2392 Ind. Eng. Chem. Res.

2007, 46, 2392-2398

Measurement and Modeling of the Kinetics of Catalyst Decay in Fixed Beds:

The Eurokin Survey
John J. Birtill*
Department of Chemistry, The UniVersity of Glasgow, Glasgow G12 8QQ, Scotland, United Kingdom

Experimental techniques for the practical measurement of catalyst decay are reviewed, and some gaps and
needs are suggested for future progress. Catalyst decay kinetics in fixed beds can be modeled according to
a hierarchy of techniques, from purely empirical to rigorously fundamental. Empirical modeling is usually
preferred for practical industrial purposes. Besides the need to decouple reaction kinetics, decay kinetics, and
any influence of pore diffusion, for slowly decaying catalysts, the slow rate of data acquisition is a limiting
factor. Hence, there is a need for better equipment design and better procedures for the efficient and informative
testing of catalyst decay.

1. Introduction Table 1. Power-Law Decay Kinetics1

This review is a concise summary of the main findings of a
study that was commissioned recently by the Eurokin consor-
tium (www.dct.tudelft.nl/eurokin). The aim of the study was to
define the current state of learning and best practice for the study
of industrial catalyst decay kinetics and to present it in a
structured, informative manner. The focus was on fixed catalyst
beds with a long life. Much of the background information was
collected from an extensive literature survey, covering >700
papers from the past 50 years. In this paper, for the purpose of
brevity, references are made to previous literature for some
concepts that have already been well-described.
The requirements for industrial research and development
include practical and efficient techniques for the experimental
measurement of catalyst decay and the empirical modeling of
decay kinetics. The end-uses include catalyst development,
catalyst selection, prediction of catalyst life, and monitoring and
optimization of process catalyst performance. From limited
published information and background knowledge, it seems that
industrial catalyst decay models typically involve significant
theoretical approximation and make use of all available per-
formance data including studies at the laboratory, pilot, and plant
scale, post mortem characterization, and, in some cases,
accelerated decay. Exact determination of catalyst decay kinetics
is time-consuming and expensive, and so some compromise
between scientific rigor and industrial pragmatism is inevitable,
especially when testing multiple catalyst formulations at an early
stage of development. Hence, simple empirical models are
favored over fundamental models for plausible fitting to a
limited range of data. However, as catalyst and process
development becomes more advanced, progressively more
accurate knowledge is required. Simple models may be adequate
for catalyst selection and process design, but their reliability
for extrapolation outside the experimental range is uncertain.
The nature of the decay mechanism should be determined in
any serious study of catalyst decay kinetics to provide some
sense of the physical basis of an empirical rate law and hence
also of its likely limitations. However, this paper is concerned
mainly with decay kinetics, and so mechanistic aspects of decay
and methods of characterization are considered only in outline
with some additional thoughts under Gaps and Needs.
* To whom correspondence should be addressed. E-mail:
john.birtill@ntlworld.com. Address: 15 Portman Rise, Guisborough
TS14 7LW, UK. Phone: 0044 1287 638265.
10.1021/ie060590v CCC: $37.00 2007 American Chemical Society
Published on Web 03/13/2007
concentration decay
activity decay dependence rate-da/dt activity-time a
independent m ) 1 none kda exp(-kdt)
independent m * 1 none kdam (1+ (m - 1)kdt)-1/ (m-1)
parallel/series reactant/product kdCnam complex
General reactant/product kd(C)am complex
1 Activity is sometimes expressed mechanistically as a ) (S/S )p, where
0
S is the number of sites still active and p is the reaction site order. If the
loss of sites -dS/dt ) kS(C)Sq, then the activity decay can still be
expressed in one of the previous forms by rearrangement: -da/dt )
pkS(C)am, where m ) (p + q - 1)/p.
2. Catalyst Decay Kinetics
Before describing test methods for catalyst decay kinetics, it
is first necessary to consider the various types of models for
catalyst decay that are in common use. The deactivation kinetics
describes the variation of catalyst activity at each point in the
catalyst bed in response to time, temperature, and composition
of the fluid phase. The concept of separable reaction and decay
kinetics is usually assumed to apply.1-3 This should be tested
at various stages of decay,4 basically by showing that the
reaction kinetics does not change during decay. The catalyst
activity can also be related to the accumulated quantity of coke
and the coking kinetics.5-8
The interrelation of the effects of pore-diffusion resistance
and decay are considered briefly in section 5. In the absence of
such effects, the following approaches are commonly used for
describing the rate of activity decay.
Table 1 shows examples of well-known empirical power-
law deactivation kinetics and related activity-time expressions.
Independent decay is not affected by the composition of the
fluid phase, and so the decay rate is uniform along a fixed
isothermal catalyst bed, although it usually varies with
temperature.1-3,9 If the decay is composition-dependent, then
the decay rate is not uniform along a fixed catalyst bed but
varies with the local fluid composition as well as temperature.1-3
Independent decay kinetics can often be fitted wrongly if the
range of data is inadequate (section 4).
The use of these empirical expressions can be extended to
include more complex cases such as a residual steady state
activity,10,11 activation-deactivation,12 additive decay kinet-
ics,1,3,13 multiplicative decay kinetics,13-15 and, in principle,
bifunctional catalysts. However, as discussed in section 6,
complex expressions require extensive data for plausible model

Table 2. Activity-Coke Expressions and Activity Decay Kinetics
activity-coke power-law decay
type dependence a kinetics -da/dt1
linear (1 - RCC) RkCCAna
exponential exp(-RCC) RkCCAna2
hyperbolic 1/(1 + RCC) RkCCAna3
1 Same activity-coke relationship for coking and main reaction. This
example: parallel coking: dCC/dt ) kCCAn
fitting. Some published studies describe the rapid initial loss of
activity to a residual near steady-state, followed by slow decay.
If the steady-state is influenced by reaction conditions, then this
could be important for an industrial catalyst, but the long, slow
decay in the main part of life is usually more important and
more difficult to determine.
Mechanistic poisoning/balance-of-sites expressions describe
the loss of active sites due to poisoning by impurities or reaction
byproducts. They are derived from decay mechanisms and may
be complex and non-separable. Although they provide insight
into poisoning decay, they often include too many adjustable
parameters for practical models. Deactivation due to impurity
poisoning can also be considered more simply in terms of axial
poison conversion models16 with progressive loss of active sites.
Empirical activity-coke relationships are used in combination
with coking kinetics.5-8 Activity-coke relationships accounted
for 25% of all experimental models found in the literature
survey, and the exponential relationship was the most common.
In practice, many catalysts accumulate quite large amounts of
coke due to multilayer adsorption or polymeric structures and,
in some cases, pore filling. The choice between empirical
activity power-law decay kinetics and empirical coking kinetics
with empirical activity-coke relationships is a matter of
judgment. As shown in Table 2, these approaches are equivalent
if the activity-coke relationship for the coking reaction is the
same as for the main reaction.17 Some authors try both
approaches.18
In general, the activity power-law expression provides a
simpler, more direct statement of decay than the combination
of coking kinetics with an activity-coke relationship. The
additional error from the measurement of the coke content will
increase the overall uncertainty in the decay model as compared
to the activity power-law approach. The choice depends on
questions of practicability, purpose, and benefit.
(i) Can the coke content and coking kinetics be well-
determined? Although in many cases the bulk coke content can
be determined accurately (e.g., gravimetrically or by complete
oxidation to CO2) bed-average activity-coke data from integral
reactors are not reliable for decay modeling (section 4).
Moreover, not all the coke is necessarily deactivating. Methods
for determining coking kinetics are discussed briefly in section
4.
(ii) Why is it desirable to measure coke? Knowledge of coking
kinetics might be important for various reasons, for example,
when feed stock conversion to coke is significant, when detailed
information on coke location and content is required for design
purposes (e.g., regeneration or reactor pressure drop), for
detailed modeling of intra-particle fouling (see following section
and section 5), or for catalyst development.
(iii) Is the additional insight justified by the additional effort?
Various mechanistic justifications can be derived for activity-
coke relationships. Frequently, however, the nature of the
deactivation by coke is unknown or poorly characterized. An
empirical activity-coke relationship is a correlation with
unproven physical significance even if it fits well to some data
sets. The relationship between coking and catalyst decay could
Ind. Eng. Chem. Res., Vol. 46, No. 8, 2007 2393
be indirect (e.g., coking rate is dependent on catalyst activity,
but activity decay is caused by some other mechanism). In
catalyst development, the coking kinetics may provide useful
mechanistic insight into the influence of catalyst composition
on catalyst stability. In some cases, selectivity may be related
to the quantity of coke (section 3).
The weakness of the activity power-law expression is that it
contains no hint of the decay mechanism, and if the range of
decay data is limited, then it might obscure and oversimplify
complex decay kinetics.
Activity power-law expressions are unsuitable when the
impact of changes in pore diffusion is significant, in which case,
if the decay is caused by fouling, it is necessary to study the
fouling (coking) kinetics in relation to the pore structure to
model the decay kinetics reliably (section 5).
Empirical power-law expressions are also used to describe
the loss of surface area due to metal particle sintering. The
expressions are formally similar to those described previously
for deactivation kinetics and may incorporate a residual term
to describe an eventual steady-state dispersion.10,19 However,
if the empirical activity-surface area relationship is nonlinear,
due to the influence of different crystal faces or surface defects,20
then it will usually be more useful to model activity decay
directly. Fundamental mechanistic models of particle sintering
are difficult to develop and so are outside the scope of this work.
Although there has been significant effort in the development
of fundamental models of sintering, no examples of fundamental
models of activity decay due to sintering were found.
3. Selectivity Change
Selectivity may increase or decrease as a consequence of
catalyst decay. If the selectivity-conversion plot at fixed
temperature does not change, then any observed selectivity
change is only apparent. The selectivity can be restored to its
original value by increasing space time so as to restore the
conversion to its original value.21 This type of selectivity change
can be described by the reaction kinetics in combination with
the deactivation kinetics. An intrinsic selectivity change is
caused by a change in the relative rate constants of contributing
parallel or series reactions due to a change in the fundamental
nature of one type of active site or in the relative abundance of
different sites or of multi-site clusters. Hence, a decay model
might need more than one power-law expression or activity-
coke relationship to describe the changing activity for different
types of site and different types of reactions.5,8 Selectivity may
also change due to changes in pore diffusion properties (section
5).
4. Experimental Techniques for Deactivation Kinetics
To determine a realistic decay model, it is necessary to
decouple activity and concentration effects in the rate equation.1-3
The main challenge is to measure a sufficient range of useful
data that contains sufficient information for fitting a decay
model. This requires decay tests with variation of space time
W/F and feed composition according to a suitable plan. This
discussion is limited to slowly decaying catalysts, and for these,
the collection of sufficient data in a reasonable period of time
is an additional challenge. The suitability of various types of
reactors for the study of decay kinetics that is not affected by
pore diffusion is summarized in Table 3. The capability of the
equipment has been graded A-C for the ease of decoupling
decay kinetics from reaction kinetics and for the range of data
that is generated in each test period.
2394 Ind. Eng. Chem. Res., Vol. 46, No. 8, 2007

Table 3. Suitability of Experimental Techniques for Studying Decay Kineticsa

controlled variation of decouple reaction data range/ % of
reactor type W/F feed composition and decay test periodb exptl refs other pros and consc
gradientless: Berty and Carberry, yes yes A C 20 commercial Berty and Carberry units;
PFR with recycle can test large pellets
fixed bed/plug-flow simple, inexpensive
no no Cd C 54 limited information
no yes Bd C 54 more information
yese no B C 2 but
yese yes A C 0 slow sequential work
fixed bed multi-portf yes no B B 4 awkward construction;
rixed bed multi-portf yes yes A B axial takeoff must be small
parallel multi-tube fixed-bed yese yes in parallel A Ag 1 commercial multi-tube units;
reactors tests can also vary T
coking micro-balance yes yes B C 5 bypassingh
flow-through micro-balance yes yes A C 4 commercial unit TEOM
pseudo-adiabatic awkward construction.
single fixed-bed
multi-zone fixed-bed
no
yes
yes
yes
B
A
B
B
2
1 } some information from axial T gradient
a Key: A ) good and C ) poor. b Range of conditions (C, W/F, T) per single test period. c Isothermality assumed unless adiabatic. d Better with p-m

activity profile. e Tests at different W/F, not the deactivation-compensation method. f Can also configure reactor tubes in series, at the same or different T.
g Parallel tests can cover a wide range of conditions (C, W/F, T) simultaneously. h Unreliable variation of W/F as the flow can bypass catalyst.

Obviously, uniform composition of the fluid phase is very

desirable, and so gradient-less reactors of various types are ideal
for systematic studies of decay kinetics.1,22a The reaction kinetics
can easily be decoupled from the decay kinetics by maintaining
constant composition during each test period by control of the
reactor feed rate and feed composition. Although the reaction
conditions can be varied over the course of an experiment, only
one decay data point is measured for each test period, and so
this approach is slow unless multiple reactor units are available
for simultaneous tests.
Integral, fixed-bed reactors are the most popular choice for
catalyst research. They are easy to design, build, and operate.
Many decay studies are carried out in these reactors with limited
variation of experimental conditions, but it is not possible to
discriminate between alternative decay models unless the
composition dependence is shown by the data. Integral conver-
sion data from a fixed catalyst bed give a bed-average value
for activity and disguise the effect of any axial decay gradi-
ent.23,24 In some cases, independent decay (or activity-time)
models can be fitted, even though a significant axial decay
gradient develops over time.25 The deactivation-compensation Figure 1. Application of deactivation-compensation method to integral
technique (gradually increasing space time, constant conversion) reactor data. (a) Plot of ln (space time) against process time for simulated
can also be used to fit an independent decay model by selecting parallel decay. (b) Activity profile at various values of process time.
the analytical solution that gives the best fit to the integral Simulated data, parallel decay with m ) 1, decreasing feed rate to maintain
data.1,2,26 However, this method is potentially misleading because fixed 98% conversion.
composition-dependent decay will also give a linear plot.25 A
simulated example for parallel decay is shown in Figure 1. The different space times and two temperatures. Each decay experi-
data have been fitted to a linear plot even though the activity ment lasted only 40 min, and so the sequence of 12 experiments
profile within the bed becomes progressively less uniform with could be completed quite quickly. In Figure 2b, the point activity
time. values for W/F ) 2.0, relative to identical reaction conditions
In general, independent decay models derived from single, (i.e., same conversion) at t ) 0, are derived from the gradients
integral tests are unreliable for process design and optimization. (differential rate values) in Figure 2a. Although the overall data
It is necessary to test for composition dependence by measuring were interpreted in terms of parallel decay, the appearance of
the activity profile along the fixed bed over life and/or by Figure 2a suggests series decay (i.e., decay is more severe at
variation of the feed composition. For fast decay, the activity higher W/F).
profile in an integral reactor can be studied by carrying out
successive experiments with different values of space time W/F For slow decay, the sequential approach described previously
(i.e., different catalyst charge or feed rate). The broad range of is impractical, and it is necessary to generate multiple data points
data can then be fitted by trial and error to alternative decay simultaneously during each test period. In a multi-port reactor,
models.27,28 There are few examples of this approach in the the local fluid composition and catalyst activity at various
literature. One example, which was part of a larger study, positions (i.e., different W/F) along the length of the reactor
including tests under both differential and integral conditions, are monitored continuously using multiple sample ports.31,32 The
is shown in Figure 2. The integral tests were carried out at six flow rate of each sample stream must be very small as compared

Figure 2. Investigation of catalyst decay by experiments at variable space
time in an integral reactor. (a) Integral conversion vs space time W/F. (b)
Point activity at W/F ) 2.0 vs process time. Data for dehydrogenation of
benzyl alcohol over 10% copper-0.5% chromia/asbestos catalyst, replotted
from Corella et al.27
to the reactor flow or else compensation must be made in
calculation of the downstream W/F. Alternatively, an in situ
analytical probe can be used.33 This problem is also avoided
by parallel testing in a multi-tube unit, simultaneously covering
a range of space time and also feed composition.21 This
technique has been used in industry for catalyst decay, but no
published studies have been found. The further potential of
parallel testing for catalyst decay is discussed further in section
8.
If the catalyst is discharged in segments from a fixed bed
after a decay test, then the post mortem activity decay profile
can be determined from measurements in a laboratory reactor.
This can be used in combination with the integral decay data
for fitting a decay model. Indeed, in some cases, approximate
catalyst decay kinetics can be derived from plant data by
matching the post mortem activity profile of a process catalyst
with the process reactor history.21
The use of pseudo-differential conditions (low integral
conversion and so almost uniform composition) in a fixed bed
is sometimes used for decay modeling, but this approximation
is not valid if the small axial composition gradient (e.g., for a
product) causes a decay gradient.28 For series decay, this gradient
can be reduced by co-feeding reactants and products.
Integral, fixed-bed reactors are often used for the study of
coking decay, and bed-average values are determined, not just
for activity but for coke content as well. Once again, these bed-
average values can disguise significant axial gradients within
the bed, and so the use of bed-average coke content in the
Voorhies relation6,29,30 or for bed-average activity-coke expres-
sions is unreliable.7 It is necessary to determine the axial
gradients of both activity and coke. A broad range of data can
be collected by operation over a range of space time and
composition. The axial coke content can also be determined by
segmental discharge and post mortem analysis.
Ind. Eng. Chem. Res., Vol. 46, No. 8, 2007 2395
Coking kinetics is best studied in a microbalance. It is difficult
with conventional equipment to avoid some degree of diffusion
control within the catalyst sample,34 but the development of the
flow-through tapered element oscillating microbalance (TEOM)
has enabled reliable variation of space time in coking decay
studies in a fixed-bed (plug-flow) reactor.32,34,35
Obviously, if the effect of temperature is to be included in a
decay model, then isothermal decay tests must be carried out
at several different temperatures. The ramped temperature,
deactivation-compensation technique (increasing temperature
to maintain constant conversion) is used in industry for catalyst
screening and pilot tests because it mimics plant operation.
However, as discussed previously, the results from integral,
fixed-bed reactors disguise internal axial decay gradients and
so are unsuitable for decay kinetics. The changing axial
temperature gradient during a life test in an adiabatic33 or
pseudo-adiabatic36,37 reactor can provide additional information
about the activity decay gradient.
Finally, the techniques in Table 3 can be used in combination
to generate a broad range of information for a decay model (e.g.,
fixed-bed multi-port reactor and coking microbalance,32 adia-
batic reactor with axial multi-port IR analysis and axial
temperature measurement33).
5. Pore Diffusion
Decay kinetics is more complex when pore diffusion is a
significant factor. The influence of an intra-pellet concentration
gradient can lead to a nonuniform intra-pellet decay profile.
Foulant deposits can reduce pore dimensions or even block
pores. The pore structure of the pellet or the dispersion of a
supported active phase can change due to sintering processes.
These changes may lead to changes in observed selectivity,
especially for consecutive reaction schemes. These mechanistic
phenomena will not be described in detail, but a key consid-
eration for practical studies is the degree to which the decay
kinetics varies with particle size. Activity decay data can be
measured and collated at the active site level (i.e., basic decay
kinetics without diffusion effects (if possible)) and at the particle
level, extending to effective pellet activity decay kinetics.8
Likewise, changes to selectivity can also be measured at both
levels. Additional data to link these two levels of kinetics can
be determined by fresh, in situ, and post mortem pellet
characterization. The characteristics of some common cases
(probably not all) of catalyst activity decay and the implications
for testing have been categorized in Table 4. For cases I-III,
useful decay tests can be carried out on crushed pellets, but
some confirmatory tests on whole pellets are desirable, and a
term is required for the pellet effectiveness factor for case III.
For other cases, tests on crushed pellets might still be useful,
but extensive testing over a range of particle sizes, including
whole pellets, is required for a reliable empirical decay model.
The choice of practical experimental techniques is limited
(see section 8), and a lengthy program of work might be
unavoidable. Tests can be carried out on various sizes of pellets
in gradient-less reactors (Table 3) or in fixed beds, subject to
the usual design criteria for particle and reactor dimensions,
preferably with multi-port analysis for variation of space time
and with segmental catalyst discharge. The activity, pore
properties, and diffusion properties can be measured for fresh
and discharged pellets and related to test conditions. If a catalyst
test is carried out on a mixed range of particle sizes, then the
segmentally discharged catalyst can be graded by particle size
and retested for effective and intrinsic activity. This particle
grading technique has been used for checking coke content
2396 Ind. Eng. Chem. Res., Vol. 46, No. 8, 2007
Table 4. Testing Catalyst Activity Decay When Affected by Pore-Diffusion Resistance
characteristics case I case II
fresh pellet: pore resistance reduces activity no no
uniform loss of active sites throughout the pellet yes no
decay reduces pore size and/or access no no
examplesa i ii
useful to study crushed pellets yes yes
need to test whole pellets for model check to confirm no effect
need to include pellet effects in decay model no yes
a Key to examples. i: Fast impurity poisoning (diffusion-limited). ii: Slow impurity poisoning. iii: Parallel or series poisoning. iv: Pore shrinkage
(sintering). v: Foulant growth. b Crystallite size is an additional factor for some microporous solids.
against particle size,29 but no references were found for post
mortem activity tests. If catalyst sample extractors are available
at a pilot or commercial scale, then the post mortem charac-
terization of catalyst pellets at various stages of decay can be
related to the previous pellet history (C, T, t) within the process.
The development of advanced NMR techniques for in situ and
post mortem characterization is noted in section 8. In the single
pellet diffusion reactor, the change in concentration of reactant
across a pressed pellet slab is measured over time. 22b This
technique has been used to assist discrimination between self-
poisoning (fouling) models. However, no recent references or
examples of commercial application were found for this
technique.
If decay is due to any sort of fouling process, then it is
necessary to study the fouling kinetics in relation to the diffusion
characteristics, the particle size, and the pore structure to model
the decay kinetics realistically.8 The theoretical problems
associated with modeling irregular catalyst pore networks in
microscopic detail are difficult. However, the growth of
computing power has led to the development of progressively
more complex theoretical catalyst decay models, including
probabilistic models to describe changes to pore connectivity.
6. Simplicity versus Complexity: Model Discrimination
The most suitable approach for decay modeling depends on
the aims of the work, the effort required, and the value of the
outcome. Many industrial catalysts decay slowly, and so decay
experiments take a long time. The quantity and range of reliable
data are usually a limiting factor in the study of industrial
catalyst decay kinetics. Whichever approach is adopted, the
preferred model must be responsive to the key variables that
affect the decay rate but no more complex than can be justified
by the available data.38 The use of activity-time expressions
or the equivalent independent decay kinetics is justified only
when decay is proven to be independent of composition.
Independent coking kinetics may be justified if reactants and
products have similar, additive coking kinetics, but this must
be supported by measurements of the axial activity and coke
gradients. In 40% of the coking models found in the literature,
the bed-average coke content was fitted without any evidence
of a uniform coke profile. Any effects due to the coke
distribution were effectively smoothed out in the data fitting.
If the decay experiments provide insufficient data to determine
a model, then computing power cannot correct this deficiency.
Good practice includes parametric sensitivity analysis and
careful model reduction. Would a simpler model fit the data
almost as well? In one study, the denominator adsorption term
was shown to be redundant because its value varied by <5%
over a wide range of space times.32 Statistical fitting does not
prove the absolute validity of a model, only that it gives a better
fit to the available data than other models and, hopefully, that
case III case IV case V case VI case VII/VIII
yes yes no yes yes/no
yes no yes yes no
no no yes yes yes
i, iii iv iv v
yes may be useful for basic decay model, then vary particle size.b
extensive testing necessary
yes but not yes but may be complex
complex
its parameters have been well-determined. How much better is
the preferred model to other possible models?38 One set of data
in the literature has been fitted to five different models by
various authors with no real indication of which model should
be preferred.
7. Accelerated Decay
During industrial catalyst development, it is often necessary
to test many catalyst formulations. If decay is slow, then life
tests under normal process conditions take a long time, and so,
in practice, only a small proportion of catalyst formulations can
be tested in this way. Accelerated decay is a common com-
mercial approximation used to examine and compare different
catalysts over a significant range of decay in a short time.21
Accelerated decay has been used successfully in the develop-
ment of many industrial catalysts and also for commercial
catalyst selection, but the subject is still controversial. Some
accelerated tests are based on industrial conditions (composition,
temperature) in reactor zones where decay is known from
experience to be severe, but in other cases, there is a tradeoff
between diminished scientific rigor and increased experimental
space (range of catalyst composition, degree of decay). Although
procedures for FCC and autocatalysts are well-documented,
there has been little published research into the design and
interpretation of tests in fixed beds. Good knowledge of the
decay mechanism and decay kinetics is essential for the design
of a reliable test procedure, and post mortem characterization
studies should be carried out to confirm that accelerated decay
is similar to normal decay. A simple checklist and risk index
have been proposed for assessing the suitability of accelerated
decay tests.21 Parallel testing presents significant opportunities
for the study of accelerated decay on crushed pellets. Multiple
test strategies can generate an adequate range of data for simple
decay models. Gradient-less reactors can also be used.39
Catalysts that are selected for development will usually be
subjected to confirmatory life-testing under realistic conditions
in laboratory reactors and/or pilot plant. The scope of these life
tests may be reduced if there is confidence in experience with
similar catalysts.
8. Gaps and Needs
There is a range of needs within industry for both catalyst
producers and catalyst users. It is suggested that developments
in the following general areas will lead to improved knowledge
and capability for the measurement and modeling of catalyst
decay kinetics and better justification of underlying mechanisms.
8.1. Better Equipment Design and Procedures for Efficient
and Informative Testing of Catalyst Decay. The required
range of experimental conditions at each stage of catalyst
development depends on the required degree of precision. Test

equipment and procedures for slow catalyst decay should be
designed to generate the maximum amount of information from
each experiment. Multi-tubular units can be used to test the
effects of temperature and space time according to a systematic
plan. They can also be adapted in more imaginative ways to
generate data for an empirical decay model.
Example: parallel series multi-tubular test units with sys-
tematic temperature variation; sets of parallel fixed beds, each
a multi-zone tube series ABCD with inter-tube analysis (hence
variable W/F) and different sequences of temperature values
TA - TD, varying up and down in a systematic manner in each
parallel series.
8.2. Better Equipment Design and Procedures for Efficient
and Informative Testing of the Influence of Pore Diffusion
on Catalyst Decay. In principle, the pellet diffusion reactor22b
could be adapted for multi-pellet arrays of commercial pellets
covering a range of depths (i.e., similar fluid composition at
the flat outer faces and a multi-channel analytical probe (e.g.,
IR, MS) for determination of fluid composition at different
values of pellet depth). The time-dependent variation of the intra-
pellet composition profile would provide complementary in-
formation to the activity decay kinetics measured in conventional
tests on small particles and whole pellets (Table 3).
8.3. Improved in Situ Analytical Techniques for Catalyst
and Reaction Fluid. For example, NMR and MRI methods
can be used for in situ imaging of the intra-pellet coke profile.
They can also be used to study the axial liquid-phase composi-
tion profile in a reactor and, in principle, its variation over time.40
8.4. More Effort for Post Mortem Investigation of Decay
for Samples with Well-Defined Process History, Covering
a Range of Conditions (t, T, C). Post mortem investigation of
decay with graded particle sizes is discussed in section 5.
Catalyst sample points could be used at pilot scale to extract
catalyst pellets at various stages of decay so that the pellet decay
characteristics can be examined over life.
8.5. Continued Development of Advanced Techniques for
the Characterization of Pore Networks and the Measure-
ment and Modeling of Intraparticle Diffusion.
8.6. More Supporting Evidence for Complex Mechanistic
Reaction and Decay Models Published in the Literature.
How well do they simulate actual decay characteristics observed
during use and in post mortem characterization (e.g., axial and
pellet decay profiles, pellet effectiveness factor, and diffusivity)?
8.7. Development and Evaluation of Simplified, Ap-
proximate Decay Models for Selected Processes, both (a)
without Significant Pore-Diffusion Effects in Decay and (b)
with Significant Pore-Diffusion Effects in Decay such as an
Intra-pellet Decay Gradient or Pore Blockage. Could pub-
lished complex mechanistic decay models be used to investigate
the potential range of validity of simpler models that could be
determined from shorter experimental programs or simpler
equipment?
8.8. Practical and Theoretical Validation of Accelerated
Decay Tests. Hopefully, when a wider range of practical studies
has been described in the literature, the improved insight will
lead to better guidelines regarding the reliability and potential
dangers of various techniques. In addition, theoretical mecha-
nistic models, developed for simulation of poisoning and fouling
(with and without significant effects of pore diffusion), could
also be used to simulate and compare normal and accelerated
decay (e.g., by increased concentration of coke precursor, feed
rate, temperature, etc).
Ind. Eng. Chem. Res., Vol. 46, No. 8, 2007 2397
8.9. More Reproducibility Checks during Catalyst Testing
at Laboratory Scale. Model parameters determined from small
scale tests may be sensitive to catalyst variability.
9. Summary and General Conclusions
(i) Even idealized studies of catalyst decay in simple model
systems take much time and effort. The systematic study of
industrial catalyst decay is much more demanding. (ii) It is
essential to investigate the influence of the fluid composition
on catalyst decay for selection of a useful decay model. An
independent decay model, if based on integral studies in a fixed
bed, requires evidence that the decay profile is uniform. (iii)
Simple power-law decay models are often used for industrial
problems, and they can readily be adapted to include the
composition dependence. The determination of coking kinetics
and the empirical activity-coke relationship is more demanding
on time and resources but is preferred in some situations. More
complex, mechanistic models should only be used if the
additional parameters are significant and can be well-determined.
(iv) The depth and complexity of the problems that can be
modeled theoretically continues to grow (e.g., fundamental
decay mechanisms at the microscale, intra-particle diffusion,
and poisoning or fouling in ordered and disordered pore
structures). (v) The elements required for a rational study of
industrial catalyst decay are as follows: understanding the
problem (scouting studies, post mortem characterization of
experimental and plant samples); systematic experimental
programs; well-defined feed stock; equipment designed to
provide the maximum amount of useful information from each
experiment; construction of a decay model; pre-validation of
the model and extension to plant feed stocks in pilot studies;
and full validation of the model at the plant scale. (vi) When a
detailed study has been performed on one representative catalyst,
including the impact of different plant feed stocks, then a
simplified test program can sometimes be devised for examina-
tion of other alternative catalysts. (vii) Parallel testing allows
decay to be monitored simultaneously under a wide range of
test conditions (e.g., feed composition, space time, temperature,
and pressure). (viii) There is potential for improved experimental
techniques for measuring catalyst decay under well-defined
process conditions using developments in automation, sampling,
type, and speed of analysis (ex-reactor or in situ). (ix) There is
potential for combining several concepts in reactor design to
gain the maximum information from each experiment and for
imaginative test sequences, designed to provide adequate
information to test a decay model. (x) The problems of catalyst
decay coupled with intra-particle diffusion resistance and
changes to the catalyst pore structure are difficult, and each case
requires its own careful research strategy for progress to be made
on a rational basis. (xi) Models with intra-particle diffusion are
not validated unless the data demonstrate the correct time-
dependent characteristics, including changes to pore structure
and intra-particle activity gradient.
Acknowledgment
I thank Kjell Moljord (Statoil), Hugh Stitt (Johnson Matthey),
Rob Berger, and other members of the Eurokin consortium for
support and advice during this study, K.M. and De Chen
(Trondheim) for critical comments during proofreading, and the
University of Glasgow for an Honorary Research Fellowship.
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ReceiVed for reView May 12, 2006
ReVised manuscript receiVed January 3, 2007
Accepted January 18, 2007
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