Chinese Journal of Chemical Engineering 40 (2021) 96–105

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Chinese Journal of Chemical Engineering

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Full Length Article

Design of process and control scheme for cyclohexanol production from

cyclohexene using reactive distillation
Mingyuan Hu 1, Hui Tian 1,2,⇑
1
College of Chemistry and Chemical Engineering, Yantai University, Yantai 264005, China
2
Collaborative Innovation Center of Comprehensive Utilization of Light Hydrocarbon Resource, Yantai University, Yantai 264005, China

a r t i c l e i n f o a b s t r a c t

Article history: Cyclohexanol is a commonly used organic compound. Currently, the most promising industrial process
Received 22 July 2020 for synthesizing cyclohexanol, by cyclohexene hydration, suffers from a low conversion rate and difficult
Received in revised form 16 November 2020 separation. In this paper, a three-column process for catalytic distillation applicable in the hydration of
Accepted 28 November 2020
cyclohexene to cyclohexanol was established to solve these. Simulation with Aspen Plus shows that
Available online 7 January 2021
the process has good advantages, the conversion of cyclohexene reached 99.3%, and the product purity
was
99.2%. The stable operation of the distillation system requires a good control scheme. The design
Keywords:
of the control scheme is very important. However, at present, the reactive distillation process for cyclo-
Cyclohexene hydration
Catalytic distillation
hexene hydration is under investigation experimentally and by steady-state simulation. Therefore, three
Control schemes different plant-wide control schemes were established (CS1, CS2, CS3) and the position of temperature
Dynamic Simulation sensitive stage was selected by using sensitivity analysis method and singular value decomposition
method. The Tyreus-Luyben empirical tuning method was used to tune the controller parameters.
Finally, Aspen Dynamics simulation software was used to evaluate the performance of the three control
schemes. By introducing DF ± 20% and xENE ± 5%, comparison the changes in product purity and yield of
the three different control schemes. By comparison, we can see that the control scheme CS3 has the best
performance.
Ó 2021 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All
rights reserved.

1. Introduction mutual solubility of cyclohexene and water, and adopting catalytic

Cyclohexanol is a commonly used organic compound. Its pro-
duction method has been widely investigated by industries and
research groups worldwide. Currently, three main methods are
used: phenol hydrogenation [1–6], cyclohexane oxidation [7–10],
and cyclohexene hydration. Cyclohexene hydration offers obvious
advantages in terms of safety, product selectivity, and cost, becom-
ing the most promising method. Since the hydration reaction of
cyclohexene is limited by the equilibrium of the chemical reaction
and the mutual solubility between cyclohexene and water is extre-
mely low [11–15], there are many azeotropes between the system
components. At present, the cyclohexene hydration process still
has problems such as low conversion rate, slow reaction rate,
and difficulty in separation. After a long-term study, it was found
that adding a co-solvent to the reaction system to improve the
⇑ Corresponding author at: College of Chemistry and Chemical Engineering,
Yantai University, Yantai 264005, China.
E-mail address: tianhui@ytu.edu.cn (H. Tian).
distillation can well solve these problems.
In the process of reactive distillation, the reaction process coex-
ists with the gas–liquid mass transfer process. The two processes
influence each other and promote each other, so that this unit
operation can proceed smoothly [16–21]. The reaction distillation
technology to hydration of cyclohexene cyclohexanol has several
advantages, (1) Increase reaction conversion rate. The hydration
reaction of cyclohexene is a reversible reaction. Due to the exis-
tence of the distillation process, the reaction products are continu-
ously separated from the system, causing a positive shift in the
reaction equilibrium, improving the reaction conversion rate;
(2) The reaction temperature is easy to control. The temperature
of each stage in the reactive distillation is always the bubble point
of the mixture at that stage under system pressure. Therefore, the
reaction temperature can be controlled by adjusting the system
pressure. In addition, the reaction heat is consumed by the distilla-
tion process, the problem of flying temperature of the rectification
tower can also be effectively avoided. (3) Reduce system energy
consumption. The heat of cyclohexene hydration reaction can be
consumed by the distillation process.

https://doi.org/10.1016/j.cjche.2020.11.029
1004-9541/Ó 2021 The Chemical Industry and Engineering Society of China, and Chemical Industry Press Co., Ltd. All rights reserved.
 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105
The cyclohexene hydration process first developed by Asahi
Kasei Corporation of Japan has the disadvantages of slow reaction
rate and low equilibrium conversion rate, because the reaction is
limited by a chemical equilibrium and the mutual solubility
between cyclohexene and water is extremely low. US Patent
0018223A1 [22] found that adding isophorone to the reaction sys-
tem and using high silica zeolite ZSM-5 as a catalyst can improve
the yield of cyclohexanol. Under the same reaction conditions,
the final yield of the reaction without co-solvent was 12.0%, and
the final yield of the reaction added isophorone as co-solvent
was 24.3%. Isophorone as a co-solvent can improve the solubility
of cyclohexene in water. It hardly participates in the reaction dur-
ing the reaction, and has a large boiling point difference, which is
easy to separate and recover in the post-treatment process. It can
be used as a suitable cosolvent for cyclohexene hydration reaction.
In the industrial process, the stable operation of the reactive
distillation column requires a reliable control scheme. Since the
reactive distillation technology involves a unit that couples a
chemical reaction process with the distillation process. The design
of the control scheme for the reactive distillation process is very
complex, and there is no universal control method. It is necessary
to carry out detailed control system design according to the physic-
ochemical properties and reaction mechanism of different systems,
so that the reactive distillation system can be effectively con-
trolled. At present, the reactive distillation process for cyclohexene
hydration is under investigation experimentally and by steady-
state simulation. No literature has reported dynamic control of
the process toward the production of cyclohexanol. In the future,
the study of control schemes will definitely be the focus of cyclo-
hexene catalytic distillation hydration process.
Our team has undertaken many years of research on this
method. Based on previous research, a three-column catalytic dis-
tillation process for cyclohexene hydration for cyclohexanol pro-
duction is established here as a result. In view of the fact that
there are many azeotropes in the system, the product is difficult
to separate. The reactive distillation column used in this article
only has a rectification section and a reaction section, and an addi-
tional azeotropic distillation column is used to complete the unfin-
ished separation of the reactive distillation column. Then, the
dynamic control scheme of this process is studied. Based on the
analysis of system characteristics. We propose a feed-forward con-
trol structure to control the content of cyclohexene in the RD col-
umn, and this structure was similar to the R/F structure. After
analyzing the control performance, it can be seen that this control
scheme has good control performance.
2. Process Studied
2.1. Thermodynamic model
According to our previous research [23–25], the NRTL activity
coefficient model can describe the non-ideality of the liquid phase
in the vapor–liquid equilibrium and in the vapor–liquid–liquid
Table 1
Comparison of the calculated values and literature values [23–25] at 101.3 kPa
Component Literature values
T/°C
ENE 82.90
W 100.00
(ENE-W) 70.80
NOL 160.10
(NOL-W) 98.10
IP 215.20
(IP-W) 99.50
Note: ENE is cyclohexene. W is water. NOL is cyclohexanol. IP is isophorone.
97
phase equilibrium of the system. We compare the boiling point
of the pure material and the boiling temperature of the binary
azeotrope with the calculated values of NRTL, obtained at
101.3 kPa in Table 1. The absolute error for the temperature was
0.74 °C, and the maximum error was 0.003 mol, which indicated
that the parameters calculated by Aspen Plus were with adequate
accuracy. The binary interaction parameters at 101.325 kPa as
shown in Table 2. The ternary diagrams and the binary diagrams
has been given in the Supplementary Materials.
2.2. Kinetics model
The direct hydration of cyclohexene to cyclohexanol is a rever-
sible reaction, and the reaction equation is as follows:
ð1Þ
According to literature, the ion-exchange resin A-36wat catalyst
and the kinetic model rNOL for the direct hydration of cyclohexene
to cyclohexanol can be used to establish the following relationship:
rNOL ¼ kf aaq
ENE aH2 O  kb aNOL
aq aq
ð2Þ
where the reaction rate constant of the forward reaction [26]:


kf ¼ 54775:19exp 57894:54 ; and the reaction rate constant of the back-
RT


ward reaction kb ¼ 1:7327exp 16451:74
RT
. Where the units of kf and kb
are L(molming)1, and the unit of activation energy is Jmol1.
2.3. Description of the process
It is well known that the mutual solubility of cyclohexene and
water is extremely small, which is disadvantageous for the pro-
gress of the hydration reaction. We increased the mutual solubility
of cyclohexene and water by adding a cosolvent isophorone,
thereby increasing the conversion of the reaction. In a previous
study, our team established a process for the production of cyclo-
hexanol by adding the catalytic distillation process of cyclohexene
hydration reaction using the cosolvent isophorone [27]. In this
work, the three-column process was established based on the pre-
vious research.
Fig. 1 shows the workflow of the process. The process is include
a catalytic distillation column (RD), two purified distillation
column (PD1, PD2), and two phase separators (Decanter1, Decan-
ter2). The RD column includes two parts, a rectification section
and a reaction section, and the feed position is the stage 9 at the
top of the reaction section. The PD1 is an azeotropic distillation col-
umn. Its function is to separate the light component (cyclohexene
and water) from the heavy component (cyclohexanol and isophor-
one). The PD2 is used to separate the cyclohexanol product and iso-
phorone. We feed water into the Decanter1 to improve the liquid–
liquid phase separation effect. The liquid–liquid phase separation
effect of Decanter1 was better than the Decanter2, so the origanic
phase of Decanter2 was feed to Decant1 for further separation.
Calculated values
Molar composition T/°C Molar composition
— 82.88 —
— 100.02 —
(0.310, 0.690) 70.75 (0.318, 0.682)
— 160.84 —
(0.930, 0.070) 97.80 (0.927, 0.073)
— 215.23 —
(0.976, 0.024) 99.31 (0.974, 0.026)
98 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105

Table 2
Binary interaction parameters for the binary systems at 101.325 kPa

ENE(i)-WATER(j) WATER(i)-NOL(j) ENE(i)-NOL(j) ENE(i)-IPHO(j) WATER(i)-IPHO(j)

aij 2.9573 90.7028 6.3667 0.57152 4.5738
aji 8.2209 106.162 2.39487 0.12129 5.7044
bij 2317.72 4573.21 3079.413 696.0906 221.3692
bji 27.1069 4763.8 1085.47 55.4479 1463.178
aij 0.2 0.2 0.3 0.3 0.3

Fig. 1. The workflow of the process.

Table 3
The conversion rate of the cyclohexene hydration reaction is Specifications of the columns (RD column, PD1,PD2)
very low, and it is difficult to ensure the purity of the product Column RD PD1 PD2
and the conversion rate of the reaction using only one catalytic rec-
Column pressure/MPa 0.2 0.1 0.1
tification column. There will be two situations in the simulation. Pressure drop/kPa 25 25 20
First, when the product purity reaches the expected value, the Column diameters/m 0.2 0.37 0.31
reaction conversion rate is very low; second, if you want to ensure Number of stage 21 25 19
that the reaction has a higher conversion rate, the product purity is Distillation section stage 2–8 2–15 2–12
Reaction section stage 9–21 — —
difficult to reach the expected value. Both of these are things are
Stripping section stage 0 16–24 13–18
undesirable, so this article uses the RD column and PD1. RD col- Feed stage 9 16 13
umn does not have a stripping section, PD1 is an azeotropic distil- Holdups (reaction section)/cm3cm3 0.35 — —
lation column, used to complete the separation work that RD Reflux ratio 0.6 2 1.479
column did not complete. In this way, the concentration of cyclo- Condenser duty/kW — 102.9342 108.9900
Reboiler duty/kW 40.4369 147.8143 121.6485
hexene in the RD column can be ensured by adjusting the reflux
ratio of the organic phase in the RD column to ensure the conver-
5 min of liquid holdup when the vessel is 50% full, based on the
sion rate of the reaction. The PD1 is an azeotropic rectification col-
total liquid entering or leaving the vessel. For the reflux drum, this
umn, and the azeotrope is cyclohexene. The ratio of cyclohexene
is the sum of the liquid distillate and the reflux. For the column
and water in the PD1 can be controlled by adjusting the reflux ratio
base, it is the liquid entering the reboiler from the bottom tray.
of the organic phase, and the water and cyclohexene can be well
Assuming a length to diameter ratio of two, the diameters and
separated from the product and the co-solvent. The distillate pro-
lengths can be calculated:
duct of column PD2 was high-purity (
99.2% (mass)) cyclohexanol.
The bottom stream was nearly 100.0% (mass) isophorone cosol- pD2
vent. We fed it to the RD column and recycled it. The specifications V¼  ð2DÞ ð3Þ
4
of the columns are shown in Table 3.
Before the dynamic simulation. It is important to remember The equipment size as shown in Table 4.
that pumps and control valve install in the steady-state simulation,
and the additional information that must be provided is the phys- 3. Control Studied
ical sizes of the various pieces of equipment. The procedure for siz-
ing the distillation column shell (diameter and height) is by Aspen For decades, catalytic distillation has been used in industrial
Plus [31]. The sizes of the reflux drum and the column base, a com- applications, and many studies on the dynamic control of catalytic
monly used heuristic is to set these holdups such that there are distillation have mostly studied the control of product purity when
 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105
Table 4
Equipment size
Equipment name Size Equipment name Size
RD column diameter 0.20 m RD column base diameter 0.56
PD1 column diameter 0.37 m PD1 column base diameter 0.54
PD2 column diameter 0.31 m PD2 column base diameter 0.49
Decanter1 diameter 0.51 m PD2 reflux drum diameter 0.49
Decanter2 diameter 0.43 m
disturbance occurred [20,28]. In this work, we studied the yield
and purity control of the product when disturbance occurred
according to the characteristics of the system. Three control
schemes were proposed. We intended to design an effective
plant-wide control scheme for this system. It is expected that basic
information can consequently be provided for the industrial pro-
duction of cyclohexanol.
3.1. Control schemes
Distillation control systems characteristically include two levels
of focus [29]. The first-level focus is concerned with stabilization of
the basic operation of the column (we called this the inventory
control scheme) and the second-level focus addresses the separa-
tion taking place in the column (we called this the separation con-
trol scheme).
The first level is the more mundane aspect of any distillation
control system. It typically includes flow controls on the material
and energy streams, inventory controls on the reboiler and accu-
mulator, and pressure controls at the accumulator and/or base of
the column. Therefore, we call this the inventory control scheme.
In the catalytic distillation process of cyclohexene hydration to
cyclohexanol, there are 11 inventory control loops—8 liquid level
control loops (organic phase, aqueous phase liquid level control
in Decanter1; organic phase, aqueous phase liquid level control
in Decanter2; bottom level control in the RD column; bottom level
control in column PD1; bottom level control in column PD2;
reflux-drum liquid level control) and 3 pressure control loops
(RD column pressure, PD1 pressure, and PD2 pressure). The
arrangement of the inventory control loops was as follows. The liq-
uid level control was controlled by the valves of each outlet. The
RD column pressure was controlled by manipulating the flow rate
of the vapor distillate. The pressures of columns PD1 and PD2 were
controlled by condenser heat removal.
In addition, there were four fresh feed flow rate control loops in
the process to control the feed composition of the RD column. One
temperature control loop was used for maintaining the tempera-
ture of Decanter 1 at 35℃ by manipulating the feed temperature
of Decanter 1.
We intended to design an effective plant-wide control scheme
for this system. The next step was the design of the second level
focus, which was the separation control scheme. Our goal was to
achieve the expected product purity (
99.2%) when the system
faced a disturbance. This is not a simple task because there very
complex phase equilibria and very complex distillation flows are
involved.
As the first unit of the whole process, the stability of the RD col-
umn directly affects the downstream unit and affects the produc-
tion of cyclohexanol. Catalytic distillation is a complicated
process. The reaction and separation processes are carried out
simultaneously and interact with each other. The control of the
RD column is thus particularly important. Thus, we propose two
different control schemes for the RD column, as shown in Fig. 2
(a) and (b).
The CS1 structure control with a temperature on a tray in the
RD column was controlled by manipulating the reboiler heat input.
99
The organic phase reflux ratio was held constant, as shown in Fig. 2
(a). The CS2 structure control with a temperature on a tray in the
RD column was controlled by manipulating the reboiler heat input
m and organic phase reflux ratio, as shown in Fig. 2(b).
m The controls of columns PD1 and PD2 were the same in the con-
m trol scheme 1 (CS1) and control scheme 2 (CS2). The temperature
m of a tray of column PD1 was controlled by manipulating the reboi-
ler heat input, and the organic phase reflux ratio was held constant.
The temperature of a tray of column PD2 was controlled by manip-
ulating the reboiler heat input and the reflux rate was held con-
stant. The selection of the manipulated variables and
temperature control tray will be described in the next section.
3.2. Sensitivity analysis
For the control of the separation of the distillation column, first
of all, it is necessary to ensure that the purity of the product
reaches the expected specifications. In the industry, temperature
control with minimal lag is often used to ensure product quality.
If tray temperatures are to be used, the criterion is to select the
best tray on which the temperature should be held constant. The
position of the temperature controller is determined by the tradi-
tional open-loop sensitivity analysis [30,31]. A very small change
(0.1% of the design value) is made in one of the manipulated vari-
ables (e.g., reflux flow rate). The resulting changes in the tempera-
tures of all the trays are examined to see which tray experiences
the largest change in the temperature. Dividing the change in the
tray temperature by the change in the manipulated variable gives
the open-loop steady-state gain between the temperature on that
tray and each manipulated variable. The tray with the largest tem-
perature change is the most ‘‘sensitive” and is selected to be con-
trolled. A large gain indicates that the temperature on that tray
can be effectively controlled by the corresponding manipulated
variable. A small gain indicates that valve saturation can easily
occur and the operability region could be limited.
The open-loop steady-state gain of the three columns is shown
in Fig. 3. Fig. 3(a) shows that the gain of the 17 trays was the largest
when the reboiler heat input changed, which indicates that the
temperature of the 17th tray can be effectively controlled by the
reboiler heat input. Similarly, in Fig. 3(b) and (c), it can be seen that
column PD1 manipulates the reboiler heat input to control the
temperature of the 9th tray, and column PD2 manipulates the
reboiler heat input to control the 17th tray.
This completes the selection of the manipulated variable and
temperature control tray for the CS1. For the selection of the
manipulated variable and temperature control tray of the RD col-
umn in the CS2, we need to use another method for further analy-
sis. The RD column in the CS2 has a double-ended control, which
not only considers the loop sensitivity problem, but also balances
the interactions between two controllers. We use singular value
decomposition analysis for further analysis [32].
A 20  2 gain matrix K was formed using our calculated RD col-
umn reboiler heat input and open-loop steady state gain between
the organic phase reflux ratio and the tray temperature. This
matrix was decomposed using the ‘‘svd” function in Matlab into
three matrices: K = UrVT (U is a 20  2 matrix, r is a 2  2 matrix,
V is a 2  2 matrix). The two U vectors were plotted against the
tray number, as shown in Fig. 3(d). The tray or trays with the lar-
gest magnitudes of U indicated locations in the column that could
be controlled most effectively. In the figure, U1 is associated with
the reboiler heat input. U2 is associated with the organic phase
reflux ratio. The SVD results are similar to the sensitivity results.
This suggests that stage 7 can be controlled by the organic reflux
ratio and stage 17 by the reboiler heat input.
The r matrix is a 2  2 diagonal matrix whose elements are
‘‘singular values.” The ratio of the larger to the smaller is the
100 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105
Fig. 2. (a) Control scheme1 (CS1); (b) Control scheme 2 (CS2). Reflux ratio controller;
controller; Multiplier.
‘‘condition number,” which can be used to assess the feasibility of
dual-temperature control. The singular values of the steady-state
gain matrix were r1 = 22.4786 and r2 = 17.9476, which gives a
condition number CN = r1/r2 = 1.25. This indicates that the two
temperatures were fairly independent, so a dual-temperature con-
trol scheme should be feasible, at least from the steady-state point
of view.
3.3. Controller tuning
Temperature control has significant inherent dynamic lags and
dead times relative to the level and flow controllers. These should
be incorporated in the control loop. This is necessary so that we
can use realistic controller tuning constants and do not predict
dynamic performance that is better than the performance achiev-
Level controller; pressure controller; Temperature Controller; Flow
able in a real plant installation. Tuning the controller during
dynamic control is very important and time consuming. It is neces-
sary to adjust the PID parameters in turn according to the degree of
response of each control loop [33].
The tray temperature controllers were tuned by inserting a
1 min dead time in the loop and using the relay-feedback test to
determine the ultimate gain (KU) and ultimate frequency (PU).
Then, the Tyreus–Luyben empirical tuning method was applied
to determine the gain (KC) and integration time (s1 ). Table 5 gives
the tuning constants. The tuning constants of the flow, pressure,
and liquid level controllers are empirical values [31], i.e.. The flow
control gain Kc = 0.5, the integration time s1 = 0.3 min. The
pressure control gain Kc = 20, the integration time s1 = 12 min.
The liquid level controller only needs proportional control, so the
gain of the controller was Kc = 2, and the integration time was
 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105 101

Fig. 3. (a) RD column open loop sensitivity analysis; (b) PD1 open loop sensitivity analysis; (c) PD2 open loop sensitivity analysis; (d) RD column SVD analysis.

Table 5 4.1. Performance of CS1

Temperature controller tuning constants

Control scheme Controlled variable Gain KC Integral time s1 The CS1 control scheme is shown in Fig. 2(a): the organic phase
reflux ratio was held at a steady-state value. The controller tuning
CS1 Decanter temp. 5.97 15.40
parameters are shown in Table 5. After 5 h of system operation, the
RD-17th tray temp. 7.31 7.92
PD1-9th tray temp. 2.87 660 disturbances of ±20% to the feed flow rate (DF ± 20%) and ±5% to
PD2-17th tray temp. 32.81 1980 the composition of cyclohexene (xF;ENE 5%) were added. The
CS2 Decanter temp. 3.70 60 dynamic response of the purity of cyclohexanol product was
RD-7th tray temp. 78.05 924
observed. Fig. 4(a) and (b) shows that the CS1 structure could
RD-17th tray temp. 4.77 396
PD1-9th tray temp. 2.19 396 quickly recover the purity of cyclohexanol to the expected value
PD2-17th tray temp. 34.06 264 when facing the disturbance in the feed flow rate. However, as
CS3 Decanter temp. 3.70 60 shown Fig. 5(a), at the change of xF;ENE 5%, although the tempera-
RD-17th tray temp. 7.29 528 ture of the three columns could quickly return to the set point, the
PD1-9th tray temp. 2.26 264
PD2-17th tray temp. 35.14 264
purity of the final product cyclohexanol was not satisfactory. The
results show that this simple control scheme can better handle
the DF ± 20% [as shown Fig. 4(a) and (b)] and xF;ENE þ5% [as shown
Fig. 5(b)] disturbances. Product purity does not reach the expected
set to be very large (s1 = 9999 min) to cancel the integral action.
value at xF;ENE 5% disturbance.
The valve is half open in steady state.

4.2. Performance of CS2

The CS2 control scheme is shown in Fig. 2(b). The temperature

4. Performance Evaluation
We wanted to determine how the control scheme proposed
above responds when facing disturbances. We observed whether
the purity of the product was close to the expected purity by intro-
ducing a disturbance of ±20% (DF ± 20%) to the feed flow and ± 5%
(xF;ENE 5%) to the composition of cyclohexene. The feed flow rate
and the composition of cyclohexene were all for a mixed feed F.
of the 7th and 17th trays of the RD column was controlled by
manipulating the organic phase reflux ratio and the reboiler heat
input. The controller tuning parameters are shown in Table 5. After
5 h of system operation, the disturbances of DF ± 20% and xF;ENE 5%
were added. The dynamic response of the purity of the cyclohex-
anol product was observed. This control scheme could better han-
dle the disturbances DF + 20% and xF;ENE þ5%, as shown in Figs. 4(b)
and 5(b). However, the scheme did not handle the changes of
102 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105

Fig. 4. (a) Cyclohexanol product purity change when DF  20%; (b) cyclohexanol product purity change when DF + 20%.

Fig. 5. (a) Cyclohexanol product purity change when xF,ENE  5%; (b) cyclohexanol product purity change when xF;ENE þ5%.

xF;ENE 5% and DF  20% well, as shown in Fig. 4(a) and 5 (a), since
the product purity did not reach the expected value.
5. Alternative CS3
5.1. Established the alternative CS3
phase of the 8, 12, 16, and 20 trays of the RD column on the yield of
cyclohexanol. As shown in Fig. 6, the yield of cyclohexanol
increases first and then decreases as the content of cyclohexene
increases. From the chemical kinetic point of view, increase the
content of cyclohexene in the aqueous phase is bound to increase
the yield of cyclohexanol. However, why does cyclohexanol pro-
duction decrease when the composition of cyclohexene is too

It can be seen from the above results that there are deficiencies
in the CS1 and CS2. Therefore, we conducted a more in-depth anal-
ysis of the system based on the thermodynamic model and the
chemical kinetics model. We hope to provide a better control
scheme for this process.
It is well-known that the mutual solubility between cyclohex-
ene and water is extremely small. Using the Aspen Plus process
simulation software, we analyzed the composition of the tray of
RD column and found that even if the cosolvent isophorone was
added, it would still forms a vapor–liquid-liquid–solid reaction
system in the RD column. The catalyst we used was a strongly
acidic cation exchange resin A-36wat. On the external surface,
where a hydrophilic sulfonic acid group was present, the catalysts
were always surrounded by the aqueous phase during the reaction.
Thus, it could be considered that the cyclohexene hydration reac-
tion occurs in the aqueous phase. Thus, the content of cyclohexene
in the aqueous phase can effect the conversion of the reaction,
By changing the reflux ratio of the organic phase, we observed
the effect of different compositions of cyclohexene of the aqueous Fig. 6. Effect of different mass fractions of cyclohexene on cyclohexanol yield.
 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105 103

Fig. 7. Alternative control scheme 3 (CS3).

high? This is because the catalytic distillation process is a complex know that the top of the RD column is distillate the azeotrope of
process, and the reaction process is carried out simultaneously cyclohexene and water. When the composition of the cyclohexene
with the separation process. In the steady state simulation, we in the RD column is too high, a large amount of azeotrope of

Fig. 8. (a) Cyclohexanol yield change when DF  20%; (b) cyclohexanol yield change when DF + 20%; (c) cyclohexanol yield change when xF,ENE  5%; (d) cyclohexanol yield
change when xF;ENE þ5%.
104 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105
cyclohexene and water is distillate from the top of the RD column.
This results in a decrease in the content of cyclohexene and water
in the reaction section. Therefore, the production of cyclohexanol
will decrease.
Through the above analysis, we can know the content of cyclo-
hexene in the system is the important factor. The RD column is the
first unit of the process. Fluctuations in the composition of cyclo-
hexene in the RD column not only affect downstream devices,
but also affect the conversion of the system. Control of the cyclo-
hexene content in the RD column is particularly important. In
the steady-state simulation, we ensured that the content of cyclo-
hexene in the RD column was optimal by adjusting the reflux ratio
of the organic phase. Therefore, when the content of the cyclohex-
ene feed changed, if there was no change in the reflux ratio of the
organic phase, it must affect the composition of cyclohexene in the
RD column, thereby affecting the purity and yield of the product.
Therefore, we propose a feed-forward control scheme to control
the content of cyclohexene in the RD column. This structure was
similar to the R/F structure, but with one difference: this structure
was controlled by the ratio of the organic phase reflux ratio (RR) to
the feed molar ratio of water to cyclohexene (F WRR =F ENE
). If FW/FENE
increased (decreased), the PID controller would result in the
organic phase reflux ratio increasing (decreasing), and conse-
quently the cyclohexene content in the RD column will increase
(decrease). The control scheme 3 (CS3) was established as shown
in Fig. 7. The temperature of stage 17 was controlled by manipulat-
ing the reboiler heat input. The tuning parameters are shown in
Table 5. This structure was essentially the same as CS1 when
FW/FENE was fixed.
5.2. Performance of the CS3
After 5 h of system operation, the disturbances of ±20%
(DF ± 20%) for the feed flow rate and ± 5% (xF;ENE 5%) for the com-
position of cyclohexene were added. The dynamic response of the
yield of cyclohexanol was observed. As shown in Fig. 8(a) and (b),
for DF + 20%, the CS1 control scheme showed a higher stable yield
than the CS3. For DF  20%, the CS3 involved a faster settling time.
In the case of a change in the feed flow rate, the seemingly identical
CS1 and CS3 control schemes showed this difference because,
when the feed flow rate changes, the change of the cyclohexene
recycling stream from Decanter 1 causes fluctuations in the flow
rate of the cyclohexene feed, which causes fluctuations in the FW/
FENE in feed F, thereby causes the CS1 and CS3 to show different
dynamic responses. As shown in Fig. 8(a) and (b), the stable purity
and stable yield of the CS1 and CS3 control schemes were similar
when the feed flow rate changed. Thus, we can consider their per-
formances to be similar.
One of the purposes of our CS3 was to ensure that cyclohexanol
production is maintained at a high level when the content of cyclo-
hexene changes in the feed. As can be seen in Fig. 8(c) and (d), the
CS3 maintained a higher cyclohexanol production at a disturbance
of xF;ENE 5% compared to that offered by the first two control
schemes.
Table 6
Comparison of performance of three control schemes
Disturbance Purity
Stable purity Settling time Fluctuating size
DF20% CS1 = CS3 > CS2 CS2 > CS1 > CS3 CS2 > CS1 > CS3
DF+20% CS3 > CS1 > CS2 CS3 > CS1 > CS2 CS3 > CS1 > CS2
xF,ENE5% CS3 > CS2 > CS1 CS1 = CS3 > CS2 CS1 > CS2 > CS3
xF,ENE+5% CS1  CS3 > CS2 CS2 > CS1 > CS3 CS2 > CS1 > CS3
Note: The purity of cyclohexanol after system stabilization is called stable purity; the production of cyclohexanol after system stabilization is called stable yield.
In order to compare the first two control schemes with this one,
we also observed the dynamic response of cyclohexanol product
purity on introducing the same perturbation. It can be seen in
Figs. 4 and 5 that this control scheme could still better control
the purity of the product.
6. Conclusions
We applied the catalytic distillation technology to the cyclohex-
ene hydration process to produce cyclohexanol. A steady-state
model for the production of cyclohexanol by catalytic distillation
and hydration of cyclohexene was established. Optimization was
achieved using the Aspen Plus process simulation software. The
conversion reached 99.3%, which is much higher than that given
by the Asahi Kasei process, and the purity of the cyclohexanol pro-
duct was
99.2%.
We established three different control schemes through differ-
ent methods, hoping to better control the purity and yield of the
products. The performances of the three control schemes were
compared by investigating the dynamic response of system to
changes in the feed flow and the feed content of cyclohexene.
The detailed comparison of the three structures in terms of the
steady-state deviation indicated that the product specifications
were not met. We also compared the three structures in terms of
stable purity, stable yield, settling time, and fluctuation size. As
shown in Table 6.
For DF20%, CS2 could not achieve the expected product purity
(
99.2%), while CS1 and CS3 showed the same stable purity and
stable yield, but because CS3 showed a shorter settling time and
less fluctuation, we considered that the performance of the CS3
structure was slightly better than CS1 for DF  20%. For
DF + 20%, the three structural products could achieve the desired
product purity (
99.2%), but the stable yield of CS1 was slightly
larger than that of CS3 and much larger than that of CS2, so we
considered that, for DF + 20%, the performance of the CS1 structure
was better. For xF;ENE 5%, it was obvious that CS1 and CS2 could
not give the expected product purity, and the stable output of
CS3 was higher than that of CS1 and CS2. For xF;ENE þ5%, CS3 per-
formed better than CS1 and CS2 in terms of product yield control.
All three structures could achieve the desired product purity, but
CS3 showed less fluctuation. When the content of cyclohexene
was changed, CS3 showed better control performance than CS1
and CS2 in terms of product purity and yield.
On comparison, CS3 exhibited better control performance in
terms of both yield and product purity. In this paper, the dynamic
control scheme of catalyzed hydration of cyclohexene coupled
with distillation toward production of cyclohexanol is discussed
to provide essential data and a theoretical basis for the industrial-
ization of the cyclohexanol production process. However, specific
considerations should be kept in mind for the industrialization of
the process, taking into account economic and performance
parameters. For example, when the product purity is expected to
be
99.0%, the CS1 structure shows better control performance
and is also simpler and faster.
Yield Performance comparison
Stable yield Settling time Fluctuating size
CS3  CS1 > CS2 CS2 > CS1 > CS3 CS2 > CS1 > CS3 CS3 > CS1 > CS2
CS1 > CS3 > CS2 CS1 = CS3 > CS1 CS2 > CS1 > CS3 CS1 > CS3 > CS2
CS > CS > CS1 CS2 > CS1 > CS3 CS2 > CS1 > CS3 CS3 > CS2 > CS1
CS3 > CS1 > CS2 CS3  CS1  CS2 CS3 > CS1 > CS2 CS3 > CS1 > CS2
 M. Hu, H. Tian / Chinese Journal of Chemical Engineering 40 (2021) 96–105
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgements
The authors acknowledge the Natural Science Foundation of
Shandong Province, China (ZR2017QB006), the Focus on Research
and Development Plan in Yantai city (2018XSCC038), and the Qing-
chuang Science and Technology Plan Innovation Team of Shandong
Province (2019KJC012).
Supplementary Material
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.cjche.2020.11.029.
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