See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/226074474

Eurokin. Chemical Reaction Kinetics in Practice

Article  in  CATTECH · May 2001

DOI: 10.1023/A:1011928218694

CITATIONS READS
92 1,245

5 authors, including:

R.J. Berger E. Hugh Stitt

Delft University of Technology Johnson Matthey
50 PUBLICATIONS   1,259 CITATIONS    167 PUBLICATIONS   3,031 CITATIONS   

SEE PROFILE SEE PROFILE

Freek Kapteijn J.A. Moulijn

Delft University of Technology Delft University of Technology
707 PUBLICATIONS   31,330 CITATIONS    919 PUBLICATIONS   40,131 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

PM in Diesel Exhaust View project

catalyst testing and characterization View project

All content following this page was uploaded by R.J. Berger on 23 February 2014.

The user has requested enhancement of the downloaded file.

 feature

Chemical reaction kinetics

in practice
The chemical reactions taking place in the chemical reactor form the heart of any
chemical process. Reaction kinetics are the translation of our understanding of
the chemical processes into a mathematical rate expression that can be used in
reactor design and rating. Because of the importance of correct and safe design
of chemical reactors, chemical reaction kinetics is a key aspect of research and
development in chemical industries, in research institutes, and academic centers,
as well as in industrial laboratories. There is, and there will always be, a strong
need for knowledge and a skill base concerning the determination of reaction
kinetics and their application in the form of a kinetic model.
This paper is a result of cooperation within Eurokin, a consortium of over 10
European companies and 4 universities. An industrial questionnaire in 1995
highlighted that industry is not only a little conservative in the methods it uses
to determine kinetics, but also that there was a wide awareness of the scope for
improvement. Eurokin was thus founded in 1998 to try and establish the best
practices and to facilitate development work in kinetics and associated areas.
The paper briefly explains some underlying theory of heterogeneously catalyzed
chemical reactions and their kinetics. It deals specifically with the acquisition of
kinetic data, and gives recommendations for the selection of the experimental
reactor and conditions. A primary aim of this paper is discuss kinetic experimen-
tation and modeling through a series of case studies, attempting to illustrate
good practice, methods in kinetic modeling, pitfalls, and recommendations. The
paper closes with some recommendations and a perspective on the future needs of
industrial reaction kinetics.

Rob. J. Berger, E. Hugh Stitt*, Guy B. Marin, Freek Kapteijn, Jacob A. Moulijn

* corresponding author
Synetix
PO Box 1, Billingham
Cleveland, TS23 1LB, USA
Tel +44 1642 522704
Fax +44 1642 522606
e-mail hugh_stitt@ici.com

30
Volume 5, no. 1, 2001

What are kinetics?
“Kinetics” is, simply, a technical term used to describe
the rate of a chemical process, such as a catalytic reaction,
as a function of the conditions. The models and their
mathematical manifestations vary enormously in the level of
complexity and the degree to which they reflect the actual
chemical and physical processes occurring.
At their simplest, they can be of the form:
rate ∝ f(T)(concentration) n (where n is termed the order of reaction)
With heterogeneous catalytic reactions, there is more than
one rate process occurring in series. The reaction process
can be broken down into a number of identifiable steps, all
with their own relevant rate equation, some of which may be
combined into an overall reaction rate equation. The steps
typically cited are:
1. Mass transfer of reactant(s) to the catalyst surface
2. Adsorption of reactant(s) onto catalyst active sites
3. Catalytic reaction
4. Desorption of reaction product(s)
5. Mass transfer of product(s) away from surface
Steps 1 and 5 are identifiable fluid phase phenomena,
as distinct from the surface processes that characterize
adsorption and reaction, and specifically a catalytic reaction.
They can, and indeed should, have their own rate equations
(but do not always do so in practice).
The surface process itself also typically comprises a
number of discrete steps. At its simplest, this may be
envisaged as the sorption–reaction–desorption sequence
cited above. The next level of model complexity therefore
includes these steps either as simple steps, or as competitive
adsorption of two reactants (or a reactant and another
component such as a solvent or diluent). This can be done
intermezzo 1 Eurokin, industry-academia collaboration towards better kinetics
Eurokin is a consortium of European-based companies, together
with a number of academic centers, focused on developing practice
in kinetic modeling (Web site: www.eurokin.org). It was established
in 1998, after the need was realized via a questionnaire (extensively
cited in this paper) and two workshops in 1996-1997 to better
define needs and collective drivers. It currently consists of 11
companies (Akzo Nobel, Dow Benelux, DSM Research, IFP,
Technip Benelux, Shell Research and Technology Centre, Statoil,
Linde, EniTecnologie, Synetix, and EC Chem Technologies) and
four academic centers (Delft University of Technology, Ghent
University, NTU Trondheim, and UC Louvain). The membership
base is evidently very broad, from seven different countries
and company activities in oil and gas, petrochemicals bulk
and fine chemicals manufacture, engineering contracting to the
oil, petrochemicals and fine chemicals markets, and a catalyst
company.
Eurokin: chemical reaction kinetics in practice
implicitly within a mathematical expression for the reaction
rate. At their most complex, the reaction rate expression
can be based on the mechanistic or elemental steps of the
reaction. This can have increased mathematical complexity,
but is generally a better physical representation of the process.
Given the above, a number of questions arise. Why are
kinetic models required? Why is there such diversity in the
form and exactitude of kinetic and rate models? How are
the experimental data measured? And how are the models
derived and fitted? This paper will attempt to answer these
questions in the context of an industrial viewpoint.
A key issue is that as kinetic models increase in complex-
ity, the (experimental) effort, the range and scope of exper-
imentation required to build, fit and validate the model
also increase. The perception in industry appears to be that
the effort required increases beyond the proportional gain
in benefit. Therefore, from the point of view of industry,
the need for complex models, based on the physicochemical
events, must either be justified, or the effort required to
derive them significantly reduced.
This paper will therefore explain and illustrate the
need for, and the methods used to obtain, reliable
kinetic data, focusing on heterogeneous catalysis. It will
deal with the acquisition of kinetic data, give some
theoretical background on kinetics and kinetic modeling,
and will provide recommendations for the selection of
the experimental reactor and conditions. A major part of
the paper will consider kinetic modeling through the use
of a series of case studies attempting to illustrate good
practice, methods in kinetic modeling, and pitfalls and
recommendations. In view of the limited space, mass transfer
and hydrodynamic aspects will not be covered in the case
Eurokin’s stated aim is to produce a precompetitive toolkit for
measuring kinetic data and model development for heterogeneous
catalytic systems. The activities are currently focused on:
i. Experimental methods to determine reaction kinetics; e.g.,
investigation of the capabilities of different types of laboratory
reactors to measure the kinetics of specific reaction classes.
ii. Development of models for a set of selected laboratory reactor
systems, to be used for processing experimental data, and/or
the determination of suitable experimental conditions; e.g.,
to assess if the proposed experimental conditions are in the
kinetically or the mass-transfer controlled regime.
iii. Methods for the determination of kinetic models from
experimental data, including model discrimination, parameter
estimation, and design of experiments.
31
Eurokin: Chemical reaction kinetics in practice
studies. The paper will close with a forward-looking section
considering the future needs of industrial reaction kinetics.
Why do we need kinetic models?
This paper is a result of cooperation within Eurokin (Inter-
mezzo 1), a consortium of over 10 European companies and
4 universities, established in 1998 specifically to facilitate
active collaboration in the field of (catalytic) reaction kinetics.
This initiative by so many leading companies gives an
indication of the importance that the chemical industry
attaches to kinetics. But why are kinetics important?
Knowledge of the rate of a catalytic reaction and its
selectivity as a function of the process conditions and reactant
concentrations is essential for the application of the catalyst
in a commercial reactor. More specifically, the kinetics of
the reaction are required in the form of a mathematical rate
expression that can be used to reliably translate laboratory
and pilot scale data into the design of a commercial scale unit.
That rate, or kinetic expression tells how the reaction rate
varies with process conditions such as temperature, pressure,
and composition, and preferably also with a measure of the
volumetric concentration of catalytic sites. The importance
of a reaction’s kinetics is that the rate and selectivity of a
reaction determine the size of the catalytic reactor for a
given overall production rate. Without a reliable means to
predict the reaction rate, the reactor design could be highly
speculative. There are several effects that can arise from this
uncertainty. Firstly, without reliable estimates of the (capital)
costs needed to build a production plant and the probable
operating costs, it is not possible to carry out a meaningful
evaluation of the economic merits of building the plant,
and without a persuasive economic imperative, the plant
is unlikely to be sanctioned. Secondly, and perhaps more
importantly, without reliable kinetics it is not fully possible to
evaluate the side reactions and the dynamic effects that may
occur in the reactor, which is a critical step in assessing the
operational safety and environmental impact of a chemicals
production unit.
mechanistic research
6%
catalyst development
29%
other 1%
Figure 1 Utilization of kinetic data in industry.
32
What does industry use kinetics for?
The importance of knowledge and of having a skill base
concerning the determination of reaction kinetics and their
application in the form of a kinetic model is clear. This
begs the question of how good industry is at measuring
and applying chemical rate models, and what precisely it
does with them. This was put to the test in 1995 when
the “Chemical Engineering in the Applications of Catalysis”
Working Party of the European Federation of Chemical
Engineering approved a survey of industrial practice in the
measurement and evaluation of kinetics. The results of this
survey were published in 1996 in summary form [1]. Twenty-
four chemical and oil companies, engineering contractors,
and catalyst manufacturers responded to the questionnaire,
and that level of return indicates how seriously industry takes
this issue. The results make interesting reading, not only
from the viewpoint of how industry treats its kinetics but
also the diversity, according to the industry sector, of how
they use them. Additionally, a survey of the gaps and
needs for catalysis in European industry [2] , stressed the
importance of further developments in kinetics research.
Consider firstly how companies use their kinetics; the
perceived reason for the determination of kinetic and rate
models. The overall results from the survey are shown in
Figure 1, and indicate a fairly even three-way split between
catalyst development, process development, and process
optimization. Significantly, there is only small minority use
of kinetic data for mechanistic research (by contrast a major
force in academia).
When the same data are presented by the industry sector
in Figure 2, some clear trends emerge. The chemical and
oil companies mainly use kinetics for process development
and process optimization, and to a smaller extent for catalyst
development. As might be expected, catalyst producers
focus on catalyst development, while engineering companies
concentrate on process development. Some mechanistic
research is done by the catalyst producers and the chemical
companies, but this does not exceed 10% of the utilization
of kinetic data.
process development
34%
process optimization 30%
 Eurokin: Chemical reaction kinetics in practice
a. chemical companies Types of commonly used rate expressions
mechanistic research for the reaction: A(g) + B(g) → C(g)
catalyst development 8% process development
26% 34%
Power law expression
-EA
r = k 0 exp ( ) pnA pBm
RT

Langmuir-Hinshelwood-Hougen-Watson type expression

krK A,adspAKB,adspB
other 1% r=
process optimization 31% 1 + K A,adspA + KB,adspB + KC,adspC

Table 1

b. oil companies Types of kinetic models

mechanistic research
Researchers in catalysis, kinetics, and reactor engineering are
catalyst
development
2% process development generally well informed about the general theory concerning
30% reaction kinetics. At the simpler level we can distinguish two
27%
common basic approaches to reaction modeling, summarized
in Table 1.

Power law kinetics

other 4%
For the irreversible gas phase reaction A + B → C the rate of
process optimization 37%
reaction may be represented by an expression of the form:
r = k pAn pBm
where pA and pB are the partial pressures of reactants A and B
c. catalyst companies respectively and k is the rate constant. The exponents, n and
m, are termed the “orders of reaction”.
catalyst development
56%
It may seem natural to assume a rate expression r = k [A] [B]
mechanistic where the orders of reaction match the stoichiometric
research coefficients, and thus a second order reaction for this
12%
example; first order in each reactant. This is not necessarily
the case! A reaction mechanism can incorporate a number of
other 0%
subreactions and the power law approach disguises this. The
process development real rate expression will reflect the kinetics of the potentially
process optimization 17%
15% slowest, or rate-determining step. The reaction order should
therefore always be determined experimentally.
The power law expression is commonly used because of
d. engineering companies its simplicity and its property that it frequently fits the data
mechanistic process development rather easily. (The ancient wonder of reconciling data by
research 56% plotting them on log-log graph paper has not faded even
1%
in this high technology age.) In catalysis this expression
is not, however, based on a sound physicochemical theory,
and therefore the reliability of the results and predictions is
limited to the range of conditions under which the kinetic
catalyst
development experiments were performed.
15% other 0% process optimization 28%
Effect of equilibrium
Figure 2 Utilization of kinetic data for different chemical industry sectors. A given reaction, such as A + B → C can often occur in
both directions, viz. A + B ⇔ C. Which direction prevails
at a given condition depends on the thermodynamics.
Equilibrium corresponds to the minimization of (Gibbs)
The later parts of the survey focused on how industry free energy. If no barrier (e.g., activation energy) exists then
measures its data and the types of models it uses to represent a system will always move towards equilibrium.
the kinetics. Before considering these aspects, it is timely to Two reactions can be defined, each with its own rate
consider the background to kinetic theory, the measurement equation. Assuming, for the sake of simplicity, a first order
of kinetic data, and reaction kinetic modeling. dependency for each component:
33

Eurokin: Chemical reaction kinetics in practice
forward reaction A+B→C rate r f = k f [A] [B]
back reaction C→A+B rate rb = kb [C]
These are not independent, except at “very low” conversions,
where equilibrium is not approached. At other conditions,
the net forward reaction rate for A + B ⇔ C is given by:
r = r f - rb = k f [A] [B] - kb [C]
Thus, equilibrium occurs when the forward and reverse
reaction rates are equal: r f = rb, and hence no net reaction
occurs. For the reaction A + B ⇔ C the equilibrium constant
is given by Keq ={ [C] / [A] [B] } eq. It may thus be shown
that Keq = kb / k f . The net forward reaction rate is therefore
given by: r = kf { [A] [B] – [C]/Keq }.
Effect of temperature
The value of the equilibrium constant is a strong function of
temperature. For endothermic reactions, Keq and equilibrium
conversion increase with temperature, while for exothermic
reactions the converse is true. This strong dependence on
temperature is also prevalent in reaction rate constants, and
so the next level of detail to be introduced may be the
temperature dependence of the rate of reaction. This is most
commonly done using an Arrhenius-type expression:
k = A0 exp (-Ea / RT)
Here Ea is known as the “Activation Energy”. Reaction
rate constants and equilibrium constants commonly show
agreement with this relationship. This relationship is shown
in Figure 3 with curves plotted for different activation ener-
gies (all based around a similar rate constant at 573 K). It
can be seen that the value of Ea has a very strong influence
on the rate dependency on temperature. This is important in
the design of chemical reactors.
intermezzo 2 Through overparameterization, the ability of the model to extrapolate beyond the
A kinetic model was derived for an effluent treatment process,
the catalytic decomposition of the pollutant. This was based
on experimental data, where the reaction was observed to be
irreversible and first-order in the reactant. The data were only
measured over a narrow temperature range; that believed to be
the probable operating domain for the industrial scale reactor. The
expression for the first-order rate constant that was used to fit the
extensive data set was:
2 0.5
(1/T - C2)
Ea
ln(k) = A - - C1
T C3
Here, it can be seen that the Arrhenius term [ A - Ea / T ] has been
supplemented by a second temperature term, intended to improve
the statistical fit, for a total of four fitting parameters for (essentially)
one variable. This worked well until a plant operating one of these
34
100
activation energy (kJ/mol): 150
relative reaction rate constant
125
100
75
10
50
increasing EA
1
300 320 340 360 380 400
Temperature (C)
Figure 3 Reaction rate strongly depends on temperature.
The activation energy is a commonly cited parameter,
and its value of course tells the reaction engineer how depen-
dent the reaction rate is on temperature. Values of 50–100
kJ/mol are typical for many catalyzed reactions. Combus-
tion and many other nonequilibrium limited reactions may
have much higher values; 150 kJ/mol for example. A rule of
thumb often quoted is that the rate of a reaction will double
for every 10 K rise in the reaction temperature. This corre-
sponds to an activation energy in the range 60 – 90 kJ/mol
at typical reaction temperatures. Thus, the reaction engineer
e
reactors wanted to increase throughput, and proposed increasing
the operating temperature to achieve this. The result obtained with
the above model is shown in Figure 1. It was surprising that at
higher temperatures the conversion was essentially independent of
temperature, and eventually experimental data showed that this was
not true. The problem lay in the additional temperature term in the
kinetic expression.
In the first instance, this additional temperature term was simply
removed and a simple Arrhenius-type relationship was fitted
through the data. This modified expression was far more able to
(1) predict performance outside the experimental temperature range.
A comparison of the predicted design catalyst volumes to achieve
a given conversion is shown in Figure 2. The revised model more
accurately predicts the expected trend, which was also observed
experimentally.

can immediately start judging the susceptibility of a reac-
tion to runaway, selectivity loss, or effective extinction if
the temperature goes outside the ideal operating window. A
side reaction with, for example an activation energy of 150
kJ/mol tells the design chemical engineer that if the temper-
ature is allowed to rise, the selectivity will fall rapidly. Fur-
thermore, unless that side reaction is constrained, then this
represents a runaway potential, and that must be considered
in the reactor and control system design.
Given the physical interpretations that can be attached
to the activation energy, it can easily be seen why this
approach is popular. It is still, however, constrained by
the flaws of the empirical power law approach. Because
of the lack of physicochemical relevance, the accuracy of
the kinetic expression and the application of the model is
restricted to the experimental conditions under which it was
determined.
For example, it may be tempting to improve a temperature
fit by increasing the number of temperature terms in the
expression. This is not advisable, (see Intermezzo 2). By
statistically improving the fit with a term that has no physical
meaning, the application of the model is tightly restricted
to the experimental range, which in this case prevented use
of the original model to evaluate a reactor operating at an
increased temperature. This emphasizes the importance of
not including too many parameters in a model, particularly
with those parameters that do not have any physical
significance. It is always worth remembering that with
enough fitting parameters, a model can be forced to fit any
data set; but just because there is a good statistical fit does
necessarily not mean that it is a good model.
experimantal domain is severely compromised: catalytic decomposition reaction
Specifically, by using a temperature term in addition to the Arrhenius
relationship, the fit within the experimental domain was improved.
However, the model was entirely useless when asked to predict
performance outside the data temperature range. The model was
improved in the first instance simply by stripping out the redundant
statistical term.
log (exit concentration)
temperature
Figure 1 Predicted exit concentration using Rate expression (1)
Eurokin: Chemical reaction kinetics in practice
Langmuir–Hinshelwood–Hougen–Watson kinetics
In order to obtain a more meaningful kinetic expression, it is
necessary to start introducing physical and chemical processes
occurring at the catalyst surface into the mathematical
representation. One of the simplest methods and most popular
approaches to this is via the Langmuir–Hinshelwood model,
and the associated Langmuir–Hinshelwood–Hougen–
Watson (LHHW) type kinetic expression.
A Langmuir–Hinshelwood–Hougen–Watson type ex-
pression is derived using the assumptions that the adsorption
of all components can be described by the Langmuir–
Hinshelwood model and that one surface reaction is rate-
determining. The shape of the rate expression depends on
the choice of the rate-determining step. A study of the
theoretical background can help the researcher to find
the most probable rate-determining step and to obtain
proper estimates of the kinetic parameters which can be
used as initial estimates for the parameter fitting. These
initial estimates should also be used to check afterwards
if the parameters found by the fitting routine are in
physicochemically acceptable ranges.
This model thus makes assumptions about adsorption
and desorption on the catalyst surface. At its simplest, the
Langmuir–Hinshelwood model assumes that all reactants
adsorb onto catalyst surfaces and that reaction occurs as a
surface process. This yields a kinetic expression of the form
(kinetic factor)(driving force)
rate ∝
(adsorption term) n
Eventually, a new model was derived, based on further
experimentation, using a Langmuir-Hinshelwood approach to
account for the inhibiting effect of the competitive adsorption
of a second (nonreacting) component present in the stream,
and provided with only the Arrhenius-type term to describe the
temperature dependence.
design catalyst volume
old model
new model
temperature
Figure 2 Predicted catalyst volume to achieve a given conversion
35
Eurokin: Chemical reaction kinetics in practice
The numerator is a basic reaction rate equation, while the
denominator accounts for the effects of the sorptive steps.
For example, for a reaction A + B → C (not equilibrium
limited), the rate of formation of C is given by the LHHW-
type expression:
KrK A,AdspAKB,AdspB
r=
1 + K A,adspA + KB,AdspB + KC,AdspC
where kr is the rate constant for the surface reaction and
K A,ads , K B,ads and KC,ads are the adsorption coefficients for the
respective species.
Strictly, the Langmuir–Hinshelwood model assumes a
homogeneous catalyst surface. Nonhomogeneity and poten-
tial adsorption onto different active sites are effectively
accounted for by differences in the values of K A,ads and K B,ads
or in the form of the adsorption term. This is in fact one of
the strengths of the LHHW mathematical expression. In the
data fitting, at its simplest, the plot is effectively of :
a xp
y versus
( 1 + bx) q
where the simple power law plot is improved by the
denominator that allows a degree of independent curvature.
The LHHW-type expressions have been found to fit a
wide range of reactions. While the Langmuir–Hinshelwood
kinetic model is a good one, its real strength lies in its ability
intermezzo 3 Zero-order kinetics for a strongly adsorbing reactant transform to first-order
Benzaldehyde was selectively hydrogenated to benzyl alcohol
in the liquid phase using molecular hydrogen over a catalyst
consisting of 2 wt-% Ni on a cordierite monolith coated with 10
wt-% Al2O3.
benzaldehyde benzyl alcohol toluene
Figure 1 shows a typical result for the concentration as a function
of the residence time in a batch recycle reactor [i] . In the first part
the selectivity towards benzyl alcohol is very high. When most
benzaldehyde has been converted, the rate of hydrogenolysis of
benzyl alcohol to toluene and water becomes substantial. The
Kinetic parameters estimated
k1 [ mol / mmonolith s ]
3
0.05
k 2 [ mol / mmonolith3 s] 0.02
K’ [ - ] 0.18
Table 1 Kinetic parameters estimated
36
to describe mixtures based on single component parameters
and the robustness of the derived mathematical expression.
These comments may appear to suggest that the model
works primarily because of its mathematical form. This is
not true. The underlying concept of competitive adsorption
equilibria on a finite number of active sites impinging on
the reaction kinetics is very important. Many systems exist
where the kinetics are in fact strongly affected by adsorption
phenomena. The most obvious effect is where a reactant is
strongly adsorbed, to the extent that it is always available in
excess on the catalyst surface. The reaction rate thus becomes
independent of its gas phase concentration, or zero order. An
example of this is shown in (Intermezzo 3), where strongly
adsorbing systems showing zero (high concentration, low
conversion) or first order (low concentration, high conversion)
dependencies are discussed. An important point is how
this kinetic behavior influences the selection of the reactor
type that would be ideal for carrying out the reaction at a
commercial scale.
linear decrease in a large part of the experiment shows that the
apparent reaction order for benzaldehyde is zero.
Kinetic modeling
A simple Langmuir–Hinshelwood model is able to describe these
typical experimental results. Under the assumptions that:
• benzaldehyde and hydrogen adsorb on different sites;
• the surface reaction is rate determining;
• nearly all active sites are occupied.
The following simplified expression is obtained for the reaction rate
of benzaldehyde (r1 ) and the formation rate of toluene (r2 ):
Cbald Cbalc
r1 = α k 1 r2 = α k 2
Cbald + K’Cbalc Cbald + K’Cbalc
where k1 and k2 incorporate the catalyst concentration and the
hydrogen pressure dependency term, K’ represents the ratio of
the adsorption constants of benzyl alcohol and benzaldehyde, and
a accounts for catalyst deactivation. The adsorption of toluene is
negligible.
The fitted parameter values, shown in Table 1, indicate that the
adsorption of benzaldehyde is stronger than that of benzyl alcohol.
This explains the apparent reaction order of zero for benzaldehyde
at high concentrations. At high conversions the term K’Cbalc in the
denominator becomes larger than the term Cbald and causes the

The role of mass transfer
Intrinsic, apparent, and extrinsic kinetics
As noted in the introductory section, an important part
of the catalytic reaction process is the mass transfer of the
reactant to the catalyst sites. This involves not only the
transfer within the bulk fluid phase, but also the transport
within the porous structure of the catalyst pellet or particle.
The actual transport in the fluid phase can be slow, and thus
the observed reaction rate is in fact affected by — and may
indeed be dominated by — the mass transfer process. Typical
examples here are catalytic reactions occurring in the liquid
phase and catalyzed oxidation processes.
It may not be simple, experimentally, to decouple the
transport and kinetic processes. After all, diffusion and
kinetic rate (for a first order reaction) have the exact same
dependency on concentration — first order. Diffusion and
mass transfer, however, have a markedly lower dependency
on temperature, and therefore mass transfer-inhibited rates
are characterized by an artificially depressed value of the
activation energy (and that the Arrhenius plot may yield a
curve rather than a straight line).
The mass transfer in a reactor occurs on several different
length scales:
kinetics at high conversion due to adsorption of the product: Benzaldehyde hydrogenation
apparent reaction order for benzaldehyde to increase to one. This
was confirmed by experiments with lower intial concentration. It is
clear that for estimation of the parameters, the main part of the
measurement should be carried out at low concentration.
What are the consequences of the transformation of 0th into 1st order
kinetics? For zero-order kinetics the reactor type is not critical and a
continuously stirred tank reactor (CSTR) is suitable for a large part
700
600
500 benzaldehyde
400
concentration / mol/m3
300
200
100
0
0 5000 10000
time / s
Figure 1 Concentrations as a function of time during benzaldehyde hydrogenation at 10 wt-% benzaldehyde at 410 K and 1.5 MPa [i]
Eurokin: Chemical reaction kinetics in practice
1. Turbulent mass transfer from the bulk fluid to near the
catalyst surface (1–100 mm)
2. Laminar mass transfer in the fluid boundary layer (or mass
transfer film) about the catalyst particle (0.01–1 mm)
3. Diffusion within the porous structure of the catalyst
(0.2–3 mm)
Aspects 1 and 2 above are conveniently lumped using the
well known Whitman film theory, as seen in Figure 4, which
assumes total mixing (zero concentration gradients) in the
bulk fluid and a laminar film, whose resistance to mass
transfer is characterized by a mass transfer coefficient (which
is actually a conductance). This rate of mass transfer is largely
dependent on the fluid properties (density, viscosity), the
fluid velocity relative to the solid, and the size of the channel
in which the fluid is flowing. There are many empirical
correlations in the literature for mass transfer coefficients [3,5] ,
and many are derived in geometries relevant to catalytic
reactors.
A further complication can arise in liquid phase reactions
involving a gaseous reactant, such as hydrogenation and
oxidation using molecular hydrogen and oxygen, respectively.
Commercially, these reactions are typically carried out in
sparged stirred tanks or trickle beds. In this case, there is
the added step of the gaseous reactant transferring into the
of the conversion. In view of the transformation into 1st order and
the undesired consecutive reaction of benzyl alcohol to toluene,
however, a CSTR is not a suitable reactor and a plug-flow reactor
is to be preferred in the final conversion stage as a “finishing reac-
tor.”
benzyl alcohol
toluene
15000 20000 25000
37
Eurokin: Chemical reaction kinetics in practice
solid surface intermezzo 4 When simplifying a model by l
or interface

concentration profiles
In hydrodesulphurization (HDS) of vacuum gas oil it is well
- Whitman
- actual In gas / liquid documented that real feedstocks (e.g., gasoil) follow an apparent
systems a second-order behavior in the amount of sulphur containing
film exists on
both sides of components (see Figures 1 and 2). How can this be rationalized?
the interface It is quite strange to find a second-order behavior while there is
not any suggestion of a bimolecular reaction step between two
sulphur-containing molecules. Moreover, the sulphur product is
H2S only.
fluid flow The explanation lies in the complex composition of the real
velocity profile feedstock, covering thioethers, thiophene, benzothiophene, di-
concentration
in solid phase benzothiophene, and substituted dibenzothiophenes (see Figures
3 and 4). They all have different reactivities over a catalyst in HDS,
Whitman resulting in the composite contribution of all these molecules in the
film thickness
overall kinetic behaviour.

Figure 4 Whitman film theory for interfacial mass transfer.

2.0
liquid phase, en route to the catalyst surface. This opens
up an additional area of mass transport in chemical reactors
1.5
that depends critically on the inter-dispersion of the phases
c
and the reactor hydrodynamics. This is beyond the scope conversion
1.0
of the present paper, but has been reviewed extensively
elsewhere. See [4] for some recommended references.
The mass transport within the catalyst pellet may 0.5

be harder to characterize. The effect is easily observed concentration

experimentally, by varying the size of the catalyst particle. 0.0
0.0 0.2 0.4 0.6 0.8 1.0
Traditionally, this has been treated mathematically using a
bed length
“pellet effectiveness,” based on the Thiele modulus [5]. A
typical plot of pellet effectiveness as a function of pellet Figure 1 Experimental results for hydrodesulfurization in a fixed bed
size for a first order reaction is shown in Figure 5. Because reactor [ii,iii]
techniques and models for characterizing porous networks
and mass transfer still do not lead to reliable predictions, 2.2
gasoil CoMo - alumina trickle flow
there is a tendency to measure kinetics using the same
2.0 L = 0.2 - 0.4 m

100 1.8

1.6
1 / S - 1 / S0 (1/wt.%)

80 1.4

1.2
effectiveness (%)

60
1.0

0.8
40
0.6

0.4
20 Diffusivity = 1E-5 m2/sec
Reaction rate constant = 5 sec-1 0.2

0 0.0
0.1 1 10 0.0 0.1 0.2 0.3 0.4 0.5 0.6

pellet diameter (mm) 1 / LHSV (h)

Figure 5 Pellet effectiveness is a function of pellet diameter. Figure 2 Fitting results for reaction order = 2

38
 Eurokin: Chemical reaction kinetics in practice
y lumping, be careful not to go too far: 2nd order effects in HDS

It was demonstrated by the summation of three first-order reactions

S
in a plug-flow reactor that the composite conversion profile as a R
R R thioethers
S S
function of space time can be described by second-order kinetics
R
over a broad range of space times [iv] . This is illustrated in Figure 5
and Table 1.
Problems will arise if this is not recognized and a reactor for deep thiophene
HDS is dimensioned on the basis of the second-order kinetics. S

This will eventually lead to required reactor volumes that are too
large, while a proper first-order description for the most refractory
components would yield the proper answer. benzothiophene
In this case, three lumps are sufficient to descibe the kinetics of S

the mixture of reactants accurately. An important question to be

answered in comparable types of problems is which and how many dibenzothiophene
lumped components should be used.
S

substituted dibenzothiophene

S
R R

Figure 4 Sulphur compounds present in vacuum gas oil.

2.0

C1 + C2 + C3 = 2nd order reaction data

concentration / mol/m3

0 5 10 15 20 25 30
1.5
Simulated distillation b.p.

Figure 3 Composition of oil fractions in vacuum gas oil.

1.0
C1

C2
0.5 C3

Kinetics of the second-order reaction 0.0

used and the fitting results for the three 0 0.5 1 1.5 2
space time / kg s / mol
first-order reactions
Figure 5 Successful fit of a simulated second-order profile by means of
the sum of three first-order reactions differing by about a factor of seven in
second-order reaction
reactivity.
k = 10 m3 /mol s c 0 = 2 mol/m3

three first-order reactions

k1 = 20.9 s-1 c1,0 = 1.438 mol/m3

k 2 = 3.06 s -1
c2,0 = 0.447 mol/m3
k3 = 0.448 s-1 c3,0 = 0.115 mol/m3

Table 1

39
Eurokin: Chemical reaction kinetics in practice
intermezzo 5 When using reaction networks, don’t ignore the possibility that intermediates react
As part of the hydrodenitrogenation (HDN) network of quinoline,
the conversion of of orthopropylaniline (OPA) into propyl benzene
(PB), propylcyclohexene (PCHE), and propylcyclohexane (PCH),
has been studied. Figure 1 shows the kinetic scheme.
The reactions starting from OPA show first-order dependencies.
The reaction also proceeds via the propylcyclohexylamine (PCHA)
intermediate which is observed only in traces.
Included in this scheme is the direct conversion of OPA to PCH
to obtain a good description of the product concentrations as a
k1
NH2
PB
OPA
k6
k3
k5
PCHE PCH
Figure 1 Reaction scheme of the HDN of orthopropylaniline (OPA)
catalyst pellet size as will be used in the operating plant.
In many cases, this leads to a kinetic model that inherently
includes intraparticle mass transport rate effects.
Clearly, it is essential to distinguish between models that
include only chemical effects, and those that include varying
degrees of mass transfer. Regarding mass transfer, we can
define three levels of a model:
a. Intrinsic — where all the effects of mass transport have
been stripped out and the model represents only the sur-
face processes.
b. Apparent — where any transport limitations internal to
the catalyst structure are included in the model. Measur-
ing kinetics on a full-sized pellet is an example of this.
While maybe not strictly correct from a scientific point
of view, it is, nonetheless, pragmatic.
c. Extrinsic — where no attempt has been made to decou-
ple the gross mass transfer from the real, or intrinsic
kinetics. The model may therefore include effects related
to gross mixing times and diffusion through the laminar
film adjacent to the catalyst surface.
One final point here is that in developing an intrinsic
model, it behoves the experimenter to verify the absence of
transport effect. There is much guidance in the literature on
how to do this [5]. It is clear, however, that this is not always
done.
40
function of the space time in the reactor (Figure 2). This is explained
by the fact that during the reaction there will be a competition
between desorption and consecutive reaction of the surface species.
That part of the adsorbed OPA will react in consecutive steps towards
the final product accounts for this ‘direct’ reaction step. Intermediate
species don’t necessarily have to desorb first before reacting further
in a consecutive step. This is an important aspect often overlooked
in consecutive reaction schemes, as in selective hydrogenations
and oxidations, and depends on the relative magnitude of the
5
4
partial pressure / kPa
3 OPA
2
PCH
1
PCHE PB
0
0 0.1 0.2 0.3 0.4
space time / s
Figure 2 Kinetics of the HDN of orthopropyl-aniline (OPA) over NiMo at 370
°C (one-site model) [v]
Modeling more complex systems
Many real systems are complex, involving multiple
components of feasible reactions. While it is possible to
treat such systems exhaustively, it is rarely practical to do
so. Techniques have therefore been developed to simplify
systems on a rational basis so that the reaction kinetics can
be characterized without excessive experimentation and by
using a mathematical model of appropriate complexity. Two
techniques commonly used are lumped models and reaction
networks.
Lumped models
As the name suggests, the essence of this is simplification by
collecting related variables. This has been referred to also as
”lumped parameter model.” This, however, is a misnomer as
it is the chemical species rather than the parameters that are
grouped. This is typically applied to groups of chemicals of
similar properties. This is a powerful method, but should be
done, however, with extreme care and with due attention to
whether the simplifications are in fact valid. As an example,
Intermezzo 4 shows the explanation of the often-observed
apparent second order behavior, but which was found unable
to describe deep HDS accurately. The cause is oversimpli-
fication. Reducing the model to one “lump” is excessive,
whereas a three “lump” model can describe the deep HDS

further without desorption and subsequent re-adsorption: Hydrodenitrogenation of quinoline
corresponding rate constants involved. Of course if adsorption-
desorption equilibrium is assumed, this phenomenon will not occur.
This type of model deviates, therefore, from the classical LHHW
model with one rate determining step.
The PCH formation can be described by first-order irreversible
reactions from OPA and from PCHE. Although OPA will strongly
adsorb at the catalyst and, hence, a zero-order is anticipated, the
equally strong ammonia product adsorption results in a constant
denominator of the rate expression independant of conversion,
competitive parallel steps
direct global routes
OPA + *
kb
OPA* PCB + *
ka slow
fast reaction steps PCHA* PCHA + *
kc
PCHE
ke
kd
the direct route to PCH PCH + *
Figure 3 Proposed mechanism for the HDN of orthopropyl-aniline (OPA) over NiMo (one-site model) [v]
results accurately. This example illustrates also that one
should avoid deriving the kinetic mechanism from visual
inspection of the experimental data only. The use of a lim-
ited range of experimental conditions may result in an over-
all picture described by simple kinetic equations that may
dramatically fail when extrapolated.
Reaction networks
A reaction network is essentially a mapping exercise of the
feasible reactions in a system where multiple reactions are
possible both in series and in parallel. A typical example
is shown in Intermezzo 5. This case study highlights a
potential problem with this approach — basic assumptions
of reaction paths. It is all too easy to assume that all reactions
occur as discrete adsorption–reaction–desorption cycles, and
neglect the fact that an intermediate does not necessarily
have to desorb before it reacts further. This is in fact quite
common.
Theoretically-based kinetic models
It is possible to build kinetic models from theoretical
and mechanistic considerations of the reaction. A common
approach is the so-called elementary step approach where
the reaction mechanism is described by a set of single events,
each of which can be ascribed a rate equation, or a term
Eurokin: Chemical reaction kinetics in practice
yielding a first-order dependency. Similar observations have been
made for the more complex reaction scheme in the selective
hydrogenation of cinnamaldehyde [vi] .
(ka + kb ) kOPA pOPA
rOPA = –
ka
1 + 1+ kOPA pOPA + kNH3 pNH3
kc + kd
HCs not adsorbed (weakly compared to N-s)
only traces found
PCHE + *
in a single rate equation. This clearly has the potential
to lead to very complex models with large numbers of
fitting parameters. If this technique is used properly, the
mechanistic understanding can in fact lead to simple models
and equations through the rational elimination of some of
the steps in order to focus on the rate-limiting steps and key
competitive processes in the case of parallel reactions.
The description of the reaction kinetics of complex
reaction networks requires a modeling approach more
sophisticated than simply adjusting the kinetic parameters for
each reaction independently. A well-established approach for
developing and using a fundamental model for hydrocracking
of paraffins is shown in Intermezzo 6. This also proves
that kinetic modeling based on fundamentals does not
necessarily require fitting of a large number of kinetic
parameters, but that, on the contrary, proper fundamental
models may reduce the total number of fit parameters
significantly without losing the reliability of the model
if extrapolated. Another method for the mathematical
treatment of the kinetics in reaction networks can be found
in Temkin [6].
What types of kinetic models does industry use?
In their report on the industrial questionnaire, Bos et al. [1]
classify models according to the complexity and the extent
41
Eurokin: Chemical reaction kinetics in practice
Classification of kinetic models
(Bos et al. [1] )
Model types
1. Simple first order or power law
2. LHHW (Langmuir–Hinshelwood –Hougen–Watson)
3) n-lumped models (for complex systems)
4) Detailed mechanistic model
5) Ab initio, molecular dynamics
Model level
A Intrinsic kinetic models excluding all transport effects
B Apparent kinetic models that include internal transport effects
C Extrinsic models including all transport effects plus kinetics
Table 2
intermezzo 6 Kinetic modeling based on fundamentals does not necessarily require a large
To the contrary, proper fundamental models may significantly
reduce the total number of fit parameters without losing the
reliability of the model, if extrapolated. This is shown here with
reference to a fundamental model for hydrocracking.
Scope
Hydrocracking of heavy hydrocarbons represents a case typical
for refining oil. The production capacity of refinery units can be
as high as one million ton per year, i.e. among the largest in
the industry. Hence, even very marginal improvements in product
yields have significant effects on the process economics. This
provides a strong incentive to use detailed kinetic models.
A key feature of refining processes is the complex composition of
the feed and product streams. Thousands, rather than hundreds,
of molecules are involved. At first sight the lumping of individual
molecules with similar physical and chemical properties seems
very attractive. Such an approach is faced with several drawbacks,
however — the lack of a clear physical meaning of the kinetic
parameters in the lumped model being the main one. This requires
a regression of experimental data to obtain estimates of the
values of the latter. Actually, these values can even depend on
the feedstock composition. Moreover, the number of parameters
increases drastically when more lumps have to be considered in
order to enable the model to calculate relevant properties of the
product streams, such as the octane number. Finally, it is hard to
account for the effect of catalyst properties on the kinetics.
None of the above disadvantages are shown by the so-called
fundamental models based on the kinetics of the elementary
reactions occurring between the individual molecules, provided
some reasonable assumptions based on the underlying chemistry
are made.
42
of decoupling of mass transfer. It will be reproduced here as
it highlights the different approaches.
Concerning the type of kinetic expressions used within
the companies, most of the respondents stated that in
principle one should strive for intrinsic kinetics, but
nevertheless the majority, for various reasons, frequently do
not separate all transport phenomena from the chemical
reaction kinetics. That is, while the advantages of intrinsic
kinetics are acknowledged, these advantages do not always
outweigh the difficulties in obtaining them. Specifically, if
any of hydrodynamics, mass transfer, and kinetics can be
lumped and scaled by similarity, then this is ostensibly the
simplest and most favored route — albeit one that may be
fraught with difficulties.
Kinetic models are mostly simple first or n th order or
Langmuir–Hinshelwood type expressions; more complex
kinetic models are scarcely used. Simplicity (and minimization
Reaction chemistry
Hydrocracking catalysts are bifunctional, i.e., they contain a
hydrogenation function on an acidic carrier. The metal-catalyzed
reactions and the elementary acid-catalyzed reactions considered in
the hydrocracking of alkanes are depicted in Figure 1. Physisorption
of alkanes and alkenes into the zeolite pores precedes these reaction
steps. Alkanes or cycloalkanes dehydrogenate on the metal sites
with formation of unsaturated (cyclo)alkenes, which in turn migrate
to the Brønsted acid sites of the carrier where they are protonated,
yielding carbenium ions. The latter undergo reactions such as
hydride and alkyl shifts, scrambling the position of the charge or
of the alkyl substituents, protonated-cyclopropane (PCP) branching
altering the number of substituents, and cracking cleaving the C-C
bond in β position of the positive charge.
Rate equations
Accounting for all the possible reaction intermediates leads to huge
reaction networks. Starting from, for example, n-nonadecane 1981
alkanes, 25065 alkenes, and 20437 carbenium ions involved in 25065
(de)hydrogenations, 42600 (de)protonations, 33352 hydride shifts,
12470 alkyl shifts, 15970 PCP branchings, and 6429 β-scissions
have to be considered in the first instance. It is very reasonable,
however, to assume that the thermodynamic and kinetic properties
of the individual hydrocarbon species are completely determined by
the nature of the carbon atoms directly involved with the elementary
reactions. In the so-called single- event approach developed by
Froment and co-workers [vii] , the possible effects of the skeletal
structure of the reacting species on the rate coefficients are
neglected except for the global symmetry. Hence, the latter only
depends on the type of the involved carbenium ions and the number
of single events, which equals the ratio of the global symmetry
number of reactant and activated complex.

of number of experiments) is paramount. Interestingly,
engineering companies are most likely to use intrinsic kinetics
while catalyst companies favor them least. Significantly, there
is no evidence for significant use of mechanistic or ab initio
models.
Acquisition of kinetic data
The amount of effort that should be put into the theoretical
aspect of a kinetic investigation depends on the complexity of
the reaction scheme, the (non-)linearity of the dependencies
of the variables, and the reliability of the required kinetic
model. This is of course the technical driver. Also to consider
is the ultimate estimated product value and the probable cost
of non-conformance of the kinetics (financial, safety, health,
and environment). As noted above, only occasionally does
industry develop complex kinetic models.
Eurokin: Chemical reaction kinetics in practice
Selection of experimental reactor
Any kinetic investigation should start with a search of the
existing knowledge concerning the reaction system. Armed
with the information available from the literature and the
start of a conceptual model of the kinetics, it is possible to
start considering the experimental approach: the equipment
to use and the experimental conditions and program.
The initial step is usually to consider the type of reactor
to be used. In many studies it may be expedient to use more
than one type. Tables 3 & 4 give overviews of some possible
laboratory reactors for kinetic date measurement for gas–
solid and gas–liquid–solid systems, respectively. Also given
are some of the important characteristics of those reactors.
Gas–solid reactions
No single reactor is right for all systems and therefore a
plurality of types exists, as demonstrated by Table 3 (which

number of kinetic parameters: Fundamental model for hydrocracking

When only secondary and tertiary carbenium ions are considered,

gas phase
acid sites the above assumptions reduce the number of different types of
physisorption zeolite +
(de-)protonation elementary reactions to 24. This includes 3 alkyl shifts, 3 intra-
alkyl-shift ring alkyl shifts, 3 PCP branchings, 3 ring contractions, 4 acyclic
(de-)hydrogenation PCP-branching β scissions, 4 endocyclic β scissions, and 4 exocyclic β scissions.
+
metal sites Assuming quasi-equilibrium of the (de)hydrogenations and that
+ the concentration of carbenium ions can be neglected compared to
+ the total concentration of acid sites leads to the corresponding rate
ß-scission equations in Figure 2.
+ +
Model parameters
Both thermodynamic and kinetic parameters are present in the rate
Figure 1 Hydrocracking reaction mechanism. equations.
The dehydrogenation equilibrium coefficient, Kdeh, can be
calculated from tabulated thermodynamic data.
The physisorption equilibrium coefficient, KL, as well as the
parameters to be estimated
sorption capacity, Csat, depend on the catalyst and have to
-Ecomp
act
kcomp = k Kprot = Acomp exp be determined experimentally, preferably independently from
RT
0 the experiments aimed at the determination of the kinetic
-Ecomp
act = Eact + ∆Hprot
parameters [viii] .
calculated via thermodynamic data The rate coefficients, k, only appear combined with the
equilibrium coefficients for protonation, Kprot. Hence, it is not
determined by NH3 -TPD
their individual value but only that of the product kKprot, the
Ccat Ct k Kprot Kdeh KL pHC pH
r = 2 composite rate coefficient, which affects the reaction rates. Of
1 + KL pHC course the latter should show an Arrhenius dependency on
temperature.
determined by physisorption experiments The composite pre-exponential Arrhenius factor, Acomp, can be
calculated without the regression of kinetic data, based on
transition state theory and on the pre-exponential factor of the
Figure 2 Hydrocracking Rate Equations (HC = hydrocarbon). physisorption equilibrium coefficient [ix,x] .
Figure 1 Reaction scheme of the HDN of orthopropylaniline (OPA)
see next

43
Eurokin: Chemical reaction kinetics in practice

Overview of characteristics of several types of gas–solid reactors which can be used to

select the reactor to carry out the kinetic experiments

G–S reactor Investigation Kinetics Isothermicity Deactivating Typical Fast Costs

of fast at high catalysts particle experimentation ( + = low, - = high)
reactions conversions size [mm]
differential fixed bed +/- + + + 0.05–1 -- +
integral fixed bed +/- - - +/- 0.1–1 - ++
entrained-flow reactor - + +/- ++ < 0.2 - -
recycle/gradientless fixed bed ++ ++ ++ + 0.1–10 - +/-
thermal gravimetric analysis -- - - - <5 - -
differential fluidized bed ++ + ++ +/- 0.05–0.15 -- +/-
pulse fixed bed +/- + +/- + 0.1–1 + +/-
temporal analysis of products +/- + + + 0.1–1 +/- --
temp. programmed reactor - - + -- 0.1–1 ++ -

Table 3

35
Hence, 24 composite activation energies, Ecomp, have to be Total conversion (%)
30
estimated, i.e., obtained by regression of kinetic data. Martens et
25
al. [ix,x] obtained such a set of parameters by regression of data 20
obtained on Pt/US-Y zeolites and feeding pure components such 15
as n-alkanes in the range C8 to C12, and cycloalkanes such as 10
methylcyclohexane, ethylcyclohexane, and n-butylcyclohexane to 5
a continuous stirred tank reactor (CSTR) at pressures from 0.5 0
0 200 400 600 800 1000
to 5 MPa, molar hydrogen to hydrocarbon ratios from 30 to 300 W/F0 / kg s mol-1
and temperatures from 493 to 533 K. At these conditions the Figure 3a Conversion vs. space time (493 K, 20 bar, inlet H2 to n-dodecane
hydrocarbons are in a gaseous state. In total more than 500 data molar ratio = 300).
were regressed. ‘Figure 3a shows a typical conversion versus
45
cracking conversion (%)

space time relation and Figure 3b shows the effect of conversion on 40

the product distribution for n-dodecane at one set of conditions. In 35
isomerization,

30 isomerization
view of the amount of experimental data, the number of adjustable 25
parameters is rather limited. This, among other things, is due to 20
15
the assumed independence of the latter on the hydrocarbon chain 10
length. The latter is totally accounted for via the physisorption 5 cracking
0
parameters, Csat and KL. 0 20 40 60 80
The adequate mathematical description of conversions and total conversion (%)
selectivities on a given catalyst as discussed till now is certainly Figure 3b Isomerization and cracking conversion vs. total conversion (for all
an important goal of kinetic modeling. The capability of taking into experimental conditions (symbols = experimental, curves = model predictions).
account the kinetically relevant properties of the catalyst is an
1.8 0.04
even more important feature of the hydrocracking model presented
mass flux / kg s-1m2

1.6 residue middle distillate

here. 1.4 0.03
Indeed, the rate equations contain two parameters related to the 1.2 LPG
1
catalyst: the total concentration of acid sites, Ct, and the standard 0.02
0.8
protonation enthalpy, ∆H o
. The latter is a measure of the average 0.6 naphtha
prot
0.4 0.01
strength of the acid [xi,xii] . Adjusting only these two parameters and 0.2
the hydrocracking on (US)Y zeolites with a different average, acid 0 0
0 2 4 6 8
strengths can be modeled adequately. axial position (m)
Figure 4 Mass fluxes of major product fractions as a function of axial reactor
coordinate at typical industrial conditions (feedstock: hydrogenated vacuum gasoil) [xiii].

44
 Eurokin: Chemical reaction kinetics in practice
Overview of characteristics of several types of gas–liquid–solid reactors
which can be used to select the reactor to carry out the kinetic experiments

G–L–S reactor Investigation of Investigation of Deactivating Typical residence Typical cata- Fast Costs
fast reactions sequential reactions catalysts time liquid lyst size [mm] experimentation ( + = low, - = high)
trickle bed +/- -- - 10 s 0.5–2 - +
upflow packed bed +/- - - 1 min 0.5–2 - +
spinning basket +/- +/- - 1–10 min >2 - -
internal recirculation reactor + + +/- 1–10 min > 0.005 - -
slurry reactor, (semi-)batch + + - 1–10 hr 0.01–0.2 - -
slurry reactor, continuous + + +/- 1–10 min 0.01–0.2 - -
bubble column - - - > 1 min < 0.1 - -
gas lift reactor - - +/- > 1 min < 0.1 - +
wetted wall + - - 1s not applic. + -
pulse trickle bed +/- -- + 10 s 1–5 +/- +/-
pulse slurry reactor + + +/- 1 min 0.01–0.2 + -

Table 4

Application to the hydrocracking of a hydrogenated vacuum gasoil

Industrially, hydrocracking is performed in an adiabatic fixed bed
reactor consisting of three phases: the fixed catalytic bed, and a
flow of gas and of liquid. In the trickle flow regime, the liquid flows
down dispersed in the form of droplets and rivulets concurrently with
the continuous gas phase. Clearly, this is quite a difference with
the hydrodynamics in the CSTR set-up used for the determination
of the reaction kinetics. Provided that the latter corresponds to
intrinsic kinetics, i.e., reflect only chemical and, hence, scale
independent phenomena, their application to industrial hydrocracking
is straightforward. It suffices to substitute the rate equations in
the reactor model equations accounting for the trickle flow in an
appropriate way. The latter consists of the conservation laws for
mass, energy, and momentum.
Figure 4 shows the evolution of the different product fractions as the
vacuum gasoil streams through the catalyst bed at typical industrial
40
conditions. The carbon number of the feed ranges from 14 to
33. The residue consists of the hydrocarbon fraction with 18 or
more carbon atoms. Note that the lumping into LPG, naphtha,
middle distillates, and residue is only performed for representation
purposes. The knowledge of the kinetics of the 24 types of
elementary reactions allows us to describe the vacuum gasoil
conversion and the resulting product distribution up to the level of
the individual molecules. Of course, such a degree of precision is
neither really required nor attainable. The major bottleneck consists
of the lack of molecular information provided by today’s state-of-
the-art analytical techniques. But again, as the fundamental kinetic
model contains information up to the molecular level, relumping
can occur to an extent deemed appropriate. Figure 5 illustrates this
by showing the evolution of the liquid concentration of components
constituting a fraction of the residue: the monocyclic naphthenic
lumps with carbon number between 18 and 32.
50

35 45
40
liquid concentration (mol/m3)

30
moN18 35
25
30

20 25
20
15
moN30 moN29 moN28 moN27 moN26
15
10
moN24 moN22 moN20 10
5 moN32 5

0 0
0 1 2 3 4 5 6 7 8
axial position (m)
Figure 5 Breakdown of the monocyclic naphthene fraction of the residue as a function of the axial reactor coordinate [xiii] .

45
Eurokin: Chemical reaction kinetics in practice

Figure 6 Six-tube micro-reactor installation (reproduced courtesy of Synetix).

is a summarized version). Easily the most common form Thermo-gravimetric analysis (TGA) is now a well-established
of reactor for measuring kinetics over a stationary catalyst technique, but consider also that the tapered element
is the fixed bed microreactor. These can be operated in oscillating microbalance (TEOM) which has much better
differential form, viz. low (<5 %) conversion or in integral gas–solid mass transfer characteristics than the TGA
mode at higher conversions. The fixed bed microreactors are due to the forced flow through a small packed bed [7].
essentially small tubular reactors, say 3–6 mm (1/8-1/4 inch) The TEOM has been successfully used to measure coke
in diameter, operated with different catalyst volumes and deposition kinetics [8,9] , and changing oxidation states of
space velocities to obtain either the very low or relatively high oxide catalysts [10]. If an important part of the kinetic
conversions required. Microreactors are now well established, information can be derived from calorimetry, differential
and the best are fully automated with more than one reactor scanning calorimetry (DSC) could be of interest. In fine
tube operating in parallel, see Figure 6. chemicals, calorimeter reactors are becoming increasingly
The third classic configuration is the well-mixed, or popular partly because they provide the key information for
gradientless reactor, typified by the Berty and Carberry type safety in addition to the rate data.
reactors. Because the reactor is well-mixed, the reactor is
effectively at the exit concentration. In the case of a Berty
reactor (see Figure 7) a turbine-type impeller drives the
gas through the catalyst. An alternate design, the Carberry
reactor, has the catalyst in a cross rotating basket that itself
acts as the impeller.
These three configurations, or operating approaches, are
compared in Figure 8 in terms of the relationship between
the rate and the conversion. The fundamental difference
between the differential reactor and the gradientless reactor
lies in the fact that in the differential reactor, with low
conversions, the reactor is predominantly at the feed
composition, whereas for the recycle reactor, assuming perfect
mixing, the concentration in the reactor approximates to the
exit concentration. Therefore, the reactors fundamentally
measure the kinetics under different process conditions
regarding composition and conversion.
The fixed bed microreactors and the gradientless version
are the workhorses of gas phase heterogeneous catalytic
kinetics. There is, however, an increasing number of
alternatives, some of which are particularly suited to
specific problems. If a catalyst mass change due to the
reaction yields important kinetic information, one could Figure 7 Diagram of a Berty-type internal recycle reactor (Reproduced
select a reactor capable of on-line mass measurement. courtesy of Autoclave Engineers).
46
 Eurokin: Chemical reaction kinetics in practice
differential integral recycle (gradientless)

F, C0 F, C0 F, C0

C = concentration C = concentration C = concentration

∆C = C0 - C1

L = distance through reactor L = distance through reactor L = distance through reactor

C1 C1 C1

r ∝ ∆C / W/F r ∝ dC/dW r ∝ ∆C / W/F

∆C = small ∆C = ∫ r/F dW ∆C = large

Figure 8 Comparison of common laboratory flow microreactors used for kinetic measurements.

For cases where the choice is not so clear, Table 3 can be
used as a guideline for the choice of the reactor. From the
table it follows that important questions to be answered are:
i. Are the reactions (relatively) fast?
ii. Is kinetic data needed at high conversions (can be
obtained relatively easy in a recycle reactor)?
iii. Are the reactions strongly exo- or endothermic? and
iv. Does the catalyst deactivate significantly?
Figure 9 Diagram of a Robinson–Mahoney reactor (Reproduced courtesy of
Autoclave Engineers).
Other aspects may also influence the choice, such as: the
approach to ideal plug flow or mixing, the risk of flow
maldistribution, the ease of measurement of the catalyst
temperature, and the ease of withdrawing samples. The
available catalyst size, the allowable reactor costs, and the
experimental efficiency (amount of kinetic data per unit of
time of experimentation) will determine the final choice.
Reactors operated at steady-state are experimentally the
most convenient, but the dynamically operated systems are
now receiving increasing attention. These include the pulsed
fixed bed, temporal analysis of products (TAP), and temper-
ature-programmed reactors mentioned in Table 3. However,
while they do allow fast acquisition of kinetic data, it is not
always clear how to translate those data into a mathematical
model. They often also require a more skilled or experienced
operator, or a significantly longer learning period. In gen-
eral, these reactors are mainly of interest for extensive kinetic
investigations, including elucidation of mechanistic aspects.
The final choice of the reactor is usually determined by the
following aspects:
• Absolute reaction rate,
• Catalyst shape and size,
• The reactors already available in the laboratory, or the
relative costs of the alternative new installations,
• Likelihood of significant transport limitations (mass and
heat transfer),
• Nonidealities such as flow distribution and hydro-
dynamics.
If possible, any complications arising from nonkinetic
parameters impinging on the observation of intrinsic kinetics
should be circumvented by choosing proper test conditions.
47
Eurokin: Chemical reaction kinetics in practice
Figure 10 Alternate reactors for multiphase kinetics measurements (a) turbine reactor; (b) screw impeller stirred reactor.
Gas–liquid–solid reactions
The choice of the reactor for investigation of the kinetics
of gas–liquid–solid systems is usually determined by the
characteristics shown in Table 4. For thorough kinetic
investigations in which the influence of the reaction products
and sequential reactions should also be investigated, only
the slurry reactor and the internal recirculation reactor are
truly recommended. The slurry reactor most commonly
— almost inevitably — takes the format of a stirred
autoclave. If not properly assessed, these systems can easily
be prone to mass transport limitations, particularly at
the gas–liquid interface. A commonly used type of gas–
liquid–solid gradientless internal recirculation reactor is the
Robinson–Mahoney reactor (see Figure 9) where the gas–
liquid dispersion is forced though a catalyst basket. Two
alternative types of internal recirculation reactors have been
proven successful for kinetic investigations: the turbine
reactor, in which the gas–liquid mixture is transported back
to the top by turbine blades located in the outer annular of
the reactor[11] , and the screw impeller stirred reactor (SISR)
having the screw in the central shaft [12]. Both reactors are
shown in Figure 10.
48
Selection of experimental conditions
It is evident that the reactor and analytical equipment
generally limit the range of the experimental conditions that
can be covered. However, several additional aspects may
further limit the ranges of conditions at which useful
kinetic data can be obtained. If intrinsic kinetics are to
be assured, it is essential to check on rate limitation due
to mass and heat transport limitations. One should also
check for other phenomena causing nonideality such as
axial dispersion in a tubular reactor, catalyst bypass, and
inadequate macromixing. There are several “tricks” used to
generate conditions where transport is not limiting. The
most common of these is the use of inert particles mixed
in with the catalyst to artificially increase the active reactor
bulk volume. This dilutes any heat effects and, by dilution
with fine particles, axial dispersion and bypassing can be
limited even for a combination of a relatively short bed and
industrial catalyst particle size. If the problem is intra-pellet,
then the only option is to operate with a smaller particle size.
Tables 3 and 4 give an indication of suitable catalyst
size and shape such as powder, small crushed particles,
and complete catalyst bodies. If intrinsic kinetics are to be

measured, the precise catalyst size to be used should be
estimated via calculations concerning transport limitations
and other phenomena, possibly causing nonidealities. As
noted above, if large catalyst pellets are to be used in prac-
tice, it may be expedient to use full-sized pellets, often
diluted with inert particles, and measure the apparent kinet-
ics with the knowledge that the data will include intra-pellet
transport effects.
The experimental requirement for intrinsic kinetics is a
major area of study in its own right, and anything more than
a statement of awareness is beyond the scope of this paper.
There is a considerable wealth of literature available in this
field (see, for example, Kapteijn & Moulijn [5] or Froment &
Bischoff [13]).
Once the range of suitable conditions is set, a choice
has to be made for the number of experiments and the
sets of conditions at which these should be carried out.
From a mechanistic point of view, it often is assumed that
most reliable results will be obtained when varying the
independent variables just one by one. However, a statistical
approach will frequently increase experimental efficiency by
varying more than one independent variable simultaneously.
Of course, this has the disadvantage that evaluation of the
data by visual inspection, rather than by statistical analysis,
becomes harder. Experimental design is also a large field,
and beyond the scope of the current paper. At its simplest,
this is epitomized by factorial design, although more
sophisticated techniques are available which are nonlinear in
their approach [14, 15, 16].
Measurement of kinetics in industry
It is time now to return to the industrial survey. The results
are fairly emphatic. All companies do employ in-house test
units for measuring kinetic data, although many also do
kinetic work in collaboration with academic institutions and
research organizations, with 40% of replies citing the use
of external data. All respondents cite the use of fixed bed
microreactors, which comes as no surprise. The use of pilot
plant for model fitting is common place, but only 20% use
full-scale plant operating data for this purpose.
As regards laboratory reactor types, however, utilization
is less widespread. Only 25% cite the use of recycled
or gradientless reactors, while as few as 12% have
used temperature programmed techniques, and only one
responding company possessed a TAP reactor.
These data are a few years old now, but in truth little
has really changed. Industry still relies heavily on fixed bed
microreactors for gas phase reactions, almost to the point of
exclusivity. Given the improvement in the techniques now
ongoing in academia there is clearly headroom, which shall
be addressed later.
It is also apparent from the survey that industry does
not believe it is as careful as it should be in selecting
experimental conditions. The absence of mass transfer
limitation is normally checked, at least experimentally. Plug
Eurokin: Chemical reaction kinetics in practice
flow and isothermicity are frequently assumed without any
such verification; the use of rigorous models to describe
the microreactor is rare. The goal should be simple reactors
that require only simple models. In more complex mixing
situations, such as multiphase and fluidized systems, the use
of cold flow models for the hydrodynamics and mass transfer
is rare.
Collectively, therefore, industry believes it is maybe not
as diligent as it should be in ensuring the intrinsic nature
of its kinetics. This is almost certainly mitigated by an
enormous accumulated experience in translating laboratory
data into kinetic models and using these to accurately and
safely predict the performance of a commercial reactor.
Kinetic modeling
When a series of experiments has been carried out, it is then
necessary to develop one or more kinetic models, and to
try to adjust the kinetic parameters by fitting the mathemat-
ical expressions to the experimental data. The amount of
work required for this is often significantly underestimated
because of unexpected complications. Common “complica-
tions” on the chemical side are low-level impurities in the
feed, unexpected side reactions, and uncertainties concern-
ing the physical properties of the mixture or of some of
the compounds present. Examples on the experimental side
are residues of chemicals in the reactor from previous work,
reactor walls taking part in the reaction, difficulties with
chemical analysis, and inaccuracies of the analytical equip-
ment. Problems also occur with the modeling itself, such as
the use of a kinetic model that is either too simple or too
complex, the use of only one or insufficient different models,
and a lack of physicochemical background of those models.
Of course, kinetic research has been carried out for many
years and accordingly there is much experience available in
the literature and in many laboratories regarding suitable
approaches for different problems, recommendations to
improve the accuracy of models, ways to enhance the entire
investigation and, last but not least, a few pitfalls to avoid. A
number of case studies have already been introduced. These,
and a few more, will now be used to tell a few salutary tales
and to try and demonstrate good practice, and lead to some
simple recommendations on key points to consider when
doing kinetic modeling.
Work on the reaction kinetics can usefully begin even
in the earliest stages of a catalyst or reactor development
program (see Intermezzo 7). Rather simple models that
describe the important reactions reasonably well can be a
relatively cheap, but very useful, input in primary economic
evaluations concerning the full-scale production and the
amount of investigation and development work required.
Although kinetic modeling usually needs the reaction
mechanism purely as an input to help build a mathematical
description of the events occurring, it can also lead to new
insights in the reaction mechanism and reaction sequences.
An example concerning the discovery of a new insight
49
Eurokin: Chemical reaction kinetics in practice

intermezzo 7 Start your kinetics studies early in the development program for maximum advantage: T

COOH COOC8H13 COOC8H17

H2
+ 4
COOH COOC8H13 COOC8H17

Figure 1 Upgrading of butadiene.

Since market prices for butadiene are low, use of butadiene
as feedstock for the production of high-grade chemicals is very
interesting. The telomerization reaction of butadiene with o-phthalic
acid yields a mixture of linear and branched ester isomers, as
shown in Figure 1. After hydrogenation of double bonds in the
alkene groups, the product has potential use as plasticizer.
The reactions are homogeneously catalyzed by a palladium–ligand
complex in a polar organic solvent. The formation of the product
proceeds through monoester species. This has been confirmed
by a combination of experimentation and kinetic modeling. A
simplified reaction scheme is shown in Figure 2.
One of the objectives of this research project was to speed
up the course of development of the new product as much as
possible. Therefore, kinetic modeling was started concurrently with
the experimental optimization of the reaction system. The results of
three experiments, in which the butadiene:o-phthalic acid ratio was
varied and other parameters kept constant, were utilized to evaluate
10 proposed kinetic models. Criteria for the selection of the most
appropriate model were: best fit for the conversion of o-phthalic
acid, and selectivities of the products using a minimum number of
parameters (minimize the product of the weighted sum of squares of
residuals and the number of parameters).

O
R3 O
O

O
O

R1 O
OH

O
O
R4
O
2 O
R5
O
O

R2 OH

R7 O O
R6 O
O

O
Figure 2 Simplified reaction scheme. A

concerning the adsorption mode in a selective hydrogenation
process is shown in Intermezzo 8.
The importance of using proper statistical tools in
the kinetic investigation should never be underestimated,
either for reasons of time effectiveness or confidence in the
resulting model. While at the basic level this can simply
be the experimental design followed by use of a suitable
optimization package for parameter estimation, it may also
include mathematical transformation of the model equation
50
in order to give more reliable fitting. Intermezzo 9 shows
how LHHW kinetic expressions may be reparameterized
by mathematically removing all kinetic parameters from
the numerator. This reparametrization suppresses the
interdependency between the parameters, and thus enhances
the fitting process.
Kinetic modeling — good practice
In order to improve the efficiency and accuracy of kinetic
modeling, a series of recommendations can be given, of
which some were illustrated or mentioned previously:
 Eurokin: Chemical reaction kinetics in practice
: The telomerization of butadiene with o-phthalic acid

The procedure resulted in a model that consists of very simple rate The effect of catalyst concentration is included in the rate constants
expressions. When the reactants are denoted by B (butadiene), PA for a certain range of concentrations. The role of the catalyst in
(o-phthalic acid), Mlinear (linear monoester intermediate) and Mbranched determining selectivities and inhibition effects by byproducts such
(branched monoester intermediate), the rate equations are given as octatriene was not considered in the model. Statistical analysis
by: of the model showed that the accuracy of the parameters would
r1 = k1[B] [PA] 2
have to be improved in order to increase the reliability of a plant
r 2 = k 2 [B] 2 [PA] scale reactor design.
r3 = k 3 [B] 2 [Mlinear] The simple model obtained from experiments that were conducted
r4 = k4 [B] 2 [Mlinear] for purposes other than kinetic modeling is suitable for two
r5 = k5 [B] [Mbranched] 2
reasons:
r 6 = k 6 [B] 2 [Mbranched] • Integration in a reactor model for flow sheet calculations in
r7 = k 7[B] 2 order to make primary economic evaluations.
An example of the comparison between experiment and model • Starting point for the development of a more sophisticated
calculations after optimization of the kinetic parameters is given in kinetic model needed for a final reactor design.
Figure 3. In this figure, o-phthalic acid, one of the intermediates, The continuation of the development of the kinetic model included
and the linear product are shown in dimensionless concentrations experiments at varying temperatures and specifically identification
as a function of time (all concentrations have been normalized to the of product inhibition (adding octatriene or one of the ester products
initial o-phthalic acid concentration). to the starting mixture).

1.2

1.0

0.8 COOH O
concentration (dimensionless)

COOH O
O
0.6
O

0.4
O

O
0.2 OH

0.0
0 25 50 75 100 125
time in minutes
Figure 3 Experiment (symbols) and model (lines) for three selected components.

Acknowledgment The authors are grateful to Johan Hoorn (DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands) for supplying this case study.

• Strive for intrinsic kinetics rather than apparent kinetics
where the transport effects and intrinsic kinetics are
lumped. This strongly improves the understanding of
the physicochemical background of the system, and may
give insight into unusual or unexpected effects, and also
improves the reliability and accuracy of the model when
extrapolated.
• The experimental reactor need not necessarily be a small-
scale copy of the industrial reactor. The use of trickle
beds and fluid beds should preferably be avoided.
• Determine in advance what kinetic information is really
needed, taking into account the resources available.
• Always search for information on comparable chemical
systems. Besides literature, one should not forget to
check if there is information available in the laboratory
from earlier research.
• Use more theoretically-based models if reliability of the
kinetics is required for extrapolation.
• Avoid estimating a large number of different kinetic
parameters from a small experimental data set. An
51
Eurokin: Chemical reaction kinetics in practice

intermezzo 8 Kinetic modeling may contribute to new insights in reaction mechanisms and reaction s

The reaction network shown in Figure 1 can describe the selective
hydrogenation of cinnamaldehyde to cinnamyl alcohol.
The development of the concentrations of the various components
in a batch reactor may be well described by a model with first-
order reaction steps, like in Intermezzo 5 for HDN, including ‘direct’
reactions from reactant to intermediate and end products. This is
examplified by Figure 2 where the lines drawn are the kinetic model
predictions for low concentrations of cinnamaldehyde in toluene [xiv] .
However, at higher concentrations (~3.5 mol/l), the selectivity for the
desired product, cinnamyl alcohol, increases considerably, while at
the same time the absolute conversion rate of cinnamaldehyde is
about the same. This selectivity change can in no way be predicted
by the low concentration derived kinetic model [xv] .
In view of the same conversion rate, it is speculated that
the adsorption mode at high concentrations differs from lower
concentrations, comparable to the adsorption of surfactants in
the form of micelles. In this sense the cinnamaldehyde adsorbs
perpendicular to the Pt surface with the aromatic rings in a parallel
arrangement — “self assembling" which is schematically depicted
in Figure 3. Now the carbonylic functionality will be most prone
to hydrogenation. Literature on this type of ordered adsorption is
scarce, but some examples with aromatic molecules have been
reported [xvi] .
This stresses the importance that in some cases even the adsorption
mode should be incorporated in a kinetic model, otherwise reaction
selectivities will not be predicted.

1 5

cinnamaldehyde (CAL) cinnamyl alcohol (COL) β-methylstyrene

2 4 6

hydrocinnamaldehyde (HCAL) 3-phenyl-1-propanol (HCOL) phenylpropane (PP)

cyclohexylpropanol (CHP)

Figure 1 Cinnamaldehyde hydrogenation reaction network

appropriate use of statistical tools facilitates the rejection
of kinetic models containing too many parameters.
• Define several different kinetic models that may describe
the system and model selection criteria to allow making
a choice between these models.
• Design additional experiments with two goals: (i) to
facilitate the selection of the ‘best’ model, and (ii) to
improve the accuracy of the kinetic parameters.
• Apply proportional weighting in order to achieve an
equally good description of small experimental response
values as for large experimental response values.
• Arrhenius and LHHW expressions can beneficially
be reparameterized [17]. This strongly reduces the
interdependency between activation energy and the pre-
exponential factor which enhances the fitting procedure.
See Intermezzo 9 for more details.
52
Finally, the researcher in kinetics has to choose a suitable
software package to perform the parameter estimation.
Because several different packages are commercially available,
with strongly varying capacities, user interfaces, and
versatility, it is difficult to choose the most suitable package.
A future paper[18] will focus on aspects to be considered
before making a choice of fitting software.
Conclusions
Kinetics studies in industry are pragmatic. Experiments are
expensive, and there must be a financial justification for
kinetic studies. There also needs to be a technical justification
for the model, and the overriding requirement is to maintain
simplicity. The majority usage of kinetic models is in process,
not catalysis research. While industry would like to obtain
intrinsic kinetics models based on mechanistic considerations,
 Eurokin: Chemical reaction kinetics in practice
n sequences: Selective hydrogenation of cinnamaldehyde to cinnamyl alcohol

0.8 0.2

HCOL
0.6 0.15
CAL
C / mol l-1

0.4 0.1

HCAL
COL CHP
0.2 0.05
PP

0.0 0.0
0 200 400 600 800
Residence time / min.

Figure 2 Experimental results cinnamaldehyde hydrogenation

C C C C C C

C C C C C C

C C C C C C
O O O O O O

Pt

Figure 3 Speculated adsorption mode of cinnamaldehyde molecules on the catalyst

it is rarely expedient so to do, due to reasons of cost and man-
hours as well as elapsed time, and economic and technical
justification.
Before setting out on a modeling exercise, it is essential
to think carefully about the requirements. What will the
model be used for? And by whom? Is a full kinetic model
what is actually needed? Will there be a need for extrap-
olation regarding operating domain as well as scale? In
assembling the mathematical expression, every effort should
be made to obtain physicochemical basis. Beware of over-
parameterization, and make maximum use of appropriate
statistical tools. In doing all this, it is worth bearing in
mind that process models do not need detailed kinetics, but
rather a reliable rate model. Even with this, the influence of
external factors changes with scale, particularly the effects of
macro mixing and transport.
Future activities
In considering what the future holds for kinetics — or
more precisely what are the main agenda items for kinetics
research — it is worth returning again to the industrial
survey. This also inquired as to opinions on the aspects of
kinetics that most urgently require improvements. Three
areas were commonly cited:
i. Improvements in the acquisition of kinetic data, since
this is considered too costly and time-consuming.
ii. There is considerable difficulty in the determination and
subsequent application of kinetics for the case of unstable
or variable catalyst performance (e.g., deactivation).

53
Eurokin: Chemical reaction kinetics in practice

intermezzo 9 Statistical techniques help to perform experimental design and to find optimal kinetic

Design of experiments is a collection of statistical techniques NO

employed for systematic experimentation and optimal model
analysis. This application illustrates the use of experimental design
for model building and analysis for the selective catalytic reduction NH 3 NO(out)
of NO by NH3.

Experimental set-up NH3 (out)

The experiments for the determination of the intrinsic kinetics have

been performed in a tubular packed bed reactor, which can be Z=0 Z=L
modeled using the plug flow reactor model, as shown in Figure
1. The separate adsorption and surface reaction steps have been Figure 1 Differential reactor model
lumped into one overall reaction describing the NO conversion.
4 NO + 4 NH3 + O2 → 4 N2 + 6 H2O
Each experiment covers a specific combination of molar fractions Power law
NO, NH3, H2O, and O2 at the reactor inlet, the reactor temperature,
and the space velocity. A small catalyst particle size has been r = k pNOa pNH3b pH2Oc pO2d
selected to avoid mass transfer limitations due to pore diffusion
effects. At the reactor outlet the molar fractions NO and NH3 have Eley Rideal:
been measured.

KNH3 pNH3 KNO pNO (pO2d )

Rate expressions r=k
1+KNH3 pNH3 + KH2O pH2O
According to the different assumptions, several rate expressions
for the surface reaction have been proposed. In Figure 2, some
reaction rate expressions are displayed. The constants a, b, c and Langmuir–Hinshelwood:
d apply to the power law model. The rate constant is given by k.
The parameters KNO , KNH3 and KH2O are the adsorption constants.
KNH3 pNH3 KNO pNO (pO2d )
The rate expressions depend on the local partial pressures PNO , r=k
(1+KNOpNO)(1+KNH3 +KNH3pNH3 +KH2OpH2O)
PNH3 , PO2 and PH2O . At given inlet concentrations, the NO and NH3
outlet values are computed using the reactor continuity equations
for NH3 and NO. The parameters are adjusted such that the sum of
Figure 2 Sample of selected models

A B
all functions controlled via simple keypad

eight individual injectors with

independant control of temperature,
pressure, reagent addition
and gas delivery.

Parallel experimentation rig with 10 reactors

for gas phase reactions over a fixed bed.

Endeavor™ unit with 8 reactors for gas-liquid-slurry reactions (e.g. hydrogenation).

Figure 11 High–throughput experimentation equipment reproduced courtesy of (a) argonaut technologies (b) zeton altamira
54

c models: A case study of the selective reduction of NO by NH3
O2
H2 O
NO/NH3
Figure 3 Central composte design
squared residuals (SSR) — the differences between the measured
and the computed NO and NH3 outlet values — is minimized.
Experimental data
Figure 3 displays the levels of the inlet concentrations. The values
have been arranged using a central composite design, consisting
of 8 corners of the cube (low/high values), 6 star points (orange)
outside the cube and one or more replicates in the center. A
composite design has been chosen as it is suitable for determination
of the nonlinear effects arising from the rate expressions and the
solution of the differential mass balances.
iii. There is considerable opportunity to improve the user
friendliness of software for modeling of reactors, for the
regression of kinetic data to rate expressions, and for its
application to experimental design.
The majority of the respondents stated that the problems
indicated should be solved by co-operation, and this of
course was the impetus that led to the formation of Eurokin
(Intermezzo 1). The above list essentially relates to simply
improving the way we use the current tools, and their
incremental development. The alternate question is what are
the potential major step changes that are going to impinge
on kinetics research in the future. Taking the medium and
long-term perspectives as one, here are some thoughts as
to what the future might bring — or what we involved in
kinetics research ought to be considering.
• Software tools (simulation, regression, experimental
design) will be improved. This will relate not only
to improved user-friendliness and calculation routines
(leading to reduced computational times) but also to
Eurokin: Chemical reaction kinetics in practice
Parameter estimation
For all selected models, the least-squares estimates of the rate
constant and the adsorption coefficients have been fitted. However,
in many cases, extremely large standard errors and mutual
correlations of the estimated parameters were experienced. (In
the Langmuir–Hinshelwood model, the correlations between k and
KNO and between KNH3 and KH2O were 0.99 and 0.99, respectively.)
This indicates ill-conditioned behavior of the estimation problem,
including very sensitive and less reliable parameter results.
Using the “parameter-in- denominator” principles, these inaccurate
results have been considerably improved. After division of the
numerator and the denominator of the Langmuir–Hinshelwood
rate by the common parameter product k KNH3 KNO and rearranging
the parameters in the denominator, nearly all high correlations
and high standard errors disappeared. This reparameterization
produces a ‘close-to-linear’ model by clearing off constants in the
numerator of the rate expression.
Model selection
In order to select the best model, a further model discrimination was
carried out. Figure 4 displays the reaction rates of four rival models,
several forms of Langmuir–Hinshelwood including a model with
surface dissociation, calculated with a high H2O fraction of 20%
at the reactor inlet. Hardly any statistically significant difference
is experienced. Figure 5 displays the rates computed with the
same parameters at a much lower H2O content of 1%. The
differences between the rate values are evident, particularly at
high NO concentrations. Adding experiments carried out at low
H2O concentration increased the discriminative power between the
relevant models; in the same way, other experimental conditions
developments in statistical, search, and optimization
techniques.
• Molecular modeling can be expected to contribute more
to useful mechanistic information and to estimation
of initial parameter values. This relates to the rapid
developments in the theoretical chemistry and compu-
tational tools, as well as to the development in associated
computer hardware. The leading companies are now
targeting increased computational power on the desktop
to facilitate this.
• High throughput experimentation has largely been
associated with combinatorial chemistry, discovery,
and screening. The potential impact of the gross
parallelization of experimental equipment on kinetic
measurements should not, however, be underestimated [19].
Parallel microreactor units are in use in industry and are
now becoming commercially available. Figure 11 shows
two examples of “off-the-shelf” parallel screening units.
Kinetic data may be more rapidly measured, but this
55
Eurokin: Chemical reaction kinetics in practice

displaying large divergence between the models have been Conclusion

added to allow for optimal discrimination — a form of sequential
experimental design. As a last step in the analysis, optimal
parameters of the best model have been refitted using all the
data.
Using statistical techniques, optimal model analysis and design for
the selective catalytic reduction of NO by NH3 has been performed.
Special attention has been paid to the statistical design of the
experiments, efficient reparameterization of the models, and the
design for optimal model discrimination.

400 500
model 1 model 1
model 2 model 2
model 3 400 model 3
300 model 4 model 4

300

Reaction rate
Reaction rate

200

200

100
100

0 0
0 50 100 150 200 0 50 100 150 200
p p
NO NO

Figure 4 Rate values at a H2O content of 20% Figure 5 Rate values at a H2O content of 1%

then puts the emphasis on the statistical tools to set
the experimental design and process the acquired data.
The theory is that combinatorial (or similar) discovery
will increase the number of new products, and so this
increase in the efficiency of kinetics research will be
required simply to keep pace.
• Nonstationary methods such as temperature programmed
reaction and temporal analysis of products are currently
quite widely used to obtain mechanistic information,
but as yet the output is used in a primarily qualitative
fashion, and relatively little quantitative information is
obtained. Unsteady state techniques have the benefit that
data is acquired much more rapidly. The challenge is to
understand how data measured in a transient condition
can be applied quantitatively.
Those in the Eurokin consortium, and their academic
partners, will be actively addressing these issues over the next
few years. The challenges should not be underestimated. It
will require major effort and innovation to achieve these
goals.
Further reading
There exist many textbooks concerning the theoretical
background of reaction kinetics.
The following books are suitable for a general and
basic introduction of chemical kinetics, homogeneous and
heterogeneous catalysis, and the thermodynamics related
with these: Boudart [20] , Boudart and Djega Mariadassou [21] ,

56
 Eurokin: Chemical reaction kinetics in practice
Guidelines for Reparameterization
• Reparameterize Arrhenius expressions according to: • Reparameterize LHHW-type expressions by removing the
kinetic parameters from the numerator according to, for exam-
ple:
-Ea -Ea
k = k o exp k = k ref exp
R·T R·T
kK ApAK BpB2
r=
Original Arrhenius expression Reparameterized Arrhenius expression 1 + K A pA + K BpB2

Original LHHW expression

Where: k = reaction rate coefficient

k o = pre - exponential factor
pApB2
r=
-Ea 1 p + pB2
k ref = k o exp + A
R · Tref k K A K B k K B kK A

Reparameterized LHHW expression

T * = the reparameterized reaction temperature (in K),
calculated from the reaction temperature T (in K) according to
1 1 1
= - Instead of k, Ka and KB the combinations 1/kKAKB , 1/kKB
T* T T ref
and 1/kKA are estimated which also enhances the fitting
T ref = an arbitrarily chosen reference temperature procedure.
within the experimental temperature window.

This reparameterization strongly reduces the interdependency

between activation energy and the pre-exponential factor, which
enhances the fitting procedure. Estimating the log of kref instead
of kref itself may further facilitate the parameter-estimation proce-
dure, because this strongly reduces the difference in uncertainty
ranges of both parameters.

Acknowledgement: The authors are grateful to Sjoerd van der Wal (formerly Shell Research and Technology Centre, Amsterdam, The Netherlands) for supplying this case study.

Froment and Bischoff [13] , and Kapteijn and Moulijn [22]. These
books cover the range from the fundamentals of chemical
kinetics up to modeling of reactors. An extensive and useful
paper concerning the modeling of catalytic kinetics is given
by Froment and Hosten [23].
Sources of more thorough fundamental background of
kinetics of heterogeneously catalyzed reactions, also defined
as microkinetics, are Dumesic et al. [24], Zhdanov[25], Van
Santen [26], and Golden and Manion [27]. A frequently used
method for microkinetic modeling is the Bond-order con-
servation–Morse-potential approach (BOC–MP approach),
see Shustorovich [28, 29] and Bell [30]. Benziger[31] describes
several methods for estimating reaction energetics on metal
surfaces. Kang and Weinberg [32] give an overview of methods
for modeling of surface rate processes. Estimations of heats
of chemisorption of gases on metal surfaces can be done
using the general rules defined by Tanaka and Tamaru [33].

57
Eurokin: Chemical reaction kinetics in practice

curriculum vitae

Rob Berger was born in 1963

in Enschede, The Netherlands. He
graduated in 1987 at the University
of Twente in Process Engineering.
He received his Ph.D. degree in
1992 at the same university, on
research concerning nickel catalysts
for internal reforming of methane
in molten carbonate fuel cells (with
Prof. Julian Ross). During a five-year postdoctoral position,
he investigated the catalytic and homogeneous partial
oxidation of methane to synthesis gas at Eindhoven
University of Technology with Prof. Guy Marin. In 1998
he accepted his current post-doctoral position at Delft
University of Technology on the Eurokin project.

Eurokin, c/o Delft University of Technology, Julianalaan 136

2628 BL Delft, The Netherlands (e-mail: R.J.Berger@tnw.tudelft.nl)

curriculum vitae curriculum vitae

E. Hugh Stitt was born in 1958 Prof. dr. ir. Guy B. Marin (1954)
in Stafford, England. He obtained is full professor of Chemical
his degree in chemical engineering Engineering at the University of
in 1981, and his Ph.D., for research Gent (Belgium). He received his
into the use of electric fields in liquid degree from the University of Gent
extraction in 1985, both at the Uni- in 1976, where he also obtained
versity of Bradford, UK. He spent his Ph.D. in 1980. After a post-
the next six years as a lecturer in doctoral stay in 1981 at Catalytica
chemical engineering at the same university, teaching and Associates and Stanford University
researching in separation processes. he obtained tenure at the University
Since joining ICI in 1990, the emphasis of Hugh’s work has of Gent in 1986. He took a position of full professor in 1988 at
moved to catalytic reaction engineering. Initially the focus the Eindhoven University of Technology (The Netherlands)
was ICI’s petrochemical businesses, involving innovation in where he taught about chemical reactors. In 1997, he
reactors and flow sheets for new processes and for modifica- returned to Gent as director of the Laboratorium voor
tions to existing plants as well as process and reactor model- Petrochemische Techniek. Chemical reaction engineering
ing. catalysis in general, and reaction kinetics in particular are
In 1994 Hugh joined ICI’s catalyst and technology licensing the main foci of his research program. He has co-authored
business, ICI Katalco, which merged with 4 other ICI busi- more than 70 papers in international journals.
nesses to form Synetix in 1998. He has continued to work
Laboratorium voor Petrochemische Techniek, Universiteit Gent,
in the evaluation, development, and commercialization Krijgslaan 281 S5, B-9000 Ghent, Belgium.
of novel reactors and catalytic processes, initially for envi-
ronmental applications, focusing on two- and three- phase
catalytic reactors. His present role is to lead the strategic
development of reactor applications and services technol-
ogies for Synetix. This involves significant internal and
external collaboration; exemplified by Eurokin, of which he
is currently chairman.

Synetix, P.O. Box 1, Billingham, Cleveland TS23 1LB, U.K. (hugh_stitt @ ici.com)

58

acknowledgement
One of the authors (RJB) acknowledges the financial
support from the eleven companies in the Eurokin
consortium: Akzo Nobel, Dow Benelux, DSM Research,
IFP, TECHNIP, Shell Research and Technology Centre,
STATOIL, Linde, Eni Tecnologie, Synetix, and EC
Chem Technologies. All of the authors are grateful to
the members of Eurokin for permission to publish this
paper.
curriculum vitae
Freek Kapteijn was born in 1952
in Amsterdam, The Netherlands.
He graduated from the University
of Amsterdam in 1974 with degrees
in chemistry and mathematics. His
Ph.D. on the metathesis of alkenes
was received at the same university.
As a postdoc he focused on coal
science and heterogeneous catalysis.
In 1987, he received a tenure position
at the University of Amsterdam and moved to Delft
University of Technology in 1993. Since 1999, he was
nominated ‘personal’ professor in Delft. He spent several
periods abroad among them in the group of Villermaux,
Nancy, France (ENSIC) and of Prins, Zürich, Switzerland
(ETH). He is co-author of more than 150 publications
and a co-promoter of 14 Ph.D. students. Current interests
cover the application of monolithic structures in catalytic
conversions and related processes, adsorption and diffusion in
zeolites and zeolitic membranes, and transient kinetics. The
related specific applications of heterogeneous catalysis cover
selective hydrogenation and oxidation, N2O decomposition,
Fischer–Tropsch, and fine chemicals production.
Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
Eurokin: Chemical reaction kinetics in practice
curriculum vitae
Jacob A. Moulijn was born in 1942
in Harlingen, The Netherlands. He
graduated in 1967 and received
his Ph.D. at the University of
Amsterdam in 1974 on the Stimulus-
Response technique applied to packed
beds. Held a tenure position since
1974 and became professor in
Chemical Engineering in 1984 at
the University of Amsterdam. Moved
to Delft University of Technology in 1990 for the Industrial
Catalysis chair. Spent a sabbatical in 1978 in Delaware,
USA with Bruce Gates and was visiting professor at the
University of Gent 1992-1997. He has been CTA for the
United Nations in China from 1995. His research interests
cover a wide field, from Coal Science to Heterogeneous
Catalysis and Engineering, with the emphasis on the
application of catalysis in practice. The use of structured
catalysts for multiphase operation is a major current research
topic. Specific subjects cover petrochemicals, chemicals and
environment. The interest in carbon is still living in the
research on the catalytic combustion of diesel soot and the
application of carbon as a catalyst support. He is co-author
of more than 450 publications, co-edited 7 books and was
promotor of over 30 Ph.D. students.
Delft University of Technology, Julianalaan 136, 2628 BL Delft, The Netherlands
59
Eurokin: Chemical reaction kinetics in practice
references
[1] A.N.R. Bos, L. Lefferts, G.B. Marin and M.H.G.M. Steijns, Kinetic research on
heterogeneously catalysed processes: A questionnaire on the state-of-the-art in
industry, Appl. Catal. A: General 160 (1997) 185-190.
[2] Survey of gaps, needs and opportunities in industrial catalysis, Network on
Catalysis in Europe (NICE), c/o DECHEMA, Frankfurt am Main, Germany
(web site: http://www.dechema.de/deutsch/dechema/pages/framenav.htm, Sep.
2000).
[3] (a) N. Wakao and S. Kaguei, Heat and mass transfer in packed beds, Gordon
and Breach Science Publishers Inc., New York, 1982 (for mass transfer coef-
ficients in fixed beds),
(b) A.P. de Wasch and G.F. Froment, Heat transfer in packed beds, Chem. Eng.
Sci. 27 (1972) 567-576 (for heat transfer coefficients in fixed beds),
(c) V.R. Choudhary and L.K. Doraiswamy, Development of continuous-stirred
gas-solid reactors for studies in kinetics and catalyst evaluation, Ind. Eng. Chem.
Process Des. Develop. 11 (1972) 420-427 (for mass transfer coefficients in
Berty type reactors)
[4] (a) P.H. Calderbank, Mixing (Eds.: V.W. Uhl and J.B. Gray), Vol. 11, Academic
Press, New York, 1967, pp. 1-114 (for gas-liquid mass transfer coefficients in
slurry reactors),
(b) Y.T. Shah, Gas-liquid-solid reactor design, McGraw-Hill, New York, 1979,
Chapter 9, pp. 304-370 (for liquid-solid mass transfer coefficients in slurry
reactors),
(c) P. Trambouze, H. van Landeghem, J.P. Wauquier, Chemical reactors, Design/
engineering/operation, Edition Technip, Paris, 1988 (for a general overview).
[5] F. Kapteijn and J.A. Moulijn, Laboratory Reactors, Chapter 9 in Volume 3 of Hand-
book of heterogeneous catalysis, (Eds.: G. Ertl, H. Knözinger and J. Weitkamp),
VCH Verlagsgesellschaft mbH, Weinheim, Germany, 1997, pp. 1359-1376 (for a
general overview).
[6] M.I. Temkin, The kinetics of steady state complex reactions, Int. Chem. Eng. 11
(1971) 709-717.
[7] D. Chen, A. Gronvold, H. P. Rebo, K. Moljord, and A. Holmen, Catalyst deactivation
studied by conventional and oscillating microbalance reactors, Appl. Catal. A 137
(1996) L1-L8.
[8] H.P. Rebo, E.A. Blekkan, L. Bednarova and A. Holmen, Deactivation of Pt-Sn cata-
lyst in propane dehydrogenation, Catalyst Deactivation 1999, (Eds.: B. Delmon
and G.F. Froment), Elsevier Science B.V., 1999 (Stud. Surf. Sci. Catal., 126 (1999)
333-340.
[9] D. Chen, H.P. Rebo, A. Grønvold, K. Moljord and A. Holmen, Methanol conversion
to light olefins over SAPO-34: kinetic modeling of coke formation, Microporous
and Mesoporous Materials, 35-36 (2000) 121.
[10] Wang, DX; Kung, HH; Barteau, MA, Identification of vanadium species involved
in sequential redox operation of VPO catalysts, Applied Catalysis A-General,
201(2), 203-213, 10 Jul 2000
[11] T.A. Nijhuis, (Delft University of Technology), unpublished results.
[12] A.C.J.M. van de Riet, F. Kapteijn and J.A. Moulijn, Internal recycle monolith reactor
for three-phase operation; hydrogenation of benzaldehyde: kinetics, Preprints of
the 2nd Int. symp. on catalysis in multiphase reactors (EFCE), Toulouse (France),
March 16-18, 1998, pp. 153-159.
[13] G.F. Froment and K.B. Bischoff, Chemical reactor analysis and design, 2nd ed.,
John Wiley & Sons, New York, 1990.
[14] K.K. Hockman and D. Berengut, Design of experiments, Chem. Engineering (Nov.
1995) 142-147.
[15] R.E. Miller, Experimental design, Chem. Engineering (June 1986) 113-117.
[16] C.D. Hendrix, What every technologist should know about experimental design,
Chemtech (March 1979) 167-174.
[17] J.R. Kittrell, In: Advances in Chemical Engineering (Eds.: T.B. Drew, G.R. Cokelet,
J.W. Hoopes and T. Vermeulen), Academic Press, New York, 1970, Vol. 8, p. 97.
[18] R.J. Berger, J.W. Verwijs, J. Verstraete and J. Hoorn, Software functionality assess-
ment for kinetic reaction model development, model discrimination, parameter
estimation and design of experiments, Accepted for the 3rd Int. Symp. on reaction
kinetics and the development and operation of catalytic processes, April 22-25,
2001, Oostende.
[19] J. Pérez-Ramírez, R.J. Berger, G. Mul, F. Kapteijn and J.A. Moulijn, The six-flow
reactor technology. A review on fast catalyst screening and kinetic studies, Catal.
Today, 60 (2000) 93-109.
[20] M. Boudart, Kinetics of chemical processes, Prentice-Hall Inc., Englewood Cliffs,
New Jersey, 1968.
[21] M. Boudart, and G. Mariadassou, Kinetics of heterogeneous catalytic reactions,
Princeton Univ. Press, Princeton, 1984.
[22] F. Kapteijn and J.A. Moulijn, Rate procurement and kinetic modeling, Section 6.1
in Volume 3 of Handbook of heterogeneous catalysis, (Eds.: G. Ertl, H. Knözinger
and J. Weitkamp), VCH Verlagsgesellschaft GmbH, Weinheim, Germany, 1997,
pp. 1189-1209.
60
View publication stats
[23] G.F. Froment and L.H. Hosten, Catalytic kinetics: modelling, In: Catalysis: science
and technology, Vol. 2 (Eds.: J.R. Anderson and M. Boudart), Springer-Verlag,
Berlin, 1981, pp. 98-168.
[24] J.A. Dumesic, D.F. Rudd, L.M. Aparicio, J.E. Rekoske and A.A. Treviro, The micro-
kinetics of heterogeneous catalysis, ACS, Washington D.C., 1993, pp. 23-53.
[25] V.P. Zhdanov, Elementary physicochemical processes on solid surfaces, Plenum
Press, New York, 1991.
[26] R.A. van Santen and J.W. Niemantsverdriet, Chemical kinetics and catalysis,
Plenum Press, New York, 1995.
[27] D.M. Golden and J.A. Manion, Applications of chemical kinetics, Advances in
chemical kinetics and dynamics (Ed.: J.R. Barker), Vol. 1, 1992, pp. 187-276.
[28] E. Shustorovich, The bond-order conservation approach to chemisorption and
heterogeneous catalysis: applications and implications, Adv. Catal. 37 (1990)
101-163.
[29] E. Shustorovich, Mechanisms and intermediates of metal surface reactions: bond-
order conservation viewpoint, In: J.B. Moffat, Theoretical aspects of heteroge-
neous catalysis, Van Nostrand Reinhold, New York, 1990.
[30] A.T. Bell, Relationship of reaction energetics to mechanism and kinetics of het-
erogeneously catalyzed reactions, In: Metal-surface reaction energetics (Ed.: E.
Shustorovich), VCH Publishers Inc., New York, Chapter 5, 1991, pp. 191-227.
[31] J.B. Benziger, Thermochemical methods for reaction energetics on metal sur-
faces, In: Metal-surface reaction energetics (Ed.: E. Shustorovich), VCH publish-
ers Inc., New York, Chapter 2, 1991, pp. 53-107.
[32] H.C. Kang and W.H. Weinberg, Kinetic modelling of surface rate processes, Surf.
Sci., 299 (1994) 755-768.
[33] K-I. Tanaka and K. Tamaru, A general rule in chemisorption of gases on metals, J.
Catal. 2 (1963) 366-370.
References from the intermezzos
[i] Nijhuis, X. (Delft University of Technology), unpublished results.
[ii] S.T. Sie, Reaction order and role of hydrogen sulfide in deep hydrodesulfurization
of gas oils: consequences for industrial reactor configuration, Fuel Processing
Technol. 1999, 61, 149-171.
[iii] S.T. Sie, Miniaturization of hydroprocessing catalyst testing systems: Theory and
practice, AIChE J. 1996, 42, 3498-3507.
[iv] H.R. Reinhoudt, The development of novel catalysts for deep hydrodesulfurisation
of diesel fuel, Ph.D. Thesis, Delft University of Technology, 1999, 225 pp.
[v] M. Jian, F. Kapteijn and R. Prins, Kinetics of the hydrodenitrogenation of ortho-
propylaniline over NiMo(P)/Al2O3 catalysts, J.Catal. 1997, 168, 491-500.
[vi] Th. Vergunst , Carbon coated monolithic catalysts. Preparation aspects and testing
in the three-phase hydrogenation of cinnamaldehyde , Ph.D. Thesis Thesis, Delft
University of Technology, 1999, 230 pp
[vii ] P.J. Clymans and G.F. Froment, Computer-generation of reaction paths and rate
equations in the thermal cracking of normal and branched paraffins, Comp. Chem.
Eng. 8, (1984) 137-142.
[viii] J.F.M. Denayer, G.V. Baron, W. Souverijns, J.A. Martens and P.A. Jacobs,
Hydrocracking of n-alkane mixtures on Pt/H-Y zeolite: chain length dependence
of the adsorption and the kinetic constants, Ind. Eng. Chem. Res. 36 (1997)
3242-3247.
[ix ] G.G. Martens, G.B. Marin, J.A. Martens, P.A. Jacobs and G.V. Baron, A
fundamental kinetic model for hydrocracking of C8 to C12 alkanes on Pt/US-Y
zeolites, J. Catal. 195 (2000) 253-267.
[x ] G.G. Martens, J.W. Thybaut, G.B. Marin, Single-Event rate parameters for the
hydrocracking of cycloalkanes on Pt/US-Y zeolites, Ind. Eng. Chem. Res.,
submitted.
[xi] Yaluris, G, Rekoske, JE, Aparicio, LM, Madon, RJ, Dumesic, JA, J. Catal. 153,
(1995). 54.
[xii] Watson, B.A., Klein M.T., Harding, R.H., Ind. Eng. Chem. Res. 35, (1996) 1506.
[xiii] Martens, G.G., and Marin, G.B., AIChE J. submitted.
[xiv] Th.Vergunst, Carbon coated monolithic catalysts. Preparation aspects and testing
in the three-phase hydrogenation of cinnamaldehyde. Ph.D. Thesis, Delft University
of Technology, 1999
[xv] Vergunst Th, Kapteijn F & Moulijn J : Kinetics of Cinnemaldehyde Hydrogenation
– Concentration Dependent Selectivity : pp 197 – 204, proc 3rd Int Symp Catalysis
in Multiphase Reactors, Naples, 29-31 May 2000.
[xvi] M. Komiyama, Adsorption characteristics of pyridine bases on zeolite (010) examined
by atomic force microscopy (AFM), Stud. Surf. Sci. Catal. Vol 109 (1998) 185-191.
[xvii] Kittrell JR in Advances in Chemical Engineering (eds. Drew TB, Cokelet GR,
Hoopes JW, VermeulenT) Academic Press, New York, 1970, Vol. 8, p.97.