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In this work, mesityl oxide was synthesized by the catalytic aldol con-
densation of acetone in a fixed and a packed-fluidized bed with open-ended
screen packing. Reaction kinetics were studied in a fixed bed, and the reactant
conversion in a packed-fluidized bed was analyzed by a two-phase model with
known reaction kinetics. The fraction of catalyst particles in the bubble phase
was obtained.
Experimental
A schematic of the experimental apparatus is shown in Figure 1. Since
oxygen gas hinders this reaction, nitrogen was used as carrier gas. Taken
from a cylinder it was passed through a deoxidation tower and divided into
two streams. One stream entered the orifice for metering the flow rate and was
fed to an acetone bottle submerged in a constant-temperature bath heated to
2 5 C . Nitrogen was saturated with acetone gas in this bath. The flow rate
of another stream of nitrogen gas was measured with orifice meter, and both
streams were combined. The concentration of acetone and the flow rate of
the feed gas to the reactor were determined by measuring the flow rate in both
streams. Acetone concentration in the feed gas was usually 5 and 10 vol % .
Gas chromatography was used to analyze acetone and mesityl oxide. Poly-
ethylene glycol 1000 was packed in the chromatograph column, and hydrogen
was the carrier gas. To prevent condensation of acetone vapor between the
exit point of the constant temperature bath and the entrance point of the
reactor, the tube was heated to 4 0 C . The reactor used for this experiment
(Figure 2) was a borosilicate glass cylinder, 5.2 cm id and 40 cm high. To
control the reaction temperature, the reactor was put into the fluidized bath,
10 cm id and 50 cm high as shown in Figure 1. Catalyst particles used in
this experiment were 80-100 mesh alumina (Tekkosha Co., Ltd.). Packing
used for a packed-fluidized bed was 1 cm id and 1 cm long 16 mesh open-
ended screen packing.
To eliminate water in catalyst particles, the reactor was heated for 1 hr
at 4 5 0 C in nitrogen and cooled to reaction temperature with flowing nitrogen
gas (100 cc/min). After the reaction temperature was reached, acetone gas
of constant concentration was fed to the reactor, and the reaction was started.
After catalyst activity was constant, experimental data were taken. In the
fixed bed operation, reactant flowed upward in the reactor. Since the porous
plate of this reactor is a good gas distributor in a packed-fluidized bed operation,
only catalyst particles are put into reactor and are fluidized among packings
with reactant gas.
Results
When the reaction temperature was 2 8 0 - 3 7 0 C , most of the product gas was
mesityl oxide. A small amount of mesitylene and polymer were detected.
The fluid flow pattern in the fixed bed is approximately plug flow, and
the fixed bed is operated at constant temperature. From material balance of
reactant gas in the small increment of the bed, the following equation is
obtained.
r = K(C - C )
eq (3)
J_ 0.2
Figure 3 shows the relationship between reactant conversion and L/U at dif-
ferent reaction temperatures. From Figure 3 the reaction rate of this reaction
is expressed as Equation 3. The reaction rate constant at 2 9 0 , 3 3 0 , and
3 6 0 C per unit volume of bed is 3.66, 5.85, and 9.1 (liters/sec), respectively.
The effect of temperature upon the reaction rate constant in this temperature
range is:
= 1.75 10 (-9500/)
4
(5)
F = 4.2 (6)
(4) The gas flow rate in the emulsion phase is the same as the minimum
fluidized gas velocity of particles.
(5) The gas in the bubble phase and emulsion phase flows through the
bed as plug flow.
(6) Since the effective thermal conductivity in a packed-fluidized bed is
considerably large and the heat of reaction of this reaction is small, the bed
is assumed to be operating under constant temperature.
Using these assumptions, from material balance of reactant in the small
increment of each phase, the following equations are derived.
Bubble phase:
(7)
dZ ' R (U-U )
h m{ Rh(U-U ) mt
Emulsion phase:
dC _ F (R -l)
(8)
e 0 h
dZ RU (Cb-C) + ( 1
"r; r e
- 0
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h m{
K b U mf
Publication Date: June 1, 1975 | doi: 10.1021/ba-1974-0133.ch021
where:
Rb =
Boundary condition:
0 Ob Ce Co
1.0
Q=0
1
^0.5
u
U f=1.36l
m
cm
/se ^
K=0.25(V ecl S
% M F =10.0W
_ m {
mf)r
/Q\
^ out JJ~ v e o T " JJ vy bo W /
phases are quite sensitive to a when the reaction rate constant is large. Figure 7
shows the relationship between the reactant conversion and KL /U with the
mt
J , 0.5 iM// /*
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Publication Date: June 1, 1975 | doi: 10.1021/ba-1974-0133.ch021
K=0.25 .^ ^ O O K = 1 2 5
y k=125
L/y (sec)
0 0-1 0.2 0.3 0.4 0.5 0.6 07
1.0
0-8 ?, 0
o 0 Reaction Temperature
0.6 ^ ^ 290C
H* 0.4
.2
Fixed Bed Reactor-.^
K=3.66 (V ec)
0.1 S
0.08
Figure 8. Conversion in packed-fluidized bed reactor vs.
that infixedbed reactor
L / U (sec]
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
1.0
0.8 -
0.6 - Reaction Temperature
e
330 C
0.4 -
x 0.2
X f i x e d Bed Reactor
0.1 K = 5.85(Vsec)
0.08
Figure 9. Conversion in packed-fluidized bed reactor vs.
that infixedbed reactor
Hulburt; Chemical Reaction EngineeringII
Advances in Chemistry; American Chemical Society: Washington, DC, 1974.
278 CHEMICAL REACTION ENGINEERING II
3.66 -
5.85 [
0.8 t> 9.10 )
Kato,Takeuchi,lto, Kubota
= 1-1
0.6- = 3.35
0.652
Publication Date: June 1, 1975 | doi: 10.1021/ba-1974-0133.ch021
4 1.36
plug flow model under the same reaction rate constant. Figure 10 compares
the experimental results with calculated ones in this model. From Figure 10,
both the reactant conversion of this experiment and that of Ishii and Osberg
(2) and Kato et al. (3) agree well with the value calculated from this model
when the fraction of catalyst in bubble phase is 0.2. From Figure 10, the
reactant conversion in a packed-fluidized bed with almost the same size of
packing as that in this experiment is calculated from this model when the
fraction of catalyst in bubble phase is 0.2.
6 8 10" 2 t 6 8 10 2 e
t 6 8 10' 2
KLmf^H
Figure 11. Conversion calculated from this model vs. that in plug flow
and perfect mixing reactors for first-order reaction rate
Discussion
and reactant conversion calculated from this model for a first-order reaction
with reaction rate a constant parameter when the minimum fluidized gas
velocity is 1.0 cm/sec. From Figure 11, when the reaction rate constant is
small (0.1 liter/sec), the reactant conversion in packed-fluidized bed is almost
the same as that in the plug flow reactor. When the reaction rate constant is
intermediate (1.0 liter/sec), the reactant conversion calculated from this model
Downloaded by UNIV LAVAL on July 12, 2016 | http://pubs.acs.org
Publication Date: June 1, 1975 | doi: 10.1021/ba-1974-0133.ch021
is smaller than that in plug flow reactor but usually larger than that in perfect
mixing flow reactor. When the reaction rate constant is large (10.0 liters/sec),
most of the reactant conversion calculated from this model is smaller than that
in perfect mixing flow reactor. When the reaction rate constant is large, the
reactant conversion in a packed-fluidized bed is affected by U/U at the same
mf
value of K L / U .
m f
6 8 10" 2 4 6 8 10 2 A 6 8 10' 2 4
KCoLmf / U ( - J
Figure 12. Conversion calculated from this model vs. that in plugflowand
perfect mixing reactors for second-order reaction rate
version calculated from this model for the second-order reaction with KC as Q
parameter. The same results as those described above are found in Figure 12.
Generally, the reactant conversion in a packed-fluidized bed may be larger
than that in fluidized bed reactor under the same reaction condition as shown
in Figures 11 and 12.
Conclusions
'Nomenclature
o u t
Publication Date: June 1, 1975 | doi: 10.1021/ba-1974-0133.ch021
(gram-mole/cc)
F = gas interchange coefficient between bubble and emulsion phase
0
(liters/sec)
= chemical reaction rate constant (liters/sec)
L = bed height (cm)
^mf bed height at the minimum fluidized gas velocity (cm)
R = bed expansion ratio
b
= absolute temperature ( K )
17 = superficial gas velocity (cm/sec)
U = the minimum fluidized gas velocity (cm/sec)
mt
Literature Cited
1. Kato, K., Imafuku, K., Kubota, H., Chem. Eng. Japan. (1967) 31, 967.
2. Ishii, T., Osberg, G. L., A.I.Ch.E. J. (1965) 11, 279.
3. Kato, K., Takeuchi, N., Ito, U., Kubota, H.,J.Chem. Eng. Japan (1969) 2, 8, 204.
4. Mathis, J. F., Watson, C. C., A.I.Ch.E. J. (1956) 2, 518.
5. Lewis, W. K., Gilliland, E. R., Glass, W., A.I.Ch.E. J. (1959) 5, 419.
6. Kato, K., Imafuku, K., Hattori, K., Kubota, H., Chem. Eng. Japan. (1966) 30, 8,
748.
RECEIVED January 2, 1974.