Short Research Communication

Production of Crotonaldehyde from Acetaldol

S.Atalay* and F.S. Atalay
Department of Chemical Engineering, Ege Universa Bomova-lzmir; TURKEY

Optimum operating conditionsfor the production of crotonaldehydefrom acetaldol were

investigated and the kinetics of the reaction were determined. The most important
operating conditions were found to be the cracking time, the pH value of the reaction
mixture, and the initial concentration of acetaldol. The order of the reaction wasfound to
be I .8 with respect to the acetaldol concentration. The kinetic parameters were
determined lo be 20.583 (rn3/kmol)0*8/minfor the frequency factor, and 341 6.800
Wlkmolfor the activation energy.

Introduction
Crotonaldehyde (2-butenal, crotonic aldehyde, P-methylacrolein) is a valuable
material for the production of n-butanol, n-butyraldehyde, 2-ethylhexanal and
2ethylhexanol [ 1-81.
The technical manufacture of crotonaldehyde is mainly by aldol condensation of
acetaldehyde with either simultaneous or consecutive dehydration of the acetaldol
[2,9- 121:

2 CH3CHO- CH3CH(OH)CH2CHO
Acetaldehyde Acetaldol

CH$H(OH)CH2CHO +CH3CH = CHCHO + H20

Acetaldol Crotonaldehyde

Crotonaldehyde may be produced at low temperature (10 to 25°C) by a batch

process, or at higher temperatures (20 to 50°C) in a continous process in the
presence of an alkaline catalyst. The reaction mixture containing acetaldehyde and
acetaldol is neutralized using a weak acid such as acetic acid. This mixture is fed to
batch reactors or a continuous still, and is maintained between 100-105°C for a
contact time of 2 hours at atmospheric pressure. A mixture of acetaldehyde, water
and crotonaldehydeis continuously removed as an azeotropic overhead product and
is condensed. Continuous distillation of this mixture is accomplished in a series of
stills. In the first still acetaldehyde is obtained as overhead, and the bottoms are fed
to a second still from which the water-crotonaldehyde azeotrope is removed as
distillate (at 84°C). The distillate composition is 24.3 w t % water and 75.7 wt.%
crotonaldehyde. This heterogeneous azeotrope is composed of a top layer and an
*Author for correspondence.

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 Production of Crotonalehydefrom Acetaldol

aqueous bottom layer. Crotonaldehyde may also be produced in a single stage in a

continuous manner and without the use of a catalyst, this process being more
applicableto large-scaleoperations121.
Experimental Study
The acetaldehyde-acetaldolmixture was neutralized, and its pH kept between 3.7 and
5.5 by the introduction of acetic acid. Preparation of the acetaldol has been
described elsewhere [13]. A known amount of the acidified mixture was charged
into a 500 ml batch reactor having three necks. The reactor temperature was
controIled by an electrical heater. One of the necks was connected to a packed
column (height of 500 mm) with a reflux condenser which was used to condense the
acetaldehyde vapors. The reaction mixture was &hydrated (cracked) by maintaining
the reactor at a constant temperature for between 1 to 4 hours at atmospheric
pressure. After dehydration, the mixture was distilled and the crotonaldehyde-water
azeoaope was removed at 84°C. The overhead distillate was separated into two
layers which were weighed and then analysed by gas chromatography with flame
ionisation detector using a Carbowax column. The top layer contained
crotonaldehyde, acetaldehyde and water. The bottom layer contained acetaldehyde,
unconverted acetaldol and water.

Results
The mass of acetaldol charged into the reactor was known, hence the yield and the
conversion of acetaldol to crotonaldehyde were calculated fiom the composition and
mass of the top layer. The experimental conditions and the conversions and yields
are given in Table 1. In the calculations, the top layer composition was assumed to
be 75.7 w t % crotonaldehyde and 24.3 wt.% water [lo]. The results presented in
Table 1 illustrate the importance of the cracking time, pH, and the initial acetaldol
concentration, upon the production of crotonaldehyde.
The kinetics of crotonaldehyde production were determined from the results
obtained at constant temperature, constant pH. and constant initial concentration.
The rate of the reaction was defined as:

Using a regression technique, the order of the reaction 'n' was found to be 1.8.
The rate constants at 80°C and 93°C were determined. The rate constant was defined
by the relation :
k = 20.583 exp(-3416.8/RT)

Nomenclature
C, Concentrationof acetaldol0<11101/m3)
k Rate constant of reaction of acetaldol to crotonaldehyde (m3/ kmol)Od/min
n Order of reaction (-)
R Ideal gas constant (kT/kmol K)
rA Rate of reaction (km0i/m3 min)
T Temperature(K)

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SAtalay and FS.Atahy

Table 1 Conditionsfor production of crotonaldehydefromacetaldol and

calculated conversion (pressure = 1 am).
~~

Experiment Initial acetaldol Cracking PH Temperature Yield Conversion

Number concentration time value
(kmovm3)xr 04 (min)
- (“C) v4 W)
1 4.08 60 3.7 93 33.130 41.649
2 4.08 120 3.7 93 50.015 62.876
3 4.08 180 3.7 93 56.731 71.319
4 4.08 240 3.7 93 66.387 83.458
5 4.08 120 3.7 93 50.015 62.876
6 4.08 120 4.0 93 7i.m 89.93
7 4.08 120 4.5 93 63572 79.919
a 4.08 120 5.5 93 64.092 80.573
9 4.08 165 5.0 93 56.871 71.486
10 6.76 165 5.0 93 60.949 76.612
11 4.16 45 4.7 ao 23.819 29.941
12 4.16 135 4.7 80 49.060 61.668
13 4.16 180 4.7 80 51.119 64.256
14 4.16 225 4.7 ao 55.41 1 69.651
15 4.16 240 4.7 ao 69.990 87.977
-
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Received: 9 November 1992;Accepted after revision: 27 August 1993.
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