International Journal of

Chemical Reactor Engineering

Volume   Article A

The Catalytic Evaluation of

Structured Zeolite Catalysts
Klaus P. Möller∗ Jonas L. L. Hedlund†
Olov Öhrman‡ Velaphi Msimang∗∗

∗ University of Cape Town, km@chemeng.uct.ac.za

† LuleåUniversity of Technology, Sweden, jonas.hedlund@km.luth.se
‡ Luleå University of Technology, Olov.Ohrman@km.luth.se
∗∗ University of Cape Town, velaphi@chemeng.uct.ac.za

ISSN 1542-6580
Copyright 2004
c by the authors.
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 The Catalytic Evaluation of Structured Zeolite
Catalysts
Klaus P. Möller, Jonas L. L. Hedlund, Olov Öhrman, and Velaphi
Msimang

Abstract
ZSM-5 films, with thicknesses between 150 and 2300 nm, supported on 3
mm diameter alumina beads are characterised in terms of their catalytic activity
and selectivity for tri-isopropylbenzene cracking and para-xylene isomerisation
at 450 ◦ C. A reaction-diffusion model adequately represents the experimental
data and is used to estimate intrinsic reactivity and diffusion properties of the
zeolite films. Results show that the external activity, overall activity and the
diffusivity increase with increasing film thickness. The variation in reactivity
and diffusivity, when compared to physio-chemical data, are a result of structural
defects and non-homogeneities of the zeolite film. The measured diffusivities are
within an order of magnitude of those extrapolated from literature. Thick zeolite
films have the largest Thiele modulus as the increase in zeolite film thickness
dominates over the structural defects. The largest selectivity improvements are
observed for thick zeolite films.

KEYWORDS: Zeolite films, xylene isomerisation, diffusion, model

Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 1

1. INTRODUCTION

The preparation of structured catalyst are becoming of increasing importance for applications in reactive separation
systems and specialised reactors in which both the properties of the catalyst and the support have a role to play (Jansen
et al., 1998, van der Puil et al., 1999, Seijger et al., 2000, 2002, Antia and Govind, 1995). Examples include the
high surface area wire mesh packings for catalytic distillation. Normally structured zeolite packings are prepared by
growing zeolites crystals onto a surface and as such the catalytic properties of these zeolites are expected to be similar
to unsupported crystals (Seijger et al., 2002). For catalytic applications a smooth uniform zeolite surface grown
on a structured packing represents a new type of zeolite catalyst which might be expected to have different activity
and selectivity compared to single crystals. The seed film method (Hedlund et al., 1999, Sterte et al., 2001) has been
shown to provide excellent uniform smooth zeolite films. These zeolite films have been extensively characterised using
standard surface analysis methods such as Scanning Electron Microscope (SEM) and BET analysis of N 2 -adsorption
isotherms at 77K. The surface and catalytic properties of typical materials are reported in Hedlund et al. (2003).

Probe reactions are a powerful tool with which to interpret relationships between catalytic and structural
properties of the zeolite catalyst (Weitkamp and Ernst, 1994, Roeger et al., 1997). It has been shown that tri-
isopropylbenzene (TIPB) cracking (Roeger et al., 1998, Manstein et al., 2002, O’Connor et al., 2001, 2002) and
xylene isomerisation (Dewing, 1984, Manstein et al., 2002) provide excellent reactions with which to characterise the
external and overall activity of ZSM-5 respectively. TIPB is too large to enter the pore system, therefore, the reaction
rate is proportional to the external surface area and the intrinsic reactivity of the surface. Although the products might
be able to react within the pores, this has no effect on the observed initial TIPB conversion. In contrast to para-xylene,
meta- and ortho-xylene have dimensions of the same order of magnitude of the ZSM-5 pores and thus provide a signif-
icant test for the influence of diffusion limitations on products provided that the reaction within the pores dominates.
Feeding para-xylene ensures that the isomerisation within the pores will not be limited by the supply of reactant and
thus a deviation in the observed selectivity of the products meta- and ortho-xylene from intrinsic kinetic selectivity
will indicate diffusion limitations within the pores. The analysis of diffusion effects for this reaction using a simple
linear first order reaction-model have been outlined by many researchers (Wei, 1982, Tsikoyiannis and Wei, 1991,
Li et al., 1992, Amelse, 1993, Bauer et al., 1991, 2001, Chen et al., 1994, Haag et al., 1982, Young et al., 1982).
Wei (1982) demonstrates that diffusion limitations in sequential reactions can be observed by the modification of the
reaction path, which in the case of para-xylene isomerisation means the conversion of a sequential reaction path, pX
→ mX → oX to a triangular reaction path in which the route pX → oX is allowed to take place and occurs in parallel
with the sequential route. The consequence and use of the triangular reaction scheme has been reviewed by Dewing
(1984). Provided that the rate equations are first order, either a diffusion model and a triangular reaction path analysis
are equivalent. The diffusion model approach is preferred because it provides a more direct relationship between the
model parameters and the physical properties of the catalyst.

As a first step to evaluating the performance of these materials, ZSM-5 films of different thicknesses have
been supported on alumina beads. These zeolite films have been evaluated for reactivity and selectivity using TIPB
and para-xylene conversion. The interpretation of these results is carried out using a reaction-diffusion model. The
variation intrinsic model parameters with film thickness are then compared to physio-chemical properties of the films.

2. EXPERIMENTAL

Four thin zeolite film ZSM-5 catalysts were prepared from a clear synthesis solution with a Si/Al = 50, using the seed
film method on 3mm diameter α -alumina supports (Sterte et al., 2001, Hedlund et al., 1999). Their properties are
given in Table 1. Further details on the preparation of these samples can be found in Hedlund et al. (2003). SEM was
used to estimate the zeolite film thickness. The BET surface area from N2 adsorption at 77K was used to estimate
the zeolite loading as the BET surface area of the support was negligible. Extensive analysis of the N 2 adsorption
isotherms by various methods were not able to provide consistent surface area’s, thus the apparent external surface
area was estimated from the loading and zeolite film thickness by assuming a uniform, smooth zeolite film with plate
geometry. The α -alumina support, although it had negligible surface area and pore volume, was not smooth. Thus the
zeolite can grow within the porous regions leading to variations in the zeolite film thickness and surface area. This

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2 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

Table 1: Characteristics of the ZSM-5 films on 3mm alumina beads

Catalyst Zeolite film thickness (L) Zeolite loading Apparent external surface area
nm 10−3 g/g m2 /g zeolite
A 150 2.5 3.8
B 350 6.9 1.6
C 800 14 0.71
D 2300 20 0.25

variation was not quantifiable by N2 adsorption. Due to the roughness of the alumina surface, the zeolite films take on
the shape of the surface as shown in Figure 1.

The reactions were carried out in a fixed bed reactor at 450 ◦ C and 1 atm. 36 g of samples A to D and also 6
g of sample D was loaded in the reactor respectively. Space velocities based on zeolite volume were varied between
0.2 - 0.6 s−1 by changing the argon carrier gas flow rate through the para-xylene (pX) or tri-isopropylbenzene (TIPB)
feed saturator. The mole fractions of pX and TIPB were 0.064 and 8.8×10 −4, respectively. The feed contained 0.001
and 0.00035 mole fraction of meta-xylene (mX) and ortho xylene (oX). At the low conversions only trace amounts of
secondary products were observed. Further information on the reaction procedure is available in Hedlund et al. (2003).

3. THE MODEL AND PARAMETER ESTIMATION

The TIPB cracking reaction is assumed to be first order irreversible. As this reaction only occurs on the external
surface, the first order rate constant (kT IPB ) is based on the apparent external surface area of the zeolite (Equation
1). The products of the reaction are smaller than TIPB and will react within the pores, but this would not affect the
conversion of TIPB on the external surface.
dCT IPB
= kT IPBCT IPB (1)
d τm
Az
The modified residence time τm = , is based on the apparent surface area of zeolite (Az ) and kT IPB is related to the
Q

volume based rate constant kT IPB by :
kT IPB = kT IPB L (2)

The xylene reaction (Equation 3) is assumed to be first order and reversible. At high temperatures and low
partial pressures, the adsorption equilibrium between the gas phase and the catalyst surface concentrations can be
assumed to be linear and thus the adsorption equilibrium constant can be lumped with the rate constants retaining the
first order rate expression.
k1 k2
pX
mX
oX (3)
Vinek and Lercher (1991) have shown that the adsorption equilibrium constant for all the xylene isomers on ZSM-5
are equal above 100 ◦ C, and thus the lumping of the adsorption constants with the rate constants should not influence
the relative ratio of the reaction rates. The chemical equilibrium constants Ke 1 = 2.25 and Ke2 = 0.475 are obtained
from thermodynamics assuming ideal gas behaviour. The rate equations are given by Equations 4 and 5.


CmX
r1 = k1 C pX − (4)
Ke1


CoX
r2 = k2 CmX − (5)
Ke2

A mass balance over a single catalyst particle in an ideal plug flow reactor and the associated boundary
conditions are given by Equations 6 and 7, where x = l/L represents the dimensionless coordinate within the zeolite

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Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 3

Figure 1: SEM images of the zeolite film catalysts : (a) - B; (b) - C; (c) - D; (d) - A.

film and τ = Vz /Q is the residence time based on the zeolite volume (Vz ) and total volume flow rate (Q).
∂ 2Ci Ri L2
+ =0 (6)
∂ x2 Di
 
∂ Ci  ∂ Ci D ∂ Ci 
=0 = 2i (7)
∂ x 0,τ ∂τ L ∂ x 1,τ


L
Because the zeolite film is very thin in proportion to the bead radius = 0.0015 , the zeolite film has been
Rbead
approximated as a flat plate with diffusion access from one side and a zero flux condition at the other. R i is the formation
R L2
rate of species i, and thus the terms i represent Thiele moduli for each of the species. Gas film resistance has been
Di
assumed to be negligible and thus the concentration in the bulk gas stream equals the surface concentration Ci (1, τ ).
The reactor operates isothermally at constant pressure. The diffusion coefficients are assumed to be independent of
concentration. Discretisation of Equations 6 and 7 using orthogonal collocation yields a system of algebraic equations
and an ordinary differential equation (ODE) for the surface boundary condition. These are solved simultaneously for
all three species using Double precision Differential Algebraic Sensitivity Analysis Code (DDASAC) (Stewart and
Caracotsios, 1996).

Preliminary simulations and parameter estimation based on simulated data show that not all the model pa-
rameters are determinable for the typical experimental data obtained in this work and more assumptions are needed.

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4 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

The ratio of the diffusion coefficients D pX : DmX : DoX have been assumed to be 1000:1:10 (Mirth et al., 1993). The
intrinsic rate constants for the xylene isomerisation reaction as described by Equation 3 are related by k 1 = 2k2 (Wei
D pX
(1982)). With these assumptions the model is reduced to 2 parameters, k 1 and 2 .
L
Parameter estimation is carried out using the Levenberg-Marquardt (Burton et al., 1980) routine. A least
squares error criterion is used (Equation 8).

species N 2
∑ ∑ i,exp i,model
j j
Error = C − C (8)
j=1 i=1

The GC analysis reflects the same absolute error for all data, and thus the equal weighting of data by least squares is
appropriate. Linear variances in the parameters were obtained from the covariance matrix.

4. RESULTS AND DISCUSSION

4.1 TIPB cracking

0.6
A
B
C
0.5 D
D : [4.79]

0.4
Conversion [-]

C : [1.67]
0.3
B : [2.73]

0.2

0.1 A : [2.72]

0
0 0.5 1 1.5 2 2.5 3 3.5 4
-5
Modified surface area residence time (τm x 10 ) [s/m]

Figure 2: TIPB conversion at 450 ◦ C over zeolite films. Symbols - experimental data; lines - first order model.
Numbers in square parenthesis represent the volume based rate coefficient k T IPB .

Figure 2 shows that the conversion as a function of modified surface area residence time are different for
each catalyst. It would be expected that the intrinsic activity of the external surface of the zeolite is the same for
all investigated catalysts independent of the zeolite film thickness. Interestingly, Table 2 shows that the rate constants
based on the apparent external surface area and thus the intrinsic activity increase with increasing zeolite film thickness
(or loading). Surprisingly, on a volume basis the differences between the rate constants are small (Figure 2). In
previous work (Manstein et al., 2002, Roeger et al., 1998) TIPB was used to characterise ZSM-5 powders and pellets

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Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 5

Table 2: Estimated TIPB rate constants and pX reaction-diffusion model parameters (σ = standard deviation).

D pX Error
Catalyst kT IPB (k1 = 2k2 ) ± σ 2
±σ D pX φ pX η pX
L N
10−6 m/s s−1 s−1 10−10 m2 /s 10−3
A 0.41 0.0378±0.00055 126±25 0.028 0.37 0.96 0.26
B 0.96 0.369±0.004 542±40 0.66 0.55 0.91 1.2
C 1.3 0.387±0.006 318±22 2.0 0.74 0.85 3.1
D 11 1.01±0.020 797±80 42 0.75 0.85 12


k1 k1
φ pX = L + (Aris,1975)
D pX Ke1 DmX

but only at 270 ◦ C, where conversions of 0.8 were obtained. The rate constant for the powdered catalyst was ca.
0.046×10−6 m/s which is between 10 and 200 times lower than those measured here. This is not contradictory to this
work where TIPB conversion was carried out at a higher temperature (450 ◦ C). Assuming that the zeolites all have
similar intrinsic reaction properties and using the rate constants at these temperatures, the apparent activation energy
is estimated to lie between 40 and 100 kJ/mol, which for zeolites, in which the adsorption of reactant molecules has a
high enthalpy, seems reasonable. This confirms that the activity of the surface of the zeolite films is as expected.

From the first order rate equation (Equation 1), keeping the flow rate and conversion constant, it can be shown
1
that k ∝ , and thus an underestimate of the external surface area would lead to a overestimate in the rate constant.
Az
Vz
The apparent external surface area Az = , does not account for cracks or surface irregularities, thus A z might be
L
underestimated. This seems to suggest that the surface of thick zeolite films contain more surface defects than thin
zeolite films, thus providing more area for reaction. Az also depends on the accuracy of the estimated loading and
zeolite film thickness (the SEM only measures a small portion of the zeolite film), which could lead to large variances
in the apparent surface area.

4.2 Xylene isomerisation

Figure 3 shows that the thickest zeolite film, catalyst D is again the most active, with the thin zeolite film, catalyst
A, being the least active. The solid lines show that the diffusion model (Equations 6 and 7) represent the data well.
A comparison of the two models in Figure 3 illustrates the effect of secondary reactions and diffusion limitations on
the progress of the xylene isomerisation reaction. As expected, at low conversion there is no difference between these
models and the first order analysis gives a first approximation to the intrinsic rate constant (k 1 ) for the conversion
of pX to mX. The trend in the intrinsic rate constant k1 with zeolite film thickness parallels that of kT IPB . The error
estimates show that k1 is accurately determined with less than 2% error (Table 2).

Figures 4 and 5 show that the model is able to predict the yield of mX and oX satisfactorily. Figure 4 shows
that the mX yield follows the usual exponential increase in yield of a primary product. On the other hand Figure 5
indicates that oX deviates from the usual secondary production behaviour showing a linear rather than a sigmoidal
increase. The yield-conversion plot of Figure 6 enables better visualisation of the effect of diffusion on the yield of
mX and oX by eliminating the influence of residence time. Firstly, this figure shows that the xylene isomerisation over
this catalyst is only weakly diffusion limited because the data remain near to the negligible diffusion limit, making
the estimation of diffusion parameters difficult. Results in Table 2 show that the standard deviation of the diffusion
time constants are considerably higher, ca. 10% compared to the less than 2% of k 1 . In the light of these experiments,
this may be deemed acceptable. Secondly, as the diffusion limitation increases, mX seems to behave more like a
secondary product, while oX appears to behave as a primary product, in the extreme case the yield of oX can exceed
that of mX. The dashed lines, in both cases represent the extremities of the influence of diffusion limitations on the
pX isomerisation reaction. The arrows indicate the movement of the product yield from no diffusion to maximum
diffusion limitations during pX isomerisation. Each group of lines indicate that approximately a variation of 3 orders

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6 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

0.40
A
B
0.35 C
D
0.30
Conversion [-]

0.25

0.20

0.15

0.10

0.05

0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6
-1
Residence time (τ) [s ]

Figure 3: The conversion of pX at 450 ◦ C over zeolite films. Symbols - experimental data; solid lines - reaction-
diffusion model as given by Equations 6 and 7; dashed lines - irreversible first order conversion of pX without diffusion
limitations.

D pX
of magnitude in 2 , which corresponds to a variation of L by a factor of 30, is sufficient to move the reaction system
L
from conditions of no diffusion limitations to conditions of maximum diffusion limitations. Although the zeolite film
thickness varied by a factor of 15, the experimental data do not display a variation in selectivity that is predicted by
the reaction-diffusion model. In contrast Table 2 shows that the first order reversible reaction Thiele moduli (φ pX )
for pX of all zeolite films only varied between 0.37 and 0.75. This can be viewed as a first approximation to the
diffusion behaviour of the reaction when the secondary product, oX, is negligible. The effectiveness factors of pX,
η pX , are between 0.96 and 0.75 which is reasonably close to 1 and large diffusion limitations are thus not expected.
It appears from these figures that one set of model parameters might well be sufficient to predict the performance of
these catalysts, due to the clustering at low conversion.

Figure 7 shows that, contrary to the previous figures, weak diffusion limitations seem to have a strong in-
fluence on the mX : oX mole ratio, the dashed lines again representing the extremities of the influence of diffusion
on the pX isomerisation reaction. Note that because of product in the feed these ratio plots do not tend to infinity at
zero conversion. This figure shows that the chemical equilibrium composition can be exceeded, but only under severe
diffusion limitations. The model seems to predict these ratios adequately, but careful inspection of the data of catalyst
D, shows that the model is unable to predict the almost constant mX : oX ratio with increasing conversion. It should be
remembered that experimental errors in product ratios are magnified at low conversions and this might be a possible
reason for this deviation. Nevertheless, it is impossible to simulate these yield-conversion profiles using a reversible
reaction with no diffusion limitations as shown in Equation 3, by only varying the rate constants. This is because oX
shows partial primary production behaviour, which means that it appears as if pX proceeds directly to oX via a double
methyl shift. It is well known (Wei, 1982) that diffusion behaviour can produce apparent mechanism shifts. In the
case of xylene isomerisation, this leads to an apparent triangular reaction scheme, an approach which has been used
to analyse diffusion effects in ZSM-5 (Dewing, 1984). In Figure 7, this means that for no diffusion limitations, the
upper most dashed line must always be followed, but the shape (height and width) and the conversion at which the

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Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 7

0.30
meta-xylene
A
B
0.25 C
D

0.20
Yield [-]

0.15

0.10

0.05

0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6
-1
Residence time (τ) [s ]

Figure 4: The yield of mX over zeolite films as a function of residence time at 450 ◦ C. Symbols - experimental data;
lines - reaction-diffusion model as given by Equations 6 and 7.

peak maximum occurs will vary with the ratio of k1 : k2 . The shape of the mX : oX ratio curve for the reaction without
diffusion limitations will always be concave upwards once the maximum mX : oX ratio has been exceeded and will
tend exponentially to the equilibrium composition from above. The reaction model without diffusion limitations is not
capable of simulating data with approximately constant mX : oX ratio and it is impossible to represent the experimen-
tal data with a single set of rate constants. Attempts to fit the data without including diffusion limitations using k 1 and
k2 only, yielded k1 : k2 ratio’s which varied over 2 orders of magnitude and poor model fits. It is thus not possible to
produce the experimentally observed response with a reversible non-diffusion limited reaction and it is not possible to
cross mX : oX equilibrium line. This behaviour is shown on triangular coordinates in Figure 8. When the rate of mX
to oX is fast (k2 ≥ 100k1 ), then the resulting reaction path is shown as the linear heavy dashed line, which proceeds
C
directly from 100% pX along the equilibrium path at a constant equilibrium ratio Ke 2 = oX . When there are no
CmX
diffusion limitations, all other reaction paths must favour more mX and lie to the left of the equilibrium line given by
Ke2 . When diffusion limitations are significant, it is possible to exceed this limiting condition, although this is not the
case here. Due to the low conversion, all the experimental data except for catalyst D, cluster near the pX vertex in
Figure 8 and it would seem that a reaction model without diffusion limitations might be able to represent these data.
However, as the ratio of k2 : k1 increases, the reaction path of the reaction model with no diffusion limitations ap-
proaches chemical equilibrium linearly at high conversion of pX. This is in contrast the reaction model with diffusion
limitations for which the reaction path continues to approach chemical equilibrium as curves (except for the conditions
that would follow the k2 ≥ 100k1 line) with increasing diffusion limitations as shown in Figure 8. Furthermore it is
unlikely that k2 would be orders of magnitude higher than k1 for the same catalyst. Thus in conclusion, this analysis
provides strong evidence that the observed trends in the yield-conversion data over zeolite film catalysts are influenced
by diffusion limitations.
D pX
The diffusion time constants, 2 , shown in Table 2 are about 2-3 orders of magnitude larger than the
L
rate constants. The time constants indicate that the reaction of pX is not diffusion limited. However, the diffusion

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8 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

0.09
ortho-xylene
0.08 A
B
C
0.07 D

0.06
Yield [-]

0.05

0.04

0.03

0.02

0.01

0.00
0.0 0.1 0.2 0.3 0.4 0.5 0.6
-1
Residence time (τ) [s ]

Figure 5: The yield of oX over zeolite films as a function of residence time at 450 ◦ C. Symbols - experimental data;
lines - reaction-diffusion model as given by Equations 6 and 7.

time constants for mX and oX will be 1000 and 100 times smaller, respectively, and are thus of the same order of
magnitude as the reaction time constant. It is thus expected that the product selectivity would reflect changes due to
diffusion limitations. Comparison of the actual diffusion coefficients with literature data (Kaerger and Ruthven, 1992)
shows that these are within an order of magnitude of results extrapolated to 450 ◦ C from non-reactive measurements.
They are about 2 orders of magnitude lower than the ones reported by Mirth et al. (1993), on which the assumption
of the ratio of the diffusivities was based. It should also be noted that when extrapolating all the xylene diffusion
coefficients in Mirth et al. (1993) to higher temperature, their diffusivities tend to converge closer to each other than
that assumed here, in contrast to the assumptions made by Wei (1982). Nevertheless a large difference in the ratio
of the diffusivities, particularly between pX and the other isomers, seems best to describe diffusion limitations within
zeolite films. Evaluation of the Thiele moduli for pX (Aris, 1975) shows that the diffusion limitations are small with
the effectiveness factors based on a reversible first order reaction between 0.96 and 0.85. Interestingly, the evaluation
of the Thiele modulus and the effectiveness factor based on the irreversible reaction of pX are essentially 1.0 for all
zeolite films. It is clear that secondary and reversible reaction steps will have a strong influence on the selectivity in
sequential reactions. Kaerger and Ruthven (1992) have shown that for a sequential first order irreversible reaction, the
decline in the intermediate product due to diffusion occurs between an effectiveness factor of 1 and 0.5 (first order
Thiele modulus between 0.1 and 5). Further increasing the Thiele modulus only causes a reduction in the reaction
rate without changing the selectivity. Thus for complex reaction systems even small diffusion limitations can have a
strong influence on the selectivity. The diffusion model shows that the concentration profile of mX in the zeolite film
is steep, leading to the reduction in the effectiveness factor. High concentrations of mX in the zeolite film lead to the
promotion of secondary reactions i.e. increased formation of oX. Thus mX is key in determining the reactivity and
selectivity of the xylene isomerisation reaction.

It now remains to interpret the observed results in terms of the zeolite film properties. These catalysts all
have the same Si/Al ratio, and thus theoretically should have the same intrinsic reactivity or rate constant k 1 . However,
the thickest zeolite films have the largest rate constant indicating that these are more reactive. This might be caused
by deviations in the Al content, although it seems unlikely that this can account for the factor of 25 increase in the

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Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 9

0.30
A : mX
B : mX
C : mX
0.25 D : mX
A : oX
B : oX
0.20 C : oX
D : oX
Yield [-]

0.15

0.10

0.05

0.00
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Conversion [-]

Figure 6: The yield of mX and oX as a function of conversion at 450 ◦ C. Symbols - experimental data; solid lines -
reaction-diffusion model as given by Equations 6 and 7; dashed lines - simulated mX yield; dotted lines - simulated
oX yield. The direction of the arrows across the dashed and dotted lines represents increasing diffusion resistance
D pX
when 2 is varied in the reaction-diffusion model.
L

rate constant that is observed. Suppose that a fraction of the loaded zeolite film is not accessible or inactive for the
pX reaction but still measured as N2 -BET pore volume, because N2 is a much smaller probe molecule than pX. Thus
the effective mass of active zeolite film is reduced. This might occur particularly for thin zeolite films grown on
rough surfaces and in the initial stages of growth, in which there may be regions of no zeolite, amorphous material and
misaligned pore systems. As the zeolite film becomes thicker, the structure becomes more uniform and crystalline thus
the inaccessible fraction would be reduced, accounting for the increase in reaction rate. The diffusivities are based on
zeolite volume and thus follow a similar trend to the reaction rate constant.

Alternatively, the model assumes that the zeolite films are homogeneous and uniform. SEM results indicate
that the thick zeolite films, although they are smoother, appear to have many small cracks. These create more surface
area and easier access to the interior of the zeolite film and this would be reflected as faster diffusion. This does
theoretically not account for the higher rate constant, although indirectly, cracks might also make more of the interior
accessible to the reactants. During zeolite film synthesis, it has been observed that as the zeolite crystals grow outwards
from a plane, the preferred orientation changes which can lead to different diffusional properties with zeolite film
thickness (Hedlund et al., 1999). During the initial growth regime of the thin zeolite films, there is competition between
the crystals and dominant crystals might subsume slower growing crystals. The pores between these structures might
be misaligned such that they still provide access to smaller molecules such as N 2 but prevent access of the larger
xylenes. When the zeolite films grow thicker, this effect would be diminished, because the dominant crystals grow with
less constraints and a smooth zeolite film develops. Thus the active volume is overestimated for the smaller crystals
and hence these would lead to the lower rate constant observed. Of course there are other sources of error such as in the
zeolite volume and zeolite film thickness, but these are small in comparison to the observed differences. Finally, the
model is very simplistic and contains many assumptions, but provides a first level analysis of the behaviour of zeolite
films during xylene isomerisation. This is sufficient to provide deeper insight into the properties of the zeolite films,

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10 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

35
increasing A
diffusion B
30 resistance C
D

25
mX : oX mole ratio [-]

20
chemical
equilibrium
15 line

10

0
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40
Conversion [-]

Figure 7: The variation of the mX : oX mole ratio with conversion over zeolite films. Symbols - experimental data;
lines - reaction-diffusion model as given by equations 6 and 7; dashed lines - increased diffusion limitations when
D pX
is changed in the reaction-diffusion model; dotted line - thermodynamic chemical equilibrium.
L2

complimenting the physio-chemical characterisation results and thus leading to better preparation methods. However,
the bottom line is that, notwithstanding the faster diffusion observed in the thick zeolite films, the increase in the
zeolite film thickness compensates for this and makes these the most ”shape selective” catalyst. Thick zeolite films
are not only more selective but also more reactive.

Returning to Figure 8, it is now possible to use the developed model to project how efficient these zeolite films
might be in the production of pX from the other isomers. The solid lines starting at 100% mX and oX respectively,
show that, only when the reaction follows a sequential path it is possible to enhance the pX production to any significant
amount, the reverse of what was observed when pX was used as a feed. This can be explained by considering the
concentrations of the isomers in the pores of the zeolite. When either pX or oX are the feed, the intermediate mX is
the slowest diffusing species, and thus the concentration of mX builds up within the pores and promotes the formation
of the secondary product. The dashed lines in Figure 8 show that even thicker zeolite films would be needed to
produce more secondary product in the case of pX and oX feeds. However, when mX is the feed species, it is the
slowest diffusing isomer and thus the supply of reactant into the pore system is rate limiting, causing the concentration
of mX to be low and keeping the concentrations of both products low. Both products are primary and there is no
diffusion limited intermediate to promote the formation of these compounds, although there is a weak trend of the
reaction path to favour the production of pX with thicker zeolite films i.e. increased diffusion limitations without
influencing the ratio of the diffusivities. Using DmX = DoX , as was done by Wei (1982), improves the yield of pX but
does not achieve yields of 90% or more that might be expected under strong diffusion limitations with mX as a feed.
The only way in which high pX yields can be achieved using mX as a feed, is when D pX ≥ DmX  DoX , a ratio which
is not supported by literature. It is noted that the data in Wei (1982) can be represented by either 1:1 or 1:10 ratio
of DmX : DoX . The reaction path followed in the triangular diagram (Figure 8) starting with mX as a feed is strongly
dependent on the DmX : DoX ratio, but just as in Wei (1982), there is no data to substantiate the choice of D mX : DoX .
A similar model, with the same diffusion ratio of the xylene isomers is able to describe the yields of xylene isomers

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Möller et al.: The Catalytic Evaluation of Structured Zeolite Catalysts 11

meta-xylene
100%
A
B
C
D

para-xylene ortho-xylene
100% 100%

Figure 8: A three component diagram of the xylene isomerisation showing the reaction paths. Symbols - experimental
data; lines - reaction-diffusion model simulations using the model parameters from sample D; dashed lines - reaction-
D pX
diffusion model simulations using the sample D parameters and varying 2 ; thick dotted line - the reaction path
L
when k2  k1 . Arrows indicate increasing diffusion limitations.

during toluene disproportionation when severe diffusion limitations are induced by crystal size variation (Chen et al.,
1994) or chemical vapour deposition (Manstein, 2001). This is because the diffusivity of toluene is approximately
the same as that of pX and the supply of feed to the pores of the zeolite is not limiting. Furthermore, oX and mX
are essentially the slowly diffusing sequential or parallel intermediates and thus their concentrations in the pores are
high and therefore they promote the formation of pX. If during toluene disproportionation, a significant portion of the
reaction where to proceed on the external surface, this would reduce the selectivity to pX by a similar mechanism as
observed above. These observations are consistent with the summaries of xylene isomerisation found in Chen et al.
(1994) and Kaerger and Ruthven (1992).

5. CONCLUSIONS

The external surface reactivity, the overall reactivity and the diffusivity has been shown to increase with increasing
zeolite film thickness. A simple reaction diffusion model was found to adequately represent the experimental data,
providing a better link between the intrinsic zeolite film properties (i.e. diffusivity and reactivity) and the physio-
chemical characterisation of the zeolite film. Diffusivities estimated from the reaction data using a reaction-diffusion
model are within the same order of magnitude of those extrapolated from literature. Thick zeolite films have the
largest Thiele modulus, lowest effectiveness factor and are thus the most ”shape selective” catalysts for the xylene
isomerisation. To achieve significant yields of para-xylene, considerably thicker zeolite films are needed.

ACKNOWLEDGEMENTS

The support of a SIDA-NRF South Africa - Sweden collaboration grant is acknowledged. JH acknowledges the support
from STINT, Sweden . KPM acknowledges sabbatical support from the University of Cape Town and NRF.

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12 International Journal of Chemical Reactor Engineering Vol. 2 [2004], Article A4

NOTATION

Az Apparent catalyst external surface area [m2 ]

Ci Concentration of species i (pX, mX, oX) [mol/m 3 ]
Di Diffusion coefficient for species i (pX, mX, oX) [m2 /s]
Error Least squares error between experiment and model [-]
kT IPB TIPB rate constant based on surface area [m/s]
kT IPB TIPB rate constant based on volume [s−1 ]
kj Xylene isomerisation rate constant for reaction j [s−1 ]
l Length coordinate in catalyst particle [m]
L Thickness of the zeolite film [m]
N Number of experimental observations [-]
Q Volume flow rate [m3 /s]
rj Rate of reaction for reaction j [mol/(m3 .s)]
Ri Rate of reaction for species i (pX, mX, oX) [mol/(m3 .s)]
Rbead Radius of alumina support bead [m]
Vz Volume of zeolite [m3 ]
x Dimensionless film thickness [-]

Greek letters
φ pX Reversible first order Thiele modulus for pX [-]
η pX Reversible first order effectiveness factor for pX [-]
σ Linear variance of estimated value [-]
τ Residence time based on catalyst volume [s/m]
τm Residence time based on catalyst area [s]

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