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NOTATION
Concentration of butanol (mol dm-3)
Initial concentration of butanol (mol dm-3)
Feed rate (mole min-l)
Gas constant (g cal g mol-' K)
Rate of reaction (mol min-l g cat.-')
Temperature (K)
Weight of catalyst (g)
Fractional conversion of butanol
Weight-time (g cat. min dm-3)
1 INTRODUCTION
Butyraldehyde is an important chemical, used in the
synthesis of polyvinylbutyral, having many important
applications in the polymer industry. Metal oxides have
been extensively used for dehydration/dehydrogenation
of alcohols' and the multipathway dehydration/
dehydrogenation of alcohols has been employed as a
model reaction for studying catalytic properties of metal
oxides. A correlation between acid/base properties and
catalytic activity, selectivity2 and mechanism3 has
~-~
emerged as a result of these studies. Acid o ~ i d e s have
2 EXPERIMENTAL
2.1 Reaction apparatus and procedure
A block diagram of the experimental set up is given in
265
V. K. Raizada et al.
266
Heating element 1
Chilled
methyl
alcohol
out
alcohol in
B
- . - . - .. .
. .- :-----
-'
__
Product
(Butyraldehyde+
n-butyl alcohol 1
Fig. 1. Flow diagram. (1) n-Butyl alcohol storage vessel. ( 2 ) Pre-heater. (3) Reactor. (4) Vertical condenser. ( 5 ) Jacketed product
vessel. (6) Capillary flow meter. (7, 8) Needle valves. (9, 10) On-off valves.
CJ
C
40-
20 -
1-
200
400
600
800
1000
1200
267
2ot-.-
f 40v
x
20 -
L
0
400
600
800
10-
o---
x 20
200
200
400
600
800 1000
w/FA, ( g catalyst mole- min)
8o
450C
425OC
801
200
400
600
800
1000
w / F ~ (g
, catalyst mole- min)
TABLE 1
Optimum Conditions for Maximum Yield of Butyraldehyde
ZnO
calcined from
Surface
area
(m28-l)
Temperature
(C)
optimum
Weight-time
Percent
conversion
36.19
44.10
44.12
450
450
400
6.24
6.00
16.65
67.00
85.40
89.84
400
15.90
88.00
WIF,,CAO
268
V . K . Raizada et al.
(4
(4
Fig. 6. SEM of ZnO from (a) carbonalte, (b) oxalate, (c) (d) hydroxide.
10
20
I
40
275T
I
I
I
I
I
I
I
I
I
I
60 80 100 120 140 160 180 200 220 240
W/f,, (g catalyst mole-' min)
269
routes, decomposition occurs by condensation of COigroups with two protons from the nearest OH- group
resulting in the release of CO, + H,O along channels
parallel to the c axis and leaving behind an open network
of zinc and oxygen while, during thermal decomposition
via the hydroxide route, zinc oxide is forced to grow in
a hexagonal platelet morphology rather than with prismlike habit. Herman et al." have reported two ranges of
zinc oxide morphologies while studying catalytic synthesis of methanol from CO and H, using Cu/ZnO/
M,O, catalyst. In one range zinc oxide appears to form
a network of crystallites with their six-fold crystal axis
parallel to major dimensions and in the second zinc oxide
crystallites are hexagonal platelets with their six-fold
crystal axis perpendicular to major dimensions. It was
observed in the SEM picture for zinc oxide prepared by
calcination of zinc hydroxide, that the hexagonal
platelets are more distinct and in greater abundance than
in the other zinc oxides.
In the present work although no cationic dopant was
present, it is possible that Zn2+form hydroxy complexes
which age during the process of precipitation and
washing, and on subsequent drying and calcination they
may be acting as seeds for crystallization of nascent zinc
oxide which is forced to grow in hexagonal platelet
morphology.
3.6 Determination of rate data
The kinetics of zinc oxide catalyst, i.e. zinc oxide
prepared by calcination of zinc hydroxide precipitated by
ammonium hydroxide, were studied between 275C and
375C at weight-time ranging between 04-50 g
cat. min drn-,. Differential method of analysis has
TABLE 2
Variation of Reaction Rate Constant with Temperature
Temperature
(K)
0.4 17
0.560
1.180
2.000
548
598
623
648
= 2.67 exp (-
17.22 x 103/RT)C ,
4 CONCLUSION
ACKNOWLEDGEMENT
The authors are thankful to Dr S. N. Pandey, Director,
for the encouragement and interest taken in the
investigation.
V. K. Raizada et al.
270
REFERENCES
1. Emmett, P. H. & Sabatier, P., Catalysis Then and Now.
Franklin Publishing Co. Inc., 1965, pp. 650-79.
2. Tanabe, K., Hattori, H., Sumiyoshi, T., Tamaru, K. &
Kondo, T., J . Catal., 53 (1978) 1.
3. Noller, H. & Kladnig, W., Catal. Rev., 13 (1976) 149.
4. Noller, H., Andreu, P. & Hunger, M., Angew. Chem., Int.
Ed. Engl., 10 (1971) 172.
5. Siddhan, S., J . Catal., 57 (1979) 191.
6. Carrizosa, I. & Manuera, G., J . Catal., 49 (1977) 189.
7. Koga, O., Onishi, T. & Tamaru, K., J . Chem. SOC.Faraday
Trans. I, 76 (1980) 19.
8. De Boer, J. & Visserer, W., Cafal Rev., 5 (1971) 55.