Ind. Eng. Chem. Res.

2002, 41, 1445-1453 1445

Catalytic Wall Reactor as a Tool for Isothermal Investigations in the

Heterogeneously Catalyzed Oxidation of Propene to Acrolein
Hubert Redlingsho1 fer,*,† Oliver Kro1 cher,‡ Wolfgang Bo1 ck,‡ Klaus Huthmacher,‡ and
Gerhard Emig†
Lehrstuhl für Technische Chemie I, University of Erlangen-Nuremberg, Egerlandstrasse 3, 91058 Erlangen,
Germany, and Feed Additives Division, Degussa AG, Rodenbacher Chaussee 4, 63457 Hanau, Germany

The vapor phase oxidation of propene to acrolein is a highly exothermic reaction. To ensure
isothermal reaction conditions, a catalytic wall reactor was used for detailed investigations on
the reaction behavior on a multicomponent bismuth-molybdate oxide catalyst. The reaction
temperature showed only small influence on the selectivity to acrolein, but a significant optimum
at about 360 °C is observed. The results further indicate a change in the rate-determining step:
while at low temperatures (<360 °C) catalyst reoxidation is rate determining, with increasing
oxygen content accelerating the formation of acrolein considerably, its influence disappears at
higher temperatures. Not only does water increase the selectivity to acrolein, but also, at low
temperatures, it improves catalyst reoxidation remarkably. Additionally, the formation of the
most important side products (acrylic acid, carbon oxides, acetaldehyde, formaldehyde, and acetic
acid) was observed, depending on the reaction parameters.

1. Introduction temperature gradients is influenced by heat transfer

The choice of an appropriate laboratory reactor for
kinetic measurements is decisive. Difficulties occur if
highly exothermic or endothermic reactions are to be
investigated. In fixed bed reactors, which are used in
many heterogeneously catalyzed reactions because of
their simple setup, often radial and axial temperature
gradients appear due to heat transfer limitations in the
bed. At reaction enthalpies larger than 60 kJ/mol,
isothermal conditions can no longer be guaranteed.1 On
the other hand, recycle reactors and fluidized bed
reactors ensure isothermal conditions, though the former
include a large internal surface area and a high free
volume, allowing homogeneous reactions to interfere
with the kinetic investigations. In the latter, catalyst
attrition is a major problem. Besides this, the process
design in both alternatives is often complicated.
A further alternative represents the catalytic wall
reactor (CWR) where the catalyst is coated on the
reactor wall and the heat of reaction can be directly
transferred through the wall without the limiting heat
resistance of the bed. Accordingly, the catalyst temper-
ature can be easily controlled during highly exothermic
or endothermic reactions ensuring isothermal condi-
tions. This combines the advantages of both plug flow
and recycle reactor. For the purpose of kinetic modeling
the CWR has already been used in different reaction
systems with high reaction enthalpies for collecting
isothermal data.2-8
The oxidation of propene to acrolein is an industrially
important process with a reaction enthalpy of -347 kJ/
mol. Promising attempts to model this reaction in an
industrial nonisothermal fixed bed reactor (FBR) have
already been carried out.9 However, the determination
of the kinetics in fixed beds with axial and radial
* Corresponding author. Fax: + 49 9131 8527421. E-mail
address: hubert.redlingshoefer@rzmail.uni-erlangen.de.
† University of Erlangen-Nuremberg.
‡ Degussa AG.
10.1021/ie0106074 CCC: $22.00 © 2002 American Chemical Society
Published on Web 02/08/2002
parameters which are barely reliable and usually have
a large effect in reactor modeling. By guaranteeing
isothermal conditions, the CWR should therefore facili-
tate reliable estimation of kinetic parameters.
The mechanism of the main reaction has already been
extensively investigated during the last 40 years in
detail and is well understood.10 However, little is known
about the formation of side products. Furthermore, the
kinetics of the main reaction show considerable differ-
ences in the activation energy. The industrially prac-
ticed addition of water in the selective oxidation of
propene is not fully understood.11
The aim of the present work is to use the CWR to
obtain detailed information of the highly exothermic
reaction on an industrial catalyst by collecting isother-
mal data including data on important side reactions.
These integral investigations will not deduce the reac-
tion mechanism, but they will allow one to suggest
founded reaction pathways and to determine the kinet-
ics without the influence of mass and heat transport
limitations.
2. Experimental Section
2.1. Experimental Setup. All laboratory investiga-
tions were performed in an automated laboratory setup
(Figure 1a).
Because of the toxicity of acrolein, the whole setup
was encapsulated. Propene, oxygen, water, nitrogen as
inert gas, and methane as an internal standard for the
gas chromatograph were fed by mass flow controllers
(Bronkhorst Hi-Tec). The gases and water were mixed,
and water was vaporized in a controlled evaporation
mixing system (CEM, Bronkhorst Hi-Tec). To avoid
condensation or polymerization the pipes were heated
to 100 °C for the feed gas and 200 °C for the product
stream.
A small part of the product mixture was analyzed by
online gas chromatography (Chrompack CP9001). A CP
PoraBONDQ column for most reactants, a HP Molecular
1446 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002

Figure 1. Experimental setup (a) and detailed scheme of the CWR (b).

Sieve 5A especially for separating the permanent gases

nitrogen, oxygen, and carbon monoxide, and a HP
INNOWAX especially for detecting acrylic and acetic
acid were linked by the coupled-column technique. The
gas chromatograph was further equipped with two
injectors, two sample loops, three two-position valves,
a flame ionization detector, a thermal conductivity
detector, and a methanizer. All C, O, and H balances
were fulfilled within deviations of less than ( 5%.
The main product stream was cooled and the organic
compounds were absorbed in a solution of sodium sulfite
which accelerates the polymerization of acrolein in
water.
2.2. Catalytic Wall Reactor and Coating Proce-
dure. For flexible control a modular assembly of the
laboratory reactor was used (Figure 1b). The CWR
consists of several (one to seven) tubular reactor seg-
ments (length, 80 mm; inner diameter, 10 mm) manu-
factured out of 316 stainless steel. The reactor segments
are threaded at both ends and could be connected by
unions. The segments were sealed by graphite gaskets.
Modular external heating devices were used to enable
varying reactor length. In the pre- and postcatalytic
zones heating coils were used, whereas, in the catalytic
zone, three heating jackets with spacers maintained
isothermal conditions. These could be ensured by mea-
suring the reaction temperature very close to the
catalyst with thermocouples positioned in radial holes
(diameter: 1.3 mm) in the wall of the reactor segments
and about 0.2 mm from the catalyst coating. A computer
controlled data logging system recorded and stored the
temperatures every 60 s. A bed of inert glass spheres
(diameter: 0.75-1.0 mm) improved the mass transport
between the gas bulk and the catalyst on the wall and
reduced the homogeneous volume. Furthermore, it
ensured plug-flow inside the reactor.
The same assembly was used for comparative studies
in a fixed bed. Therefore, the temperature in the gas
bulk could be determined in axial direction by a move-
able thermocouple in the center of the tube.
Figure 2. Coating procedure for the CWR.
The inner wall of the reactor segments was coated
with catalyst using a suspension process (Figure 2). A
similar coating procedure was used by Amon et al.2 for
a different reaction system and catalyst. In our study,
an industrial multicomponent oxide catalyst based on
bismuth and molybdenum containing montmorillonite
as carrier with a shape of hollow cylinders has been used
as starting material. To ensure sufficient adhesion of
the catalyst coating on the wall very small particles with
a diameter of less than 40 µm have to be used in the
suspension procedure. Unfortunately, grinding the in-
dustrial catalyst to the desired particle size led to
changes in the catalyst structure and phase composition
which was observed by XRD measurements. This re-
sulted in a massive decrease in activity and a loss in
the selectivity to acrolein. Due to this influence of the
particle size the catalyst was only crushed to 250-400
µm. Milled montmorillonite powder (diameter: 0.1-40
µm) was physically mixed with the crushed catalyst in
a ratio of 1:1 and thus acted as a cementing material.
The mixture was suspended in xylene inside the reactor
segment. During rotation at 1000 rpm of the closed tube
containing the suspended solid mixture, the solvent

slowly evaporated at room temperature. The solid
remained at the inner wall of the tube and built up a
uniform layer. Finally, the coated reactor segment was
calcined at 250 °C for 8 h. This procedure ensured
reproducible coatings with an adjustable thickness
between 300 and 600 µm. The coatings were thermally
and mechanically stable for the use in the CWR.
However, scraping could be used to remove the coating
from the wall.
2.3. Preliminary Investigations. To determine the
influence of homogeneous reactions in the free volume
and at the free metal surface of the reactor wall or in
the inert bed, experiments under typical reaction condi-
tions were performed in the CWR without catalyst
coating. Starting at about 300 °C, the conversion of
propene increased nearly exponentially with tempera-
ture. Up to 400 °C less than 3% and up to 450 °C less
than 5% of propene were converted, mostly to carbon
oxides and acetaldehyde. Different authors12-15 mention
that the homogeneous or surface initiated homogeneous
reactions have just a small influence on kinetics in the
reaction system investigated. Wragg et al.16 further
mention that the presence of a catalyst reduces homo-
geneous reactions by scavenging gas-phase radicals and
thus suppressing chain propagation.
To minimize the homogeneous volume in the post-
catalytic zone, 1/16 in. tubes were used as feed pipes to
the gas chromatograph. Furthermore, the internal
standard methane was fed in front of the reactor to
avoid additional tubing and mixing zones after the
reactor. It was already shown by Fehlings et al.17 that
methane is inert in the reaction system investigated.
This was confirmed by our own preliminary measure-
ments.
The fresh catalyst took about 1 week to reach a steady
state condition. During this period the activity decreased
steeply at the beginning whereas the selectivities showed
only minor changes.
The detected products could be divided into three
groups: (i) the desired product acrolein with a selectivity
between 82 and 92%; (ii) side products with selectivities
in the range 0.5-5.0% (CO2, CO, acrylic acid, acetalde-
hyde, formaldehyde, acetic acid); (iii) minor side prod-
ucts (selectivity 0.1-0.5%, allyl alcohol, acetone, propi-
onaldehyde; selectivity < 0.1%, benzene, benzaldehyde,
ethene, ethane, butadiene, furfural).
In the following, only the main reaction to acrolein
and side products from group ii will be considered.
The influence of external or internal diffusion resis-
tance was excluded by both the use of a priori criteria
and by appropriate experiments. The conversion of
propene and the selectivities to the products did not
change significantly with variable gas velocity or with
catalyst thickness on the reactor wall.
By means of the positioned thermocouples (section
2.2), the temperature of the catalyst could be measured.
A simple heat balance with the assumption that all the
heat is removed through the wall showed that the
temperature difference between the catalyst and the
thermocouples in the radial holes was less than 1.0 °C
and thus is in the range of the thermocouples’ error.
Therefore, the measured temperatures correspond to the
true temperature at the catalyst surface. A temperature
profile during the oxidation of propene is shown in
Figure 3. There is only a small deviation of less than 2
°C in the catalytic zone from the set temperature. Thus,
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1447
Figure 3. Temperature distribution during the oxidation of
propene in the CWR (T ) 430 °C).
Table 1. Comparison between CWR and FBRa
convn (%) selectivity (%)
PR O2 AC CO2 acrA CO FA AA aceA
CWR; 410 °C 73.0 44.1 86.5 4.3 3.3 2.2 1.1 1.2 0.57
FBR; 410-425 °C 74.2 45.9 87.5 3.7 3.8 1.9 0.9 1.0 0.43
CWR; 430 °C 78.0 57.7 83.5 6.0 4.0 2.7 1.3 1.1 0.50
tot ) 1.2 bara; τmod ) 14.6 (kg s)/mol; x(PR) ) 7.2 %; O2/PR )
a p
1.8; H2O/PR ) 0.5 (PR ) propene, AC ) acrolein, acrA ) acrylic
acid, FA ) formaldehyde, AA ) acetaldehyde, and aceA ) acetic
acid).
the CWR had no temperature gradients and could be
regarded as isothermal.
For comparative studies between the CWR and the
FBR, the same amount of catalyst was distributed over
the same reactor volume. Therefore, the industrial
catalyst had to be crushed to smaller pellets (0.5-0.8
mm) to avoid limitations due to internal diffusion
resistance in the FBR. In contrast to the CWR the
diluted FBR was not isothermal and temperature
gradients of about 10-20 °C between the wall and the
bulk were observed. Nevertheless, a comparison be-
tween both reactor types is shown in Table 1 to roughly
check the performance of the CWR and to confirm that
the reaction behavior of the catalyst did not change
because of the coating procedure. Two isothermal mea-
surements in the CWR at 410 and 430 °C are compared
with measurements in the nonisothermal FBR, where
the temperature at the wall was 410 °C and a hot spot
of about 425 °C occurred in the center of the fixed bed.
Accordingly, the conversion of propene in the FBR was
between the measurements in the CWR at lower (410
°C) and higher (430 °C) temperatures. Strictly speaking,
it was closer to 410 °C because hot spots in fixed beds
are only local and a large part of the catalyst bed was
quite close to the temperature at the wall. Moreover,
the selectivity to acrolein in the FBR was slightly higher
than in the CWR, whereas most side products showed
the opposite behavior. However, these differences were
minor and close to measurement accuracy. Therefore,
it is not possible to attribute them to the different
reactor types.
This shows that the CWR is a useful tool for inves-
tigating in detail the oxidation of propene.
2.4. Experiments. The aim of the experimental
investigations in the CWR is to obtain a detailed insight
into the reaction behavior and to collect data for the
subsequent kinetic modeling of the steady-state kinetics
of the reactions.
All the experiments were performed after the catalyst
reached steady state. To check that the catalyst did not
further deactivate replications were carried out in
1448 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002

Table 2. Replicationsa
convn (%) selectivity (%)
PR O2 AC CO2 acrA CO FA AA aceA
max 61.4 40.3 89.7 3.03 2.79 1.86 0.78 1.68 0.86
min 59.6 37.4 89.1 2.63 2.07 1.68 0.64 1.58 0.71
mean value 60.3 38.4 89.5 2.85 2.32 1.81 0.73 1.64 0.76
95% confdnc interval (() 0.43 0.64 0.29 0.10 0.24 0.04 0.03 0.02 0.04
tot ) 1.0 bara; T ) 370 °C; τmod ) 21.0 (kg s)/mol; x(PR) ) 6.8 %; O2/PR ) 1.8; H2O/PR ) 0.5 (PR ) propene, AC ) acrolein, acrA )
a p

acrylic acid, FA ) formaldehyde, AA ) acetaldehyde, aceA ) acetic acid).

certain intervals during the series of experiments. Table

2 shows the result of 11 replications done within about
1000 h on stream. The observed deviations were negli-
gible. Accordingly, the catalyst did not change, and
reproducibility is very good.
The series of experiments included about 160 mea-
surements under different reaction conditions. All ex-
periments were performed at atmospheric pressure. The
temperature was varied between 330 and 430 °C, the
inlet molar fraction of propene was within 5.0 and
15.0%. The molar ratio of oxygen to propene was
adjusted between 1.4 and 2.2, and the molar ratio of
water to propene was investigated between 0.0 and 2.0.
The modified residence time was varied in the range
12-70 (kgcat s)/mol to obtain conversions of propene
between 20 and 90%. To compare results with conver-
sions of propene in the same range, data with different
temperatures and different residence times were chosen
for representation. At low temperatures and low resi-
dence times, it is difficult to detect small amounts of
side products. At high temperatures, the oxidation is
less selective and more oxygen consuming. Therefore,
high conversions at highest temperatures were not
performed to avoid an irreversible deactivation of the
oxide catalyst at low oxygen content. Tube segments
with a length of 40 cm and a catalyst weight of 4.3 g
were used. After the steady state was reached for each
set of reaction conditions (time normally about 1 h), four
samples were analyzed within 5 h with the gas chro-
matograph and average values were determined. The Figure 4. (a) Conversions of propene and oxygen plus selectivity
and yield of acrolein vs modified residence time at T ) 370 °C. (b)
replications with the gas chromatograph were per- Yield of acrolein vs conversion of propene for different reaction
formed to identify outliers but were almost identical and temperatures (x(propene) ) 6.8%; O2/propene ) 1.8; H2O/propene
always showed negligible standard deviations. ) 0.5).

3. Results and Discussion
3.1. Main Reaction. Figure 4a shows a typical
dependence on modified residence time of the conver-
sions of propene and oxygen as well as selectivity to and
yield of acrolein. Conversions increase the most at low
reaction time, where the rate of the main reaction is
highest. With increasing reaction time, consecutive
reactions are accelerated and the selectivity to the
desired intermediate decreases. During all experiments
oxygen was not fully converted in order to guarantee
molar fractions of oxygen at the reactor outlet above
4.0%. This avoids an irreversible over-reduction of the
metal oxides. Thus the molar ratio of O2/propene had
to be adjusted especially at high reaction times and
temperatures.
Figure 4b represents the yield of acrolein in depen-
dence on the conversion of propene for different reaction
temperatures and various reaction times (modified
residence times) which were always adjusted to reach
conversions of propene in the range of 20 and 90%. At
low conversions (<60%) the influence of reaction tem-
perature is negligible. Whereas looking at desirable high
conversions of propene, the yield of acrolein shows a flat,
but significant optimum at about 360 °C.
When the reaction temperature was varied between
330 and 430 °C, the increase in the conversion of
propene with temperature was clearly higher at low
temperatures (Figure 5). Between 330 and 350 °C, an
increase of 20 °C results almost in a doubling of the
conversion. At higher reaction temperatures (T > 370
°C), this influence, which is attributed to the rise in
reaction rate, is clearly smaller. This suggests a higher
activation energy at lower temperatures and perhaps a
change in the rate-determining step of the main reaction
as the temperatures increases.
Varying the molar ratio O2/propene (Figure 6, parts
a and b) confirms this assumption. At low temperatures
(330 and 350 °C) a higher oxygen content increases the
conversion strongly (Figure 6a) and simultaneously
improves the selectivity to acrolein (Figure 6b). This
behavior does not depend on the degree of conversion
and was also observed at higher conversions. In the
reaction of propene to acrolein therefore, the reoxidation
of the catalyst seems to be rate determining at low
temperatures. At higher temperatures the rise of the

Figure 5. Conversion of propene vs modified residence time for
different reaction temperatures (x(propene) ) 6.8%; O2/propene
) 1.8; H2O/propene ) 0.5).
Figure 6. Conversion of propene (a) and selectivity to acrolein
(b) vs molar ratio O2/propene for different reaction temperatures
(x(propene) ) 6.8%; H2O/propene ) 0.5).
conversion of propene with higher oxygen content
decreases (Figure 6a). Moreover, the selectivity to
acrolein decreases with increasing oxygen at high tem-
peratures (Figure 6b). This suggests that catalyst oxida-
tion is no longer rate determining at high reaction
temperatures.
Increasing the propene concentration in the reaction
mixture, Fehlings et al.18 observed on a multicomponent
Bi-Mo catalyst that at temperatures above 370 °C the
conversion of propene is determined by both the reduc-
tion and the reoxidation step whereas at lower temper-
atures only catalyst reoxidation is decisive. The tem-
perature where the change of the rate-determining step
occurs (370 °C) is in close accordance with our observa-
tions. Monnier and Keulks19 determined in the selective
oxidation of propene over β-Bi2Mo2O9 that the activation
energy for catalyst reoxidation is more than twice as
high as for the reduction step. Accordingly, Krenzke and
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1449
Figure 7. Conversion of propene (a) and selectivity to acrolein
(b) vs molar ratio H2O/propene for different reaction temperatures
(x(propene) ) 6.8%; O2/propene ) 1.8).
Keulks20 observed changing reaction orders for both
oxygen and propene with temperature.
The molar ratio H2O/propene shows a similar influ-
ence on the reaction behavior (Figure 7, parts a and b)
as oxygen. At low temperatures where catalyst oxidation
is rate determining, water also increases the conversion
of propene (Figure 7a) and the selectivity to acrolein
(Figure 7b) remarkably. The improvements are espe-
cially high at low water content and reach a level of
saturation at large H2O/propene ratios. Here again, this
behavior does not depend on the degree of conversion.
At higher temperatures water still improves the selec-
tivity to acrolein, but compared to 330 and 350 °C, its
influence is reduced (Figure 7b). Above 360 °C, water
hardly affects the conversion of propene.
Saleh-Alhamed et al.11 show that water suppresses
the formation of side products by blocking the most
active sites and thus improves the selectivity to acrolein.
They further observe that water increases catalyst
activity by keeping a high degree of oxidation at the
catalyst surface and by preventing the formation of
strongly bonded oxygenates. Saleh-Alhamed et al.21
describe the formation of H218O without the oxidation
reaction by addition of H216O and 18O2 and conclude that
water exchanges oxygen on the catalyst surface and
suggest dissociative adsorption of water. Novakova et
al.22 even demonstrated the incorporation of oxygen
from water via hydroxyl groups in acrylic acid by mass
spectrometric measurements in the presence of H218O.
These explanations are in close accordance with our
experimental results and confirm that water improves
catalyst reoxidation. One further explanation is the
hydrolysis of the catalyst surface by water which might
facilitate the incorporation of oxygen in the lattice of
the catalyst or create additional sites for the reoxidation
1450 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002

Figure 8. Selectivity to acrolein vs molar fraction of propene for

different reaction temperatures (O2/propene ) 1.8; H2O/propene
) 0.5).

Figure 9. Yield of the most important side products vs modified

residence time (T ) 370 °C; x(propene) ) 6.8%; O2/propene ) 1.8;
H2O/propene ) 0.5).

step. Furthermore, it is possible that the hydroxyl

species on the surface might accelerate the formation
of acrolein by acting as nucleophilic agents in the
oxidation of propene. Accordingly, the increase in con-
version by the addition of water is high for low water
contents whereas the fully hydrolyzed surface at high
molar fractions of water shows no improvements by
further addition of water. On the other hand, water
might suppress the formation of strongly bonded hy-
drocarbons at low temperatures and thus keep the
catalyst surface clear. However, the kinetic measure-
ments did not allow us to clearly distinguish between
the above-mentioned mechanisms concerning the special
role of water on the catalyst surface.
Figure 8 represents the influence of the molar fraction
of propene on the selectivity to acrolein. Increasing the
propene content results, with the exception of 330 °C
data, in a decrease in the selectivity to acrolein. Fur-
thermore, higher initial propene content reduced the
conversion of propene to a lesser degree. Experiments
in which the total pressure was varied instead of the
molar fraction of propene under otherwise identical
conditions always showed the same results.
3.2. Side Reactions. In the following, only side
products showing selectivities above 0.5% (section 2.3)
will be considered.
Figure 9 indicates the dependence of the yield of the
most important side products on the modified residence
time. A common way to distinguish if these compounds
are formed in parallel (from propene) or consecutive
(from acrolein) reactions is to extrapolate the yield-time
curves to reaction time zero and to determine the initial
slope. Accordingly, acrylic acid, which always showed
an extrapolated initial slope of 0 (Figure 9), is formed
Figure 10. Yield of acrylic acid vs conversion of propene at O2/
propene ) 1.8 and H2O/propene ) 0.5 (a), selectivity to acrylic
acid vs molar ratio O2/propene at H2O/propene ) 0.5 (b), and
selectivity vs molar ratio H2O/propene at O2/propene ) 1.8 (c) for
different reaction temperatures (x(propene) ) 6.8%).
in a consecutive reaction from acrolein. Using this
method, other side products could not be confidently
classified.
The temperature dependency of the yield of acrylic
acid is shown in Figure 10a where different conversions
of propene were adjusted by varying the reaction time.
Higher temperatures increase the rate to acrylic acid
and suggest a higher activation energy for the oxidation
of acrolein compared to the oxidation of propene.
However, above 410 °C, the yield decreases (Figure 10a).
A possible explanation is the total oxidation of acrylic
acid at higher temperatures. The molar ratio of O2/
propene has only a minor influence at temperatures
below 410 °C (Figure 10b). However, from 410 °C on,
the selectivity to acrylic acid decreases with higher
oxygen content which further suggest the total oxidation
of acrylic acid being a significant consecutive reaction

Figure 11. Yield of carbon dioxide vs conversion of propene at
O2/propene ) 1.8 and H2O/propene ) 0.5 (a), selectivity to carbon
dioxide vs molar ratio O2/propene at H2O/propene ) 0.5 (b) and
selectivity vs molar ratio H2O/propene at O2/propene ) 1.8 (c) for
different reaction temperatures (x(propene) ) 6.8%).
especially at higher temperatures. In contrast to the
main reaction (section 3.1), no change in the rate-
determining step in the formation of acrylic acid is
observed. In parallel to the reaction to acrolein, the
selectivity to acrylic acid is improved by the addition of
water (Figure 10c). Again, the improvements are higher
for low water contents. Consequently, also the total
oxidation of acrylic acid is suppressed by the addition
of water, which corresponds with the fact that its
influence gets smaller at lower temperatures. Addition-
ally, a higher content of propene increased the selectiv-
ity to acrylic acid by probably favoring consecutive
reactions of acrolein which selectivity decreased (section
3.1).
Figure 11a shows the influence of the reaction tem-
perature on the yield of carbon dioxide with a minimum
at 370 °C. At lower temperatures, where the incorpora-
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1451
tion of lattice oxygen seems to be rate determining in
the formation of acrolein and the catalyst exists in a
higher degree of reduction (section 3.1), the total oxida-
tion of propene is intensified possibly by electrophilic
oxygen species or due to a stronger bonding of reaction
intermediates at the surface. At temperatures above 370
°C, consecutive oxidation forming carbon dioxide is
accelerated significantly. The same reaction behavior
was described by Fehlings et al.18 who further postu-
lated coke intermediates in the total oxidation of pro-
pene.
Figure 11b depicts the selectivity to carbon dioxide
depending on the molar ratio O2/propene. When catalyst
reoxidation is rate determining (i.e., if T < 360 °C),
addition of oxygen suppresses total oxidation by ac-
celerating the main reaction. At T > 360 °C a higher
oxygen content possibly favors consecutive oxidation of
acrolein and acrylic acid whose selectivities decrease
under these conditions resulting in an increase of the
selectivity to carbon dioxide.
The special role of water in the main reaction has
already been described in detail in section 3.1. The
improvement in the selectivities of acrolein (Figure 7b)
and acrylic acid (Figure 10c) by addition of water is
achieved due to a suppression of total oxidation. This
can explicitly be seen in Figure 11c. Accordingly, the
suppression of total oxidation is especially high at low
water content and reaches a level of saturation at large
H2O/propene ratios.
Varying the molar fraction of propene between 5.0
and 15.0% which is not illustrated here had no influence
on the formation of carbon dioxide.
Carbon monoxide which was detected with the same
accuracy as carbon dioxide is not described with data
plots, but it showed exactly the same reaction behavior
as CO2 concerning the influences of temperature, molar
ratio of propene, oxygen, and water content. However,
the molar ratio CO2/CO varied depending on the reac-
tion conditions between 1.3 and 2.2.
Both the selectivity of formaldehyde (Figure 12a) and
acetaldehyde (Figure 12b) increase with higher molar
fraction of propene. This might be an indication for a
common reaction forming both side products. The same
behavior was observed for acrylic acid which is formed
from acrolein. Correspondingly, the selectivity to ac-
rolein declines with higher molar fraction of propene
(Figure 8). The influence of the oxygen and the water
content on the selectivities to formaldehyde and acetal-
dehyde is not shown with data plots. Oxygen favored
especially the formation of formaldehyde whereas the
selectivity to acetaldehyde was not influenced. While
higher water contents suppressed the formation of
acetaldehyde only at low temperatures the selectivity
to formaldehyde decreased mainly at high temperatures.
Though both aldehydes must be formed from an attack
on a C-C bond which is more difficult to break than a
C-H one they behave quite opposite. This suggests that
more than one side reaction contributes to breaking of
C-C bonds.
The temperature dependency of the yield of formal-
dehyde, acetaldehyde, and acetic acid is shown in Figure
13, parts a-c. Whereas the formation of formaldehyde
(Figure 13a) increases with temperature, acetaldehyde
(Figure 13b) and acetic acid (Figure 13c) again behave
in the opposite way. At least acetaldehyde and acetic
acid seem to be further oxidized, especially at higher
temperatures. Accordingly, for a complete mathematical
1452 Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002
Figure 12. Selectivity to formaldehyde (a) and acetaldehyde (b)
vs molar fraction of propene for different reaction temperatures
(O2/propene ) 1.8; H2O/propene ) 0.5).
description of the reaction behavior including all side
products during kinetic modeling, the reaction scheme
in the oxidation of propene has to include various
consecutive and parallel reactions.
4. Summary and Conclusions
The CWR guarantees isothermal conditions even
during highly exothermic or endothermic reactions.
These are essential for investigations of complex reac-
tion systems and especially for kinetic measurements
free from mass or heat transport interference. The
chosen coating procedure allowed the use of industrial
catalysts by a simple suspension process. In the highly
exothermic vapor phase oxidation of propene to acrolein
on an industrial multicomponent oxide catalyst based
on bismuth and molybdenum, the CWR provided iso-
thermal conditions.
The results suggest a change in the rate-determining
step of the main reaction depending on temperature.
At T < 360 °C catalyst reoxidation is rate determining
with increasing oxygen content accelerating the forma-
tion of acrolein considerably. At higher temperatures,
oxygen has only a small influence on the formation of
acrolein and catalyst reduction by propene seems to be
the rate-determining step. The reaction temperature
indicated only a small influence on the selectivity to
acrolein, but a significant optimum at about 360 °C was
observed. This temperature apparently corresponds to
the point where the rate-determining step changes (i.e.,
about 360 °C). Apparently, at low temperatures a higher
degree of reduction of the catalyst favors side reactions.
This was evident for the formation of carbon oxides
which attained a minimum at about 370 °C. Consecutive
reactions to carbon oxides and acrylic acid lower the
yield of acrolein at higher temperatures.
Figure 13. Yield of formaldehyde (a), acetaldehyde (b), and acetic
acid (c) vs conversion of propene for different reaction tempera-
tures (x(propene) ) 6.8%; O2/propene ) 1.8; H2O/propene ) 0.5).
Not only does water increase the selectivity to acrolein
by suppressing the formation of carbon oxides, at low
temperatures but also it further improves catalyst
reoxidation remarkably.
With respect to these results, the CWR appears to be
a very useful tool for investigating exothermic reactions
especially when changes of the reaction behavior are
closely linked to reaction temperature. These would not
have been easily detectable in fixed bed reactors with
nearly unavoidable temperature gradients for highly
exothermic reactions.
The experimental results indicate a reaction scheme
consisting of several consecutive and parallel reactions.
The formation of carbon oxides must be considered as
consecutive and parallel steps so that the ratio CO2/CO
is not constant. Acrylic acid seems to be formed as
consecutive reactions from acrolein exclusively.
The collected extensive data containing the reaction
behavior of many side products are currently used to
develop a detailed kinetic model of the oxidation of

propene including side reactions, which is intended to
be published in a following paper.
Acknowledgment
This research was carried out with the financial
support of Degussa AG, Hanau, Germany.
Nomenclature
CWR ) catalytic wall reactor
FBR ) fixed bed reactor
ptot ) total pressure (bara)
S ) selectivity (%)
T ) temperature (K)
τmod ) modified residence time, mass(catalyst)/total molar
flow [(kg s)/mol]
X ) conversion (%)
x ) molar fraction (%)
Y ) yield (%)
z ) reactor length (mm)
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Received for review July 16, 2001
Revised manuscript received November 26, 2001
Accepted December 7, 2001
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