Sie sind auf Seite 1von 6

J . Chem. Tech. Biotechnol.

1993, 56, 265-270

Kinetic Studies on Dehydrogenation of Butanol


to Butyraldehyde Using Zinc Oxide as Catalyst
V. K. Raizada, V. S. Tripathi, Darshan Lal, G. S. Singh, C. D. Dwivedi
& A. K. Sen
Defence Materials and Stores Research & Development Establishment (DMSRDE), PO GT Road,
Kanpur 208 0 13, India
(Received 17 February 1992; revised version received 4 August 1992; accepted 2 October 1992)
Abstract: Butyraldehyde is an important chemical for many industrial
applications, especially in the production of polyvinylbutyral. A systematic study
of its synthesis by catalytic dehydrogenation of butanol, using zinc oxide as
catalyst has been carried out. The effect of the method of preparation of zinc oxide
on its catalytic activity for the title reaction has also been studied. The optimum
conditions for maximum yield have been worked out and on the basis of secondary
electron micrograms the reasons for higher activity/selectivity in the case of zinc
oxide calcined from zinc hydroxide is attributed to the presence of hexagonal
morphology. A kinetic study for the best zinc oxide catalyst has been carried out
and the rate equation has been determined.
Key words : dehydrogenation, kinetics, order of reaction, energy of activation,
optimum conditions.

been found to give predominantly dehydration products


while non-reducible basic oxides are good dehydrogenation catalysts.'*' Rare earth oxides fall between
these
The review of literature reveals that no systematic
study has been reported for the synthesis of
butyraldehyde using zinc oxide or other oxides of a basic
nature. In the present work, studies have been made to
synthesize butyraldehyde in a single step by dehydrogenation of butanol, using zinc oxide as catalyst in a
fixed bed glass flow reactor. The effect of method of
preparation of zinc oxide on its activity/selectivity has
also been studied. The kinetics of the reaction using zinc
oxide catalyst showing maximum yield of butyraldehyde
have been studied. An attempt has also been made to find
out the factors responsible for maximum activity of zinc
oxide calcined from zinc hydroxide by studying its
morphology using scanning electron microscopy (SEM).

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

J . Chem. Tech. Biotechnol. 0268-2575/93/$06.00 0 1993 SCI. Printed in Great Britain

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.

adopting the area normalization procedure. The gas in


the exit stream was analysed separately in the same
conditions as above using a gas-tight syringe.

2.2 Preparation of catalyst


/

CJ
C

40-

20 -

1-

200

400

600

800

1000

1200

w/FA, ( g catalyst mole-' min)

Fig. 2. Effect of temperature and flow rate: ZnO calcined from

zinc hydroxide precipitated by NH,OH.

Fig. 1. A 9 in. long heated ceramic tube was used to


house the reactor. The catalyst bed length was 10 cm, in
which the fine zinc oxide powder was packed with glass
wool. The design of the reactor was such that it facilitated
uniform heat and mass transfer between vapour and the
catalyst particles. No more than f 1C temperature
variations were observed during the run after steady
state was attained and the samples were collected after
attaining steady state. The feed was delivered to the
reactor via a preheater by means of a calibrated fine
capillary flow meter applying pneumatic pressure in a
closed system. The product was collected through a heat
exchanger (4ft long condenser) cooled to -15C by
circulating chilled methyl alcohol. The collection was
easy and efficient as no diluent was used with feed. The
liquid products were analysed by Aimil Nucon 5700 dual
column GC, using TCD detector. The column was a
2 m x 3 mm i.d. stainless steel tube packed with 10%
carbowax 20 m on DMCS-coated chromosorb WAW.
The flow rate of carrier gas was 50 cm3min-l and the
column temperature was 100C. Quantitative estimation
was done by an integrator (Hewlett Packard, USA)

Zinc oxide for the study was prepared using different


methods by precipitation of (a) zinc carbonate from an
aqueous solution of ZnS0,.7H20 and sodium carbonate, (b) zinc oxalate from an aqueous solution of
ZnS0,.7H20 and ammonium oxalate, and (c) zinc
hydroxide from an aqueous solution of ZnSO, .7H,O
and ammonium hydroxide/potassium hydroxide. All the
chemicals used were AR/GR grade and were added in
equimolar ratio in case of (a) and (b) and in the ratio of
1: 1.6 mole in the case of (c). The precipitated gel was
aged for 6 days under identical conditions in all cases and
was collected and washed by repeated redispersionfiltration cycles till free from anions. The gel was dried at
140C to 150C for 2 h and was calcined at the
temperature of 550C for 5 h.

3 RESULTS AND DISCUSSION


3.1 Synthesis of butyraldehyde from butanol
The synthesis of butyraldehyde from butanol by catalytic
dehydrogenation, using zinc oxide as catalyst is a single
step reaction. A detailed study of the effect of various
operating parameters such as method of preparation of
zinc oxide, temperature and weight-time has been
studied and optimum conditions determined.
The butanol used was 99% pure. The liquid product
collected was analysed by GC and contained only
butanol and butyraldehyde. The other products found
were below 1 % and hence were not identified. The
gaseous product consisted of butene and hydrogen. The
percentage of butene in the gaseous product was below

267

Dehydrogenation of butanol to butyraldehyde


1001

2ot-.-

f 40v

x
20 -

L
0

400

600

800

10-

Fig. 5. Effect of temperature and flow rate; ZnO calcined from


zinc oxalate.

showed very good activity as well as selectivity giving


yields from 67 to 90 YO.

3.3 Effect of temperature


4 5 0 C
425C

o---

x 20

200

w / F ~ ,( g catalyst mole- min)


I

200
400
600
800 1000
w/FA, ( g catalyst mole- min)

Fig. 3. Effect of temperature and flow rate: ZnO calcined from


zinc hydroxide precipitated by KOH.

8o

450C
425OC

801

200

400

600

800

1000

w / F ~ (g
, catalyst mole- min)

Fig. 4. Effect of temperature and flow rate: ZnO calcined from


zinc carbonate.

2 % on the basis of alcohol feed. The material balance in


the results was 93 k 2 YO.

The effect of temperature is given in Figs 2-5. A series of


experiments was conducted in the temperature range
350C to 450C. Conversion in different grades of zinc
oxide increased with increase in temperature in the range
studied. In the case of zinc oxide prepared by decomposition of carbonate and oxalate, though the
conversion kept on increasing with increase in temperature, at higher temperatures beyond 450C a lot of
carbonization took place making the catalyst lose its
activity. The material balance dropped sharply and
percent conversion dropped to 55.2% in the case of
carbonate and 62.5% in the case of oxalate at a
temperature of 475C and at a flow rate of 965.11 g
cat. mol-I min.

3.4 Effect of flow rate


3.2 Effect of method of preparation of catalyst

The effect of zinc oxide prepared from three different


methods as detailed in Section 2.2 is given in Figs 2-5.
All types of zinc oxide prepared by different precursors

Weight-time (z) was studied in the range 3.4 to


19.6 g cat. min dm-3 and it was found that conversion
increased rapidly with weight-time increase and became
steady at higher W/FA,,.

TABLE 1
Optimum Conditions for Maximum Yield of Butyraldehyde
ZnO
calcined from

(a) Zinc carbonate


(b) Zinc oxalate
(c) Zinc hydroxide precipitated from
ammonium hydroxide
(d) Zinc hydroxide precipitated from
potassium hydroxide

Surface
area

(g cat. rnin dm-3)

(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)

Fig. 7. Effect of flow rate and temperature.

3.5 Optimum conditions


Zinc oxide prepared from the different methods detailed
in Section 2.2 showed maximum conversion at different
temperatures and different flow rates as given in Table 1.
The results in Table 1 as well as Figs 2-5 show that zinc
oxide prepared by calcination of zinc hydroxide
precipitated by ammonium hydroxide gave maximum

activity/selectivity giving 90 YOyield of butyraldehyde at


a temperature of 400C and weight-time of 16.65 g
cat. min dm-3 in spite of the fact that the surface area
did not differ much. A general mechanism for dehydration and dehydrogenation of alcohols on acidic
and basic oxides has been proposed by Van Reyen and
Sachtler." According to these authors, in the case of
dehydrogenation large cation-basic oxides behave
differently, in that the cation interacts with hydrogen
followed by the interaction of the anion with the -OH
group of the alcohol. As such the dehydrogenation will
be more facile on the catalyst surface, having a greater
abundance of metal cations on the surface that is the
0001 plane of the zinc oxide. We have tried to
substantiate this observation by SEM studies. The
secondary electron micrograms of zinc oxide catalyst
prepared via different routes are given in Fig. 6(a)-(d)."
The electron micrograms of zinc oxide calcined from zinc
carbonate and zinc oxalate shown in Fig. 6 ((a) and (b))
do not show any hexagonal structure even at
magnifications of x 30000 and x 40000 while the zinc
oxide calcined from zinc hydroxide shown in Fig. 8 ((c)
and (d)) shows clear hexagonal platelet morphology at
x 20000. It seems that, during the process of calcination
of the catalysts obtained via carbonate and oxalate

269

Dehydrogenation of butanol to butyraldehyde

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 (dm3 min-' g cat.?)

(K)
0.4 17
0.560
1.180
2.000

548
598
623
648

been used to determined the rate equation. The catalyst


quantity was varied between 1 and 5 g keeping W/<,
constant. The percent conversion remained practically
constant. The results indicated that bulk diffusion did
not have any significance in the range studied. The zinc
oxide catalyst used was fine powder having average
cm, hence the internal or pore
particle size 071 x
diffusional resistance did not affect the chemical kinetics
studied. The gaseous product contained butene below
2 YO,hence the parallel dehydration reaction has been
neglected. Percent conversion vs W/&, was plotted at
different temperatures, and from the slopes of the graphs
at different temperatures (Fig. 7), rate vs concentration
data have been determined. A rate vs concentration
graph gives a straight line showing the reaction to be first
order. The rate constants determined are given in Table
2. The Arrhenius plot from these values is given in Fig.
8. The energy of activation calculated from Arrhenius
plot (Fig. 8) is 17.22 x lo3 cal g mo1-l. The complete rate
equation as determined is
-Y,

= 2.67 exp (-

17.22 x 103/RT)C ,

4 CONCLUSION

Fig. 8. Arrhenius plot.


In k , = 9.8 x 10-1 = 0.98
k, = 2 6 7
d(ln k ) - 1.3 x 10-1
= 8.67 x 103 K
El R = slope of the curve = -d(l/T) 0.15 x
E = 17.22 x lo3 cal g mol-'
k = k , exp (- E / R T )
k = 2.67 x exp ( - 17.22 x 103/RT)

Zinc oxide catalyst has shown very good activity/


selectivity in the synthesis of butyraldehyde. The effect of
method of preparation of zinc oxide on its catalytic
activity for the reaction has been studied. The zinc oxide
calcined rom zinc hydroxide gave maximum activity and
selectivity giving a very high conversion to butyraldehyde
at a temperature below 400C. The kinetics of best grade
zinc oxide have been studied and a rate equation has
been determined. An attempt has also been made to
explain the reasons for the best activity in the case of zinc
oxide calcined from hydroxide.

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.

9. Rosynek, M. P., Koprowski, R. J. & Dellisante, G. N., J.


Catal., 122 (1990) 80.
10. Van Reyen, L. L. & Sachtler, W. M. H., In Mechanism of
Heterogeneous Catalysis, ed. J. H. de Boer. Elsevier
Publishing Co., Amsterdam, 1960, pp. 23-48.
11. Sen, A. K., Dwivedi, C. D., Raizada, V. K., Singh, G. S.,
Tewari, R. K. & Rajagopalan, P. T., Recent Deoelopments
in Catalysis: Proceedings of 10th National Symposium on
Catalysis and 4th Ind+Soviet Seminar on Catalysis, Dec.
1990, eds B. Vishwanathan & C. N. Pillai. Narosa Publishing House, New Delhi, 1990, pp. 608-15.
12. Herman, R. G., Klier, K., Simmons, G. W., Finn, B. P.,
Bulko, J. B. & Kobylinski, T. P., J . Catal., 56 (1979)
407.