Reactive distillation with side draw

Suman Thotla, Sanjay Mahajani

Department of Chemical Engineering, Indian Institute of Technology, Bombay, Mumbai 400 076, India

a b s t r a c t

Keywords:
Reactive distillation
Lactic acid
Esterication
Acetone
Aldol condensation
Fatty acid
Biodiesel
Mesityl oxide
Diacetone alcohol

We demonstrate the applicability of a new reactive distillation conguration, i.e. reactive distillation with
side draw, for certain industrially important reactions. For the reacting systems which involve products
with intermediate volatility, a side draw facilitates its in situ removal and enhances either conversion or
selectivity. It further reduces the downstream processing in some cases. The concept is proved for three
representative systems, viz. esterication of lactic acid, aldol condensation of acetone and for esterication
of fatty acid by methanol. Experimental proof is also provided in some cases.

1. Introduction
The applicability of reactive reactive distillation (RD) for many
industrially important processes is well known [1]. In the case of
equilibrium controlled reactions such as esterication and etherication, the objective is to surpass equilibrium conversion whereas
in the case of multiple reaction systems, RD can be used to improve
selectivity. In most of the studies reported in the past, a conventional reactive distillation conguration involves a reactive zone
placed in the distillation column at an appropriate location. In
addition to this section, two non-reactive zones viz. rectifying and
stripping sections may also be employed. The products are withdrawn through distillate and/or the bottom streams depending
on the volatilities. Thus, reactive distillation has been successfully
applied for the mixtures wherein, at least one product is either
the most volatile or the least volatile component. Sometimes minimum/maximum boiling azeotropes in the system can be exploited
advantageously to achieve in situ removal. If the pure products
can be separated efciently then one can use close to stoichiometric feed mole ratio of the reactants. Some relevant examples are
esterication of acetic acid by methanol or butanol, MTBE synthesis from methanol and isobutene, etc. However, in some cases, the
volatilities are such that the separation of the product as either top

product and bottom product is difcult or sometimes infeasible,

e.g. a case in which the product is intermediate boiling and product
does not form an azeotrope with other component(s). In a conventional reactive distillation conguration the reactant being more
volatile, tends to move away from the reactive zone, leaving behind
the intermediate boiling product, thereby creating unfavorable conditions for the reaction. In such cases one may need to use one of
the reactants in excess to expedite the reaction and facilitate separation. The excess reactant thus may not serve the purpose of reactive
distillation and RD option may be unattractive compared to the conventional approach of reaction followed by separation performed
in a sequential manner. In this paper, we present an alternative
to the conventional notion of removing products only through top
or bottom streams. A conguration that involves removal of product(s) as side stream(s) has been suggested, which may provide
more exibility in design and as a result, improve the performance
of the existing RD applications and encompass under its umbrella
many more reactions which are otherwise written off as potential candidates. A list of some potentially important applications is
given in Table 1. In most of the cases, water is the component with
intermediate volatility, to be removed through the side draw.
We have chosen three industrially important reactions as representative examples. In the rst case i.e., esterication of lactic acid,
water being an intermediate boiling component is removed as a
side draw to facilitate much lower mole ratio of methanol to lactic acid and yet yield relatively pure methyl lactate in the bottom
stream with enhanced conversion level. This also helps avoid unfa-

928
Table 1
Potentially important reactions for reactive distillation with side draw.
Reactions
Esterications
Adipic acid (A) + methanol (B)  monomethyl adiapate (C) + water (D)
1.
Mono methyl adiapate (C) + methanol (B)  dimethyl adiapate + water (D)
Glutaric acid (A) + methanol (B)  monomethyl glutarate (C) + water (D)
2.
Monomethyl glutarate (C) + methanol (B)  dimethyl glutarate (E) + water (D)
Maleic acid (A) + ethanol (B)  monoethyl maleate (C) + water (D)
3.
Monoethyl maleate (C) + methanol (B)  diethyl maleate (E) + water (D)
4. Fatty acid (A) + methanol (B)  ester (C) + water (D)
5. Lactic acid (A) + methanol (B)  methyl lactate (C) + water (D)
Acetalizations
Glyoxal (A) + methanol (B) monoacetal (C) + water (D)
1.
Monoacetal (C) + methanol (B) diacetal (E) + water (D)
2. Diol (A) + acetone (B)  acetal of diol (C) + water (D)
Aldol condensation
2Acetone (A) diacetone alcohol (B)
1.
Diacetone alcohol (B) mesityl oxide (C) + water(D)
Cross Aldol condensation
Acetaldehyde (A) + methyl ethyl ketone (B) methyl pentanone (C) + water (D)
1.
2Acetaldehyde (A) crotanaldehyde (E) + water (D)

vorable uncatalysed hydrolysis of lactate in the bottom section of

the column. In the second case, i.e. aldol condensation of acetone to
mesityl oxide (MO) and diacetone alcohol (DAA), removal of intermediate boiling water as a side stream is studied. In the third case,
i.e. esterication of oleic acid with methanol to methyl oleate and
water, the removal of intermediate boiling water as a side stream is
studied. In the rst two examples experimental support is provided
to validate the simulation results. In all the cases simulations are
performed using ASPENPLUS [11].
2. An illustrative example
A reacting system involving following irreversible liquid phase
reaction is considered.
2A B + C
The reaction is assumed to be elementary and the kinetics is
given by the following equations:
r1 = k1 x2 A

(1)

In this case both the products, B and C, are less volatile than the reactant A. Hence, we choose hybrid reactive distillation unit operated
under total reux condition. For volatility of AC = 12.2, BC = 10.5
and for 100% conversion of A, the composition prole of the column
is shown in Fig. 1a. It can be seen that the mole fraction of intermediate boiling component (B) which is to be removed as a side
draw is close to 1 between the stages 2 and 6. Hence, by removing
relatively pure B as side draw from any of these stages, the composition prole of the stages above this side draw is unaffected. This
is mainly due to the total reux. Fig. 1b shows the composition prole of RD column with side draw. Hence, for a given reaction system
to remove intermediate boiling component through the side draw,
one should provide sufcient number of non-reactive stages below
the reactive zone to realize a region of maximum concentration of
intermediate boiling component. Intermediate boiling component
is removed as a side draw from this region. It can be seen from
these gures that side draw does not inuence the composition
proles in the upper part for the column. However, as expected,
the composition proles in the region below the side draw change
signicantly. Further, as shown in Fig. 2, for an insufcient number
of stages one may not obtain a region of pure B. The number of nonreactive stages thus required to obtain the region of pure B depends
on the relative volatility of B with respect to C and more the relative
volatility, less is the number of non-reactive stages (Fig. 3).

Desired product

Side draw

Reference

Dimethyl adipiate

Water

[2]

Dimethyl gluterate

Water

[2]

Dimethyl maleate

Water

[3]

Ester of fatty acid

Methyl lactate

Water
Water

[4]
[5]

Diacetal

Water

[6]

Acetal of diol

Water

[7]

Diacetone alcohol

Water

[8,9]

Methyl pentanone

Water

[10]

3. Experimental work
A multipurpose reactive distillation (RD) setup, used to study
esterication of lactic acid and aldol condensation of acetone, is
shown in Fig. 4. A column with 5.1 cm diameter contains reactive
section (2.3 m) and non-reactive stripping section (1 m). It can be
operated in batch, semi-batch or continuous modes. The setup has
a provision to withdraw a side product from various positions as
indicated. Reactive section is packed with Sulzer Katapak-S packing lled with pre-treated dry cation exchange resin Amberlyst 15 .
The non-reactive sections are packed with HYFLUX packing from
Evergreen India Ltd. In between the two sections, a weir is provided to facilitate enough accumulation of liquid hold up (6 ml) for
side withdrawal. Temperature sensors and sampling ports are provided for analyzing liquid composition and temperature on each
stage to monitor the state of RD run periodically. The heights of the
individual sections, location of feed and product withdrawal were
varied as desired in each case.
3.1. Materials and catalyst
l(+)-Lactic acid (90% wt) was obtained from Spectrochem India
Ltd. Methanol and acetone (AR grade, moisture < 0.02%) were supplied by Merck Ltd. The catalyst used in the experiments is
commercial strong cation exchange resin Amberlyst 15 and was
obtained from Rohm and Hass, Philadelphia, PA. Before its use,
the fresh catalyst was carefully washed with pure water, isopropyl
alcohol, dilute hydrochloric acid and then again with pure water
sequentially. It was then dried at 70 C under vacuum for about
12 h to remove the moisture present in it.
3.2. Analysis
A gas chromatograph (GC-911; Mak Analytica India Ltd.)
equipped with thermal conductivity detector (TCD) was used to
analyze the reaction mixture of methanol, water and methyl lactate. The analysis was carried out in a Porapack-Q column and
elution was established using hydrogen as a carrier gas at a ow
rate of 40 ml/min with isopropyl alcohol as external standard. The
oven temperature was varied from 120 C to 240 C for the methyl
lactatewater system. The concentration of lactic acid was determined by titration method. Samples were titrated with standard
0.05 N alcoholic sodium hydroxide solution using phenolphthalein
as an indicator.

929

Fig. 1. Liquid phase composition proles in (a) conventional reactive distillation (b) reactive distillation with side draw for 2 kW of re-boiler duty; FA = 0.02 kmol/h and side
draw = 0.01 kmol/h.

A gas chromatograph (GC-911; Mak Analytica India Ltd.)

equipped with ame ionization detector (FID) was used to analyze the reaction mixture of acetone, MO and DAA. The analysis
was carried out in a 30 m long BP-5 column (SGE, Australia) with
an inner diameter of 0.55 mm. Elution was established using nitrogen at a ow rate of 0.5 ml/min. Methyl ethyl ketone (MEK) was

used as an external standard. Water concentration was calculated based on the material balance. The molar amount of water
formed was assumed to be same as that of mesityl oxide because
the formation of heavier side-products was negligible compared
to the amount of acetone converted or mesityl oxide formed
[8].

Fig. 2. Effect of non-reactive stages on liquid phase composition prole of B for 2 kW of re-boiler duty; FA = 0.02 kmol/h.

930
Table 2
UNIQUAC model binary interaction parameters [11].

Lactic acid
Methanol
Methyl lactate
Water

Lactic acid

Methanol

0
1040.75
208.41
499.38

452.35
0
41.42
351.0861

Methyl lactate
288.41
7.37
0
219.62

Water
357.47
165.26
394.57
0

4. Case 1: Esterication of lactic acid

K1

Lactic acid + methanolmethyl lacate + water

(2)

K2

Fig. 3. Effect of volatility on liquid phase composition prole of B for 2 kW of reboiler duty; FA = 0.02 kmol/h.

Esterication of lactic acid is relevant in the synthesis of methyl

lactate which nds applications as a solvent in chemical industry.
The reaction can also be used to recover lactic acid in the form of its
methyl ester from the aqueous solution obtained by fermentation
of carbohydrates [5]. Recovery by normal distillation is expensive
due to the large amount of water that exists in the feed. Moreover,
the impurities (e.g. succinic acid) formed in the fermentor also get
carried away with lactic acid. Esterication reactions are equilibrium controlled reactions and the presence of large amount of water
poses limitations if one desires to obtain substantial conversion.
Hence, excess methanol is required for close to 100% conversion
of lactic acid. By using reactive distillation, the chemical equilibrium can be shifted towards the formation of methyl lactate through
continuous removal of water and methyl lactate from the reactive
zone. However, as mentioned in the earlier section, since water is
an intermediate boiling component, its separation is not easy and
large amount of methanol is required not only from the reaction
view point but also to strip off water and remove it as an overhead
product. Hence, a conventional reactive distillation conguration
with close to stoichiometric ratio of lactic acid to methanol is not
an attractive option. Moreover, the hydrolysis of methyl lactate
which is a self-catalysed reaction may take place in the lower portion of column in the presence of small quantities of water. Lactic
acid thus formed by hydrolysis may undergo polymerization, which
further complicates the operation. Side removal of water not only
drives the reaction to completion but also facilitates column operation at relatively less mole ratio of methanol to lactic acid in the
feed.
Here, we show the importance of side draw with three representative experimental and simulation results. All the binaries
except water and methyl lactate are non-azeotropic and the volatility order is methanol (b.p.: 64.7 C) > water (b.p.: 100 C) > methyl
lactate (b.p.: 144 C) > lactic acid (b.p.: 224 C), respectively. Water
is an intermediate boiling component. In such cases, reactive zone
is placed in the rectifying section and non-reactive stages are provided below the reactive zone thus leading to a hybrid reactive
rectication conguration.
Lactic acid is a relatively strong acid (pKa = 3.85) and selfcatalyses its esterication. Similarly, traces of lactic acid present
in the lactatewater mixture are known to catalytically trigger the
hydrolysis [12]. In a conventional reactive distillation conguration,
methyl lactate is expected to leave the column from the bottom.
Relatively high temperature in the reboiler, presence of water and
unconverted lactic acid would result in hydrolysis of lactate and
Table 3
Kinetic parameters for esterication of lactic acid [5].

Fig. 4. A multipurpose reactive distillation setup with total reux and side draw B:
bottom product; SD: side withdrawal.

Parameter

Value

Ef (kJ/mole)
Eb (kJ/mole)
Log kf0 (mole/(kg h))
Log kb0 (mole/(kg h))

53.1
40.1
25.40
20.01

6.51
16.066
2.25
5.56

931

Fig. 5. (a) Liquid phase mole fraction of methyl lactate and water in reboiler, (b) liquid phase mole fraction of lactic acid and (c) temperature of reboiler ( C) with respect to
conversion of methanol.

subsequent oligomerization of lactic acid making the operation

unstable. We observed this behavior through the experiments conducted in semi-batch mode. The results are described in the next
section.

4.1. Semi-batch reactive distillation (SBRD)

As the rst step to evaluate the feasibility of reactive distillation,
a representative SBRD run was conducted under total reux without removing any product from the RD column. SBRD runs are less
time consuming and use less amount of chemicals. Hence, these
experiments can be performed as the rst step in process development to quickly ascertain the potential of reactive distillation
and foresee undesired problems, if any. The setup shown in Fig. 4
was used to conduct the experiments at 0.5 kW reboiler duty by
charging the reboiler with 650 ml methanol initially and feeding
80% (w/w) lactic acid at 1.5 ml/min continuously above the reactive zone. The samples were withdrawn at different time intervals
(every 15 min up to rst hr and then, every 30 min till the end

of the experiment) from the re-boiler to assess the performance.

It should be noted that unlike the conventional RD conguration that removes water as an overhead product, we allow the
accumulation of both water and ester in the reboiler. In the continuous version as well, the column will be operated under total
reux.
An equilibrium stage model based simulations are performed
using Aspen Plus simulator (Aspen Custom Modeler) [11]. The heat
losses from the column wall and reboiler were considered while
simulating the column performance. Similarly, the number of theoretical stages for the reactive and non-reactive sections were
determined independently by performing simple distillation of the
standard methanolwater mixture (NTSM for the reactive zone: 3;
NTSM for the non-reactive zone: 6). The equations involved in a
semi-batch reactive distillation model are well known and one may
refer to our earlier work for more details [13]. The UNIQUAC binary
interaction parameters used for the prediction of VLE are given in
Table 2.
A pseudo-homogeneous activity-based kinetic model was used
to explain the experimental results. The kinetic model is taken from

Fig. 6. Steady state (a) liquid phase composition prole (b) temperature prole along the height of the column for 0.5 kW; FLA = 150 ml/h; mole ratio (methanol/lactic acid) = 2.1;
reux rate 1.18 kg/h; side draw = 180 ml/h.

932

Fig. 7. Unsteady state experimental (a) liquid concentration prole of reboiler, (b) temperature prole of reboiler for 0.5 kW; FLA = 150 ml/h; mole ratio (methanol/lactic
acid) = 2.1; reux rate 1.18 kg/h; side draw = 120 ml/h.

[5].
r =

n0 dx
= kf 0 exp
Wcat dt

 E 
b

kb0 exp

RT

Ef

RT

(aLA aMeOH )

(aMLA aW )

(3)

where ai is the activity of the ith component. Activity coefcients

were calculated using the UNIQUAC method and UNIQUAC binary
interaction parameters are given in Table 2. The values of kinetic
parameters are given in Table 3.
The experimental and simulation results of SBRD are shown in
Fig. 5ac and are found to be in good agreement. Fig. 5ac show
how reboiler concentration and temperature vary with respect to
conversion of methanol in a typical SBRD run. As anticipated, the
temperature of the reboiler and hold up increase over a period due
to accumulation of reactants and products. As shown in Fig. 5a,
SBRD run can be divided into two different regimes, region-I is
below 80% conversion of methanol and region-II is above 80%
conversion. The simulation results match well with experimental
results in the region-I that corresponds to relatively low conversion of lactic acid and high concentration of methanol. On the other
hand, in the region-II, i.e. at high conversion of lactic acid and low
concentration of methanol the experimental results deviate from
the predicted ones. The deviation between simulation and experimental results in region-II is due to self-catalysed hydrolysis of
methyl lactate that takes place leading to formation of lactic acid
which further polymerizes due to relatively high temperature in the
reboiler. The uncatalysed hydrolysis and polymerization reactions
are not included in the simulation of RD. SBRD run shows that if one
desires to achieve higher conversion levels in RD, water from the
stripping section needs to be removed completely to avoid polymerization of lactic acid. A side withdrawal of water may be employed
and in the next section, we demonstrate the importance of side
draw through experiments.

column and reboiler to the surrounding, was solved using Aspen

Plus simulator (RADFRAC) [11]. The relevant model equations and
underlying assumptions may be found elsewhere [14]. Fig. 6a and b
show the steady state concentration and temperature proles along
the height of the column, obtained by experiments and simulation, in a representative CRD run. The side draw contains methanol,
water and methyl lactate. In the setup used, it is not possible to
obtain pure water or pure methyl lactate through the side draw as
the height of the column is not sufcient to separate pure water
and pure methyl lactate in the stripping section. From Fig. 6a, water
concentration in the reactive zone is less and almost all the water is
removed as a side draw from the bottom most reactive stage avoiding the self-catalysed hydrolysis of methyl lactate in the stripping
section. Hence, a high conversion of lactic acid (i.e. 78%) is realized
compared to a conventional equilibrium reactor (65%) [5] for the
mole ratio of lactic acid to methanol as 1:2.1. Moreover, undesired
reaction of oligomer formation that takes place in conventional RD
without side draw is suppressed. We observed that with a decrease
in the side draw rate, oligomerization is enhanced to reduce yield
and conversion. Fig. 7a and b show unsteady state composition
and temperature proles of reboiler. Due to hydrolysis of methyl
lactate in the stripping section and the reboiler, lactic acid concentration increases leading to continuous increase in the temperature
that results in an unstable operation and the steady state is never
achieved. Hence, in the esterication of lactic acid with methanol,
removal of water from the column at a desired rate is crucial as
water reacts with methyl lactate to give lactic acid that undergoes

4.2. Continuous reactive distillation (CRD)

The set up shown in Fig. 4 was used to conduct CRD experiments under total reux by continuously feeding lactic acid at the
top of the reactive section and methanol below the reactive zone,
respectively. The products, methyl lactate and water, are continuously withdrawn through the bottom product and side stream
(from 6th stage), respectively. Samples at several locations in the
column were analyzed at different time intervals (every 30 min)
to monitor the performance. The attainment of steady state was
ensured by constancy in temperatures and concentrations at different locations. Typically, it takes 910 h to attain the steady state.
An equilibrium stage model, considering the heat losses from the

Fig. 8. Comparison of reactive stripping and reactive distillation with side draw for
0.6 kW; FLA = 150 ml/h.

933

Fig. 9. Effect of mole ratio of methanol to lactic acid on concentration of water in the column for (a) reactive distillation with side draw and (b) reactive stripping for 0.6 kW;
FLA = 150 ml/h.

uncontrolled oligomerization and results in a rise in temperature of

the reboiler. Hence, it is very important to control the side stream
ow rate so as to remove most of the water that is formed in the
reaction and that comes with the feed.
4.3. Comparison of conventional RD conguration and RD with
side draw
As mentioned before, water in conventional RD is stripped off
using excess methanol and is removed as the top product. Excess
methanol is used not only to expedite the reaction but also to
increase the vapor ow rate that improves the efcacy of water
removal. This conguration may also be called as reactive stripping.
In this section, we compare the performances of such conventional
RD conguration with that of RD with side draw. The experimentally validated simulator is used in both the cases and the results are
compared. In both the congurations water is removed completely
to avoid its presence in the stripping section. This removes the
chances of possible instability due to self-hydrolysis. Fig. 8 shows
the comparison of simulation results for reactive distillation with
side draw and conventional reactive distillation with superheated
methanol as feed. From Fig. 8, it can be concluded that reactive distillation with side draw offers much better performance than that
of conventional reactive distillation. On increasing the mole ratio
of methanol to lactic acid from 3 to 15, one can expect an increase
in conversion of lactic acid. But in the case of reactive distillation
with side draw the conversion of lactic acid does not change signicantly after a certain mole ratio (7). This may be attributed to
Table 4
UNIQUAC model binary interaction parameters [11].

Acetone
DAA
MO
Water

Acetone

DAA

MO

Water

0
36.17
61.65
87.7160

79.56
0
102.1
351.0861

30.80
212.5
0
1044

642.7335
1188.5242
56.94
0

the presence of small amount of water in the reactive zone. As can

be seen from Fig. 9, in the conventional RD, since excess methanol
(90 C) is used to strip water off from the reactive stages, concentration of water decreases with increase in mole ratio of methanol
to lactic acid from 9 to 15. On the other hand, in reactive distillation
with side draw, concentration of water on the reactive stages is not
affected by changing the mole ratio of methanol to lactic acid and
conversion cannot be improved beyond a certain level, i.e. 92% for
the conditions given in Fig. 8.
5. Case 2: Aldol condensation of acetone
DAA is produced by selective aldol condensation of acetone. Subsequent dehydration of DAA produces 4-methyl-3-penten-2-one,
commonly known as mesityl oxide (MO). Both diacetone alcohol
(DAA) and mesityl oxide (MO) are useful products derived from
acetone. Condensation of mesityl oxide and acetone further produces heavier products, such as isophorone. Eqs. (4) and (5) show
the reactions of interest.
2Acetone dicetonealcohol

(4)

Dicetonealcohol mesityloxide + water

(5)

The main reason behind the use of reactive distillation for this reaction is to achieve exibility over the relative production rates of
DAA and MO. An efcient removal of DAA from the reactive zone
results in the suppression of its further reaction to MO and improves
DAA to MO ratio. The reaction in RD has been well studied in the
past [15]. It is known that the equilibrium constant for the reaction of acetone to DAA is very low and DAA concentration does not
rise beyond a particular limit. Further, at relatively large conversion (>10%), the formation of high molecular weight compounds is
signicant. Water plays an important role in this reaction and its
presence makes a favorable impact on the DAA formation and it
can be advantageously exploited to further increase the selectivity
of DAA.

934
Table 5
Kinetic parameters for aldol condensation of acetone [8].
Parameter
Ef (J/mole)
Eb (J/mole)
EMO (J/mole)
kf0 (mole/(kg h))
kb0 (mole/(kg h))
kMO0 (mole/(kg h))
KW

Value
71056.8
97539.5
61296
1.26 1012
3.04 1018
1.07 1013
2.90

6668.58
11272.8
6766.92
5.928
56.876
11.081
0.474

below the reactive section, a phase split occurs due to the miscibility gap between water and MO. A phase split in distillation column
is known to exhibit instability in column operation. This phase split
can be advantageously utilized to remove water as a side stream and
obtain a water-free mixture of DAA and MO as bottom products. It
is also possible to remove MO as a separate side stream and obtain
pure DAA and MO.

5.1. Kinetics of aldol condensation of acetone

In our earlier work [8] and [9], we proposed reactive distillation (RD) for simultaneous production of DAA and MO using cation
exchange resin with and without water dosage. RD was found to
offer better performance than the conventional reactors. It has distinct advantages of shifting the chemical equilibrium towards the
formation of DAA and also suppressing the consecutive dehydration
of DAA to MO. By changing operating conditions such as reboiler
duty and catalyst concentration (kg of catalyst/meter of reactive
zone), one may achieve DAA:MO ratio over a wide range. The combined effect of simultaneous separation of DAA and water inhibition
can result in an enhanced performance. As acetone (boiling point of
56.3 C) is the lightest compound compared to water (b.p.: 100 C),
MO (b.p.: 129.5 C) and DAA (b.p.: 169.2 C), the reactive section
is placed in the rectifying section for the best performance [16].
It should be noted that MO and water form a minimum boiling azeotrope at atmospheric pressure. However, in the present
case, since both MO and water are removed as bottom products,
this azeotrope is not relevant in context to the process feasibility.
Except for the MOwater mixture, all the other binaries are nonazeotropic. The VLE data used for simulations is taken from Aspen
Plus [11]. In reactive distillation experiments, acetone is present
on reactive stages in large proportion thereby homogenising the
reaction mixture and avoids a possible liquidliquid split on reactive stages. Whereas in the non-reactive section which is placed

The kinetic model developed in our earlier work [8] is used

to explain the experimental reactive distillation run. According
to the kinetic model, the rst step (i.e. dimerization of acetone
to DAA) is insensitive to the water content and can be best
explained using a pseudo-homogeneous type model whereas, the
second step (i.e. dehydration of DAA to MO) is explained using the
LangmuirHinselwood type model as it is strongly inuenced by
adsorption of water on the resin.

rDAA =

dnDAA
= Mcat (kf a2Ac kb aDAA ) rMO
dt

(6)

rMO =

dnMO
Mcat kMO aDAA
=
dt
(1 + KW aW )2

(7)

where Mcat is the weight of catalyst, KW is adsorption constant for

water and ai is the activity of the ith component. The UNIQUAC
model was used to determine the activities of the components and
the UNIQUAC binary interaction parameters were determined by
UNIFAC method using Aspen property plus [11]. The binary interaction parameters of UNIQUAC model are given in Table 4. The values
of kinetic parameters are given in Table 5.

Fig. 10. Steady state experimental and simulated (a) liquid phase composition prole, (b) temperature prole along length of column for 0.5 kW of reboiler duty; total catalyst
loading = 280 g; FAcetone = 2 ml/min; reux rate = 1.7 kg/h) and side draw = 1.2 ml/min.

935

Fig. 11. Steady state simulated liquid phase composition prole along length of column for 0.5 kW of re-boiler duty; total catalyst loading = 280 g; FAcetone = 2.5 ml/min; side
draw for water = 0.4 ml/min; side draw for MO = 1.69 ml/min; total number of stages = 24; reactive stages = 8.

5.2. Continuous reactive distillation (CRD)

The set up shown in Fig. 4 was used to conduct CRD experiments
under total reux condition by feeding acetone continuously at the

top of the reactive section. The products are continuously withdrawn through the bottom stream and the side stream (from 4th
stage). Samples at several locations in the column were analysed
at different time intervals (30 min) to monitor the performance. An

Fig. 12. Steady state simulated (a) conguration (b) liquid phase composition prole (c) temperature prole along length of column for 0.5 kW of re-boiler duty; total catalyst
loading = 280 gms; FFA = 3 ml/min; FMeOH = 2 ml/min and side draw = 3 ml/min; shows side draw stage.

936

equilibrium stage model, considering the heat losses from the column and reboiler to the surrounding, was solved using Aspen Plus
simulator (RADFRAC) [11]. Fig. 10a and b show the steady state concentration and temperature proles along the length of the column,
obtained by experiments and simulation in a representative CRD
run. The side draw is a heterogeneous mixture of two liquid phases.
There is no effect of side draw on the ratio of DAA:MO obtained
but it adversely affects the conversion of acetone slightly due to the
loss of acetone through the side stream, the conversion decreases
from 99.5 to 96.2%. The motivation behind using side draw here is
to remove only water effectively by taking advantage of phase split.
However, it was not possible to conduct experiments in the present
setup with selective aqueous phase removal as side draw because it
requires relatively tall column with 25 stages (i.e. 2 m reactive section and 3 m non-reactive section). The experimentally validated
model can be further used to obtain the conditions under which
near to 100% conversion of acetone can be achieved by removing
water using decanter on the side draw stage. Further, an additional
side draw may be used to separate MO and DAA as shown in the
Fig. 11a. The corresponding simulation results are shown in the
Fig. 11b.
6. Case 3: Esterication of fatty acid
Esterication of fatty acid such as oleic acid and palmitic acid
is an industrially important class of reactions especially with an
increasing interest in biodiesel as a renewable energy source. The
product of this reaction i.e., fatty acid ester can be used as a
substitute for diesel or blend in diesel. The reaction system is
similar to the one in the esterication of lactic acid discussed
before with the only difference that the self-hydrolysis of fatty acid
ester in this case is not as fast as that of methyl lactate. Moreover, the miscibility gap between water and fatty acid ester results
in phase splitting in the stripping section similar to that in the
case of aldol condensation of acetone discussed in the earlier section. All the binaries are non-azeotropic and the volatility order is
methanol (b.p.: 64.7 C) > water (b.p.: 100 C) > methyl oleate (b.p.:
344 C) > oleic acid (b.p.: 360 C).
Here, we demonstrate that the phase splitting along with side
draw can be advantageously utilized for the production of methyl
oleate by removing water as a side stream in reactive distillation column. The phase split between methyl oleate, methanol and water
can be effectively utilized to obtain pure methyl oleate as a bottom
product in a single RD column. The reaction kinetics is given by Eqs.
(9) and (10) and is taken from [4].
K1

Oleic acid + methanol methyl oleate + water

K2


r = CCat (kf 0 exp

Ef
RT

 E 
b

kb0 exp

RT

(9)


(xFA xMeOH )

(xMFA xW ))

(10)

Ccat is the catalyst concentration and xi is the mole fraction of the

ith component. The UNIFAC-LL model was used to determine the
activities of the components and the binary interaction parameters were determined by UNIFAC method using Aspen property plus
[11]. The binary interaction parameters of UNIFAC-LL model and the
values of kinetic parameters are given in Tables 6 and 7 Simulation
results shown in the Fig. 12b indicate that it is possible to remove
water along with methanol as a side draw and obtain pure methyl
oleate as bottom product in a single reactive distillation column
conguration shown in Fig. 12a.

Table 6
UNIFAC-LL model binary interaction parameters [11].

Oleic acid
Methanol
Methyl oleate
Water

Oleic acid

Methanol

Methyl oleate

Water

0
46.99
106.26
232.04

405.09
0
579.72
351.0861

83.44
24.03
0
252.11

377.08
165.26
645.17
0

Table 7
Kinetic parameters for esterication of fatty acid [4].
Parameter

Value

Ef (kcal/mole)
Eb (kcal/mole)
Ln kf0 (mole/h)
Ln kb0 (mole/h)

14
2.68
12.93
4.17

0.99
0.05
2.87
0.04

7. Conclusion
Reactive distillation with side draw is a promising alternate conguration which has not been used and investigated well in the
past. In the case of esterication of lactic acid, it not only enhances
the conversion level at a given methanol to acid mole ratio but
also avoids possible ester hydrolysis leading to polymerization and
hence, instability in column operation. The conguration can also
be used successfully for many other industrially important reactions. It has been shown to work well for aldol condensation of
acetone and esterication of fatty acids with methanol.
Appendix A. Nomenclature

Abbreviation
CRD
continuous reactive distillation
DAA
diacetone alcohol
FID
ame ionization detector
MEK
methyl ethyl ketone
MO
mesityl oxide
MTBE
methyl tertiary butyl ether
NSTM
number of theoretical stages per meter
RD
reactive distillation
SBRD
semi-batch reactive distillation
TCD
thermal conductivity detector
Notation
ai
E
ki
M
n
ri
t

activity coefcient of component i

activation energy (kJ/mole)
rate constant (mole/min)
mass (gm)
number of moles (g mole)
reaction rate (g-mole/min) of component i
time (min)

Sufxes
f
b
Ac
DAA
MO
FA
LA
MFA
MLA
MeOH
cat
W

forward reaction
backward reaction
acetone
diacetone alcohol
mesityl oxide
fatty acid
lactic acid
methyl ester of fatty acid
methyl lactate
methanol
catalyst
water

937

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