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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.
Figure 1. Experimental setup (a) and detailed scheme of the CWR (b).
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
3. Results and Discussion conversions of propene, the yield of acrolein shows a flat,
but significant optimum at about 360 °C.
3.1. Main Reaction. Figure 4a shows a typical When the reaction temperature was varied between
dependence on modified residence time of the conver- 330 and 430 °C, the increase in the conversion of
sions of propene and oxygen as well as selectivity to and propene with temperature was clearly higher at low
yield of acrolein. Conversions increase the most at low temperatures (Figure 5). Between 330 and 350 °C, an
reaction time, where the rate of the main reaction is increase of 20 °C results almost in a doubling of the
highest. With increasing reaction time, consecutive conversion. At higher reaction temperatures (T > 370
reactions are accelerated and the selectivity to the °C), this influence, which is attributed to the rise in
desired intermediate decreases. During all experiments reaction rate, is clearly smaller. This suggests a higher
oxygen was not fully converted in order to guarantee activation energy at lower temperatures and perhaps a
molar fractions of oxygen at the reactor outlet above change in the rate-determining step of the main reaction
4.0%. This avoids an irreversible over-reduction of the as the temperatures increases.
metal oxides. Thus the molar ratio of O2/propene had Varying the molar ratio O2/propene (Figure 6, parts
to be adjusted especially at high reaction times and a and b) confirms this assumption. At low temperatures
temperatures. (330 and 350 °C) a higher oxygen content increases the
Figure 4b represents the yield of acrolein in depen- conversion strongly (Figure 6a) and simultaneously
dence on the conversion of propene for different reaction improves the selectivity to acrolein (Figure 6b). This
temperatures and various reaction times (modified behavior does not depend on the degree of conversion
residence times) which were always adjusted to reach and was also observed at higher conversions. In the
conversions of propene in the range of 20 and 90%. At reaction of propene to acrolein therefore, the reoxidation
low conversions (<60%) the influence of reaction tem- of the catalyst seems to be rate determining at low
perature is negligible. Whereas looking at desirable high temperatures. At higher temperatures the rise of the
Ind. Eng. Chem. Res., Vol. 41, No. 6, 2002 1449
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