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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
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
Cyclohexane
Decanter
Water
OH
+ H 2O
Catalytic
Section
Cyclohexene/Cyclohexane
Cyclohexanol
Fig. 1. Flowsheet of the proposed reactive distillation column.
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)
1514
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).
(1)
(2)
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)
H
H
:
+ H
(5)
(6)
1515
Water
100 C
1
0.9
0.8
0.7
x 10
_3
0.6
0.5
0.4
0.3
0.2
Binodal Curve at T=450 K
0.1
0.6
0.8
1
Cyclohexene
82.9 C
yi = 1;
NC
xi = 1;
i=1
NC
xi = 1:
(7ac)
i=1
1516
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
= kfphase (T )
|r |Ar
kf
kb
cp
|p |Ap ;
(10)
p=1
cp
cr
1
| |
r phase = kfphase (T ) ar|r |
ap p
Ka
r=1
p=1
1
aene aH2 O
aol
Ka
(11)
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
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).
(13)
Da
phase
phase
H0 kf;
ref
V0
(16)
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
Combining Eq. (13) with the rate expression Eq. (11) yields
(15)
(17)
1518
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
1519
Cyclohexane
Water
Catalytic Section
Forward Reaction
Cyclohexene
Catalytic Section
Back Reaction
(Da > 0.109)
Cyclohexanol
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
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
Greek letters
i
i
T
R
Indices
ene
i
cyclohexene
species