9534 Ind. Eng. Chem. Res.

2009, 48, 9534–9545

Two-Step Reactive Distillation Process for Cyclohexanol Production from

Cyclohexene
Amit Katariya,† Hannsjörg Freund,† and Kai Sundmacher*,†,‡
Max Planck Institute for Dynamics of Complex Technical Systems, Sandtorstrasse 1,
39106 Magdeburg, Germany, and Process Systems Engineering, Otto-Von-Guericke UniVersity Magdeburg,
UniVersitätsplatz 2, 39106 Magdeburg, Germany

The present work deals with a novel and attractive alternative process route for the production of cyclohexanol
by indirect hydration of cyclohexene using reactive distillation. The proposed two-step process comprises the
esterification of cyclohexene with formic acid followed by the hydrolysis of the formed ester. The principle
feasibility of this new process has recently been proved by means of residue curve analysis [Steyer et al. Ind.
Eng. Chem. Res. 2008, 47, 9581-9587]. In the present contribution, detailed equilibrium stage simulations
are performed to identify the optimum design and operating conditions for the coupled reactive distillation
column scheme. The simulations reveal that it is possible to achieve almost complete conversion of cyclohexene
to cyclohexanol with a comparatively low amount of catalyst. To the best of our knowledge, this is the first
time that such an outstanding performance of a process for the production of cyclohexanol is reported.

Introduction formation due to the addition of formic acid as a reactive

Cyclohexanol, a bulk chemical needed as an intermediate for
nylon production,1 is a high volume chemical with its production
exceeding 1 million pounds annually only in the U.S. The
conventional processes for the production of cyclohexanol are
currently based on the oxidation of cyclohexane, the hydrogena-
tion of phenol, or the direct hydration of cyclohexene. The most
commonly used method, the gas phase oxidation of cyclohexane
to cyclohexanol, implies severe safety risks associated with the
operation due to formation of explosive mixtures when mixing
cyclohexane with air for oxidation. It also has a fairly low
selectivity, even at very low conversions, and is very energy
consuming because of large external recycle streams. Phenol
hydration mainly suffers from high phenol prices as compared
to benzene and again has the drawback of large hydrogen
consumption.
An alternative process has been developed by Asahi Chemical
Co.,2 where a zeolite catalyst of the HZSM5-type is used. The
process involves the liquid-phase synthesis of cyclohexanol by
hydration of cyclohexene using acidic catalysts. This is already
an improved approach for the cyclohexanol production; how-
ever, due to strongly limited mutual solubilities of cyclohexene
and water, two liquid phases are formed. This leads to a kinetic
limitation of the reaction, and thus, the use of large amounts of
catalyst is unavoidable. High reaction rates can only be obtained
when the mutual solubility of the reactants is improved and/or
the wettability of the heterogeneous catalyst with both the
organic and the aqueous phase can be adjusted individually.
As a promising alternative we propose a reactive distillation
process where cyclohexene is hydrated indirectly to cyclohex-
anol. Since the direct hydration of cyclohexene is very slow,
we use formic acid as a reactive entrainer. In the first step the
respective ester is being produced. Then, the addition of water
leads to the hydrolysis of the ester, and finally, the desired
product cyclohexanol is obtained. There is a significant im-
provement in the overall rate of the reaction for cyclohexanol
* To whom correspondence should be addressed. Tel.: +49-391-
6110-350. E-mail: sundmacher@mpi-magdeburg.mpg.de.
†
Max Planck Institute for Dynamics of Complex Technical Systems.
‡
Otto-von-Guericke University Magdeburg.
10.1021/ie801649v CCC: $40.75  2009 American Chemical Society
Published on Web 04/03/2009
entrainer, implying an enhancement of the process performance
even at moderate catalyst loadings. The aspect of limited mutual
solubilities of the components is also important for this process;
however, its influence on the process performance is by far not
as limiting as for the direct hydration process.
In our earlier contribution,3 we have confirmed the feasibility
of the process by means of residue curve maps (RCM) using
experimentally approved thermodynamic and kinetic data.4,5 In
the present contribution, the results from the feasibility analysis
carried out earlier are used as a basis for identification of
optimum design and operating conditions for the coupled
cyclohexanol production process. Simulations were carried out
using a rigorous equilibrium stage model with consideration of
phase stability analysis and splitting calculations and chemical
reaction in one of the liquid phases.
The special feature of the process presented here is that
theoretically complete conversion of cyclohexene to cyclohex-
anol can be obtained. To the best of our knowledge, no other
process with such a performance has been reported so far. Due
to the presence of the coupled reactions, the interaction of
reaction and distillative separation, and the liquid-liquid phase
splitting, the task of modeling this process is very complex.
The challenge is involved in identifying a suitable column
configuration and appropriate design and operating parameters.
Reactive Distillation Process
Process Description. Cyclohexene can be produced by partial
hydrogenation of benzene. However, the reaction involved is a
series reaction in which benzene is first hydrogenated to
cyclohexene which is easily further hydrogenated to cyclohex-
ane. Various experimental studies on the partial hydrogenation
of benzene to cyclohexene using different catalyst systems are
reported in the literature.6-10 Most of these studies report that
selectivities toward cyclohexene of up to 90% can be achieved
but only at the costs of very low conversions of benzene. An
exception is the work by Nagahara et al.,8 who observed, for
90% conversion of benzene, a selectivity toward cyclohexene
of 75%. A ruthenium based metallic catalyst which consisted
of zink compounds has been utilized. The presence of zink salts

Figure 1. Reaction triangle involved in the production of cyclohexanol by
indirect hydration of cyclohexene using formic acid as a reactive entrainer.
of strong acids have remarkably improved the selectivity. In
1990, Asahi Chemical Co. commercialized the process for
production of cyclohexanol from benzene in Japan.1 The process
involves three steps: In a first step benzene is selectively
hydrogenated to cyclohexene. Then, in the second step cyclo-
hexene is separated from the unreacted benzene and the
overhydrogenated product cyclohexane. As benzene, cyclohex-
ene, and cyclohexane are close boiling components, a series of
azeotropic distillation columns are used to obtain pure cyclo-
hexene from this mixture. After this upstream part of the process,
in the third step cyclohexene is hydrated to cyclohexanol.
In our studies we focus on the hydration step of the process.
We first considered a pure cyclohexene feed in our analysis of
the indirect hydration process for cyclohexanol production. With
regard to the upstream hydrogenation part of the process, it is
reasonable to consider a cyclohexene feed with impurities, such
as cyclohexane and benzene. The use of cyclohexene feed mixed
with inerts such as unreacted benzene and overhydrogenated
cyclohexane to the reactive distillation unit leads to a better
separation of inerts. Otherwise separation of inerts would require
separate distillation units as well as solvents for the azeotropic
separation. Hence an analysis of the column with cyclohexane
impurities in the feed mixture and their influence on the
proposed process scheme is also presented.
Figure 1 shows the triangle of reactions, taking place in the
cyclohexanol production by indirect hydration of cyclohexene
using formic acid as reactive entrainer. Both of the reaction steps
involved in the production of cyclohexanol, i.e. the esterification
and the ester hydrolysis, are moderately fast and mildly
exothermic. Also, there is a significant difference in the
volatilities of the species; the difference in the boiling points
of cyclohexene and formic acid cyclohexyl ester is more than
80 °C. In addition, the conditions for the reaction and distillation
are matching. This makes the esterification of cyclohexene using
formic acid and the subsequent hydrolysis of the ester a potential
candidate for the use of reactive distillation. Similar conclusions
have been obtained with the help of feasibility analysis using
residue curve maps (RCMs).3
The process flow scheme for the preparation of cyclohexanol
from cyclohexene is shown in Figure 2. Here the reactions are
carried out in a series of two reactive distillation columns. In
the first column the ester formation takes place, followed by
the subsequent hydrolysis of the formed ester in the second
column to give cyclohexanol as a bottom product. Formic acid
can be recovered and recycled to the process. It turned out3
that only the upper part of both columns should be realized as
reactive zones. In the first column, a nonreactive lower part is
necessary in order to avoid a back-splitting of the formed
cyclohexyl ester to formic acid and cyclohexene. In the case of
Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9535
the second column, residue curve map (RCM) analysis revealed
that pure cyclohexanol can be obtained without any nonreactive
stripping section. However, the presence of a nonreactive
stripping section accelerates the cyclohexanol formation reaction
due to the simultaneous separation of cyclohexanol from the
reactive section. This also leads to a reduced height of the
reactive section. Hence, the lower part of the second column
can be designed as a nonreactive zone for economical reasons.
With the results of the RCM analysis as a starting point, a
simulation based approach is utilized to arrive at a theoretically
optimum process performance, and optimum design and operat-
ing parameters are identified.
Kinetic and Thermodynamic Data. There are three reactions
taking place in the proposed production process of cyclohexanol,
viz.
Reaction 1 cyclohexene + formic acid T cyclohexyl formate
Reaction 2 cyclohexyl formate + water T
cyclohexanol + formic acid
Reaction 3 cyclohexene + water T cyclohexanol
In our earlier work,5 we have studied the detailed kinetics of
all the three reactions using commercial ion-exchange resin
catalyst (Amberlyst 15). The kinetic investigations were carried
out in the two liquid phase region due to the strong immiscibility
between the components involved. It was observed that a
significant decomposition of formic acid to carbon monoxide
and water takes place at temperatures higher than about 60 °C.
To avoid any formation of carbon monoxide, the reaction
temperature in the experiments is kept below 60 °C.
Equation 1 is a generalized Langmuir-Hinshelwood type rate
expression to describe the kinetics of all the three reactions:
[ ]
Kads,AKads,B
R ) mcatkfhet + nFAkfhom ×
[1 + ∑K ads,iai]
2
( )
i
∏a
∏a
products
reactants - (1)
Keq
In this equation, mcat denotes the catalyst amount used, kfhet and
kfhom are the forward rate constants (Arrhenius type) of the
heterogeneous and homogeneous reactions, respectively. Kads,i
are the adsorption equilibrium constants for species i taking part
in a particular reaction, and the notation A and B is given for
the reactants adsorbed on the catalyst surface for the corre-
sponding reaction. Keq is the temperature-dependent chemical
equilibrium constant, the ai is the liquid phase activity of the
chemical species, and nFA is the molar amount of formic acid
which acts as a homogeneous catalyst. The reaction is also
taking place homogeneously due to the presence of formic acid
in the reaction mixture. Table 1 contains the parameters needed
for the calculation of the reaction rate.
The presence of water and formic acid makes the system
highly nonideal. There is a significant miscibility gap between
various components involved. Figure 3a and b illustrates the
limited mutual solubilities of the components. Hence, the NRTL
model has been used for calculating the liquid phase activity
coefficients. In our earlier work, we have carried out detailed
experiments and published the thermodynamic data for all the
components in question.4
Model Description. As a first step toward the design and
optimization of the reactive distillation process, detailed simula-
tions of the coupled columns, as shown in Figure 2, have been
carried out and are presented here. The considered design case
is a cyclohexanol production process for a cyclohexene feed of
9536 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009

Figure 2. Flow scheme for the proposed two-step reactive distillation process.

Table 1. Kinetic Parameters for Reaction Rate Calculations5 equation (DAE) systems. An external subroutine has been
EAhom het
kf,0 EAhet incorporated for analyzing the stability of the liquid phase on
hom
reaction kf,0 [1/s] [J/mol] [mol/(kgcat s)] [J/mol] each stage as well as for performing the liquid-liquid equilib-
esterification 1.7089 × 1011 95467 4.5701 × 1025 114395
rium calculation. For the details of the phase splitting calcula-
ester hydrolysis 7.2738 × 105 52287 1.2148 × 1016 100240 tions and the implementation of the algorithm within the column
cyclohexene 7.7083 × 1012 93687 simulations, one can refer to the work of Bausa and Marquardt,13
hydration Steyer et al.,14 and Gangadwala et al.15
0
∆fHliquid S0 CP
substance [J/mol] [J/(mol K)] [J/(mol K)] Kads
Results and Discussion
cyclohexene -37820 216.33 148.83 0.056839
cyclohexanol -351831 203.87 213.59 0.77324 Esterification Column with Pure Cyclohexene Feed. The
water -285830 69.95 75.38 19.989 base case for the esterification column was identified with the
FCE -487129 275.50 219.50 3.6770
formic acid -425379 129.00 99.84 7.7290 × 10-7 help of exploratory simulation studies and is given in Table 2.
The 15 theoretical stages include the condenser, the reboiler,
F ) 10-3 m3/h (pilot scale). The assumptions used for the and 6 reactive stages [1 + 6(reactive) + 7 + 1]. Cyclohexene
modeling of the process are the following: is fed at the bottom of the reactive section (stage 7), and the
1. Constant molar holdup of liquid and negligible vapor formic acid feed is sent in a stoichiometric amount at the top
holdup (although we restrict our analysis to steady state, the of the reactive section (stage 2). As the feed is at stoichiometric
constant holdup assumption is required due to the presence of conditions and both are pure feeds, the total vapor from the top
the homogeneous reaction) of the column is condensed and sent back to the column. The
2. Equilibrium stage model reflux point is placed at the top of the column (stage 2). The
3. Liquid phase reactions only design objective is the complete conversion of cyclohexene. As
4. Ideal vapor phase and nonideal liquid phase, the mixing there is no water present in the esterification column, only
behavior of which is described by the NRTL activity coefficient reaction 1 (i.e., the esterification) takes place. Various simula-
model tions have been carried out to arrive at optimum performance.
5. Adiabatic and constant pressure operation of each column. The results of the analysis are presented in Figures 4-6.
Due to the presence of polar components such as water and Figure 4 shows the effect of the change in the number of
formic acid, liquid-liquid phase splitting is expected to occur reactive stages and the reboiler duty on the conversion of
within the reactive distillation columns. The experimentally cyclohexene in the esterification column. It can be seen from
validated thermodynamic parameters (NRTL and vapor pres- the diagram that for any number of reactive stages it is possible
sure) are taken from previous studies.4 Due to the observed to achieve 100% conversion of cyclohexene. The reason for
decomposition of formic acid at high temperatures, the column the 100% conversion is the fact that cyclohexene is the lightest
is operated at below atmospheric pressure. The pressure was boiler in the system and is kept in the upper column part at
set such that the temperature in the reactive section does not total recycle, and the column has only one outlet which is the
exceed 60 °C. bottom product stream. The increase in the reboiler duty causes
The equilibrium stage model has been formulated based on unreacted cyclohexene and formic acid to move up in the
the MESH (Mass-Equilibrium-Summation-Enthalpy) equations. column. Total recirculation from the condenser to the top of
The details about the model equations and the solution methods the column leads to a high residence time of the two reactants
can be found elsewhere.11 The model has been implemented in in the reactive section. From the analysis of the simulation
the simulation environment DIVA.12 DIVA uses the equation results depicted in Figure 4, we have chosen the column design
oriented approach for solving all the differential and algebraic with 7 reactive stages, because for this configuration 100%
equations simultaneously. DIVA provides a built-in package for conversion of cyclohexene is obtained at the smallest possible
continuation and stability analysis of the differential-algebraic reboiler load.
 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9537

Figure 3. Liquid-liquid phase equilibrium diagram illustrating the limited mutual solubilities of the components.

Table 2. Base Case Configuration for the Esterification Column

Number of Theoretical Stages
total 15
reactive section 6
stripping section 7

Operating Conditions
reflux ratio total reflux
reboiler load 110.0 W
operating pressure 0.1 bar
catalyst amount 2.0 kg

Feed Location and Condition

cyclohexene feed 2.6746 × 10-3 mol/s, (294 K) on stage 7
formic acid feed 2.6746 × 10-3 mol/s, (310 K) on stage 2

Further simulations were carried out by fixing the value

of seven reactive stages and varying the cyclohexene feed Figure 5. Sensitivity of the cyclohexene conversion with regard to the
location. The results are presented in Figure 5. It has been cyclohexene feed location and the reboiler heat load (base case configuration
observed that, as the cyclohexene feed point is moved up in (Table 2) with seven reactive stages).
the column, a better performance of the column is achieved
at a lower reboiler load. This is because, for the column with
total reflux, locating both feed points at the top provides mole
ratios of the reactants close to the equimolar condition at
each reactive stage. Moreover, due to the distillation effect,
the formed ester is simultaneously separated from the reactive

Figure 6. Effect of the reboiler heat load and the catalyst amount on the
cyclohexene conversion (base case configuration (Table 2) with seven
reactive stages and feed of cyclohexene on the third stage).

zone. This will suppress the reverse reaction of ester to

cyclohexene and formic acid and will thus enhance the ester
formation.
Figure 4. Effect of the number of reactive stages and the reboiler heat load In further simulations, presented in Figure 6, the cyclo-
on the conversion of cyclohexene (base case configuration (Table 2)). hexene feed location is fixed at the third stage with seven
9538 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009
Figure 7. Column composition (mole fractions) and temperature profiles for the optimized column configuration (Table 4).
reactive stages in the column. All other parameters are given
in Table 2. The sensitivity of the cyclohexene conversion
with respect to catalyst loading at four different levels of
the reboiler load was investigated. To select the optimum
parameters in this case, it is necessary to carry out detailed
energy and catalyst cost analysis. Here, a reboiler load of
130 W and a catalyst amount of 2 kg is selected as the most
reasonable choice.
It is also possible to improve the performance of the
column at reduced reboiler loads or reduced catalyst amounts.
This can be achieved by increasing the pressure, which leads
to a temperature increase in the column, which in turn
increases the rates of chemical reactions. But still one has
to restrict to a pressure value such that the decomposition of
formic acid is avoided, i.e., the pressure is set such that the
temperature in the reactive section does not exceed 60 °C.
In conclusion, the final optimized esterification column
consists of in total 15 theoretical stages including condenser
and reboiler. The reactants, pure cyclohexene and formic acid,
are fed in a stoichiometric ratio on stage numbers two and three
of the column, respectively. A decanter is provided at the top
of the column to separate unreacted cyclohexene and formic
acid, which form a heterogeneous azeotrope. The upper section
of the column is the reactive section, consisting of seven
theoretical stages. The esterification column is operated at total
reflux whereby achieving complete conversion of cyclohexene
to formic acid cyclohexyl ester. The ester is then fed into the
second column of the process scheme, where ester hydrolysis
is performed. The final column profiles for the optimal config-
uration of the esterification column are depicted in Figure 7.
As indicated by the phase fraction plot in Figure 7, phase
splitting takes place only in the upper part of the reactive section.
Also, it can be clearly observed that a nearly equimolar ratio of
the reactants is obtained at the top of the column which is
desirable for a reasonable reaction rate.
Esterification Column with Cyclohexene/Cyclohexane
Feed. In the presence of cyclohexane as an inert in the feed
mixture, residue curve map analysis reveals that the heteroge-
neous azeotrope of cyclohexane and formic acid will be the
expected top product.3 The presence of the inert cyclohexane
decreases the overall mole fraction of the high boiling ester on
each stage. In particular, the lower boiling cyclohexane will
preferably be accumulated in the upper reactive section of the
column. This effect leads to a reduction of temperatures in
Table 3. Base Case Configuration for the Esterification Column
with Consideration of Cyclohexane in the Feed
Number of Theoretical Stages
total 20
reactive section 12
stripping section 6
Operating Conditions
reflux ratio total reflux of polar phase (at stage 2)
partial reflux of organic phase
reboiler load 120.0 W
operating pressure 0.1 bar
catalyst amount 2.0 kg
Feed Location and Condition
cyclohexene feed mixture 3.20952 × 10-3 mol/s, (294 K) on stage 12
formic acid feed 2.67460 × 10-3 mol/s, (310 K) on stage 2
comparison to the temperature values at pure cyclohexene feed.
This implies that there is a restriction with regard to the temp-
erature being achieved in the column at a fixed pressure. To
achieve complete conversion of cyclohexene, it is necessary to
maintain a certain value of the Damköhler number in the reactive
section. The Damköhler number can be modified either by
increasing the catalyst amount or by varying the pressure which
governs the bubble point temperature of the mixture. This
implies that there will be significant modifications in the design
and operation of the esterification column when dealing with a
feed that contains an additional inert component besides the
reactant cyclohexene.
As the heterogeneous azeotrope of cyclohexane and formic
acid is the feasible top product, the base case column
configuration as given in Table 3 is considered for the
simulation based design. The RCM analysis with cyclohexene
and cyclohexane in the feed mixture performed in our
previous work3 revealed the need for a longer reactive section.
Therefore, the base case for a mixed feed has to be changed
accordingly. In addition, we are now removing a part of the
distillate as a top product; hence, there is no total recirculation
at the top as in the case of a pure cyclohexene feed.
Therefore, the cyclohexene/cyclohexane feed is sent at the
bottom of the reactive section to provide a longer residence
time and to avoid short-circuiting of the reactant through
the distillate. In the following subsections, we first present
the analysis for the cyclohexene feed mixture with 20 mol
 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9539
Table 4. Comparison of the Base Case and Optimized Column Configuration
Number of Theoretical Stages
0% cyclohexane 20% cyclohexane 30% cyclohexane 40% cyclohexane
base optimum base optimum base optimum base optimum
total 15 15 20 20 20 20 20 20
reactive 6 7 12 15 12 15 12 15
stripping 7 6 6 3 6 3 6 3

Operating Conditions
reflux ratio
organic phase total 85% 89% 80% 83% 80%
polar phase total total total total
reboiler load [W] 110 130 120 130 133 140
pressure [bar] 0.1 0.1 0.2 0.1 0.247 0.1 0.248
catalyst amount [kg] 2.0 2.0 2.0 2.0

Feed Location and Condition

cyclohexene feed mixture [mol/s] 2.67460 × 10-3 3.20952 × 10-3 3.47698 × 10-3 3.74444 × 10-3
temperature [K] 294 294 294 294
feed location 7 3 12 12 12
formic acid [mol/s] 2.67460 × 10-3 2.67460 × 10-3 2.67460 × 10-3 2.67460 × 10-3
temperature [K] 310 310 310 310
feed location 2 2 2 2

% inert cyclohexane in it. Then, the comparison is also
presented for cases with 30 and 40 mol % of inert material.
20% Cyclohexane in the Cyclohexene Feed Mixture. The
base case configuration features in total 20 theoretical stages
including the condenser, the reboiler, and 12 reactive stages [1
+ 12(reactive) + 6 + 1]. The cyclohexene feed mixture is sent
to the bottom of the reactive section (stage 12), and pure formic
acid feed is introduced in a stoichiometric amount to cyclo-
hexene at the top of the reactive section (stage 2). The vapor
from the top of the column is condensed and sent partially back
to the column. The condenser contains a heterogeneous mixture
of cyclohexene, cyclohexane, and formic acid. The organic
phase of this mixture, which is rich in cyclohexene and
cyclohexane, is partially recycled to the bottom of the reactive
section. The second liquid phase, being rich in formic acid, is
completely sent back to the top of the reactive section. We refer
to this formic acid rich phase as the polar phase. As a starting
value for the simulation, 85% of the organic phase from the
decanter is recycled back to the column.
Simulations were carried out under variation of the reboiler
load, the number of reactive stages, the organic phase reflux
rate, and the reflux position at the column. These are the crucial
parameters for optimal process performance. The remaining
parameters such as the two feed locations, the polar phase reflux
position, the catalyst amount, and the column pressure are kept
constant at values and/or positions that appeared to be optimal
from practical considerations. For example, the complete polar
phase from the condenser has to be recycled to the top of the
column, as it is rich in formic acid. Initially, simulations were
carried out by varying the number of reactive stages, keeping
the total number of stages constant. The maximum conversion
is obtainable with 16 reactive stages.
Figure 8a and b show the effect of the reboiler heat load, the
organic phase reflux amount, and the reflux position on the
cyclohexene conversion for the base case column configuration
(Table 3), but here with 16 reactive stages. When increasing
the reboiler load, the conversion first increases, reaches a
maximum, and then decreases with a further increase in the
reboiler load. This decrease in the conversion is the result of
an increase in the vapor flow rate, which reduces the extent of
the liquid phase reaction. It can be seen that the maximum
conversion of cyclohexene that can be achieved in these cases

Figure 8. Diagram showing the effect of the reboiler heat load, the organic phase reflux amount, and the position of the reflux on cyclohexene conversion
(base case column configuration (Table 3) with 16 reactive stages).
9540 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009
Figure 9. Diagram showing the effect of the reboiler heat load and the
number of reactive stages on the cyclohexene conversion (base case column
configuration (Table 3) with 88% organic reflux on the ninth stage).
Figure 10. Diagram showing the effect of the reboiler heat load and the
organic phase reflux position on the cyclohexene conversion (base case
column configuration (Table 3) with 16 reactive stages, 88% organic reflux,
and a very high amount of catalyst (9 kg)).
does not exceed 86.0%. Also, by changing the number of
reactive stages, the maximum conversion could not be increased
above 86.0% (Figure 9). This is due to the fact that for a fixed
amount of the catalyst and a fixed pressure inside the column,
Figure 11. Bifurcation diagrams for esterification column: Effect of column pressure, number of reactive stages, and position of 88% organic phase reflux
(see Table 3 for the base case configuration).
there is a restriction with regard to the maximum Damköhler
number that can be achieved in the reactive section of the
column.
This fact can be verified by changing the Damköhler number
in the reactive section. There are three ways to change the
Damköhler number: the first one is to increase the amount of
the catalyst, the second possibility is to increase the pressure
of the column, and the third way is to reduce the feed flow
rates in order to increase the residence time. Figure 10 illustrates
that up to 99% conversion of cyclohexene can be achieved if
one can increase the Damköhler number correspondingly in the
reactive section.
As there is a restriction with regard to the maximum amount
of catalyst that can be installed in the column, we vary the
pressure of the column. However, we have to keep in mind
that the maximum temperature in the reactive section of the
column should not exceed 60 °C, since above this temperature
the decomposition of formic acid in the presence of acid catalyst
has been observed experimentally.5
Figure 11a-c shows the influence of the column pressure
on cyclohexene conversion for a fixed amount of organic reflux
sent at various reflux positions and for different numbers of
reactive stages. It can be seen that, with an increase of the
number of reactive stages, the conversion attains a maximum
for the column with 15 reactive stages; a further increase in the
number of reactive stages leads to a decrease of conversion.
This happens due to the increasing occurrence of the reverse
reaction of the formed ester in the lower part of the reactive
section.
Multiple operating points have also been predicted (see Figure
11a) for the column with 14 reactive stages, which has
importance when studying the dynamics of the system. The
diagrams also show that as we increase the number of reactive
stages, the maximum conversion is obtained at lower pressures.
Hence for the further simulations, we selected the column
configuration with 15 and 16 reactive stages to find the optimum
values for the reboiler load, the reflux amount, and the reflux
position.
In Figure 12a, the fixed amount of organic reflux (i.e., 88%)
was positioned at the seventh stage of the column, which has
15 reactive stages. Then, the effect of the reboiler load and the
column pressure was investigated. A similar analysis was also
carried out for the column with 16 reactive stages and a reflux
position on stage 8 (Figure 12b). In both cases, more than 98%
conversion of cyclohexene can be achieved. Also, for the column
with 16 reactive stages, the maximum is obtained at lower
pressure as compared to the column with 15 reactive stages.

Figure 12. Bifurcation diagrams for esterification column: effect of column pressure and reboiler load.
Figure 13. Bifurcation diagrams for esterification column: effect of column pressure, amount of organic phase reflux, and the reflux position (base case
column as given in Table 3; 15 reactive stages, 130 W heat load).
Figure 14. Optimal column composition and temperature profiles [optimized
column configuration as given in Table 4].
To identify a column configuration that allows for a further
improvement of the conversion of cyclohexene, simulations were
carried out for the column with 15 reactive stages to optimize
the organic phase reflux amount and the position. Figure 13a
Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9541
represent the results of the analysis of the column performance
by varying the organic reflux amount at fixed location (ninth
stage). The maximum conversion is obtained with 89% organic
reflux, which is then used to verify its location as shown in
Figure 13b. The remainder of the organic phase, which is taken
as a distillate from the column, is >99% pure cyclohexane which
is an inert contained in the feed mixture coming from the
upstream process.
The final optimum column configuration and the correspond-
ing design and operating parameters can be found in Table 4,
which involves in total 20 theoretical stages [1 + 15(reactive)
+ 3 + 1] including condenser and reboiler. Formic acid is fed
at the top (stage 2) of the column. The mixture cyclohexene/
cyclohexane is fed at stage 12. From the total condenser, the
polar phase, rich in formic acid (more than 99%), is recycled
to the top (stage 2) of the column and 89% of the organic phase
(mixture of cyclohexene/cyclohexane) is recycled to stage 9.
The column is operated at 0.2 bar pressure, and 130 W heat is
supplied to the reboiler.
Figure 14 shows the optimum column profiles, for which
99.20% cyclohexene conversion is achieved. The bottom product
of the column is the formic acid cyclohexyl ester (FCE) with
greater than 99.5% purity.
9542 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009

Figure 15. Esterification column (30% cyclohexane in feed mixture): (a) effect of the organic phase reflux amount on cyclohexene conversion at 130 W heat
supply to the reboiler; (b) effect of the reboiler heat load on cyclohexene conversion for 83% organic reflux (base case column configuration as in Table 3
with 15 reactive stages, organic phase reflux on stage 9).

Table 5. Base Case Configuration for the Ester Hydrolysis Column cyclohexane in the feed puts a restriction on the maximum
Number of Theoretical Stages conversion obtained to 86%. This situation can be improved
base case optimum case
by increasing the Damköhler number on each stage as well as
the number of theoretical stages in the reactive section. For fixed
total 20 20 feed conditions and fixed amount of catalyst installed in the
reactive section 12 12 reactive section of the column, the only way to increase
stripping section 6 6
the Damköhler number is to increase the pressure. Although
Operating Conditions the desired conversion of cyclohexene to FCE is achieved at
reflux total organic phase returned at stage 2 higher pressures, the temperature level in the reactive section
distillate total polar phase as a distillate does not exceed 45 °C, which ensures that the decomposition
reboiler load 120.0 W 502.1 W of formic acid is suppressed.
operating pressure 0.1bar 0.1bar Ester Hydrolysis Column. The feed streams for the second
catalyst amount 2.0 kg 2.0 kg
column are the pure ester, irrespective of the feed used for the
Feed Location and Condition esterification column, and the water. It has been observed that
ester feed 2.6748 × 10-3 mol/s (363.15 K)
along with the hydrolysis reaction, the back-splitting of the ester
ester feed location stage 2 stage 4 to formic acid and cyclohexene is unavoidable. This implies
water feed 2.6748 × 10-3 mol/s, (319.15 K) that all the three reactions, as specified in Figure 1, are taking
water feed location stage12 stage12 place in the hydrolysis column, which makes the design of the
In addition to the simulation studies presented above, similar column a challenging task.
simulations were carried out assuming a cyclohexene feed A decanter has to be provided for the hydrolysis column to
mixture with 30% and 40% cyclohexane. The formic acid is recycle the cyclohexene rich organic phase. This internalizes
fed in a stoichiometric amount with regard to cyclohexene in the cyclohexene and the selectivity toward the desired product
the feed mixture. As the amount of inert in the feed is increased, cyclohexanol can be improved. A similar simulation-based
it is necessary to increase the distillate rate. As an example for design approach as presented for the esterification column has
30% inert in the feed mixture, Figure 15a gives the optimum also been carried out for the hydrolysis column in order to find
value of the amount of reflux required to obtain nearly 99% an optimum column design and optimal operating conditions.
conversion of cyclohexene, which turns out to be 83% of organic The base case configuration of the ester hydrolysis column
reflux. Similarly, the optimum value of the reboiler heat load is given in Table 5. A column with in total 20 theoretical stages
can be identified from the simulations reported in Figure 15b. including condenser, reboiler, and 12 reactive stages has been
The optimal point turned out to be at a reboiler load of 133 W considered. The formic acid cyclohexyl ester (FCE) is fed at
and a column operating pressure of 0.247 bar, where the the top of the reactive section (stage 2), and water is fed at the
maximum conversion of 98.78% is obtained. A further increase bottom of the reactive section (stage 12). The reactants are fed
in the reboiler load does not significantly improve the conver- in a stoichiometric quantity according to the hydrolysis reaction.
sion; in fact, there is a reduction in the conversion level. This The vapor from the top of the column is condensed and sent
happens due to an increase in the vapor flow rate, which reduces partially back to the column.
the extent of the liquid phase reaction. The detailed comparison The condenser contains a heterogeneous mixture of cyclo-
of the base cases and the optimized column configurations is hexene, formic acid, and water. The organic phase of the
given in Table 4. mixture, rich in cyclohexene, is recycled completely to the top
Summary of Esterification Column Simulations. As com- of the column. The polar phase, rich in formic acid, is withdrawn
pared to the design of the column with pure cyclohexene, a as a distillate and can be recycled by using it as a feed for the
longer reactive section is required if the feed contains significant esterification column. Here, the polar phase can also be referred
proportion of cyclohexane. At 0.1 bar pressure, the presence of to as aqueous phase, as it might be the water containing phase
 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9543

Figure 16. Bifurcation diagram for ester hydrolysis column: effect of ester feed position and reboiler load (base case column configuration as in Table 5).

Figure 17. Bifurcation diagram for ester hydrolysis column: effect of water feed position and reboiler load (base case column configuration as in Table 5
with ester feed at stage 4).

Figure 18. Bifurcation diagram for ester hydrolysis column: effect of the number of reactive stages and reboiler load (base case column configuration as in
Table 5 with ester feed at stage 4 and water feed at stage 12).

if unreacted water is present. The ester hydrolysis column is reactive section, etc., to arrive at an optimum column config-
operated at 0.1 bar pressure. Various simulations were carried uration and optimum operating parameter values. The design
out by changing the feed position, reboiler load, height of the objective for the ester hydrolysis column is to maximize the
9544 Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009
Figure 19. Steady state composition and temperature profiles for optimized
ester hydrolysis column (optimum column configuration as given in Table
5, R1 esterification; R2 ester hydrolysis reaction; R3 direct hydration).
conversion of FCE and the selectivity toward cyclohexanol
simultaneously (i.e to maximize the cyclohexanol yield).
In Figure 16a and b, the conversion of FCE and the purity of
cyclohexanol (i.e., the mole fraction) in the bottom product have
been analyzed by varying the reboiler heat load and the ester
feed position. For the ester feed at stage 4, the maximum yield
of cyclohexanol (>99%) is obtained. Therefore, for the analysis
presented in Figure 17a and b, the FCE feed position is fixed at
stage 4, and the water feed position is varied with the reboiler
load to analyze the yield of cyclohexanol from the column. The
optimum is obtained when water is fed on stage 12 (as in the
base case). After the identification of the optimum feed positions,
the sensitivity of the column performance with respect to the
number of reactive stages in the column was analyzed. Figure
18 shows that with 12 reactive stages in the column and for a
reboiler duty of about 500 W, greater than 99% yield of
cyclohexanol in the bottom is observed.
Although in all cases the desired performance is achieved,
as can be seen in Figures 16-18, the operating range with
regard to the reboiler load is quite narrow. The reason for
this complex system behavior is the interaction of multiple
competing chemical reactions and the reactive separation
process along with the presence of liquid phase splitting in
the column, showing multiple operating points. The highly
nonlinear nature of the curves in Figures 16-18, showing
multiple operating points, illustrates the complexity of the
process under investigation.
Finally, the simulated optimum column temperature and
composition profiles are presented in Figure 19; the optimum
design and operating parameters are given in Table 5. It can be
seen from the diagram that, in the upper part of the reactive
section, from stages 2 to 7, the ester formation reaction (reaction
1) is dominating. In the lower part of the reactive section, from
stages 8 to 13, the cyclohexanol formation by ester hydrolysis
(reaction 2) is dominating. In this section along with cyclohex-
anol formation, the splitting of ester back to cyclohexene and
formic acid is taking place. However, this is compensated by
the ester formation taking place in the upper section. The direct
hydration of cyclohexene (reaction 3) is also occurring simul-
taneously; but, the rate of this reaction is negligibly small. In
contrast to the esterification column, where only one reaction
(reaction 2) is taking place, in the ester hydrolysis column all
reactions feature significant reaction rates. This makes the
operation of the second column very complex.
Figure 20. Steady state column composition profiles for the coupled column
configuration (optimum column configurations are given in Tables 4 and 5).
Coupled Reactive Distillation Process. In case of the
coupled column scheme, as shown in Figure 2, pure cyclohexene
is fed slightly below the top of the esterification column (similar
conclusions can be made for the coupled column scheme with
cyclohexene/cyclohexane feed mixture as one can obtain pure
ester in any case). The formic acid has to be fed to the
esterification column only during start-up, and then formic acid
from the hydrolysis column can be totally recycled to the first
column with a small makeup stream of formic acid. The distillate
stream from the hydrolysis column is the polar phase stream of
the two liquid-phase mixture formed in the decanter. This stream
is rich in formic acid, but it also has cyclohexene and water in
small amounts. It is important to know that by fixing the
temperature of the decanter of the hydrolysis column, the molar
fractions of the components involved can be fixed. For the
success of the coupled process, it is essential to minimize the
water going to the esterification column with the help of a proper
control mechanism since the presence of large amounts of water
will seriously affect the yield of the ester obtained in the
esterification column.
Figure 20 illustrates the steady state composition profiles for
the coupled column scheme. It is possible to continue with the
design parameters, same as those being discussed for the
individual columns in the previous sections, with small modi-
fications of the operating parameters. In case of the esterification
column, heat supplied to the reboiler has to be increased due to
the presence of small amount of water in the formic acid feed
stream and the formation of cyclohexanol due to this water.
The bottom product from the esterification column consists of
more than 96% of ester and remaining cyclohexanol. The
presence of cyclohexanol, in the feed to the hydrolysis column,
does not have any influence on the design and operating
parameters of this column.
Hence, it is possible to achieve complete conversion of
cyclohexene to cyclohexanol using a coupled reactive distil-
lation scheme. As another advantage, we expect that a
significantly lower amount of catalyst is required when
compared to the direct hydration process for the production
of cyclohexanol from cyclohexene. This is due to the fact
that the rate of the direct hydration reaction is very low. With
the presented steady state simulations, it is straightforward
to couple the columns using the formic acid recycle stream.
However, the dynamic operation of such a coupled scheme
is a challenging task. Slight variations in the operating
conditions may change the composition of the formic acid
recycle stream, and this can severely affect the dynamic

operation of the esterification column. To achieve (and
maintain) optimum process performance, a reliable model
based control scheme is a prerequisite. Therefore, a detailed
study of the dynamics of the coupled process with respect
to perturbations of operating parameters has to be carried
out in the future.
Conclusions
In this work, a novel process for the production of cyclo-
hexanol is proposed and investigated by means of rigorous
simulations. The process scheme consists of two coupled
reactive distillation columns and involves the esterification of
cyclohexene with formic acid, followed by hydrolysis of the
ester. For the simulation, an equilibrium stage model is
formulated and solved, using the kinetic and thermodynamic
data which were thoroughly identified in previous experiments.5,4
Due to the limited mutual solubilities of the reactants, phase
stability analysis and phase splitting calculations (VLLE) at each
stage in the column are performed. The presence of the coupled
reactions, the interaction of reaction and distillation, and the
presence of liquid-liquid phase instability all make the model-
ing of the system a demanding task. The simulations of the two-
step reactive distillation process are carried out in order to
identify the optimal design and operating parameters.
The results show that using the proposed novel process
scheme, almost complete conversion of cyclohexene to cyclo-
hexanol can be achieved with moderate amounts of catalyst.
For the esterification column with a pure cyclohexene feed and
formic acid in a stoichiometric amount, it is possible to achieve
complete conversion of cyclohexene to the respective ester if
sufficient heat is supplied to the reboiler. From the overall
process point of view (i.e., with regard to the upstream
hydrogenation of benzene), it seems appropriate to additionally
consider the case of a cyclohexene/cyclohexane feed mixture
for the esterification column. Although there are significant
differences in the design and operating conditions, complete
conversion of cyclohexene to the ester can still be achieved since
cyclohexane can be regarded as an inert component that can
easily be separated in the first column. Irrespective of the feed
composition, a product stream with an ester purity of almost
greater than 99.20% can be achieved. This stream is then fed
to the second column where the ester hydrolysis to cyclohexanol
and formic acid is realized. In this column, along with the ester
hydrolysis reaction, a back-splitting of the ester to cyclohexene
and formic acid takes place. The competing reactions along with
the distillative separation increases the complexity of the system
which makes the design and operation of this column more
difficult. Due to multiple operating points, the operation of this
column has to be restricted to a relatively narrow operating
window where a yield of >99% of cyclohexanol can be realized.
To the best of our knowledge, such a performancesa process
with nearly 100% conversion of cyclohexene to cyclohexanolshas
Ind. Eng. Chem. Res., Vol. 48, No. 21, 2009 9545
thus far not been reported in the literature concerning cyclo-
hexanol production. This fact clearly demonstrates the at-
tractiveness of the proposed coupled reactive distillation process
scheme. The next step in the process development is to perform
an experimental validation of the simulation studies. Such
experiments are currently being carried out by our group in a
pilot plant.
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ReceiVed for reView October 30, 2008
ReVised manuscript receiVed March 9, 2009
Accepted March 11, 2009
IE801649V