytically active phase through the interaction with
reactants in the vapour phase, are for instance alkoxides [13].

4.1.2 Sintering
The catalytically active phase is usually in a dispersed form, i.e. small crystallites either
in a particle or on a support. The high surface energy contribution to the energy of small
crystallites yields a driving force to grow the small crystallites resulting in large
crystallites. This will thus result in a reduction of the surface area of the catalytically
active phase realising that the mass of the catalytically active phase remains constant.

101
Crystallite growth may occur for crystallites in close proximity due to surface melting (see
Figure 4.3). Crystals may come in close proximity to each other by crystallite migration,
which may originate from a 2-dimensional (surface type of) Brownian motion of the
crystallites [14] (particle migration and coalescence). The average rate of migration of
crystallites is thus expected to decrease with increasing mass (size) of the crystallites,
and the support-crystallite interaction (i.e. ‘friction’ to the surface migration). For example
Au-crystallites with a size of 3.1 nm would have a mean velocity in the gas phase of ca.
1.4.109 nm/s [15], whereas the mean velocity of these crystallites on KCl have been
determined to be 0.1-0.4 nm/s [16]. The support-crystallite interaction on oxidic supports
may take the form of Me-O-Support bonds. These bonds might be hydrolyzed with water
resulting in higher sintering rates observed in the presence of water vapour [1].

Support surface

Figure 4.3: Sintering as a surface melting process

The mobility of the catalytically active phase is expected to be greatly enhanced, when
present in liquid form. The melting temperature is strongly dependent on the crystallite
size of the solid and is expected to decrease strongly for crystallites with a size of less
than 5 nm [17,18]. For instance, the melting temperature of 2.5 nm gold crystallites has
been reported to be as low as 800 K (in comparison to 1336 K for bulk gold) [17]. Thus,
the mobility of crystallites is expected to increase with decreasing crystallite size (due to
the reduced mass of these crystallites), which can be further enhanced due to the
reduction in the melting temperature.

The surface melting process would require mobility of at least the surface atoms on the
crystallite, which is typically characterized by the Hüttig temperature (T Hüttig = 0.3.Tmelt).
The size dependent melting temperature might imply a size dependent mobility of the
surface atoms [17] resulting in sintering of adjacent crystallites with a size in the range of
1-3 nm at even lower temperatures. Bulk atoms should also change their position, if two
crystallites should yield a single crystallite. The mobility of atoms in the bulk structure
occurs at higher temperatures and is characterized by the Tamman temperature (TTamman
= 0.5.Tmelt).

Sintering requires the transport of material from one crystallite to another, if crystallites
are not adjacent to each other. The transport may occur via atomic diffusion over the
support surface or via the transport through the vapour phase (see Figure 4.4; Ostwald
ripening)). Hence, sintering of metals in the presence of oxygen is typically larger than in
the presence of hydrogen [1]. Both the formation of volatile compounds and the release
of atomic species from the catalytically active phase is expected to be dependent on the
size of the crystallite size containing the catalytically active phase, viz. smaller
crystallites (and in particular crystallites with a size less than 5 nm) are expected to form
both the atomic species and the volatile compounds more easily than larger crystallites.
Hence, the “disappearance” of small crystallites can be regarded as an auto-catalytic
process, which becomes faster since the formation of volatile compounds or the release
of atomic species will result in smaller crystallites. These crystallites are expected to be

102
even less stable, due to the lower stability of small crystallites and thus form faster the
volatile compound or release faster atomic species. In a similar manner the rate of
attachment to a larger crystallite will be size dependent, resulting in growth of the larger
crystallites at the expense of the small crystallites.

volatile compound
formation

surface
migration
Figure 4.4: Ostwald ripening: sintering through atomic diffusion or transport through the
vapour phase

The size dependent behaviour of the release of atomic species and the formation of
volatile compounds (and the reverse reaction, viz. the attachment of atomic species and
the decomposition of the volatile component) will result in a decrease of the rate of
sintering with time. Thus, sintering is expected to be more rapid, when small crystallites
are still present in the catalyst, but slow down significantly when small crystallites have
been converted into larger crystallites. Hence, the sintering process is modelled using
the so-called Simple Power Law Expression (GPLE) [1,19] (see 4.4), in which the
dispersion is assumed to reach an asymptotic equilibrium value. However, the rapid
slowing down of transport of material with changing crystallite size may lead to the
formation of quasi-equilibrium state (i.e. a state, which remains virtually unchanged),
which cannot be regarded as a true equilibrium state. Hence, the appropriate kinetics
describing the rate of sintering should consider the size dependent behaviour of nano-
sized materials showing a severe slowing down of the rate of sintering with increasing
size, but never achieving an equilibrium state.

4.1.3 Creep of support

A variety of materials can be used as the carrier for the catalytically active material. The
deposition of mid to late transition metals on typical support materials such as alumina
and silica lead to the formation of metal particles and not to the formation of a film over
the support material [20] (some metal oxides such as WO3, and MoO3 may form a film
on surfaces [21]). Commonly used supports are stable materials with typically a
relatively low surface energy, which is typically lower than that of the catalytically active
materials (see Table 4.1). This may result in the formation of support overlayers (see
Figure 4.4) as observed for Ru/TiO2-systems [22].

103
 Support Support

Figure 4.5: Creep of support material over the catalytically active materials leading to
the formation of support overlayers.

The driving force for the creep of support materials over the catalytically active phase is
the minimisation of the energy of the system. The coverage of a hemispherical metal
particle of a size dparticle with a layer of support material with a thickness tsupport is
thermodynamically feasible if:
G  Gcov ered particle  Gexposed particle  0
with
 2 
Gexposed particle  A support   support  gas phase   d   support Me   d2  Me  gas phase
4 2
3 2 
Gcov eredparticle  A'support  support  gas phase   d   support Me   d  t 2   support  gas phase
4 2
The interaction energy, support-Me, arises from electronic and chemical interactions
between the support and the metal [20,22]. This is a complex variable but can be
determined from the adhesion energy (Eadhesion) [20] (see Table 4.1).

For systems in which the surface area of the support is much larger than the surface
area of the catalytically active metal, the decrease in the area of the support not in
contact with the metal particle remains almost constant, i.e.
A support   support gas phase  A'support  support gas phase
. The thickness of the layer of the
support over the metal particle can then be estimated as:
 Me  gas phase   support Me   Eadhesion 
t  d  1  d    1  1
  support  gas phase    support  gas phase 
   
It can thus be deduced that overlayers will be formed if:
 sup port gas phase  Eadhesion  2   sup port gas phase

Hence, the formation of overlayers of support material, such as silica and alumina, over
the noble metals is hardly likely due to the small adhesion energy (see Table 4.1). The
formation of overlayers becomes more likely with transition metals such as iron, cobalt
and even nickel. Support materials with a lower surface energy such as TiO2 (TiO2 = 280
mJ/m2 [23]) will more readily form overlayers.

Creep of support material over the catalytically active material might be

thermodynamically feasible, but requires bond-breaking within the support. This process
might be facilitated by certain gas phase compounds. The oxygen bridge in oxidic
support materials can be reversibly broken with the aid of compounds, such as water,
halides and even alcohols. These compounds may thus facility the creep of support
material over the catalytically active materials.

104
Table 4.1: Surface energy of some catalytically active materials and the adhesion
energy1 on alumina and silica [20] (values in italics indicate systems, which
may form support material overlayers over the catalytically active metal)
Me-gas phase Eadhesion on Al2O32 Eadhesion on SiO23
mJ/m 2
mJ/m2 mJ/m2
Ag 814-926 323 174
Au 1131 265 227-246
Co 1870 1140 901
Cu 1220-1350 490 474
Fe 1787 1205 913
Ni 1720-1780 1192-1260 803-942
Pd 1470-1500 735
1 Eadhesion   sup port gas phase   Megas phase   sup port Me
2
Al2O3-gas phase = 650 – 925 mJ/m2
3
SiO2-gas phase = 307 – 605 mJ/m2

4.1.4 Phase transformation of the catalytically active phase

The catalytically active phase within a catalyst may not be the thermodynamically most
stable phase. There might thus be a driving force for a phase transformation of the
catalytically active material to a more stable state, which might be catalytically less
active or even inactive for the reaction under consideration. Hence, phase
transformations within catalysts have long be seen as one of the possible origins of
catalyst deactivation. For instance the transformation of the active KFeO2-phase to
Fe3O4 and KOH has been regarded as one of the deactivation mechanisms in the
styrene production by dehydrogenation of ethylbenzene [24].

The most obvious circumstance under which phase transformation may take place
occurs when the fluid phase changes from an oxidative to a reductive environment or
vice versa. Hence, phase transformation in the PdO-catalyzed combustion [25], V2O5-
catalyzed SO2 oxidation [26], Fe2(MoO4)3 catalyzed methanol and propene oxidation [27]
have been reported as the origin for catalyst deactivation.

Another example of reaction fluid condition induced phase transformation is the

transformation of iron-based catalysts in the Fischer-Tropsch synthesis (see Figure 4.6),
in which the initially present iron phase may transform into magnetite and a number of
carbides [28] depending on the reaction conditions. It should be noted that particularly in
the case of the transformation of the iron catalyst does not necessarily lead to catalyst
deactivation, but may also result in catalyst activation.

105
 Composition iron phases in

Composition iron phases in

100 100

80 c-Fe5C2 80
catalyst, %

catalyst, %
FexC c-Fe5C2
60 60

40 40
Fe3O4
20 -Fe Fe2C 20

0 0
0.1 1 10 100 10 100 1000
Time on line, hrs Time on line, hrs

Figure 4.6: Phase transformation in iron-based catalysts during the Fischer-Tropsch

synthesis
Left: Phase transformation of initially reduced Fe2O3 during the Fischer-
Tropsch synthesis at 513 K and 1 bar (feed: H2:CO:He = 1:1:3) with
XCO<5% (drawn from data in [29] with phase assignment according
to [30])
Right: Phase transformation of initially carburized Fe2O3 during the
Fischer-Tropsch synthesis at 543 K and 12.2 bar (feed H2:CO =
0.68) with XCO = 12-85% (drawn from data in [31])

The phase transition can be dependent on the crystallite size of the catalytically active
phase [32], in particular when the crystallites are small (a few nanometer in size) and
when the difference between the surface energy of the catalytically active phase and the
inactive phase differ significantly. In those cases, the contribution of the surface energy
to the overall energy of the system can be significant. This may lead to the occurrence
of, based on bulk thermodynamics, unexpected phase transformations. For instance, the
oxidation of metallic cobalt with water in the presence of hydrogen is at temperatures of
ca. 493K not expected at a ratio of the water partial pressure to hydrogen partial
pressure lower than 128. The fluid phase composition dependent oxidation of metallic
cobalt to Co(II)O with water may occur for nano-sized materials (assuming spherical
crystallites) if:
 pH   2 
6        3 
Co(II)O  H2  Co  H2O  RT  ln
0 0 0 0 2  Co
 CoO
  Co   1  0
 pH O  Co  dCo   Co  CoO  
 2   
Using surface energies for Co and Co(II)O estimated using DFT, de Swart [18]
estimated that metallic cobalt crystallites with a size less than 2.2 nm might oxidize in the
presence of water if the water partial pressure equals the hydrogen partial pressure.
Hence, the oxidation of nano-sized metallic cobalt crystallites is more facile than the
oxidation of bulk metallic cobalt, since the surface energy of Co(II)O is lower than that of
bulk metallic cobalt. The surface energy of oxides is generally lower than that of the
corresponding metal [23], and thus the oxidation of nano-sized metallic crystallites is
more facile than the oxidation of the bulk metal.

The appearance of the catalytically active component in two or more phases is typically
linked to a kinetic limitation on the phase transition (see Figure 4.6). The presence of a
gradient of the concentration of the relevant components in the fluid phase (see Chapter
5) may lead to a change in the phase of the catalytically active component. Furthermore,
it should be realized that crystal size dependent thermodynamics may also lead to the
presence of the catalytically active component in more than one phase. Crystallites

106
within a catalyst have a size distribution rather than a single size. Crystallites with a
diameter less than a critical diameter may occur in phase , whereas crystallites with a
size larger than a critical diameter may occur in phase . The latter may become more
pronounced when other processes take place simultaneously. For instance [5], it has
been observed that iron is present as magnetite and carbide in iron-based Fischer-
Tropsch catalysts. Small iron carbide crystallites are expected to transform into
magnetite under typical Fischer-Tropsch conditions. However, the magnetite crystals
within iron-based Fischer-Tropsch crystallites are typically much larger than expected
based on this transition leading to the suspicion that sintering of magnetite crystallites
has occurred. The large sintered magnetite crystallites are no longer stable under
Fischer-Tropsch conditions and will transform into carbides. The latter occurs by
cleaving off small carbide crystallites due to the density difference between carbide
crystallites and magnetite crystals [33]. Hence, the co-existence of two mechanisms for
morphology change, viz. phase transition and sintering, may lead to a steady-state
catalyst, in which two phases co-exist (see Figure 4.7).

sintering in the
presence of H2O
Fe3O4 Fe3O4

Fe3O4 Fe3O4
Fe3O4

Fe3O4
oxidation with H2O
with formation of H2/CO Fe3O4
Fe2C Fe C
2
Fe2C
Fe2C Fe2C Fe2C Fe2C
Fe2C
Fe2C Fe3O4 Fe C Reductive carburisation with
2
simultaneous crystallite break-up
Fe2C

Figure 4.7: Dynamic transitions of in a precipitated iron-based Fischer-Tropsch catalyst

[5]

4.1.5 Coking
Most organic compounds are thermodynamically unstable against their decomposition
into carbon and the other elements (see Figure 4.8). Hence, the carbon deposition can
always be expected to be a possible route for catalyst deactivation, since the coverage
of the active metal surface with a graphene sheet (single layer carbon sheet) will impede
access of the reactants to the active sites and thus retard the catalytic reaction. This can
be classified as inherent deactivation if the function of the catalyst is to form or convert
organic compounds which may also yield carbon deposited on the catalytically active
site.

Coking is not precisely the same as carbon deposition, although the thermodynamic
driving force is similar. Coke should be considered as a collective name for the formation
of all kinds of carbonaceous deposits ranging from graphitic carbon, poly-aromatic
structures, single aromatic structures, to even long chain hydrocarbons. They may,
depending on the feed, incorporate to some extent other elements (oxygen, nitrogen,

107
sulphur and even metals). The type of coke formed depends on the type of catalyst
used, the feed/product molecules and the reaction conditions.

1E+40
1-decene
n -decane

n-1
Kp, pH2 /phydrocarbon, bar 1E+30 n -butylbenzene

naphthalene
1-hexene
1E+20
n -hexane

benzene
1E+10
n

Methane
1

1E-10
300 600 900 1200

Temperature, K
Figure 4.8: Thermodynamic stability of some hydrocarbons (as given with data from
[34])
For instance, the Kp for the decomposition of methane (CH4  C + 2H2) at 700K is given as
0.11 bar. This means that if the partial pressure of methane is 1 bar, carbon will not form if
the hydrogen partial pressure is larger than 0.33 bar.

On metallic catalysts the formation of carbonaceous deposits may occur via the
decomposition of the carbon containing precursor yielding atomic carbon on the surface
is related to the metal catalysed formation of carbon nanotubes and fibrils from organic
feedstock [35]. Carbon atoms adsorbed on metallic surfaces may recombine (it should
however be recognized that these carbon atoms may also diffuse into the metal lattice,
e.g. with iron, yielding metal carbides). The recombination of adsorbed carbon atoms
seems to yield with a light preference linear chains of carbon adsorbed on the metal
surface [18,37], which upon branching and formation of larger rings will yield a graphene
overlayer covering the metal [38]. The resulting graphene layer is bonded strongly to the
surfaces, due to the large number of carbon atoms in these structures resulting in a low

108
mobility of these overlayers [39]. The presence of various types of carbon has been
observed experimentally, and is classified in terms of their reactivity towards hydrogen
as C, C and C [40-42]

Figure 4.9: Formation of graphene overlayers on metal surface (FCC(111)) [17,37]

A: adsorption of atomic carbon and small linear carbon clusters
B: formation of long carbon chains by sequential addition of atomic
carbon atoms
C: joining of carbon chains leading to formation of graphene overlayers

In other type of catalysts other mechanisms may play a role. For instance, in acid
catalysed reactions the formation of extended aromatic structures typically involves
hydrogen transfer from the adsorbed species yielding hydrogen enriched compounds in
the fluid phase (e.g. paraffins in the conversion of methanol, olefins or aromatics over
acid catalysts) and hydrogen-poor adsorbed species on the catalyst. The exact
mechanism of the formation of these adsorbed species is not known, but it may proceed
via the activation of the C-H bond in the reactant yielding a carbonium ion (rather than

109
the activation of the -bond yielding a carbenium ion) [43,44]. Cyclization and further
dehydrogenation via hydride transfer [1] may lead to the formation of carbonaceous
deposits with a hydrogen to carbon content lower than that of the feed.

Zeolites can be used as acid catalysts and their specific pore structure, with pore sizes
in the order of the size of molecules may result in a specific type of carbonaceous
deposit leading to catalyst deactivation. The size of the pores prohibits the formation of
large aromatic (graphene-like) structures due to geometric constraints within the pores
although the formation of these structures on the external surface of these materials
remains feasible and similar structures may be formed in the large cavities present in
some of the zeolitic structures. Hence, catalyst deactivation in reactions catalysed by
zeolites is expected to depend on the structure of the zeolite and on the crystal size of
the zeolites. Analysis of coke on a deactivated zeolite HY used for the conversion of n-
heptane at 450oC [45] showed that it consisted mainly of poly-aromatic compounds,
whereas coke on the deactivated zeolite H-ZSM-5 consisted mainly of alkylated
monocyclic and bicyclic aromatic compounds. Similar compounds were also observed in
the coke formed in the methanol conversion over H-ZSM-5, which could be extracted in
CH2Cl2 [46]. The presence of these bulky compounds in the pores of the deactivated
catalyst may induce severe diffusional limitation and thus reducing the catalyst activity.

coke on external surface

Figure 4.10: Coke on the external surface of the zeolite crystal in the form of extended
aromatic structures and extractable coke in the form of mono and bicyclic
aromatic compounds within the pore structure of the zeolite crystal

Although coke is generally thought to be hydrogen-poor, i.e. containing less hydrogen

than the feed, sometimes catalytic reactions can be retarded by the formation of
oligomeric species of the reactant. The oligomeric species may diffuse slowly away from
the catalytically active site and impose an additional diffusion resistance in the approach
of the reactants to the active site. The formation of oligomeric species can be expected
for reactions performed at a low temperature (and high pressure), since oligomerisation
(and polymerisation) are thermodynamically favoured at these conditions.

The prevalence of different coking mechanisms at different temperatures can have

unexpected consequences for the catalyst life time. Figure 4.11 shows the catalyst life
time in the conversion of methanol to gasoline over the acid catalyst H-ZSM-5 as a
function of the reaction temperature. With increasing temperature the catalyst life time
initially increases and reaches a maximum at temperatures around 400oC. Higher
reaction temperatures result in a decrease in the catalyst life time. At low temperature

110
the pores of the zeolite will be filled with relatively bulky aromatic compound, e.g. tri and
tetra methyl benzene, which will convert rather slowly in slimmer isomers (the latter can
diffuse rather fast out of the pore system). With increasing temperature the conversion of
the bulky intermediates will be accelerated, resulting in less blockage of the pore
system. At temperatures higher than 350oC coking on the external surface will start
playing a role.

1000
Catalyst life time, h

100

10

0.1

0.01
200 300 400 500

Reaction temperature, Trxn, oC

Figure 4.10: Catalyst life-time in the methanol conversion (pMeOH,inlet=2.5 bar; WHSV = 1
gMeOH/(gcatalyst.hr) as a function of the reaction temperature (catalyst life time
defined as the time to obtain methanol in the reactor outlet – graph redrawn
from [46])

4.2 Operational catalyst deactivation

The industrial application of catalysts may give rise to deactivation phenomena not
observed under clean laboratory conditions. In industrial operation the feed to the
catalytic reactor is usually cleaned, but an important question is what kinds of impurities
and how much are allowed to pass over the catalyst without reducing the catalytic
activity and catalyst life-time too much. These impurities may physically adsorb on the
catalyst (fouling) or strongly chemisorb on the active site (poisoning). Furthermore, the
hydrodynamic environment of the catalyst under industrial conditions may affect the
mechanical stability of the catalysts.

4.2.1 Fouling
Fouling is defined as the physical deposition of compounds from the fluid phase on the
catalytic surface and in the catalyst pores [1]. These compounds may land up in the
process stream through the use of e.g. pumps. The physical adsorption of these
compounds is a particular problem in catalytic processes operating at low temperature,
since at high temperatures these compounds may adsorb on the catalytically active site
(poisoning) and even be converted (and may then act as a coke precursor). The
presence of these compounds may result in emerging the catalytically active site in a
different phase, and thus an additional diffusional resistance, which may lead to a

111
reduction in the catalytic activity if the reaction becomes controlled by mass transfer
limitations.

4.2.1 Catalyst poisoning

Poisoning of the catalyst occurs when compounds from the fluid phase chemisorb on the
active site replacing the reactants due to their strong affinity for the catalyst. For
instance, the adsorption of a base stronger than the reactants in an acid catalysed
reaction (e.g. ammonia in the conversion of hydrocarbons over a zeolite). The term
poison is therefore related to a particular reaction and a particular catalyst system (see
Table 4.2). Carbon monoxide is known to adsorb strongly on metal surfaces and is thus
a poison for most metal catalysed reactions, but it is a reactant in the Fischer-Tropsch
synthesis.

Table 4.2: Poisons for catalytic reactions [1]

Reaction Catalyst Poison
system
NH3-synthesis Promoted Fe O2, CO, S, H2O, C2H2
Steam reforming CH4/naphta Ni H2S, As
Hydrogenation/dehydrogenation Ni, Pd, Pt Compounds of S, P, As, Zn, Hg,
halides, Pb, NH3, CO, C2H2, O2
Fischer-Tropsch Co, Fe H2S, COS, carbonyls, halides, As,
HCN, NH3
Hydrocracking Pt,Pd/zeolite NH3, S, Se, Te, P
Catalytic cracking zeolites NH3, organic bases, metals
Ethylene oxidation Ag C2H2
Complete oxidation of hydrocarbons Pt, Pd Pb, P, Zn, SO2, Fe
Oxidation/selective reduction Vanadium oxide As, Fe, K, Na from fly ash
Hydrotreating of residue CoMo-sulphide Asphaltenes, N compounds, Ni, V

A basic understanding of the effect of poisoning of the catalyst can be obtained by a

simple Langmuir-Hinshelwood model for a chemical reaction with competitive
adsorption. Consider the adsorption of the reactant A with the subsequent conversion of
adsorbed A as the rate limiting step in a heterogeneously catalysed reaction (and the
adsorption of all other intermediates to be negligible):
A + *  A*  products  rA  k  A
A poison (P) present in the feed will compete with the reactant A for the active sites:
P + *  P*
The site balance is now given by: *  A  P  1
K ads,A  p A
A 
1  K ads,A  p A  K ads,P  pP
Substituting the pseudo-equilibrium condition:
k  K ads,A  p A
 rA 
1 K
ads,A p  K
A ads,P P p
and the rate of consumption of A is given by:
The rate of consumption of A is thus retarded, and the extent of this retardation depends
on the strength of adsorption of the poison and its concentration. This simplified picture
may thus yield some insight in the behaviour of poisons which compete for the same
active site, but does not react further. It should be realised that if the concentration of
the poison in the feed is temporarily increased to a higher level, the return to the original

112
level of poison concentration in the feed will restore the catalyst activity, if poisoning
occurs by competitive adsorption.
Sulphur and analogue compounds are often mentioned as possible poisons for a variety
of catalytic reactions. The heat of associative adsorption of e.g. H2S on a variety of
metals is not that strong (Au(111): -22 kJ/mol [47]; Cu(111): -20 kJ/mol [47]; Pt(111): 88
kJ/mol [48]; Pd(111): 60-70 kJ/mol [49]; Fe(110): - 48 kJ/mol [50]) in comparison to the
heat of adsorption of e.g CO (Fe(100): 109-183 kJ/mol [51]) or even the dissociative
chemisorption of H2 (Pd(111): 110 kJ/mol [52]; Fe(100): 58 kJ/mol [51] ). However, H2S
may dissociate on some metal surface forming very stable surface SH-groups and
surface S-species [48-50, 53]. Hence, the poisoning effect due to the presence of
sulphur compounds is not primarily due to their strength of adsorption, but rather due to
the formation of very stable decomposition products. This can be regarded as an
irreversible reaction if the side products of the decomposition are continuously removed
from the catalyst surface. This kind of poisoning, i.e. the formation of a strongly bound
surface species upon adsorption of the poison can be better modelled as an irreversible
process:
P + *  X* + Y
A non-steady state process will now occur, which can be modelled for example as:
X
 kpoison  ppoison  *
t
Suppose that the catalyst catalyzes the reaction of A to products, with the conversion of
adsorbed A as the rate limiting step and the adsorption of all other intermediates to be
negligible”:
A + *  A*  products  rA  k  A
A  Kads,A  pA  *

Together with a site balance: *  X  A  1

1  X
* 
1  K ads,A  p A
This can be interpreted as the Langmuir isotherm on the non-poisoned (deactivated)
surface. Substituting this back into the non-steady-state balance:
 X 1  X
 kpoison  ppoison 
t 1  K ads,A  p A
k poison ppoison
 t
1K ads ,A p A
X  1  e

Thus, the rate of consumption of reactant A is now given by:

poison poison k p
k  K ads,A  p A  1K ads ,A p A t
 rA  e
1  K ads,A  p A
The rate of reaction is thus retarded relative to the reaction in the absence of the poison
with a factor corresponding to the irreversible coverage of the surface with the strongly
bonded surface species. The catalyst deactivates stronger with time if the concentration
of the poison in the feed increases, but also if the transformation of the poison into the
strongly bonded surface species is enhanced. The catalyst deactivates less strongly if A
adsorbs strongly on the surface and if the partial pressure of the reactant A is high. It

113
should be noted that if the concentration of the poisons doubles, the time to reduce the
activity to e.g. 50% of its original activity halves. In other words, if the catalyst life time
with a feed containing 5 ppm of a particular poison is given as 1 year, doubling the
poison concentration to 10 ppm will lead to a reduction in the catalyst life time to 0.5
year. Furthermore, a temporary upset in the poison concentration to the feed will lead to
a permanent reduction in the catalytic activity.

The formation of strongly bonded surface species from poisons will typically lead to a
concentration profile of the strongly bonded surface species over the catalyst bed with
the highest amount being present at the bed entrance. Hence, the reduction in the
catalyst activity will be strongest at the bed entrance.

Poisons, e.g. sulphur containing compounds, may induce a phase change. This would
lead to a change in the catalytically active phase and thus rendering the catalyst
inactive. For instance [54], the addition of a small amount of 2-chlorobutane to the feed
of the iron-based Fischer-Tropsch synthesis (p2-chlorobutane, inlet = 0.01 bar; pCO,inlet = 6.7 bar;
pH2,inlet = 13.3 bar) lead to an initial increase in the CO-conversion, but removal of the
chlorinated compound rendered the catalyst virtually inactive (see Figure 4.11). Chlorine
was found to be incorporated in the catalyst as FeOCl, a phase transformation leading to
the formation of a catalytically inactive phase.

period of addition
2-chlorobutane
CO-conversion, XCO, mol-%

80

60

40

20

0
0 20 40 60
Time on line, hrs

Figure 4.11: CO-conversion as a function of time-on-line in the iron-based Fischer-

Tropsch synthesis (ptotal= 20 bar; (H2/CO)inlet = 2; SV = 600 mlsynthesis
.
gas/(gcatalyst min). After 40 hrs on-line, 2-chlorobutane was added to the feed
(CO:2-chloro-butane = 670:1). After 45 hrs on-line, 2-chlorobutane was
removed from the feed [54].

Sometimes, the presence of a poison on the surface in small amounts may yield even a
positive effect. For instance, it has been reported that a limited sulphur poisoning of the
nickel reforming catalyst leads to a reduction in the extent of coke formation on these
catalysts [55]. Thus, the blocking of the surface area with strongly adsorbed sulphur

114
containing species is off-set by the reduction of the active metal surface area with coke.
In another case, it has been reported that surface modification of an iron-based Fischer-
Tropsch catalyst with sulphur may result an increase in the catalytic activity [56] due to
an electronic promotion of the surface [57].

4.2.3 Mechanical failure of catalysts

Catalyst in industrial environment may experience loss in activity due to carriage out of
catalyst fines from the reactor. This will result in a reduction of the catalyst mass present
in the reactor and thus a reduction in the observed activity (although the intrinsic activity
of each particle is maintained). Fines can be generated in different ways:
1. crushing of extrudates/pellets in fixed bed reactors due to load
2. erosion of particles in high velocity flow fields (e.g. in monoliths)
3. shattering of catalyst particles in fluidized bed or slurry bed reactors (the result of
the impact of the catalyst particle on the wall would result in the formation of
smaller particles)
4. abrasion of catalyst particles in fluidized bed or slurry bed reactors (the result of
the impact of the catalyst particle on the wall would result in the formation of fines
leaving the main particle at approximately the same size)
5. Break-up due to particle expansion, e.g. via coke or carbon formation [58]

Intuitively, the crushing of extrudates/pellets should be related to the porosity of the

catalyst particle, with highly porous materials less resistant against crushing [1]. Porosity
is required to enhance the transport of the reactants to the catalytically active sites.
Hence, methods to strengthen the particles without a loss in porosity are still required.

The collision of particles with walls and internals in fluidised bed and slurry bed reactors
may lead to shattering of particles and/or abrasion of the particles. The likelihood for
shattering of spray-dried catalyst particles was shown to increase with increasing particle
diameter, whereas abrasion showed an inverse proportionality to the particle diameter
[58].

A rather poorly understood mechanical failure of the catalyst is the so-called ‘chemical’
attrition [58]. Other deactivation mechanisms, such as carbon formation or phase
transition, may put strain on the catalyst particle and result in particle shattering. Hence,
the deactivation due to these mechanisms may result in a more severe activity loss than
expected based on the single deactivation mechanism.

4.3 Catalyst regeneration

The objective of catalyst regeneration is to recover (at least partially) the original activity
of the catalyst. This is of great economic importance, especially for catalysts with a
relative short life time. In some cases, the whole reactor design and operation of the unit
is centred around the need for catalyst regeneration. This is especially the case for
reactions with a very short catalyst life time, such as fluid catalytic cracking (FCC) where
the catalyst life time is in the order of seconds.

The removal of coke from a catalyst can be achieved by burning of the coke in air. The
high temperature associated with this process may induce further deactivation of the
catalyst, e.g. via sintering in supported metal catalysts. The decoking process on
zeolites typically proceeds stepwise [46], i.e. coke is firstly dehydrogenated forming
water followed by the conversion of carbon to CO and CO2. The formation of water at

115
high temperatures may lead to additional deactivation processes. For instance, the
presence of water around zeolites (alumino-silicates) at high temperatures may lead to
the removal of aluminium from the crystal structure. The activity of these materials is
typically related to the number of aluminium atoms within the crystal structure and
removal of these atoms may thus reduce the number of active sites present in the
catalyst.

Sintering is in principle from a thermodynamic point of view an irreversible step.

However, the sintering process can be reversed by application of a suitable chemical
treatment of the catalyst. For instance, the regeneration of the bi-functional Pt/Al2O3-Cl
naphtha reforming catalyst treatment of the catalyst in a water/HCl containing
atmosphere [59], which results in the formation of Pt-containing particles with a metallic
core coated with [Pt(OH)4Cl2]2- species. Upon reduction of these species, small Pt-
crystallites are formed [60] (‘splitting crystal’ model). The splitting of crystals may be
expected with other treatments, such as those yielding materials with a significantly
different density from the metal and e.g. the formation of a metal oxide. The reduction of
metal oxide crystallites may result in the formation of significantly smaller metal
crystallites upon reduction, if the original crystallites are large enough. The governing
factor here should be the stress induced in the crystal upon reduction in relation to the
surface energy of the smaller crystallites. An alternative metal re-dispersion model is the
so-called thermodynamic model [61], in which the metal oxide crystallites break off
during the oxidation of the metal particle.

4.4 Consequences of catalyst deactivation for activity/selectivity

Catalyst deactivation leads primarily to a decrease in the catalytic activity by reducing
the number of active sites available for the catalytic reaction. The time-dependent
decrease in the rate of reaction in the case of coke formation is often denoted with the
term a:
 rA t  t   rA t  0  at 

The deactivation parameter a can be empirically related to:

da
 k deact  an
dt with a=1 @ t=0 [62]
Thus,
1

n=1 a  ek deact t n≠1 a  1  k deact  t  1  n1n

(Note: the 1st order deactivation kinetics (n=1) results in a similar result as obtained in
kpoison  ppoison
k deact 
1 K p
ads,A A , i.e. a global ‘rate’
the deactivation by poisoning with
constant dependent on the partial pressures of the poison and the reactant).

For sintering processes, another form of a simple power law expression (SPLE) has
been proposed [1], which describes the increase in the crystallite size of the catalytically
active phase with time:

116
  dcrystallite,t  t 
d  n
 dcrystallite,t 0   dcrystallite,t  t 
  k  
sin tering   
dt d
 crystallite,t 0 
The magnitude of n is determined by the mechanism of sintering, viz. for Ostwald
ripening n is typically between 2-5, whereas n is larger than 8 for particle migration and
coalescence [63]. Thus, the change in the average crystallite diameter can be
determined from:

 
dcrystallite,t  t 1
 1  n  k sin tering  t  1 1n
dcrystallite,t 0

The change in the catalytic activity is however related to the available surface area,
which is a function of the surface area of a single crystallite and the number of
crystallites present.
2
Area  ncrystallites,t  t    dcrystallit
e,t  t
If only sintering takes place, a mass balance around the catalytically active phase leads
to:
 3 
ncrystallites,t t   dcrystallite,t t  ncrystallites,t 0   d3crystallite,t 0
6 6
d3crystallite,t 0
ncrystallites,t  t  ncrystallites,t 0 
d3crystallite,t  t

d3crystallite,t 0 2 dcrystallite,t 0
Area  ncrystallites,t 0     ncrystallites,t 0    dcrystallit
e,t 0 
dcrystallite,t  t dcrystallite,t  t

 
dcrystallite,t 0 1
 1  n  k sin tering  t  1 n1
Area

Area t 0 dcrystallite,t  t

The decrease in the catalytic activity for a surface insensitive reaction can be expressed
with the deactivation factor a and is given by:

 
1
a  1  n  k sin tering  t  1 n1

The various deactivation mechanisms do yield differences in the plot of the activity factor
as a function of time, however often insufficient information is gathered over a too limited
time period to make definite statements about the deactivation mechanism. A study on
the deactivation at various temperatures would allow a determination of the activation
energy for deactivation, which would assist in developing a better understanding on
catalyst deactivation.

In the presence of mass transfer limitations, the extent of loss in catalyst activity can be
masked. Consider a catalyzed, first order reaction:
A  Products  rA  k  CA

117
The rate constant, k, is a function of the number of sites available for reaction. If the
catalyst is poisoned randomly, only a fraction of the active sites ((1-) sites) are
available for reaction. The observed rate of reaction is then,
 rA, observ ed  η  k  1  α  CA
Hence, the rate over the poisoned catalyst relative to the fresh catalyst in the absence of
mass transfer limitations ( = 1) is given by:
 rA, observ ed,poisoned
F  1  α 
 rA, observ ed,unpoisoned
When the reaction is severely affected by internal mass transport limitations, the
effectiveness factor can be approximated by the reciprocal value of the Thiele module:
1
η

The rate of reaction is then given by:

 rA, observ ed   1  α  CA   k  1  α   CA
k 3 Def f

 Rparticle ρcataly st

The rate over the poisoned catalyst relative to the rate over the fresh catalyst is therefore
 rA, observ ed,poisoned
F  1  α 
 rA, observ ed,unpoisoned
A catalyst operating under severe mass transfer limitations shows therefore a lower
extent of deactivation than the same catalyst operating unaffected by internal mass
transfer limitations. Catalyst deactivation results in a higher concentration of the reactant
at the active site, compensating partially for the decline in active sites. This is also called
“anti-selective poisoning” [1].

Catalyst deactivation is not always caused by random removal of active sites. In some
cases, the active sites near the outer surface of the catalyst particle are taken out
selectively, e.g. when the deactivating agent adsorbs very strongly on the active site or
when the deactivating agent is bulky. The selective removal of active sites near the outer
surface of the catalyst particle is also called “pore-mouth poisoning” [1] (see Figure
4.13). The concentration of the reactant at the outside of the catalyst particle is CA,out,
and the concentration of the reactant at the end of the zone containing the poisoned
catalyst sites is CA,1. The concentration gradient over the zone of poisoned catalyst sites
is thus:
ΔC

CA,out  CA,1
Δr 1 - α 0.33  Rparticle
The concentration of the reactant at the end of the zone of poisoned catalyst sites, CA,1,
can be estimated by realizing that the amount of material diffusing through the pore
mouth equals the amount reacted in the pore:
2
4    Rparticle  dC A 
robserv ed   DA,ef f ectiv e    ηp  k    CA,1
4 3
ρcataly st     Rparticle  dr r Rparticle
3

118
 Poisoned
sites,
(1-)

Active
Sites, 

CA, out
CA, 1

CA

⅓.R
(1-)⅓.R
r
Figure 4.12: Pore mouth poisoning of catalyst particles (Note that catalyst deactivation
takes out a fraction of  active sites which corresponds to a reduction in the
radius of the catalytically active material ith a factor of 0.33)

3  D A,ef f ectiv e
1 - α 0.33  Rparticle
2
C A,1   C A,out
 
3  D A,ef f ectiv e 
ρ  η k  
 cataly st p 1 - α 0.33  Rparticle
2 
 
1
CA,1   CA,out
 R2 ρ  k 
 particle

cataly st
   1   0.33  ηp  1 , which can thus be expressed
 3 DA,ef f ectiv e 
 

in terms of the Thiele module of the unpoisoned catalyst:

Rparticle k  ρcataly st
u  
3 D

1
 1  0.33  ηp  1
CA,1   CA,out
2
u 

The observed rate of reaction over the poisoned catalyst relative to the rate over the
unpoisoned catalyst is now:
- rA, observ ed,poisoned ηp  k    CA,1 ηp 
F
- rA, observ ed,unpoisoned

ηu  k  CA,out
 

ηu u2    1   0.33  ηp  1 

119
The effectiveness factors of the poisoned and fresh catalyst can be estimated based on
the Thiele module of the respective catalyst. The Thiele module for the poisoned catalyst
is linked to the Thiele module for the fresh, unpoisoned catalyst:
0.33  Rparticle  k    ρcataly st
p    0.83  u
3 D

Thus, the ratio of the effectiveness factor for the poisoned to the fresh, unpoisoned
catalyst is given by
P 1  1 1 
 
 

u 0.83  tanh 0.83  u 0.83  u  
Hence, the effect of pore mouth poisoning on the activity can be estimated knowing the
Thiele module for the fresh unpoisoned catalyst.

Figure 4.13 summarizes the effect of internal mass transfer limitations on the resulting
activity (for isothermal catalyst particles). In the absence of internal mass transport
limitations, the observed extent of catalyst deactivation, 1-F, is directly proportional to
the loss in the number of active sites. In the case of random catalyst deactivation, the
extent of deactivation is less than obtained in the absence of internal mass transfer
limitations, due to the compensation of the higher average concentration of the reactant
in the pore. Pore mouth poisoning leads to a higher observed loss in activity, then
observed for random poisoning. This can be attributed to the lower concentration on the
outside of the catalytically active zone.

1
Rate over poisoned catalyst
relative to rate over fresh

Random poisoning,
severe mass transfer limitations
0.8
catalyst, F

0.6
Pore mouth poisoning:
0.4 u=1
u=2
0.2
u=10

0
0 0.2 0.4 0.6 0.8 1
Fraction of poisoned catalyst, 
Figure 4.13: The effect of catalyst deactivation on the catalyst activity as a function of
the fraction of the catalyst radius

External mass transfer limitations will reduce the extent to which catalyst deactivation is
observed. External mass transfer limitations will result in a lower concentration of the
reactant on the outside of the catalyst particle. A reduction in the rate of reaction due to

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catalyst deactivation will result in an increase in the concentration of the reactant on the
outside of the catalyst particle mitigating the effect of catalyst deactivation.

Catalyst deactivation does not necessarily lead to a change in the product selectivity.
For example, when active sites act independently taking out a number of active sites will
not lead to a change in the activity of the non-deactivated site – the effect is similar to
reducing the catalyst mass in the reactor. However, catalyst deactivation may affect the
selectivity when catalyst sites do not operate independently, since the disappearance of
adjacent catalyst sites may result in a slower deliverance of one the reactants and so
affecting the selectivity.

Catalytic reactions performed under mass and heat transfer limitations will affect not only
the activity but also the selectivity of the catalytic reaction, if the selectivity is influenced
by mass transport limitations. The presence of deactivated catalytic sites results in a
change in the concentration (and temperature) profile within the catalyst pores.

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