Chinese Journal of Chemical Engineering, 19(5) 808814 (2011)

Kinetic-Thermodynamic Analysis of the Reactive Distillation Process

of the Cyclohexene Hydration Using the Zeolite Catalyst
YE Jianchu (), HUANG Jiali (), LIN Handan (), CAO Keteng ()
and SHA Yong ()*
College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, Fujian China
Abstract Reactive distillation could be utilized to produce cyclohexanol through the cyclohexene hydration. By
means of highly active zeolite catalyst HZSM-5, the kinetic-thermodynamic analysis of this reactive distillation has
been carried out to get the characteristics of the reactive distillation. Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation process should be set to higher pressure such as 0.3
or 0.4 MPa. To avoid the recovery of cyclohexanol at the top of the column, an unreactive section should be allocated at the upper column. In addition, the inert component benzene is more unfavorable to the reactive distillation
process in comparison with the inert cyclohexane.
Keywords hydration, reactive distillation, residue curves, phase splitting, cyclohexanol

INTRODUCTION

Cyclohexanol is an important chemical intermediate, and billions of kilograms are produced annually,
mainly as a precursor to nylon [1]. Nowadays, cyclohexanol is produced mainly by means of complete
hydrogenation of benzene to cyclohexane and subsequent oxidation of cyclohexane to cyclohexanol, but
there are some intrinsic disadvantages, for example,
high hydrogen consumption, operational safety as well
as by-product issue in the oxidation process. Cyclohexanol can also be produced via the partial hydrogenation of benzene to cyclohexene and the subsequent hydration of cyclohexene to cyclohexanol. The
corresponding process can save the consumption of
hydrogen, and also improve operational safety since
no dangerous oxidation is involved [1]. Therefore, the
latter route should be concerned with more interest.
In the conventional hydration of cyclohexene to
cyclohexanol, usually a slurry reactor is employed to
carry out the hydration operation, and then the hydration product is split into an unreactive organic phase
and an aqueous phase in a liquid-liquid decanter [1].
Finally, the distillation separation process is utilized to
separate cyclohexanol from the organic phase which
includes cyclohexanol, unreactive cyclohexene, benzene and cyclohexane. Benzene comes from the preceding step of hydrogenation of benzene as the unreactive material, and cyclohexane is by-product of the
hydrogenation.
It is well known that the cyclohexene hydration
is slightly exothermic, and it is also limited by the
reaction equilibrium. Meanwhile, the boiling point of
cyclohexanol is much higher than that of cyclohexene,
cyclohexane and benzene. Therefore, it is possible to
utilize the reactive distillation process to replace the
sequential hydration-separation process. Although the
interaction among the simultaneous reaction, liquid-

phase splitting and distillation in the reactive distillation of cyclohexene to cyclohexanol is complicated,
its influence on the reactive distillation was investigated by means of the reactive residue curve map with
or without the liquid-phase splitting [2, 3]. Furthermore,
on the basis of the kinetic-thermodynamic analysis,
some corresponding reactive distillation processes
were proposed theoretically [2, 3].
However, due to lack of the detailed kinetics data
of the hydration, all studies on the reactive distillation
process of cyclohexene to cyclohexanol have been
based on the kinetic data reported by Panneman and
Beenackers [4], and this kinetics was acquired by
means of the cation exchange resin as the catalyst. For
the resin exchange catalyst, it is feasible theoretically
for the reactive distillation, but it is impossible to be
applied in the reactive distillation due to the low catalytic activity of the resin [5]. In addition, in the kinetic
data reported by Panneman and Beenackers, the initial
water content was set to be close to 100%, and it actually means a homogeneous reactive system [4]. However, the reactive distillation process of cyclohexene
to cyclohexanol involves simultaneous reaction, distillation and liquid-phase splitting, and it has to be
operated in the heterogeneous region. Therefore, the
kinetic data reported by Panneman and Beenackers is
unsuitable for the reactive distillation process of
cyclohexene to cyclohexanol.
Zhang et al. investigated experimentally the hydration kinetics with hydrophilic zeolite as the catalyst
[6]. The kinetic data were acquired in the heterogeneous region under the condition close to the practical
hydration process, and the data showed that the hydration rate was affected significantly by the liquid-liquid
phase equilibrium in the heterogeneous system.
Therefore, these data are suitable for the kineticthermodynamic analysis of the reactive distillation
process. Moreover, the hydrophilic zeolite catalyst has

Received 2011-06-10, accepted 2011-07-25.

* To whom correspondence should be addressed. E-mail: [email protected]

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higher catalytic activity and temperature tolerance

than the cation exchange resin, and it is also more
suitable for the practical reactive distillation operation.
In addition, according to the catalytic kinetics of
cyclohexene hydration, the operating pressure has
significant influence on the compound distribution
between the heterogeneous liquid phases in the reactive
distillation. However, this characteristic was neglected
in the previous works related to kinetic-thermodynamic
analysis of this reactive distillation, so it is worthy of
further survey.
In this work, through taking the operating pressure, new zeolite catalytic kinetics and liquid-phase
splitting into account, a further kinetic-thermodynamic
investigation on the reactive distillation of cyclohexene hydration has been carried out, and the feasibility
of this reactive distillation has been discussed in view
of developing the practical process.
2 MODELING FOR KINETIC-THERMODYNAMIC
ANALYSIS
According to results of Zhang et al. [6], through
utilizing hydrophilic zeolite HZSM-5 as the hydration
catalyst for cyclohexene to cyclohexanol conversion,
the hydration selectivity is very high, and the side reaction can be ignored. The reversible hydration reaction can be expressed as the following reaction:

In spite of the existence of the organic phase, the

hydration occurs only in the aqueous phase which has
stronger affinity with the catalyst [6]. Therefore, the
reaction just involves those compounds in the aqueous
phase. In addition, the reactant cyclohexene and reaction product cyclohexanol have low solubility in the
aqueous phase, and the content of water in the aqueous phase is very high and almost constant. Therefore,
the concentration of water can be ignored in the formulation of the hydration rate. The catalytic hydration
rate by hydrophilic zeolite HZSM-5 can be expressed
as below [6]:

ene
ol
k xaq
 xaq
/K

E
Ak exp 

RT

(2)

'H r
AK exp 
(3)

RT
When the hydration reaches equilibrium, the reactive equilibrium composition can be solved by the
following equation:
0

Table 1

(4)

The kinetic parameters in Eqs. (2) and (3) are

The reactive kinetic parameters

in Eqs. (2) and (3) [6]

Ak/kmols1kg1

E/kJmol1

AK/kmols1kg1

Hr/kJmol1

6.8201107

71.221

3.3356104

31.123

With respect to the vapor-liquid-liquid phase

equilibrium of the water-cyclohexene- cyclohexanol
ternary system, the thermodynamic method NRTL
models experimental data very well according to the
survey by Steyer el al. [7], so in this work the NRTL
method is utilized to calculate the phase equilibrium
in the following kinetic-thermodynamic analysis.
In order to analyze the kinetic-thermodynamic
feasibility, various models have been proposed, for
example, the reactive residue curve [812], the model
of concurrent flash-cascades [13,14] and the
tray-by-tray calculation [15, 16]. The reactive residue
curve is utilized widely to analyze the reactive distillation process, and has been verified by lots of studies
so far. Therefore, it is utilized to carry out the kinetic-thermodynamic analysis of the reactive distillation of cyclohexene to cyclohexanol in this work. The
computation of the reactive residue curve is based on
the following well-known differential equation [12].
dxi
xi  yi 
dW
k
k
Xi  Xsum xi  Da Da xaqene  xaqol / K (5)
kf
kf

where Da is the Damkhler number, and it can be

calculated by kfVcat/F.
For a reactive distillation column, according to
the work of Qi et al. [17], its potential compositions at
the top and bottom can be calculated by means of
solving the following nonlinear equations:
k
ene
ol
 xaq
/ K 0 (6)
xi  yi  Xi  Xsum xi  Da xaq
kf
yi  xi  Xi  Xsum yi 

(1)

ene
ol
xaq
 xaq
/K

presented in Table 1, and are utilized to calculate the

hydration rate of cyclohexene to cyclohexanol in the
subsequent kinetic-thermodynamic analysis.

k
ene
ol
 xaq
/K
Da xaq
kf

(7)

Solutions of Eqs. (6) and (7) are also known as

fixed points or reactive azeotropes. Combined with the
reactive residue curve, analysis to the fixed point is
helpful for the feasibility analysis and conceptual design of the reactive distillation column.
3

KINETIC-THERMODYNAMIC ANALYSIS

3.1
Kinetic-thermodynamic characteristics at
different operating pressures

For the reactive distillation process of cyclohexene

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hydration by means of zeolite HZSM-5 catalyst, the

reaction occurs only in the aqueous phase on the trays
due to the hydrophilicity of the catalyst. Alteration of
the operating pressure in the reactive distillation process leads to the change of both temperature and composition in the aqueous phase, and in this way it affects
the hydration in the aqueous phase. Generally, high
operating pressure can lead to high equilibrium temperature, and the latter results in turn in high hydration
rate. However, high temperature is in favor of decomposition of cyclohexanol because the hydration is
exothermic. Therefore, influence of the operating pressure on hydration rate and hydration equilibrium is
opposite. It is necessary to understand influence of the
operating pressure on the reactive liquid-liquid phase
and to survey the suitable operating pressure region.
The effect of the operating pressure on the region
size of the forward reaction and the liquid-phase splitting is shown in Fig. 1, and the dash lines represent
the reactive equilibrium lines which are the solutions
of Eq. (4) combined with the phase equilibrium equation under the different operating pressure. The right
side of the dash line is the region of forward reaction
which is the feasible reactive distillation region. The
region above the solid line is the liquid-phase splitting
region, i.e. the heterogeneous region. As demonstrated
in Fig. 1, the effect of the operating pressure on the
area of the liquid-phase splitting region is negligible.
This means that the liquid-phase splitting region is
almost invariable at different temperatures, and this
characteristic is proved by experimental results of
Steyer et al. [2, 7]. Meanwhile, it also indicates that
thermodynamic calculation is valid in this work.

significant influence on the feasible region of the reactive distillation.

The effect of the operating pressure on the
maximum formation rate of cyclohexanol is shown in
Fig. 2. It is considered in this work that the maximum
reactive rate occurs when the concentration of cyclohexanol is zero. When the initial volume ratio of water/cyclohexene is set to 0.89 and the amount of catalyst is 38% of the mass of water, the maximum formation rate in the aqueous phase is calculated at different
operating pressures using Eq. (1) and the phase equilibrium equation. Figure 2 indicates that the maximum
formation rate is close to zero at 0.1 MPa, but it increases quickly with the increasing operating pressure.

Figure 2 Effect of the operating pressure on the maximum

formation rate of cyclohexanol

In the case of the reaction time of 100 min, the

effect of both the operating pressure and the volume
ratio of water to cyclohexene on the conversion ratio
of cyclohexene are represented in Fig. 3. The conversion ratio can be calculated by means of Eq. (1) and
the phase equilibrium equation. The conversion ratio
always increases with the increase of the volume ratio
of water/cyclohexene, but the effect of the operating
pressure on the conversion ratio shows that there is an
optimal value corresponding to the highest conversion
ratio of cyclohexene. This optimal operating pressure
is about 0.4 MPa. The calculation of Fig. 3 is only for
the kineticsthermodynamics feasibility analysis, and
the computational method is significantly different

Figure 1 Effect of the operating pressure on reaction and

liquid-phase splitting
p/MPa:0.1;0.2;0.3;0.4;0.5

As shown in Fig. 1, the effect of operating pressure on the reactive equilibrium line indicates that the
operating pressure has important influence on the feasible region of this reactive distillation process, and
the feasible region shrinks with the increasing operating pressure. However, beyond the operating pressure
of 0.4 MPa, variation of the operating pressure has no

Figure 3 Effect of reaction conditions on the conversion

ratio of cyclohexene

Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011

from the rigorous simulation of the actual reactive

distillation, so it should be noted that this optimal operating pressure can not represent the optimal operating pressure in the actual reactive distillation process.
However, it shows that it is important to consider influence of the operating pressure on the reactive distillation of this system.
Influences of the operating pressure on the feasible region and the reaction rate are opposite, and there
is an optimal operating pressure for the conversion
ratio of cyclohexene, so the influence of operating
pressure on the reactive distillation of hydration is
complicated. Taking the reaction rate as priority due to
the slow hydration rate, it is considered in this work
that the reactive distillation process should prefer to a
higher operating pressure than the atmospheric pressure.
When the catalytic kinetics provided by Panneman and Beenackers [4] is utilized to calculate the
conversion ratio of cyclohexene at the same conditions as Fig. 3, generally the conversion ratio is about
1000 times less than that in Fig. 3. It indicates that the
hydrophilic zeolite HZSM-5 has higher catalytic activity for the hydration of cyclohexene than the cation
exchange resin, so the zeolite catalyst is more suitable
for the reactive distillation process of the cyclohexene
hydration.
3.2 Influence of the pressure and Da on the reactive distillation

Under the different pressure and Da, the composition of the fixed point is acquired through solving
the nonlinear Eqs. (6) and (7). Noted that stable fixed
points could be the compositions at the bottom and top
of the column, and the stable point analysis is very
useful for the kinetic-thermodynamic feasibility analysis of the reactive distillation process.
Figure 4 demonstrates distribution of stable fixed
points in the ternary diagram by solving Eq. (6) at
different pressure and Da, and they represent the

811

potential composition at the top of the reactive distillation column. In calculation, the range of Da is between 0 and 15. The increasing direction of Da is presented by the arrow in Fig. 4. As shown in Fig. 4, the
reaction product cyclohexanol could appear at the top
of column when Da>0, and in this case the distillate of
the column need be separated again to recover cyclohexanol. Furthermore, large Da can result in more loss
of cyclohexanol from the column top. Therefore, it is
reasonable that there is an unreactive section at the
upper column, which is helpful to reduce the loss of
cyclohexanol from the top. Fig. 4 also shows that the
increase of the pressure can reduce the content of the
expensive reactant cyclohexene at the column top due
to the increase of the water content at stable points.
According to computational results, variation of
operating pressure and Da has no effect on the composition of the stable fixed point of Eq. (7), and this
stable fixed point is always located in the composition
point of pure cyclohexanol. It means that the discharge
at the bottom of column is always the pure cyclohexanol even if the reactive distillation is operated under
the different pressure and Da. This result is significantly
different from results from the work of Steyer et al.
and Qi et al. due to the difference of the reaction kinetics [2, 3]. In their work, it was impossible to acquire
pure cyclohexanol at the bottom of column if the reactive section existed at the bottom of the reactive distillation column, and the reactive distillation process
was unachievable in the case of Da>0.109 due to disappearance of both stable points and saddle points [2].
These new conclusions can be expressed clearly
through residue curve maps, and Fig. 5 shows the
computational results by means of solving Eq. (5) at
two different pressures when Da is 0.05. Residue
curves represent approximately the change of the
composition in the column, and it shows that the pure
cyclohexanol is always a stable point while the saddle
point and unstable point vary with the operating pressure. Results of this work are driven by the hydrophilic zeolite HZSM-5 as the catalyst, so these residue
curve maps are also different from those provided by
Steyer et al. that were acquired by means of the cation
exchange resin as catalyst [2].
3.3 Effect of inert components on the reactive
distillation

Figure 4 Effect of the pressure and Da on the stable point

of Eq. (6)
p/MPa:0.1;0.2;0.3;0.4;0.5

In industry, cyclohexene is produced through the

hydrogenation of benzene. Besides cyclohexene, the
product of hydrogenation also includes benzene and
cyclohexane due to the reversible reaction and selectivity of the reaction. It is very difficult to separate
cyclohexene from benzene and cyclohexane because
the boiling points of these components are very close.
Inevitably, the whole hydrogenation product is fed
into the reactive distillation process with benzene and
cyclohexane as inert components. The existence of
benzene and cyclohexane affects the liquid-phase
splitting, and changes the hydration rate and reactive

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Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011

(a)

(b)

Figure 5 Residue curve maps when Da 0.05 at the pressure of (a) 0.1 MPa and (b) 0.5 MPa

(a)

(b)

Figure 6 Effect of the content of the inert component on (a) the equilibrium conversion ratio of cyclohexene and (b) the
maximum formation rate of cyclohexanol at different pressure
benzene;
cyclohexanol
p/MPa:0.1;0.2;0.3;0.4;0.5

equilibrium conversion ratio. Furthermore, taking inert components into consideration, the composition of
the fixed point in the reactive distillation also changes.
Therefore, it is worthy of surveying effects of inert
components on the reactive distillation. However, it
should be noted that there was no existence of inert
components in the hydration kinetics developed by
Zhang et al. [6], so the results in this section are only
of qualitative nature.
At different pressure, effects of the content of inert components on the reactive equilibrium conversion
ratio and maximum formation rate of cyclohexanol are
calculated in the presence of either benzene or cyclohexane. The initial volume ratio of water to cyclohexene is set to be 0.89 in the calculation. Computational results are showed in Fig. 6 by means of solving
both Eq. (4) and the phase equilibrium equation. In
Fig. 6, the solid and dashed lines represent benzene
and cyclohexane respectively, and the x-coordinate
represents the volume ratio of the inert component to
cyclohexene.
As shown in Fig. 6(a), the effects of benzene and

cyclohexane on the reactive equilibrium conversion

ratio are very different. The existence of cyclohexane
reduces the reactive equilibrium conversion ratio at
either pressure. However, the effect of benzene is
complicated, and the reactive equilibrium conversion
ratio increases slightly at first, then decreases with the
increase of the volume ratio.
The effect of the content of the inert component
on the maximum formation rate of cyclohexanol is
showed in Fig. 6 (b) at different pressure. As mentioned above, the maximum formation rate appears at
the beginning of reaction when there is no existence of
cyclohexanol. Fig. 6 (b) shows that existence of benzene or cyclohexane can reduce the maximum formation rate. Furthermore, benzene is more effective for
reduction of the maximum formation rate than cyclohexane, especially at the higher pressure.
Taking the very low reaction rate into account, it
can be concluded that it is impossible to achieve the
reactive equilibrium conversion ratio on a single tray
of the reactive distillation column. Therefore, the priority is to achieve the faster reaction rate, so that the

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Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011

Table 2

Data on azeotropes solved through Eq. (6) in existence of benzene or cyclohexane

Pressure

Benzene

Cyclohexane

0.1 MPa

60.43% (by mass) benzene

31.20% (by mass) water
8.370% (by mass) cyclohexene
341.48 K
61.43% (by mass) benzene
12.41% (by mass) water
26.15% (by mass) cyclohexene
392.22 K

8.320% (by mass) water

91.68% (by mass) cyclohexane
342.34 K

0.5 MPa

loaded catalyst on a tray may be reduced. From this

viewpoint, the existence of benzene is more unfavorable in comparison with cyclohexane, and this conclusion indicates that the conversion ratio of the reaction
is more important than selectivity for the hydrogenation process of benzene conducted before the reactive
distillation of the cyclohexene hydration, or there
should be the presence of a removal process of benzene before the reactive distillation.
The boiling point of cyclohexanol (433.99 K) is
much higher than that of inert components, the existence of inert components has no influence on the stable point solved through Eq. (7), and this means that
the composition at the bottom of the reactive distillation column still is 100% cyclohexanol. However, the
influence of inert components on the stable points
solved through Eq. (6) is significant because some
new binary and ternary azeotropes emerge due to
feeding of benzene or cyclohexane. As mentioned
above, an unreactive section should be added in the
upper section of column for reducing loss of cyclohexanol from the top of the column, so it is necessary
to calculate the composition of azeotropes which
could be recovered from the top of the column. The
data on azeotropes in existence of benzene or cyclohexane are shown in Table 2. In the presence of
cyclohexane, the cyclohexane content in the corresponding binary azeotrope decreases with the increase
of the pressure. However, in the presence of benzene,
with the increase of the pressure the cyclohexene content in the corresponding ternary azeotrope increases.
According to compositions of azeotropes calculated,
benzene can entrain cyclohexene, and this leads to a
high energy duty of the process because cyclohexene
entrained by benzene has to be recycled. Therefore,
existence of benzene is unfavorable from the viewpoint of separation.
4

CONCLUSIONS

In the case of the zeolite HZSM-5 as the catalyst,

the operating pressure has significant influence on the
reactive distillation process of cyclohexene hydration.
Results from kinetic and thermodynamic analysis indicate that the optimal pressure of this reactive distillation
process should be set to the higher pressure such as 0.3
or 0.4 MPa. According to the kinetic-thermodynamic

12.39% (by mass) water

87.61% (by mass) cyclohexane
393.40 K

analysis, an unreactive section should locate at the

upper part of the column to reduce the recovery of
cyclohexanol at the top of the column, and pure
cyclohexanol can be acquired from the bottom of the
column even if there is no unreactive section at the
lower part of the column. Meanwhile, the increase of
the pressure can reduce the content of the reactant
cyclohexene at the top of the column.
In the presence of either benzene or cyclohexane
as the inert component, benzene is more unfavorable
to the reactive distillation process in comparison with
cyclohexane. The existence of benzene reduces the
reaction rate, and meanwhile benzene can entrain
cyclohexene to the top of the column. An unreactive
section at the upper column is suggested to avoid loss
of cyclohexanol from the column top. Results from
this work are helpful to develop a practical reactive
distillation process of the cyclohexene hydration.
NOMENCLATURE
AK
Ak
Da
E
F
Hr
K
k
kf
R
r
rol_max
T
Vcat
x
y

sum

pre-exponential factor
pre-exponential factor, kmols1kg1 (based on catalyst)
Damkhler number
activation energy, kJmol1
flow rate, kmols1
enthalpy of reaction, kJmol1
reaction equilibrium constant
forward reaction rate constant, kmols1kg1 (based on catalyst)
forward reaction rate constant at reference temperature, kmols1kg1
(based on catalyst)
molar gas constant, 8.314 Jmol1K1
hydration rate, kmols1kg1 (based on catalyst)
maximum formation rate of cyclohexanol, kmols1kg1 (based
on catalyst)
temperature, K
amount of catalyst, kg
mole fraction of component in liquid phase
mole fraction of component in vapor phase
dimensionless time
stoichiometric coefficient of component
total mole change of reaction

Subscripts
aq
i

aqueous phase
component i

Superscripts
ene
ol

cyclohexene
cyclohexanol

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Chin. J. Chem. Eng., Vol. 19, No. 5, October 2011

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