Catalyst deactivation

Common causes
MOHAMED ABDEL AATY AHMED
MOPCO
Egypt

The causes of deactivation are basically three-fold: chemical, mechanical and thermal.
The development during the past two decades of more sophisticated surface spectroscopies
and powerful computer technologies provides opportunities for obtaining substantially better
understanding of deactivation mechanisms, catalysts have only a limited lifetime. Some lose
their activity after a few minutes, others last for more than ten years. The maintenance of
catalyst activity for as long as possible is of major economic importance in industry. A decline
in activity during the process can be the result of various physical and chemical factors like
Blocking of the catalytically active sites and Loss of catalytically active sites due to the
following mechanisms.
The mechanisms of catalyst deactivation in ammonia plant can be classified into different
common types: (i) poisoning, (ii) coking, (iii) thermal degradation, (iv) vapor compound
formation accompanied by transport, (vi) crushing. The most common causes are: Poisoning
of the catalyst, Typical poisons are H2S, Pb, Hg, S, P in primary reformer and low shift, coke
and Deposits on the catalyst surface block the active centers and change the pore structure,
Thermal processes and sintering of the catalyst lead to a loss of active surface area and
catalyst losses by evaporation of components (e. g., formation of volatile metal carbonyls with
CO in methanation reaction). These processes are shown schematically in Figure 1. We a
brief discussion about these phenomena to understand these deactivation mechanisms.

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 M. Abdel Aaty

Fig. 1: Mechanism of catalyst deactivation (M=metal) Keywords: Catalyst deactivation; Catalyst poisoning;
Catalyst sintering; Catalyst coking; Kinetics of catalyst deactivation.

WHAT DOES CATALYST DEACTIVATION MEAN?

One of the major problems related to the operation is the catalyst loss of activity with time-on-stream; this
process is both of chemical and physical nature and occurs simultaneously with the main reaction.
Deactivation is inevitable, but it can be slowed or prevented and some of its consequences can be
avoided.

Catalyst deactivation, the loss over time of catalytic activity and/or selectivity, is a problem of great and
continuing concern in the practice of industrial catalytic processes. Costs to industry for catalyst
replacement and process shutdown total billions of dollars per year. Time scales for catalyst deactivation
vary considerably; for example, in the case of cracking catalysts, catalyst mortality may be in the order of
seconds, while in ammonia synthesis the iron catalyst may last for 5–10 years. But it is inevitable that all
catalysts will decay. Steam reforming of methane or naphtha great care must be taken to avoid reactor
operation at excessively high temperatures or at steam to hydrocarbon ratios below a critical value.
Indeed, these conditions can cause formation of large quantities of carbon filaments which plug catalyst
pores and voids, pulverize catalyst pellets, and bring about process shut down all within a few hours. The
maintenance of catalyst activity for as long as possible is of major economic importance in industry.

Table 1
An overview of catalyst deactivation in large-scale industrial processes is
given in
Reaction Reaction Catalyst Catalyst Deactivation
conditions lifetime process
[years]
Ammonia synthesis 450 – 550 C Fe/K2O/ Al2O3 5-10 Slow sintering
N2 + H2 2NH3 200- 500 bar
Methanation 250-350 C Ni/ Al2O3 5-10 Slow poisoning by S
CO + 3H2 CH4+H2O 30 bar and As compounds
Methanol synthesis 200-300 C Cu/Zn/Al2O3 2-8 Slow sintering
CO+2H2 CH3OH 50-100 bar
Hydrodesulfurization 300 – 400 C CoS/MoS2/Al2O3 0.5 - 1 Deposits (decomp.
of light petroleum 35 – 70 bar Of sulfides)

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Catalyst deactivation, also known as ageing, is expressed by the

decrease in catalyst activity with time Fig. (2). Catalyst activity a
is the ratio of the reaction rate at a given time t to the reaction
rate at the time that use of the catalyst began t = 0

Activity (t) = r (t) / r (t = 0)

Not only does the decreasing catalyst activity lead to a loss of

productivity, it is also often accompanied by a lowering of the
Fig. 2: Deactivation behavior of
selectivity. Therefore, in industrial processes great efforts are made catalysts
to avoid catalyst deactivation.

COMMON CAUSES FOR CATALYSTS DEACTIVATION

Catalysts are evaluated for their activity and stability. The performance of the catalyst is determined by
parameters like lower pressure drop, lower tube wall temperature and longer operation close to
equilibrium methane conversion. These parameters can be achieved by optimizing the properties of
catalyst like — better coke resistance, easy reducibility, higher crushing strength, higher metal dispersion,
higher surface area, higher pore volume, higher geometric surface area, resistance to thermal shocks,
better heat transfer properties. Earlier catalyst average life used to be 2–3 years but because of the latest
improvement in the preparation of the catalyst the life of the catalyst was increased to 5–6 years. All
catalysts deactivate with time, although the spent material must then be processed, the nature of the
processing depends markedly on the means of deactivation. The three most common causes of catalyst
decay are coking, poisoning or thermal degradation. Coke deposition is the most common process
[Furimsky, 1996], Poisoning involves strong chemical interaction of a component of the feed or products
with active sites on the catalyst surface. Sulphur poisoning of metals is the most widely quoted example
[McCulloch, 1983 and Dowden, 1978]. Catalysis involves interfaces, and heterogeneous catalysts are
prepared with high surface areas, a condition that is thermodynamically unstable. If a suitable condition
arises such as high temperatures in the absence or presence of a suitable chemical environment catalysts
will rearrange to form the more favorable lower surface area agglomerates a process known as sintering.
The relative importance of the different deactivation processes has been reviewed by many researchers
[Al-Dalama, 2006 and Marafi, 2007]. These processes will now discuss these effects in more detail and
examine some examples from the catalysts in ammonia industry.

Deactivation processes
Catalyst Poisoning
Catalyst poisoning is a chemical effect and involves strong interaction between a component of the feed or
products and the active sites of the catalyst. Therefore, even very small quantities of catalyst poisons can
influence the adsorption of reactants on the catalyst. The term catalyst poison is usually applied to foreign
materials in the reaction system. Reaction products that diffuse only slowly away from the catalyst surface
and thus disturb the course of the reaction are referred as inhibitors. Table (2) lists some catalyst poisons
and inhibitors and the way in which they act. The poisons involve molecules that can chemisorb strongly to
a catalyst and are entirely specific. Thus, for example, carbon monoxide poisons iron, but has little effect
on copper or silver. Prevention or removal is often reasonably facile. Thus, for example, the most active
sites on a catalyst may be prepoisoned or an additive may be used that preferentially adsorbs the poison.
Removal may involve only increasing temperature, or may involve treatment with a chemical that reacts
with the poison or competes with the poison for active sites.

The critical question in the context of a poisoning process is whether it is reversible. If it is, the catalyst
may be re-usable. If not, the catalyst must be discarded. As a result, it is useful to consider the general

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classes of poison while remembering that any strong chemisorptions or interaction can poison a catalytic
surface. However, prevention is the preferred option either by using a guard process (such as
hydrodesulphurization), a guard bed (such as ZnO) or by including an additive in the catalyst that will
selectively adsorb sulphur. The total removal of poisons is often difficult, and even residual traces may
decrease activity as the catalyst is brought back on line.

Poisons can be also classified as "reversible'' or "irreversible''. In the first case, the poison is not too
strongly adsorbed and accordingly regeneration of the catalyst usually occurs simply by poison removal
from the feed. This is the case, for example, of oxygen containing compounds (e.g. H2O and CO x) for the
ammonia synthesis catalysts. These species hinder nitrogen adsorption, thus limiting the catalyst activity,
but elimination of these compounds from the feed and reduction with hydrogen removes the adsorbed
oxygen to leave the iron surface as it was before. However, gross oxidation with oxygen leads to bulk
changes which are not readily reversed: in this case poisoning is "irreversible'', and irreversible damages
are produced.

Poisoning of Metals [Hagens, J., 2005]

Metal catalysts are highly sensitive to small amounts of certain impurities in the reaction medium.
Catalytically active metals make their d orbitals available for adsorption, and this is the key to
understanding both their catalytic activity and their sensitivity to poisons.
• Poisons for metals can be classified in three groups:
– Nonmetallic ions
– Metal ions
– Unsaturated molecules

Particularly strong catalyst poisons are the ions of elements of groups 15 (P, As, Sb, Bi) and 16 (O, S, Se).
The poisoning activity depends on the presence of electron lone pairs, which have been shown to form
dative bonds with transition metals on chemisorption. If these are involved in bonding to other elements,
then the ions are nonpoisons:

Poisons : H2S, thiophene, NH3, PH3, AsH3

Non poisons: SO42- , NH+4, PO3, AsO3, sulfones

The poisoning effect of metal ions depends on the number of d electrons. Metals with an empty d shell,
such as alkali and alkaline earth metals, and those with less than three d electrons are non poisons, as
shown in the following for the example of platinum:

Poisons : Zn2+, Cd2+, Hg2+, Sn2+, Pb2+, Cu+, Cu2+, Fe2+, Mn2+, Ni2+, etc.
Non poisons: Na+, Be2+, Mg2+, Al3+, La3+, Ce3+, Zr4+, Cr2+, Cr3+

Metals readily adsorb unsaturated molecules such as CO and olefins. If they are adsorbed irreversibly in
molecular form, then they act as poisons. If dissociation or decomposition occurs, then this can lead to
deactivation by coking. Catalyst poisoning can be reversible or irreversible, depending on the reaction
conditions. For example, sulfur poisoning of nickel catalysts is irreversible at low temperatures, and
methanation catalysts cannot be regenerated, even by treatment with hydrogen. At higher temperatures
sulfur can be removed by hydrogenation and steam, so that nickel catalysts for steam reforming are
considerably more resistant to sulfur - containing poisons.

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Table 2
Catalyst poisons and inhibitors in chemical processes [Ullmann, 1985]
Process Catalyst Catalyst Mode of action
Poison,
Inhibitor
NH3 synthesis Fe S, Se, Te, P, poison: strong chemisorptions or
As compounds, formation of compounds
Halogens

O2, H2O, NO weak poison: oxidation of Fe

surface; reduction possible but
causes sintering

CO2 inhibitor : reaction with alkaline

promoters

CO poison and inhibitor: strong

chemisorption, reduction to
methane; accelerates sintering

unsaturated inhibitor : strong chemisorption, slow

hydrocarbons reduction
Hydrogenation Ni, Pt, Pd, Cu S, Se, Te, P, poison: strong chemisorptions
As compounds,

Halogens
Hg and Pb poison: alloy formation
Compounds

O2 poison: surface oxide film

CO Ni forms volatile carbonyls

Poisoning of metal catalysts can best be avoided by pre-treatment of the reactants by: Chemical treatment
(expensive; can lead to other impurities), Catalytic treatment (very effective for organic poisons) and Using
of adsorbers (e. g. ZnO to remove sulfur-containing compounds in natural gas reforming) the incorporation
of promoters can also neutralize catalyst poisons.
Thus the sulfur poisoning of nickel catalysts is reduced by the presence of copper chromite since copper
ions readily form sulfides. The appropriate treatment method and the decision whether the catalyst or the
process should be modified requires detailed knowledge of the cause of deactivation.
Thus, poisoning has operational meaning; that is, whether a species acts as a poison depends upon its
adsorption strength relative to the other species competing for catalytic sites to physically blocking of
adsorption sites, adsorbed poisons may induce changes in the electronic or geometric structure of the
surface [Hegedus, 1980 and Bartholomew, 1987].

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Sulphur poisoning
Sulphur is a severe poison for steam reforming catalysts of group VIII metals. Nickel is most susceptible
to sulphur poisoning of the group VIII metals as shown by Wise et al. (1985). Sulphur must be removed to
a very low level from the feed before it enters the reformer. Under steam reforming conditions all sulphur
compounds will be converted into H2S, which is chemisorbed on the nickel surface through the reaction:

H2S + Ni surface Ni surface-S + H2

The adsorbed sulphur forms a well defined 2-dimentional surface structure with a stoichiometry of
approximately 0.5 [Rostrup-Nielsen et al., 2002]. This corresponds to a sulphur uptake of 440 mg S per m2
nickel surface [Rostrup-Nielsen, 1984; Rostrup-Nielsen et al., 2002]. The surface coverage of sulphur on
nickel depends on the temperature and the partial pressures of H2S andH2.
The uptake of sulphur correlates with the Ni-surface area. The low H2S equilibrium pressure is also
reflected in the sulphur uptake of a catalyst pellet as illustrated in Fig. (3). A sharp sulphur profile is seen
and only the interior of the pellet furthest away from the exterior surface and the holes are unpoisoned.
The poisoning by sulphur takes place as shell poisoning due to pore diffusion. The average coverage of
sulphur in the particle will be lower than in the shell and it may take years before the chemisorption front
has moved to the centre of the particle [Christensen, 1996].

Fig. 3: Conceptual model of poisoning by sulfur atoms of a metal Surface.

Sulphur has a strong impact on the reaction rate of the reforming catalyst and will decrease the rate
significantly [Rostrup-Nielsen, 1984]. It was shown that the intrinsic activity of a catalyst decreases rapidly
with the coverage of unpoisoned sites. Other poisons reported are arsenic, lead, phosphorous, silica and
alkali metals [Rostrup-Nielsen, 1984]. Silica may substantially reduce the activity of the catalyst by acting
as a pore mouth poison [Christensen and Rostrup-Nielsen, 1996]. The alkali metals reduce the reaction
rates in some cases by orders of magnitude.

Mechanisms by which a poison may affect catalytic activity are multifold as illustrated by a conceptual two-
dimensional model of sulfur poisoning on a metal surface shown in Fig. (3). To begin with, a strongly
adsorbed atom of sulfur physically blocks at least one three- or four-fold adsorption/reaction site (projecting
into three dimensions) and three or four topside sites on the metal surface. Second, by virtue of its strong
chemical bond, it electronically modifies its nearest neighbour metal atoms and possibly its next nearest
neighbour atoms, thereby modifying their abilities to adsorb and/or dissociate reactant molecules, although
these effects may not extend beyond about 5 a.u. [Bartholomew,1987]. A third effect may be the
restructuring of the surface by the strongly adsorbed poison, possibly causing dramatic changes in
catalytic properties, especially for reactions sensitive to surface structure. In addition, the adsorbed poison
blocks access of adsorbed reactants to each other and finally prevents or slows the surface diffusion of
adsorbed reactants. Toxicity increases with increasing electro negativity [Bartholomew, 1987].

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Another approach to prevent poisoning is to choose proper catalyst formulations and design. For example,
both Cu-based methanol synthesis and low-temperature shift catalysts are strongly poisoned by S-
compounds. In these catalysts significant amounts of ZnO are present that effectively trap sulfur leading to
the formation of ZnS. The catalyst design (e.g. surface area, pore size distribution, pellet size) can also
modify the poison resistance. Finally, it is noted that the operating conditions also affect the poison
sensitivity of several catalysts: for example 5 ppm sulfur in the feed poison a Ni/Al2O3 steam reforming
catalyst working at 800 C, less than 0.01 ppm poison a catalyst working at 500 C, due to the increased
strength of S adsorption.

Sulfur adsorbs so strongly on metals and prevents or modifies the further adsorption of reactant molecules,
its presence on a catalyst surface usually effects substantial or complete loss of activity in many important
reactions. Erekson and Bartholomew (1983), study the methanation activities of Ni, Co, Fe, and Ru relative
to the fresh, unpoisoned surface activity as a function of gas phase H2S concentration. The results indicate
that Ni, Co, Fe, and Ru all suffer 3–4 orders of magnitude loss in activity at 15–100 ppb of H2S, i.e. their
sulfur tolerances are extremely low! Moreover, the sharp drop in activity with increasing H2S concentration
suggests highly selective poisoning. Nevertheless, the rate of sulfur poisoning and hence sulfur resistance
varies from catalyst to catalyst and is apparently a function of catalyst composition and reaction conditions
Indeed, it is possible to significantly improve sulfur resistance of Ni, Co and Fe with catalyst additives such
as Mo and B which selectively adsorb sulfur.

Thermal degradation and sintering

Thermally induced deactivation of catalysts results from (i) loss of catalytic surface area due to crystallite
growth of the catalytic phase, (ii) loss of support area due to support collapse and of catalytic surface area
due to pore collapse on crystallites of the active phase, and/or (iii) chemical transformations of catalytic
phases to non-catalytic phases. The Sintering processes generally take place at high reaction
temperatures (e.g. >500 ◦C) and are generally accelerated by the presence of water vapor. Most of the
previous sintering and redispersion work has focused on supported metals. Experimental and theoretical
studies of sintering and redispersion of supported metals published before 1997 have been reviewed fairly
extensively [Bartholomew, 1997].

Three principal mechanisms of metal crystallite growth have been advanced: (1) crystallite migration, (2)
atomic migration, and (3) (at very high temperatures) vapor transport. The processes of crystallite
and atomic migration are illustrated in Fig.4. Crystallite migration involves the migration of entire crystallites
over the support surface followed by collision and coalescence. Atomic migration involves detachment of
metal atoms from crystallites, migration of these atoms over the support surface and ultimately, capture by
larger crystallites. Redispersion, the reverse of crystallite growth in the presence of O2 and/or Cl2, may
involve (1) formation of volatile metal oxide or metal chloride complexes which attach to the support and
are subsequently decomposed to small crystallites upon reduction and/or (2) formation of oxide particles or
films that break into small crystallites during subsequent reduction. In general, sintering processes are
kinetically slow (at moderate reaction temperatures) and irreversible or difficult to reverse. Thus, sintering
is more easily prevented than cured.

Fig. 4: Two conceptual models for crystallite growth due to sintering by (A) atomic migrationor (B)
crystallite migration.

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Effects of important reaction and catalyst variables on sintering rates of

supported metals
Promoters Some additives decrease atom mobility, e.g. C, O, CaO, BaO, CeO2, GeO2,Cs; others
Increase atom mobility, e.g. Pb, Bi, Cl, F, or S; oxides of Ba, Ca, or Sr are “trapping agents” that decrease
sintering rate.

Pore size Sintering rates are lower for porous vs. non-porous supports; they decrease as crystallite
diameters approach those of the pores

Alkali metals, for example, accelerate sintering; while calcium, barium, nickel, and lanthanum oxides form
thermally stable spinel phases with alumina. Steam accelerates support sintering by forming mobile
surface hydroxyl groups that are subsequently volatilized at higher temperatures. Chlorine also promotes
sintering and grain growth in magnesia and titania during high temperature calcinations

As a general rule, the rearrangement of most solids will start to occur due to sintering of metal at ca. 0.3–
0.5 times the melting point of the material, and will be accelerated in particular chemical environments.
Thus, for example, moist atmospheres accelerate structural changes in oxide supports. The resulting loss
in surface area decreases the catalytic activity. Component interaction can also occur on overheating. The
formation of nickel aluminate from the reaction between nickel and alumina is a good case in point, with
the catalytic activity of Ni-aluminate being much lower than that of the metal [Ponec, 1995]. Alloy formation
or phase separation can also occur [Chinchen, 1985] which could lower overall catalytic activity.

For example, the Sintering of small Ni-particles in size and thereby loss in surface area, which will reduce
the activity. It is a complex process influenced by several parameters including chemical environment,
catalyst structure and composition, and support morphology. Factors that promote sintering include high
temperature and high steam partial pressure [Sehested, 2003, 2006; Sehested et al., 2001, 2004, 2006
and Rasmussen et al., 2004]. The sintering mechanisms have been followed by in situ electron microscopy
[Sehested et al., 2001]. Particle movement is associated with diffusion of Ni2-OH dimers on the nickel
surface; A simple model was proposed to account for the Ni-particle size growth with time as a function of
exposed gaseous environment and temperature [Sehested, 2006]. The sintering of the Ni-particles is
initially fast and will slow down as the Ni-particles growing size. The increase in the sintering rate in
H2O/H2 atmospheres is seen at temperatures above 600 C [Sehested, 2006]. Furthermore, the
dependence of H2 partial pressure is seen to be stronger. This is interpreted as a change in sintering
mechanism from particle migration and coalescence via atom migration at the support.

Accordingly, over high-surface area catalysts it is desirable to minimize the water vapor concentration at
high temperatures during both operation and activation procedures as well. The presence of specific
additives is known to reduce the catalyst sintering. For example BaO, CeO2, La2O3, SiO2 and ZrO2
improve the stability of γ-alumina towards sintering [Bartholomew, 2001], whereas Na2O enhances its
sintering. In addition to a decrease in the surface area, sintering may also lead to a decrease in the pore
openings, and eventually the pores close completely making the active species inaccessible to the
reactants.

Gas/vapor–solid reactions
Reactions of gas/vapor with solid to produce volatile compounds
Shen et al.,1981 found that Ni/Al2O3 methanation catalysts deactivate rapidly during methanation at high
partial pressures of CO (>20 kPa) and temperatures below 425◦C due to Ni(CO)4 formation, diffusion and
decomposition on the support as large crystallites; under severe conditions (very high PCO and relatively
low reaction temperatures) loss of nickel metal occurs. Thus, loss of nickel and crystallite growth are

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serious problems at the entrance to methanation reactors where the temperature is low enough and PCO
high enough for metal carbonyl formation. Agnelli et al., (1994), investigated kinetics and modelling of
sintering due to formation and migration of nickel carbonyl species. They found that the initially sharp
crystallite size distribution evolved during several hours of sintering under low temperature (230◦C)
reaction conditions to a bimodal system consisting of small spherical crystallites and large faceted crystals
favoring (111) planes. The sintering process was modelled in terms of mass transport of mobile
subcarbonyl intermediates (Fig. 5). For example is the use of nickel catalysts in the methanation of
synthesis gas. If the temperature of the catalyst bed drops below 150 C, catalyst is lost by formation of
highly toxic nickel tetracarbonyl. Long term simulations were found to predict reasonably well the
ultimate state of the catalyst. Based on their work, they proposed two solutions for reducing loss of nickel:
(1) increasing reaction temperature and decreasing CO partial pressure in order to lower the rate of
carbonyl formation, and (2) changing catalyst composition, e.g. alloying nickel with copper or adding alkali
to inhibit carbonyl species migration [Bartholomew, 2001].

Fig. 5: Formation of volatile tetra-nickel carbonyl at the surface of nickel crystallite in CO atmosphere.

Table 3
Types and examples of volatile compounds formed in catalytic reactions

Gaseous environment Compound type Example of compound

CO,NO Carbonyls and nitrosyls Ni(CO)4, Fe(CO)5 (0–300◦C)
carbonyls
O2 oxides RuO3 (25◦C), PbO (>850◦C),
PtO2(>700◦C)
H2S sulfides MoS2 (>550◦C)

Deposits on the catalyst surface (Coking)

The blocking of catalyst pores by polymeric components, especially coke, is another widely encountered
cause of catalyst deactivation. Chemical aspects of coking for catalytic reactions involving hydrocarbons
(or even carbon oxides) side reactions occur on the catalyst surface leading to the formation of
carbonaceous residues (usually referred to as coke or carbon) which tend to physically cover the active
surface. Coke deposits may amount to 15% or even 20% (w/w) of the catalyst and accordingly they may
deactivate the catalyst either by covering of the active sites, and by pore blocking.

The mechanisms for carbon formation from carbon monoxide over Ni catalysts have been reviewed by
Bartholomew. The formation of such species depends on the operating conditions, catalyst formulation,
etc. In the case of the steam reforming of hydrocarbons on Ni-based catalysts, three different kinds of
carbon or coke species were observed [Forzatti, 1999]. It appears that under certain conditions the coke is
very non-uniform, with preferential deposition of carbon in the exterior of the particle. The non-uniform
coke deposition inside the catalyst pores may be related to the existence of intra particle diffusional
limitation, as reported by Levinter et al., (1967).

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It is noted that as coke accumulates within the catalyst pores, the effective diameter of the pores
decreases, leading to an increase of the resistance to the transport of reactants and products in the pores.
If coke is concentrated near the pore mouth it will be more effective as a barrier than the same amount
evenly distributed on the pore wall, and eventually pore blockage can occur [Richardson, 1972]. The
catalyst composition does also affect significantly the coke deposition. Promoters or additives that enhance
the rate of gasification of adsorbed carbon or coke precursors and/or depress the carbon-forming reactions
minimize the content of carbon on the catalyst surface. For this reason alkali metal ions, e.g. potassium,
are incorporated in several catalysts (e.g. Ni-based steam reforming catalysts). Potassium has several
effects: it neutralizes acid sites which would catalyze coke deposition via the carbonium ion mechanism
and catalyzes the gasification of the adsorbed carbon deposits, thus providing an in situ route for catalyst
regeneration.

Coke deposition mechanism

According to Froment; (2000), the filamentous carbon formation involves the following three processes:

(1) Dissolution of adsorbed-carbon through Ni: **C ↔ CNi,f

(2) Diffusion of carbon through Ni : CNi,f ↔ CNi,r
(3) Precipitation / Dissolution of carbon : CNi,r ↔ Cf

CNi,f - Carbon concentration below the Ni surface (mol C/m3 Ni)

CNi,r - Carbon concentration on the support side (mol C/m3 Ni)

The adsorbed surface carbon, **C, at first dissolves in the Ni particle, therefore it diffuses and precipitates
at rear of the nickel crystallite. The continuous precipitation of this adsorbed carbon will form filamentous
carbon. For this process to take place, the carbon concentration in the layer just below the Ni surface, CNi,
f must exceed the carbon solubility in Ni, Csat. The higher the difference between CNi, f and Csat, the
bigger the driving force for this process of filamentous carbon formation. One carbon atom occupies two
active sites on the catalyst.

However, the critical problem in this process is catalyst deactivation caused by carbon deposition (coking)
and It has been proposed that catalyst deactivation by carbon deposition depends on the amount, type and
location of carbon formed. Basically, there are two types of carbon formation in this reaction, i.e.
encapsulating carbon and filamentous, CaO-modified Ni catalysts present high stability and good activity
with respect to Ni/Al2O3 [Ding and Yan, 2001]. Quincoces et al. (2001) suggested that catalyst promoted
with 3% of Ca presents lesser amount of whisker (filamentous) carbon with respect to Ni/Al2O3 catalyst.
The CaO addition inhibits the whisker carbon formation and is therefore more stable. This stability is
related to the formation of more reactive carbonaceous residues that act as reaction intermediate during
methane reforming. According to Kim et al. (2000) the minimum metal particle diameter needed to form
filamentous carbon is 6 nm.

According to Wang and Lu; 1998, who evaluated the catalyst performance of various Ni catalysts with
different supports, it was discovered that both types of Ni/Al2O3 catalysts, namely Ni/γ-Al2O3 and Ni/α-
Al2O3, give very high CO2 and CH4 conversions. Recent research catalyst Deactivation Simulation through
Carbon Deposition in Carbon Dioxide Reforming over Ni/CaO-Al2O3 [Istadi and Anggoro, 2011].

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Fig. 6: Schematic of encapsulating and filamentous Carbon on nickel catalyst

1. CH4 + 2* → *CH3 + *H

2. *CH3 + *H → CH4 + 2*

3. *CH3 + * → *CH2 + *H

4. *CH2 + *H → *CH3 + *

5. *CH2 + * → *CH + *H

6. *CH + *H *CH2 + *

7. *CH + 2* → **C + *H

Catalyst indicates that the fraction of vacant sites decrease drastically at beginning of the CO2 reforming
reaction. This result shows that the catalyst has a high activity. The fraction of vacant sites becomes
stagnant after a short time in the reaction. The maximum amount of encapsulating carbon is treated as a
monolayer of carbon on the Ni surface, and this monolayer is sufficient to block the active sites and
consequently deactivate the catalyst. Any multiple layers of carbon are treated as filamentous carbon in
this model. It is observed that the rate of encapsulating carbon formation increases initially at the reaction.
This is because the reaction takes place very fast in the beginning, and the site coverage of adsorbed
carbon is high. Therefore, this will increase the rate of encapsulating carbon formation. However, after a
certain period of time, the rate starts to decrease until the end of the simulation time. According to Mieville,
(1991), who studied the kinetics of coking for a reforming process, there is an inverse relationship between
the coking rate and the amount of coke formed.

Studying the carbon formation for Nickel catalysts

(i) Steam reforming reaction
Carbon formation is a challenge in steam reforming processes. The potential for carbon formation is
highest when the steam-to-carbon ratio is low or under CO2 reforming. In steam reforming processes,
carbon formation is avoided through proper design of the catalyst and steam reforming process. The
reactions leading to carbon formation are given in Table 4. Reaction (1) in Table 4 is commonly referred to
as “the Boudouard reaction”, reaction (2) as “CO reduction”, and reaction (3) as “methane cracking”.
Reaction (4) describes how hydrocarbons polymerise into long-chain hydrocarbons. The reaction product
is often referred to as “encapsulating carbon” or “gum” as mentioned. Different types of carbon may be
formed by the carbon forming reactions as illustrated in Fig. (7, 8), i.e. whisker carbon, encapsulating
carbon also called gum and pyrolytic carbon (Rostrup-Nielsen, 1984; Rostrup-Nielsen et al., 2002 and
Sehested, 2006).

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 M. Abdel Aaty

Carbon formation from higher hydrocarbons (reaction 4 in Table 4) is an irreversible reaction that can only
take place in the first part of the reactor with the highest concentration of C2 compounds. The criterion for
carbon formation can be described as a kinetic competition between the carbon forming and steam
reforming reactions. A thorough kinetic analysis, both with fresh catalyst, and towards end-of-run at each
point in the reactor, is required to accurately evaluate this criterion. In general the limits for carbon
formation from higher hydrocarbons are approached with reduced ratio of steam to higher hydrocarbons
and with increased temperature [Rostrup-Nielsen, 1994 and Christensen, 1996]. The knowledge of the
carbon limits is imperative for optimal design. Examples of pilot plant experiments at low pressure
performed to gather information about these limits are given in Table 5.

Whisker carbon formation is the most destructive form of carbon as mentioned before. It is characterised
by long filamentous nanofibres formed from the decomposition of carbon monoxide, methane or higher
hydrocarbons on the Ni-particles in gas mixtures where the steam to - hydrocarbon ratio is too low and the
temperature above a certain limit. Carbon whiskers grow by the reaction of hydrocarbons at one side of the
nickel particle and nucleation of carbon as a whisker on the other side of the nickel particle. Continued
growth may cause catalyst disintegration and increase the pressure drop. The carbon whisker has a higher
energy than graphite (Rostrup-Nielsen, 1984). This means that operation under conditions at which
thermodynamics predict formation of graphite may be feasible without carbon formation of the catalyst.

Smaller nickel crystals are more resistant towards carbon formation. The temperature at the onset of
whisker carbon formation was approximately 100 0C higher for the catalyst with small nickel crystals
(around 7 nm) than for that with large crystals (around 100 nm) (Rostrup-Nielsen et al., 2002).

In tubular reformers the formation of pyrolytic carbon is seen as reddish zones known as ‘hot bands’ on the
walls of the tubes. The pyrolytic carbon is a result of carbon formed by thermal cracking of higher
hydrocarbons, often related to loss of catalyst activity due to sulphur poisoning. Detailed insight into the
mechanism of carbon formation has emerged from a combination of in situ electron microscopy studies
and density functional calculations (Helveg et al., 2004; Abild- Pedersen et al., 2006 and Saadi et al.,
2010). Adsorbed atomic carbon is much more stable at steps than at terrace sites (Fig. 7D), and steps are
therefore much better nucleation sites for carbon. When carbon atoms cover step sites, a single graphite
layer can grow from the step as illustrated in Fig.8A. After a graphene is land has nucleated, the growth
may continue by surface or bulk transport of carbon atoms or carbon containing fragments to the island. In
this case gum has formed. Alternatively new layers may nucleate below the first graphene layer and grow
by addition of carbon atoms. This growth is accompanied by surface transport of nickel to the free nickel
surface resulting in the growth of carbon whiskers from the Ni particle (Fig. 8B and C).

Step sites thus play an important role both in having a higher turnover frequency of the steam reforming
reaction but also in carbon formation. Potassium and gold are known to retard carbon formation (Bengaard
et al., 2002; Rostrup-Nielsen et al., 2002). DFT calculations have shown that these species are
preferentially located at step sites, thus explaining their retarding effect on carbon formation.
Table 4
Reactions in steam reforming leading to carbon formation
Reaction Std. enthalpy of reaction ( - ΔHo298, kJ/mol)
1. 2CO C + CO2 172
2. CO + H2 C + H2O 131
3. CH4 C + 2H2 -75
4. CnHm/‘carbonaceous deposits’ -

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 Catalyst deactivation - common causes

(D)
Fig. 7A, B, C: Electron microscopy images Fig. 7D: Calculated energies along the
of whisker carbon (A), encapsulating carbon reaction path for steam reforming on the
gum (B) and pyrolytic carbon on the MgAl2O4 Ni(111) and Ni(211) surfaces
carrier (C) of a Ni/MgAl2O4 reforming
catalysts (Sehested, 2006)

Fig. 8: Schematic illustration of the process by which carbon whiskers are formed at the nickel particle
during steam reforming. (A) Illustration of a graphene island nucleated from a Ni (211) step at a Ni (111)
surface (Bengaard et al., 2002). (B) Schematic illustration of whisker formation. (C) In situ electron
microscopic picture of ‘lift off’ for a nickel particle from the carrier due to whisker carbon formation (Helveg
et al., 2004 )

Table 5
Carbon species formed in steam reforming of hydrocarbons on nickel catalysts
[Bartholomew,1982]

Encapsulating film Whisker-like Pyrolytic carbon

Formation Slow polymerization of Diffusion of C through Ni crystal, Thermal cracking of
CnHm radicals on Ni nucleation and whisker growth hydrocarbon;
surface, into with Ni-crystal at top deposition of C precursors
encapsulating film on catalyst

Effects Progressive No deactivation of Ni-surface; Encapsulation of catalyst

deactivation breakdown of catalyst and particle; deactivation and
increasing Δ P increasing Δ P

Temperature range (◦C) <500 >450 > 600

Critical parameters Low temperature High temperature High temperature

Low H2O/CnHm Low H2O/CnHm ratio High void fraction
Low H2/CnHm No enhanced H2O adsorption Low H2O/CnHm
Aromatic feed Low activity High pressure
Aromatic feed Acidic catalyst

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 M. Abdel Aaty

(ii) During Methanation Reaction

By Characterization and studying of surface processes at the Ni-based catalyst during the methanation
reaction [Czekaj, et al. 2007] investigated by X-ray photoelectron spectroscopy (XPS), it was found that,
publications on the methanation reaction over supported Ni highlighted the general formation and the early
steps of carbon whiskers detaching Ni clusters from the support [Helveg et al., 2004 and Bartholomew,
2001]. Especially an identification of certain nickel carbide compounds like Ni3C formed only after
extended exposure times is of importance, which will be shown in the present work, because the initiation
of the detachment mechanism of the nickel clusters from alumina support could be closely related to the
appearance and existence of Ni3C. Before only ‘‘general’’ NiCx and nickel carbide were described on pure
metallic nickel using XPS technique [Klink, et al., 1995; Tanaka, et al., 1992 and Nakano and Nakamura,
1995].

Globally, the methanation process can be described as proceeding between two stoichiometries:

CO + 3H2 CH4 + H2O

2CO + 2H2 CH4 + CO2

Ideally, the methanation reaction requires a H2/CO ratio of more than three to avoid carbon deposition at
the surface [Seemann, et al., 2006]. There are several interesting theoretical studies (mostly DFT
calculations) of the pure Ni system [Sehested, et. al., 2004; Bengaard, et al., 2002 and Abild-Pedersen,
2005]. They include the stability and diffusivity of surface species, methane activation, and graphite /
graphene formation at the surface of nickel particles (mainly whiskers formation). Also numerous
theoretical studies about pure and modified γ-Al2O3 surfaces were performed [Handzlik, et al., 2005;
Digne, et al., 2004 and C. Arrouvel, et al., 2005]. Helveg et al. (2004), proposed a mechanism of carbon
nanofibre formation, where the graphene–Ni interface is responsible for carbon fibres/whiskers formation.

Another important issue that has been extensively debated is the nature of catalytically active species. It is
well known that the hydrogenation process occurs only at metallic Ni0 sites [Ertl, 1997] and that other Ni-
species, like oxides, hydroxides or carbides are not active in the methanation reaction. Catalytically
inactive Ni-species are generated under specific conditions, especially over γ-Al2O3 support. Generally,
small lattice differences at the interface are energetically favorable (see Table 1). This is due to better
structural compatibility between the γ -Al2O3 support and these nickel compounds (Ni3C, NiO or Ni(OH)2),
whose interface with the γ -Al2O3 support is more stable than the one of pure metallic nickel particles as
illustrated in Table (6) and Fig. (9).

Fig. 9: Sketch of the catalyst structure and form of nickel carbid during methanation reaction

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 Catalyst deactivation - common causes

Table 6
Comparison of structure parameters of NiYx compounds and support
[Wyckoff, 1965]
Compound M and M–Y distance [A° ] Crystal structure
Y definition
Ni Ni metal - Cubic
Ni3C Ni, C 1.86 Trigonal
NiO Ni, O 2.08 Cubic
Ni(OH) Ni, OH 2.01, 2.39 Trigonal
NiAl2O4 Ni or Al, O 1.83, 1.96 Cubic
γ-Al2O3 Al, O 1.78, 1.93 Cubic

Mechanism of surface processes in formation of the carbon whiskers

The surface becomes decorated with carbon species (working catalyst, phase 1; 10C). Longer
methanation under fixed bed-conditions results in a severe carbon deposition and C-whiskers formation,
followed by a detachment of Ni particles from the support (working catalyst, phase 2; Fig. 10d and TEM
image; Fig. 9). It was possible to remove the deposited carbon easily, which results in partial loss of the Ni
particles (C-removal; Fig. 10e). Hansen et al. (2002) described a mechanism of a carbon migration to the
support. The study support this and in addition showed that the Ni3C and/or the NiCx are observed
described compatibility of the Ni compounds with the γ- Al2O3 support (see Table 6), we can speculate that
one of the most probable mechanism for the detachment of the Ni particles from the surface appears due
to the lattice mismatch between the smaller Ni0 particles and the γ -Al2O3 forming an additional thin
interface composed by mixed Ni–NiCx or Ni3C. The existence of the M–M3C phase was already shown by
Tanaka et al. (1992). The binding between nickel particles and the support is weakened, and smaller Ni-
clusters can be easily removed from the surface, leading to the carbon whiskers formation.

Fig. 10: The suggested mechanism for carbon deposition on Ni/Al2O3 catalyst surface (a) fresh catalyst; (b)
reduced catalyst; (c) initial state of working catalyst(d) working catalyst with carbon and C-whiskers and (e)
catalyst after C removal.

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 M. Abdel Aaty

Catalytic Physical properties to avoid carbon formation

In order to ensure good performance and a long lifetime of the catalyst in the plant, optimal physical
properties of the catalyst are just as important as optimal catalytic properties (Aasberg-Petersen et al.,
2004 and Rostrup-Nielsen, 1984). Key aspects to consider are pore size distribution and pellet shape, size
and mechanical strength. The pore size distribution must be optimised for large surface area and good
access to the active sites. The pellet shape is important with respect to packing density in the reactor and
thereby the void fraction. The pressure drop over the reactor strongly depends on the void fraction: the
higher the pellet diameter the lower is the pressure drop.
In tubular reformers the pressure drop can be large and a compromise between pellet size and void
fraction is made. The result is catalyst pellets with large external diameters and high void fraction achieved
by rings or cylinders with several holes. The shape of the catalyst is also important with respect to ensuring
a high heat transfer. This is important in tubular reformers where a high heat transfer coefficient results in a
lower tube wall temperature, thereby increasing the Life time of the tubes. A catalyst pellet with high
external surface is also desirable to maximize the effective activity. Good mechanical pellet strength is of
importance since deterioration of the pellets will increase the pressure drop in the reactor, may create hot
spots and eventually require shutdown and reload of the reactor. This means that the catalyst support
material must be stable under process conditions and under the conditions during start-up and shutdown
of the plant. The initial catalyst pellet strength should be high, but also the strength under operating
conditions should be high. Fig. (8) shows two typical shapes of commercial reforming catalyst.

Fig. 11: Examples of commercial reforming catalyst.

Mechanical failure
Attrition / crushing forms and mechanisms of failure
Mechanical failure of catalysts is observed in several different forms, including (1) crushing of granular,
pellet or monolithic catalyst forms due to a load, (2) attrition, the size reduction and/or breakup of catalyst
granules or pellets to produce fines, especially in fluid or slurry beds, and (3) erosion of catalyst particles or
monolith coatings at high fluid velocities. Attrition is evident by a reduction in the particle size or a rounding
or smoothing of the catalyst particle easily observed under an optical or electron microscope. Wash coat
loss is observed by scanning the wall of the honeycomb channel with either an optical or electron
microscope. Large increases in pressure drop in a catalytic process are often indicative of fouling, masking
or the fracturing and accumulation of attired catalyst in the reactor bed. Commercial catalysts are
vulnerable to mechanical failure in large part because of the manner in which they are formed; that is
catalyst granules, spheres, extrudates, and pellets ranging in diameter from 50 µm to several centimetres
are in general prepared by agglomeration of 0.02–2 µm aggregates of much smaller primary particles
having diameters of 10–100 nm by means of precipitation or gel formation followed by spray drying,
extrusion, or compaction [Pham, 1999].

These agglomerates have in general considerably lower strengths than the primary particles and
aggregates of particles from which they are formed. Two principal mechanisms are involved in mechanical
failure of catalyst agglomerates: (1) fracture of agglomerates into smaller agglomerates and (2) erosion (or
abrasion) of aggregates of primary particles having diameters ranging from 0.1 to 10mm from the surface
of the agglomerate. While erosion is caused by mechanical stresses, fracture may be due to mechanical,
thermal and/or chemical stresses. Mechanical stresses leading to fracture or erosion in fluidized or slurry
beds may result from (1) collisions of particles with each other or with reactor walls or (2) shear forces
created by turbulent eddies or collapsing bubbles (cavitations) at high fluid velocities.

228 Nitrogen + Syngas 2013 International Conference (Berlin, Germany 5-8 March 2013)
 Catalyst deactivation - common causes

Thermal stresses occur as catalyst particles are heated and/or cooled rapidly (start up and shutdown); they
are magnified by temperature gradients across particles and by differences in thermal expansion
coefficients at the interface of two different materials, e.g. catalyst coating/monolith interfaces; in the latter
case the heating or cooling process can lead to fracture and separation of the catalyst coating.

Chemical stresses occur as phases of different density are formed within a catalyst particle via chemical
reaction; for example, carbiding of primary iron oxide particles increases their specific volume and micro-
morphology leading to stresses that break up these particles [Kalakkad, et al., 1995]. A further example
occurs in supported metal catalysts when large quantities of filamentous carbon overfill catalysts pores
generating enormous stresses which can fracture primary particles and agglomerates.

Metal dust
Metal dusting corrosion can be a challenge in all process equipment involving synthesis gas operating with
metal temperatures in the range of 400 - 800 C. In particular, in all process concepts using heat
exchangers heated by process gas, e.g. gas heated reformer applications; the problem of avoiding metal
dusting corrosion on the heat transfer surfaces is a significant challenge. Metal dusting corrosion results in
loss of material, in some cases as ‘metal dust’, a mixture of metal, carbides, and/or carbon. In severe
cases the material wastage can be very fast, leading to catastrophic failure of equipment as well as
plugging of downstream equipment.

The attack is most often seen as shallow pits, but in other cases the attack is over the entire surface. The
corrosion product is a mixture of carbon, metal oxides and metal particles. The mechanism behind metal
dusting involves the formation of carbon from CO and, more rarely, hydrocarbons. The carbon forming
reactions are the Boudouard reaction, the CO reduction reaction and the methane cracking reactions (see
Table 3). Carbon atoms are believed to adsorb on the metal surface, dissolve in the base metal and form
carbides (iron carbides if the base metal is carbon steel, chromium carbides if the base metal is stainless
steel or a nickel alloy).

Carbides decompose into solid carbon and metal particles that on one hand further catalyse the formation
of carbon and on the other hand oxidise to inhomogeneous scales on the surface. The most current
theories of the mechanisms behind metal dusting are described in Agüero et al. (2011). It is well known
that some alloys are more prone to attack by metal dusting than others. This is ascribed to the fact that
some alloys are better at forming and maintaining sound and stable chromium oxide scales (alternatively
alumina scale) that restrict the carbon diffusion into the material. Industrial experience has demonstrated
that commercial alloys like Inconel 690, Alloy 602 CA, Inconel 693 and most recently Sumitomo 696 all
have significant resistance to metal dusting attack [Baker et al., 2002; Agarwal et al., 2001; Nishiyama and
Otsuka, 2009].

In severe synthesis gas environments, the afore-mentioned alloys are not immune but do exhibit longer
incubation times (for the first pits to appear) and low rates of material wastage compared to other
materials. Apart from alloy composition, many factors impact whether metal dusting will be seen or not in a
specific synthesis gas environment. The pre-treatment of the alloy is of the utmost importance. A surface
with a mixed oxide or a surface depleted of Cr will tend to corrode rapidly. The severity of the gas
composition is critical. It is, however, clear that the partial pressure of CO plays a major role but also the
presence of steam and hydrogen is determining for the gas aggressively. Carbon penetration into the
material can also be prevented by application of a coating on the metal surface. Various coating systems
have been proposed and investigated (Agüero et al., 2011).

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 M. Abdel Aaty

Fig. 12: Micrograph showing typical (severe) metal dusting attack

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