Chemical Engineering Science 57 (2002) 1511 1520

www.elsevier.com/locate/ces

Synthesis of cylohexanol by three-phase reactive distillation:

in%uence of kinetics on phase equilibria
Frank Steyera , Zhiwen Qia , Kai Sundmachera; b; ,
a Max-Planck-Institute
b Process

for Dynamics of Complex Technical Systems, Sandtorstrae 1, D-39106 Magdeburg, Germany

Systems Engineering, Institut fur Verfahrenstechnik, Otto-von-Guericke-University Magdeburg,
Universit+atsplatz 2, D-39106 Magdeburg, Germany

Abstract
A reactive distillation process is being suggested for the production of the commercially interesting intermediate cyclohexanol from
cyclohexene and water, which avoids some of the drawbacks of the conventional liquid-phase cyclohexane oxidation process, especially
with respect to operational safety. This reactive distillation process has its own intricate challenges due to the fact that reaction, distillative
separation and liquid-phase splitting occur simultaneously. The interaction of these three phenomena is studied using residue curve maps
for both, model simulations and experimental data. Based on the 1xed point analysis of the residue curves, a novel process is proposed
for the reactive separation of cyclohexene=cyclohexane mixtures which is di2cult to be carried out by conventional distillation due to
very close boiling temperatures. ? 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Reactive distillation; Residue curve maps; Multiphase reactors; Phase equilibria; Reactive separation

1. Introduction
Cyclohexanol is being synthesized on an industrial scale
today as an intermediate in the production of adipic acid
and -caprolactame. These in turn are intermediates for the
production of Nylon 6,6 and Nylon 6. Since Nylon is a bulk
polymer the world production of cyclohexanol had already
reached 1.1 million tons per year in the beginning of the
1980s (Industrial Organic Chemicals, 1999).
Currently there are three commercial routes to produce
cyclohexanol. The route to produce over 90% of western
European and the US cyclohexanol is based on the hydrogenation of benzene to cyclohexane and its subsequent oxidation by air to cyclohexanol=cyclohexanone. This process
suAers from several disadvantages. Besides the high consumption of hydrogen for the hydrogenation step and the associated high energy demands of the process, the oxidizing
step has the disadvantage of producing multiple by-products.
The main disadvantage of the oxidizer is the risk with respect to its operational safety. Since cyclohexane has to be

Corresponding author. Process Systems Engineering, Institut fur

Verfahrenstechnik, Otto-von-Guericke-University Magdeburg, UniversitDatsplatz 2, D-39106 Magdeburg, Germany. Tel.: +49-391-671-8704;
fax: +49-391-6711245.
E-mail address: kai.sundmacher@vst.uni-magdeburg.de
(K. Sundmacher).

mixed with air, there is a zone with an explosive mixture

within the reactor. This has resulted in an explosion of an
oxidizer in Flixborough, England in 1974 with several fatalities and the complete destruction of the plant (Industrial
Organic Chemicals, 1999).
An alternative still being used to a smaller extent in western Europe and the US is the hydrogenation of phenol. The
attractiveness of this process is directly coupled to the availability and price of phenol in comparison to benzene. Also
this process suAers from the high hydrogen consumption for
the hydrogenation step.
The third process currently in use by Asahi Chemical Co.
also starts with benzene which is hydrogenated to cyclohexene. This saves one-third of the input hydrogen normally
necessary for the conversion to cyclohexane. Cyclohexene is
then hydrated to cyclohexanol using a strongly hydrophilic
zeolite catalyst (H-ZSM 5, high Si=Al ratio) which avoids
the formation of signi1cant amounts of by-products (Mitsui, Osamu, Fukuoka, & Yohei, 1986). This process also
overcomes the operational safety problems associated when
mixing air with the organic reactant by entering the necessary hydroxyl group in the form of water. Asahi is currently operating plants in the 10,000 100,000 ton=yr range
using this technology. The process consists of a slurry reactor with a subsequent decanter and a distillation column.
Water and cyclohexene are fed to the reactor together with

0009-2509/02/$ - see front matter ? 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 2 ) 0 0 0 2 3 - 4

1512

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

Cyclohexane
Decanter
Water

OH

+ H 2O

Catalytic
Section

Cyclohexene/Cyclohexane

Cyclohexanol
Fig. 1. Flowsheet of the proposed reactive distillation column.

very 1ne catalyst particles ( 1 m). The resulting slurry is

separated in the decanter leading to an organic phase and an
aqueous phase. The catalyst particles are recovered quantitatively in the aqueous phase which is recycled back to the
slurry reactor.
The organic phase is composed of cyclohexanol as the
reaction product, unreacted cyclohexene as well as benzene
and cyclohexane which are impurities coming from the preceding benzene hydrogenation step. Due to the very close

boiling points of benzene (80:10 C), cyclohexene (82:98 C)

and cyclohexane (80:74 C), they are di2cult to separate

by conventional distillation (Industrial Organic Chemicals,
1999). Cyclohexanol, on the other hand, has a signi1cantly

higher boiling point of 161:1 C at normal pressure and is

therefore easily separated from the rest of the mixture in a
distillation column. This rest is then partly recycled back to
the slurry reactor.
Taking into account that the cyclohexene hydration is
slightly exothermic and is equilibrium limited it is presumably well suited to be carried out in a reactive distillation
column. This reactive distillation column would replace the
slurry reactor, the decanter and the distillation column in the
conventional process. The proposed novel process is illustrated in Fig. 1.
From a more fundamental perspective, this system is
also of major interest due to the fact that cyclohexene
and water have a very limited mutual miscibility. Only
little research has been done on reacting systems with
simultaneous distillation and liquid-phase splitting. Most

recent papers dealing with this subject were written on

the butyl acetate esteri1cation system and only mentioned
phase-splitting behaviour as a side phenomenon (Venimadhavan, Malone, & Doherty, 1999; Zhicai, Xianbao,
& Jing, 1998; LDoning, Horst, & HoAman, 2000). Westerberg, Lee, and Hauan (2000) gave a good survey over the
possible combinations of many phenomena including the
three involved in this case, but they did not deal in detail
distillation with the occurrence of liquid-phase splitting in
reactive distillation. Gumus and Ciric (1997) speci1cally
tried to simulate such a system. Their focus was on the
simultaneous reaction=distillation=phase-splitting behaviour
because its prediction is computation time intensive so that
it is ideally suited to show the e2ciency of a new numerical
algorithm. Recently, Qi, Kolah, and Sundmacher (2002)
have started to systematically investigate reactive distillation with liquid-phase splitting considering model reaction
systems as well as real reaction systems.
In this paper, the in%uence of the reaction kinetics and the
phase equilibria on the reactive distillation process has been
studied by both, model simulations and experimental work.
Based on these investigations, novel processes are proposed
to produce cyclohexanol by hydration of cyclohexene, or
to separate cyclohexene=cyclohexane mixtures by reactive
distillation.
2. Residue curve maps of the nonreactive mixture
As a 1rst step towards the design of a reactive distillation
process, the nonreactive vapourliquid equilibria were studied by means of residue curve maps for the ternary system
cyclohexene=water=cyclohexanol.
2.1. Experimental
A residue curve describes what happens to the composition of the liquid residue in an open batch vessel as more and
more liquid is evaporated. From any starting point within the
composition space of a given system, the concentrations will
change towards the highest boiler as more and more lighter
boiling components are evaporated. Consequently, the boiling temperature in the batch still will increase. A residue
curve map is a compilation of such residue curves with different starting points (usually near the lightest boiler). Since
such a system can be easily simulated and is also easy to set
up experimentally, residue curve maps are very often used
as a tool not only to predict the potential products of reactive and nonreactive distillation columns but in addition,
they can also be directly used to experimentally validate
physicochemical models for reactive distillation processes.
The experimental set-up used in this work (Fig. 2) is a
0:5 l glass batch vessel which is stirred at 600 rpm with
a glass propeller stirrer and heated by an oil-1lled heating
mantle to the boiling point. The stirring speed was adjusted
to assure good mixing and very 1ne droplets during the

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

M
GC
GC

H D'
H'

H D''

H ''

1513

used see Qi et al. (2002). For the explanation of the symbols used in Fig. 3 please refer to Table 1. As can be seen,
the experimental data do not agree very well with the simulated residue curves. Also, there are signi1cant deviations
between the simulated azeotropic points and the corresponding literature data.
To understand why there are such substantial deviations,
one has to recall that the system investigated here is known
to undergo phase splitting. This was also observed in the
experiments, but was not considered in the simulated residue
curves shown in Fig. 3.
2.3. Liquidliquid equilibria (LLE)

Fig. 2. Experimental setup for the measurements of phase equilibria with

and without chemical reaction.

measurements in order to avoid any possible mass transfer

limitation. The vapour is condensed by a distillation bridge
mounted on the vessel and is collected in a decanter that allows to measure the volumes of the two liquid phases. Alternatively to the distillation bridge, a total re%ux cooler can be
attached to the top of the vessel. The distillation bridge and
re%ux cooler are necessary to prevent the resulting vapour
from forming explosive mixtures in the exhaust system.
Since liquid-phase splitting was expected, a method had
to be developed to determine the molar holdups of the two
phases, H
and H

, within the batch vessel. Only with the
knowledge of these holdups and their compositions, the average liquid-phase composition can be calculated. For the
determination of the holdups, a mass-balance based approach was applied. For this purpose, the initial amounts of
all three components were noted. As the batch experiment
went on, the holdups and the compositions of the two phases
in the decanter were measured. This allowed to calculate the
amounts of the substances left within the vessel by means of
mass balances. The compositions of the two liquid phases
within the batch vessel were directly measured.
Analysis of the samples drawn from the batch and the decanter was done with a gas chromatograph (GC, HP 6890,
HP Innowax column 30 m; 250 m diameter) equipped with
a TCD and an FID. On account of the high diAerence in
boiling points, a GC temperature program was applied start
ing at 50 C for 3 min and then raising the temperature to

170 C at a heating rate of 30 C=min. This temperature was

then held for 3 min to clean the GC column. The chemicals used were cyclohexene ( 99%) and cyclohexanol
( 99%), both from Merck, and deionized water.
2.2. Vapourliquid equilibria (VLE)
First, residue curves were simulated using the VLE model
published by Doherty and Perkins (1978). The UNIFAC
group contribution method was used to predict the liquid
phase activity coe2cients. For the interaction parameters

To take this eAect into account, additional measurements

and more detailed simulations were carried out. Again the
UNIFAC method was used to estimate the activity coe2cients. The predicted binodal curves and liquidliquid tie
lines are shown in Fig. 4. For comparison, the experimental
data as well as a literature data point representing the solubility of water in cyclohexanol were inserted into the diagram.
The agreement between UNIFAC-based predictions and the
experimental data is satisfactory on a qualitative basis. On
the quantitative side, however, some discrepancies have to
be noticed. The predicted solubility of water in pure cyclohexene (xWater =0:019) deviates signi1cantly from the experimentally observed solubility (xWater 0:005). On the other
hand, the solubility of water in pure cyclohexanol is higher
than predicted. These deviations between UNIFAC-based
calculations and experimental results are signi1cant in their
size, which is due to the fact that the UNIFAC group contribution model does not rely on any data measured directly at
the special substances considered here. However, the model
gives correct qualitative results, which should be a reasonable basis for the prediction of phase splitting under conditions of reactive distillation, too.
The scattering of the experimental data towards the
cyclohexanol corner in Fig. 4 is due to a tendency of
water=cyclohexanol mixtures to form very small and relatively stable droplets due to their small diAerence in densities ( ol = 0:94 kg=l; H2 O = 1:00 kg=l). To reach phase
equilibrium quickly, the mixtures were agitated strongly.
Since even a small droplet of water in the cyclohexanol
phase can signi1cantly change the measured water solubility, some scattering of the experimental data always occurs.
2.4. Vapourliquidliquid equilibria (VLLE)
From the results reported in Section 2.3, one can conclude that the system cyclohexene=water=cyclohexanol
shows a strongly nonideal mixing behaviour in the liquid
phase which leads to an extremely broad miscibility gap.
Therefore, a VLLE calculation has to be implemented into
the residue curve simulations. This is outlined in the following. The component mass balances for the considered

1514

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

Water
100 C
1
97.8 C
0.9
Azeotrope 1
96.42 C

Distillation
Boundary

0.8
0.7
0.6
0.5

Azeotrope 2
59.75 C

0.4
70.8 C

0.3
0.2
0.1
0
0
0.1
Cyclohexanol
161.1 C

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9
1
Cyclohexene
82.9 C

Fig. 3. Residue curve map for nonreactive vapourliquid equilibrium system with the experimental data and the literature azeotropes (p = 105 Pa).
Table 1
Legends of symbols and curves for all ternary diagrams in this work

Legend of
symbols

Open symbols
a Gmehling,

Meaning of
symbols

Legend of
curves

Meaning of
curves

Stable node
Unstable node
Saddle point
Literature dataa

--
------

Residue curve
Distillation boundary
Binodal curve
Chemical equilibrium curve

Experimental data
(this work)
Menke, Kranfczyk, and Fisher (1994); Industrial Organic Chemicals (1999).

batch distillation are given by

d xi
= xi yi
d

(1)

with xi as the average liquid-phase mole fraction and yi

as the vapour-phase mole fraction, d = (V=H ) dt as the
dimensionless time, V as the vapour %ow rate, and H as the
total molar liquid holdup in the still. Eq. (1) is subject to
the initial conditions
xi ( = 0) = xi; 0 :

(2)

The mole fractions in the vapour phase have to satisfy the

relations
xi

i (x
; T )pisat (T ) xi



i (x

; T )pisat (T )
=
:
(3)
P
P
In Eq. (3), the activity coe2cients of the two liquid phases,

i and 

i are dependent on the corresponding liquid-phase
yi =

compositions expressed in terms of the vectors of mole fractions, x
and x

, in the respective phase and on the temperature T: P and pisat are the total pressure of the system and
the saturation pressure of component i at the boiling temperature, respectively. The equality between the two right
parts of Eq. (3) is based on the phase equilibrium condition
between the two liquid phases, i.e.
xi

i (x
; T ) = xi



i (x

; T ):

(4)

The ratio of the molar organic phase holdup (H
) to the total

molar liquid holdup (H
+ H

) is de1ned as
=

H

H

:
+ H

(5)

Therefore, the average liquid mixture mole fractions are

given by
xi = xi
+ (1 )xi

:

(6)

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

1515

Water
100 C
1
0.9
0.8
0.7
x 10

_3

0.6
0.5

L-L Tie Lines

0.4
0.3
0.2
Binodal Curve at T=450 K

0.1

Binodal Curve at T=298 K

0
0
0.2
0.4
Cyclohexanol
161.1 C

0.6

0.8

1
Cyclohexene
82.9 C

Fig. 4. Phase diagram for the liquidliquid equilibrium at isothermal conditions.

The mole fractions in all three phases have to obey the

following summation equations:
NC


i=1

yi = 1;

NC

xi
= 1;

i=1

NC

xi

= 1:

(7ac)

i=1

From this set of equations a new set of residue curves were

simulated as shown in Fig. 5, where the experimental data
points and the reference data from the literature indicating
the azeotropic points are plotted, too. As can be seen, the
simulated liquid-phase compositions agree much better with
the measured data points than those which were predicted
by VLE only. But there still exists a discrepancy between
the predicted azeotropes and the corresponding literature
values. These diAerences can presumably be attributed to
the use of UNIFAC as the activity coe2cient model with its
drawbacks as mentioned before.
3. Residue curve maps of the reactive mixture
3.1. Chemical equilibrium
As stated before, the reaction of cyclohexene with water to cyclohexanol is signi1cantly limited by its chemical
equilibrium. When trying to predict the reaction equilibrium, some di2culties are encountered because the Gibbs
enthalpies of formation for the reaction components nearly

cancel each other out as can be seen from the data in

Table 2. As a consequence, the chemical equilibrium constant


0
SR G298:15;
l
= 5:6
(8)
Ka (298:15 K) = exp
R 298:15
is di2cult to 1x exactly due to the uncertainty of the standard
Gibbs enthalpy of reaction SR G 0 . However, the measurements of Panneman and Beenackers (1992) seem to con1rm
the Ka value in Eq. (8). The temperature dependence of the
equilibrium constant was estimated by assuming that the reaction enthalpy SR H 0 is independent on temperature in the
range of boiling temperatures which can be expected at ambient pressure. This allows the use of the following equation
given by Panneman and Beenackers (1992):


30;236
Ka (T ) = 2:37 105 exp
:
(9)
RT
As Qi et al. (2002) have shown, phase splitting has a strong
in%uence on the chemical equilibrium curve. As can be
seen in Fig. 6i, the equilibrium curve follows a unique line
within the region of liquidliquid phase splitting. This is
because only mixtures located on this unique tie line ful1ll both the chemical equilibrium condition and the VLLE
conditions.

1516

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

Water
100 C
1

97.8 C
Azeotrope 1
96.21 C

0.9

Distillation
Boundary

0.8

0.7

0.6

0.5

Azeotrope 2
58.84 C

0.4

70.8 C

0.3

0.2

0.1

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

Cyclohexanol
161.1 C

Cyclohexene
82.9 C

Fig. 5. Residue curve map for the nonreactive vapourliquidliquid system with the experimental data and the literature azeotropes (p = 105 Pa).
Table 2
Thermodynamic data for the system cyclohexene=water=cyclohexanol

Cyclohexene
Water
Cyclohexanol

0
a
Sf H298:15;
l ; kJ=mol

0
a
Sf S298:15;
l ; kJ=mol K

0
Sf G298:15;
l ; kJ=mol

37:82
285:83
352:00

214.60
69.95
203.87

101:803
306:686
412:784

0
SR H298:15;
l = 28:35 kJ=mol
a Lindstrom

0
SR G298:15;
l = 4:295 kJ=mol

and Mallard (2001).

3.2. Reaction kinetics

= kfphase (T )

To allow for the eAect of the reaction kinetics on the

reactive distillation process with phase splitting, the batch
still model is modi1ed taking into account that a reaction
can occur in both the liquid phases. In general, the chemical
reaction can be expressed by
cr


r=1

|r |Ar

kf

kb

cp

|p |Ap ;

(10)

p=1

where Ai represents the reacting species, r and p are indices

for the reactants and products, and i are the stoichiometric
coe2cients (i 0 for educts, i 0 for products). The
overall sum of stoichiometric coe2cients is T ; cr and cp
are the total number of reactants and products, respectively.
The reaction rate in each liquid phase is expressed as

cp
cr


1
| |
r phase = kfphase (T ) ar|r |
ap p
Ka
r=1

p=1

1
aene aH2 O
aol
Ka


(11)

with kfphase as the temperature-dependent rate constant of

the forward reaction in the considered liquid phase. Due to
the fact that the liquid phase activities ai in the two liquid
phases are equal at liquidliquid equilibrium conditions, in
Eq. (11), the reaction rates in the two liquid phases can diAer
in case of diAerent rate constants kfphase , only. These rate
constants can be diAerent due to diAerent catalyst activities
in the two liquid phases, e.g. by solvent eAects, or=and due
to diAerent catalyst holdups as a result of the fact that the
catalyst itself is distributed between the two liquid phases.
The temperature dependency of kfphase is described by the
Arrhenius equation



EAphase 1
1
phase
phase

kf = kf; ref exp

;
(12)
R
T
Tref
where EA stands for the activation energy in the considered
liquid phase.

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

Water
1

Water
1

Water
1

0.9

0.9

0.9

0.8

0.8

(g)

500 (fast)

0.7

0.6

0.5

0.5

0.5

0.4

0.4

0.4

0.3

0.3

0.3

0.2

0.2

0.2

0.1

0.1

0.1

0.3

0.4

0.5

0.6

0.7

0.8

0.9 1
0
0.1 0.2
Cyclohexene Cyclohexanol

0.05 (moderate)

0.4

0.5

0.6

0.7

0.8

0
0
0.1 0.2
0.9 1
Cyclohexene Cyclohexanol

Water
1

0.9

0.9

0.8

0.8

(d)

0.7

0.5

0.5

0.4

0.4

0.4

0.3

0.3

0.3

0.2

0.2

0.2

0.1

0.1

0.1

0.5

0.6

0.7

0.8

0
0.9 1
0
0.1 0.2
Cyclohexene Cyclohexanol

0.3

0.4

0.5

0.6

0.7

0.8

0
0.9 1
0
0.1 0.2
Cyclohexene Cyclohexanol

Water
1

Water
1
0.9

0.9

0.8

0.8

(a)

0.7

0.5

0.5

0.4

0.4

0.4

0.3

0.3

0.3

0.2

0.2

0.2

0.1

0.1
0.5

0.6

0.7

0.8

0.9
1
Cyclohexene

0.3

0.4

0.5

0.6

0.7

0.9 1
Cyclohexene

0.8

0.9 1
Cyclohexene

(c)

0.1

0
0.1 0.2
Cyclohexanol

0 (none)

0.8

(f)

0.7

0.5

0.4

0.9 1
Cyclohexene

0.8

(b)

0.7

0.6

0.3

0.8

0.9

0.6

0
0.1 0.2
Cyclohexanol

0.7

Water
1

0.6

0.6

0.7

0.5

0.4

0.5

0.8

(e)

0.7

0.6

0.3

0.4

0.9

0.6

0
0.1 0.2
Cyclohexanol

0.3

Water
1

0.6

0 (none)

0.3

(i)

0.7

0.6

Water
1

Da (reaction rate watery phase)

0.8

(h)

0.7

0.6

0
0.1 0.2
Cyclohexanol

1517

0.3

0.4

0.5

0.6

0.7

0.8

0
0.9 1
0
0.1 0.2
Cyclohexene Cyclohexanol

0.3

0.4

0.5

0.6

0.7

500 (fast)

0.05 (moderate)
Da (reaction rate organic phase)

Fig. 6. Residue curve maps at diAerent DamkDohler numbers in the two liquid phases (p = 105 Pa).

3.3. Mass balances

By de1ning the phase DamkDohler number

If the occurrence of the chemical reaction in the two liquid

phases is incorporated into the component mass balances,
they take the following form:
d xi
H
= (xi yi ) + (i T xi )[r
+ (1 )r

]:
d
V

(13)

Da

phase

phase
H0 kf;
ref

V0

(16)

the mass balances, Eq. (14), can be rewritten as

d xi
H
= (xi yi ) + (i T xi )[kf
+ (1 )kf

]R (14)
d
V

d xi
H V0
= (xi yi ) +
(i T xi )
d
V H0


kf

kf







R:
+ (1 )Da


Da

kf; ref
kf; ref

with R as the dimensionless reaction rate:

aol
R = aene aH2 O
:
Ka

In this work, the heating policy V=V0 = H=H0 was applied

that holds the basic qualities of residue curves also for other
heating policies (Venimadhavan et al., 1994) and can also be

Combining Eq. (13) with the rate expression Eq. (11) yields

(15)

(17)

1518

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

realized experimentally. Then, the component mass balances

can be given in the following simpli1ed form:
d xi
= (xi yi ) + (i T xi )
d


kf

kf







R:
(18)
+ (1 )Da


Da

kf; ref
kf; ref
For the determination of the ratios of the rate constants,
phase
kfphase =kf;
ref , Eq. (12) was used. The parameter values were
adopted from Panneman and Beenackers (1992). The activation energies were assumed to be equal for the two phases,
i.e. EA
and EA

.
3.4. Discussion of simulated results
Using Eq. (18), a systematic simulation study was performed at diAerent DamkDohler numbers in the organic and
aqueous phase, Da
and Da

, respectively. These DamkDohler
numbers were set to 0 (no reaction), 0.05 (moderately fast
reaction), and 500 (very fast reaction approaching chemical equilibrium). The resulting nine residue curve maps are
shown in Fig. 6. For the symbols and curves used in these
diagrams please refer to Table 1.
To explain the diAerent eAects involved, 1rst the three
diagrams with equal Da numbers in the two liquid phases,
i.e. Da
= Da

, are discussed (Figs. 6a, e, and i). When the
reaction rates in both phases are zero, the nonreactive distillation behaviour is recovered as shown in Fig. 6a. In this
case the possible stable nodes are cyclohexanol and water,
the unstable node is the azeotrope between water and cyclohexene (Azeotrope 2). Moreover, pure cyclohexene and
the azeotrope between cyclohexanol and water (Azeotrope
1) are saddle points. When a moderately fast reaction occurs in both phases, as shown in Fig. 6e, cyclohexanol is no
longer a stable node because it is decomposed into cyclohexene and water. Therefore, the stable node moves out of
the cyclohexanol corner. Due to the appearance of a second
distillation boundary in the cyclohexene corner with the onset of reaction, now pure cyclohexene is an additional stable
node.
At very high Da numbers in both phases (Fig. 6i), the upper distillation boundary disappears. This is due to the fact
that at a critical DamkDohler number, i.e. Da
= Da

= 0:109
(see Qi et al., 2002), the saddle point which is responsible
for the existence of the distillation boundary coincides with
the stable node coming from the cyclohexanol corner and
they cancel each other. Moreover, pure water and pure cyclohexene remain stable nodes. As can be seen quite well
in this diagram the chemical equilibrium curve is a straight
line within the two-phase region.
Now, the cases (see Figs. 6b, c, d, and g) in which the
chemical reaction takes place only in one of the two liquid phases are discussed. One should be aware that these
cases are only theoretical extremes. In practice, very often an applied catalyst is not only present or active in one

single phase, but it has a certain activity in each phase. However, these theoretical extremes may help to understand the
principal behaviour of reactive distillation at conditions of
liquid-phase splitting. In the four involved diagrams, the reaction only takes place as long as the reactive phase exists.
Outside the two-phase region in the nonreactive phase, the
pure distillation behaviour is recovered. Inside the two-phase
region, the residue curves are qualitatively similar to those
that are obtained if the reaction takes place in both liquid
phases at the same Da numbers. But their quantitative properties such as the trajectories, locations of the singular points
and separatrices, are diAerent. Moreover, note that the aqueous phase region close to the water corner is almost invisible
in the ternary diagrams whereas the organic phase region is
quite large. Therefore, compared to the case that the reaction occurs in both liquid phases at the same Da, the residue
curve maps are qualitatively and quantitatively similar to
the diagram where the reaction occurs only in the organic
phase (compare Figs. 6b and c to Figs. 6e and i), but they
are quite diAerent when the chemical reaction occurs only
in the aqueous phase (compare Figs. 6d and g to Figs. 6e
and i). At very high reaction rates (Da
= 500, see Fig. 6g),
there is a distillation boundary partly coinciding with the
binodal curve at the organic side, which intersects with the
chemical equilibrium curve at a certain point. Below this
distillation boundary, pure cyclohexanol is the stable node,
the boundary pure water above is the stable node.
Of the two 1gures which show reaction with diAerent Da
numbers in the two liquid phases (Figs. 6f and h), the one
with a high reaction rate in the organic phase (Fig. 6f) is almost indistinguishable from the case of high reaction rates
in both phases (Fig. 6i). This is because the aqueous phase
region is so small that the system behaviour for reactive distillation behaviour diAers very little from that for the nonreactive conditions.
Fig. 6h shows an interesting type of behaviour. In the organic phase region below the binodal curve, the same behaviour as in the case with equal moderate Da numbers (Fig.
6e) is retained. In the two-phase region due to the very high
Da number in the aqueous phase, Da

= 500, all trajectories move straight towards the chemical equilibrium line.
For those trajectories which meet the chemical equilibrium
line within the two-phase region, the 1nal product will be
pure water as the stable node. For those trajectories which
cross the binodal curve before reaching the chemical equilibrium curve, the cyclohexanol-rich stable node de1nes the
1nal product composition. Between the attractive domains
of these two stable nodes, there is a separatrix.
4. Conceptual design of continuous processes
The residue curve maps discussed in the previous section
can be used for the conceptual design of a continuous reactive distillation process for the production of cyclohexanol.
Due to the existence of a stable node near the cyclohexanol

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

1519

Cyclohexane
Water

Catalytic Section
Forward Reaction

Cyclohexene

(Da < 0.109)

Cyclohexene/
Cyclohexane

Catalytic Section
Back Reaction
(Da > 0.109)
Cyclohexanol

Fig. 7. Coupled process to the reactive separation of cyclohexene=cyclohexane mixtures.

corner at low Da
numbers, the operation at these reaction

rates in the organic phase is advisable because this allows
to overcome chemical equilibrium limitations. Especially,
one should be careful not to achieve Da
numbers above the
critical value 0.109.
Since pure cyclohexanol is not a stable node in any case
if the chemical reaction takes place in the organic phase, a
nonreactive stripping section in the column will be required.
Evidently, a hybrid column is necessary to achieve the process goals. At the top of the column nonreacted water and
cyclohexene will be found. To separate these two reactants
a simple decanter can be used on account of the very low
mutual solubilities.
Under industrial conditions, the hydrocarbon feed will
consist of cyclohexene=cyclohexane mixtures. However, the
principal reactive distillation column con1guration will still
work since cyclohexane will act as an inert component leaving the column at the top together with the non-reacted cyclohexene.
In a similar manner, the conceptual design of a cyclohexanol splitting column can be derived from the simulated
residue curves. For the lower column section one has to
choose a DamkDohler number above the critical value, i.e.
Da
0:109; so that there is no stable node near the cyclohexanol corner. The upper part of this splitting column will
be nonreactive to avoid any cyclohexanol in the distillate.
Again, a simple decanter will separate water and pure cyclohexene in the top product.
If one combines these two hybrid columns just mentioned,
a very e2cient process can be designed to reactively separate
cyclohexene and cyclohexane leading to very high purities
that are not easily achievable by conventional distillation.
Fig. 7 shows the %ow scheme of this process. This is another
example of a separation process based on two coupled reactive distillation columns as suggested by Stein, Kienle, and
Sundmacher (2000) for the separation of isobutene from C4
hydrocarbon mixtures.

5. Conclusions
A novel process for the production of cyclohexanol by
cyclohexene hydration in a hybrid reactive distillation column is suggested and analysed. Due to the very low mutual
solubility of the reactants water and cyclohexene, chemical
reaction and vapourliquid transfer phenomena in the column will be accompanied by liquid-phase splitting.
First simulations of the simultaneous occurrence of chemical reaction, distillation and phase splitting in a batch still,
and experimental investigations of the nonreactive phase behaviour have shown that liquid phase decomposition has a
substantial in%uence on the reactive distillation behaviour.
This has to be accounted for when designing countercurrent reactive distillation columns. For this purpose, residue
curve maps are used as an e2cient tool to determine the stable nodes whose corresponding mixtures can be expected as
column products. From the residue curve analysis, it turns
out that a hybrid column is needed in order to obtain pure
cyclohexanol as the bottom product. The same is true for a
column to split cyclohexanol back to the educts water and
cyclohexene. Most important, the ratio of the chemical reaction rate and the vaporisation rate, i.e. the DamkDohler number, has to be adjusted such that a critical value is not exceeded (Da
0:109 for cyclohexanol formation) or is exceeded (Da
0:109 for cyclohexanol splitting). This could
be achieved by adjustment the amount of a heterogeneous
catalyst which has to be installed on the reactive column
trays.
The liquid-phase splitting behaviour is advantageous as
an additional and simple separation mechanism that allows
to bypass the azeotropes within the considered reaction system. On the other hand, it remains to be seen whether the
desired DamkDohler numbers can be realised within a reactive distillation column. The reaction engineering challenge
here lies in the very low mutual solubilities of the two reactants that make it hard to achieve a good contact between

1520

F. Steyer et al. / Chemical Engineering Science 57 (2002) 15111520

them and the heterogeneous catalyst. But this contact will

be necessary to obtain reasonable reaction rates.
Depending on the catalyst used, its distribution between
the two liquid phases and its intrinsic activities within the
phases will vary signi1cantly. This will aAect the Da numbers in this system. Therefore, the focus of our future research activities will be on the experimental determination
of the reaction kinetics under well-de1ned conditions of
catalyst-liquid phase contact.

NC
ol
p
r
ref

number of components
cyclohexanol
product
reactant
reference state (point of lowest boiling temperature in the system)
organic phase
aqueous phase

References
Notation
ai
Ai
Da
EA
H
kf
kf; ref
Ka
pisat
P
r
R
t
T
V
xi
x
yi

liquid phase activity of species i

chemical species
DamkDohler number
activation energy, J=mol
molar liquid holdup, mol
rate constant for the forward reaction,
mol=(mol s)
rate constant at reference conditions,
mol=(mol s)
chemical equilibrium constant
saturation pressure of species i, Pa
total pressure, Pa
reaction rate, mol=(mol s)
universal gas constant, =8:314 J=(mol K)
time, s
temperature, K
vapour %ow rate, mol=s
average liquid phase mole fraction of component
i
vector of liquid mole fractions
vapour phase mole fraction of component i

Greek letters

i
i
T

R

relative molar organic phase holdup, mol=mol

activity coe2cient of component i
stoichiometric coe2cient of component i
mole change of reaction, here = 1
dimensionless time
dimensionless reaction rate

Indices
ene
i

cyclohexene
species

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