Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

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Chemical Engineering & Processing: Process Intensification

journal homepage: www.elsevier.com/locate/cep

Design and analysis of an intensified column with side reactor configuration

for ethylene glycol production from ethylene oxide
Lianghui Dinga,*, Jihai Tangb, Xu Qiaob, Congrong Liua, Yunbo Xuea, Gongde Wua
a
School of Environmental Engineering, Nanjing Institute of Technology, Nanjing 211167, PR China
b
College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: The side reactor concept (SRC), comprising a non-reactive column coupled with side reactors, is proposed for the
Reactive distillation synthesis of ethylene glycol (EG) by ethylene oxide (EO) hydration. Parallel isothermal continuous stirred tank
Side reactor reactors are employed and the combinations of the reactors and the column are cautiously examined. A pre-
Reaction temperature liminary analysis of the operating conditions for the reaction and separation and the detailed SRC configurations
Pressure
(such as the side stream rate, side stream location) are performed to generate the suggested values or ranges for
Ethylene glycol
their further optimization. The decisive variables are subsequently optimized by a sequential design procedure.
The significant effects of the key decision variables on the trade-off between the reaction cost and the separation
cost are well investigated. The reactor–separation unit, configured with a total liquid withdrawn and recycled
back to the column stage below, demonstrates better system performance. Furthermore, the reaction at elevated
temperature (150 °C) conductive for reaction and the separation occurring at the distillation temperature range
of 106∼204 °C (124 kPa) gives out improved economic performance. Flexibility in the operating conditions in
SRC makes it a competitive alternative to the RD process for EG production.

1. Introduction
Ethylene glycol (EG) is an important raw material for industrial
applications. EG is widely used as engine coolants, antifreezes, and
precursors for the manufacture of polyester fibers, resins and cosmetics
[1]. Currently, the dominant industrial method for EG preparation is
the non-catalytic hydration of ethylene oxide (EO), which proceeds
with diethylene glycol (DEG) and tri-ethylene glycol (TEG) formed as
the major byproducts [1–3]. The catalyst-free reactions generally pro-
ceed at elevated temperatures (e.g., 423–493 K) [4–6]. To achieve high
conversion and high selectivity, a large excess of water (e.g., 10–25 M
ratio of water/EO) is generally used in the commercial process [1,6,7].
This increases the capital investment for the purification operations
(e.g., remove excess water) [4–7]. Alternative reactive distillation-
based processes, typically using a nearly stoichiometric feed ratio, have
been explored to improve the yield for EG and simplify the whole
process [8,9].
Reactive distillation (RD), combining the reaction and separation
into a single unit, is a good example of process intensification [10].
Parker [8], Ciric and Gu [11], in their pioneering work, extended the
RD technique to the synthesis of EG from EO, while Gao and others
[12,13] also applied it to the separating process for EG production via
other routes based on syngas. In the reactive column producing EG from
EO, a large excess of water to EO in the reactive trays (because of the
high volatility of EO) and the timely removal of produced EG from the
reaction zone will contribute to the suppression of the side reaction of
EG and EO. Large recycling of fresh water is thus avoided and less
pieces of equipment are needed [8,11,14–17].
In order to achieve the fullest potential of RD in EG preparation,
studies on the process synthesis and optimization have been conducted
to generate the optimum designs. For example, Ciric and Gu [11] pre-
sented the mixed-integer nonlinear programming (MINLP) formulations
and solved the optimization problem using the generalized benders
decomposition algorithm. Further, Okasinski and Doherty [14] suc-
cessfully extended the fixed point design method to the EG system via
RD. Cardoso et al. [15] proposed a simulated annealing-based algo-
rithm for the optimization of MINLP problems. Salcedo et al. [16]
employed the SIMOP method to improve the optimization efficiency of
stochastic methods. Huang et al. [17] focused on the reinforcement of
the internal heat integration between the reaction and separation

Abbreviations: DEG, diethylene glycol; EO, ethylene oxide; EG, ethylene glycol; RD, reactive distillation; SRC, reactive distillation process based on side reactor
concept
⁎
Corresponding author.
E-mail address: lianghuiding@163.com (L. Ding).

https://doi.org/10.1016/j.cep.2019.107744
Received 10 June 2019; Received in revised form 19 October 2019; Accepted 18 November 2019
0255-2701/ © 2019 Elsevier B.V. All rights reserved.

Please cite this article as: Lianghui Ding, et al., Chemical Engineering & Processing: Process Intensification,
https://doi.org/10.1016/j.cep.2019.107744
L. Ding, et al.
Nomenclature
Ac Condensers area, m2
Ar Reboiler area, m2
DC Column diameter, m
DR Reactor diameter, m
k Reaction rate constant, kmol/(m3∙s)
operations and considered the effect of utilization of reaction heat on
energy efficiency. Additionally, some researchers focus on mathematic
models [18,19], multiple steady states [18,20], dynamic behavior and
control strategies [19,21,22].
Despite the advantages of RD in EG production and the rapid pro-
gress in the optimization-based techniques, the inherent design chal-
lenges in the optimal selection of operating conditions still remain,
which are resulted from the limited freedoms in the RD columns. For
example, lower column pressure (e.g., 1 atm) facilitates the distillation,
but also leads to lower reaction temperature and thus requires a large
holdup [14,22]. Whereas, higher column pressure (e.g., 15 atm) pro-
duces a more realistic reaction rate [14,22] but requires more costly
high-grade energy at the column base (∼320 °C). Mismatch between
the reaction temperature and the separation temperature may make the
RD less effective, as shown by Kaymak and Luyben [23].
An alternative is to couple a non-reactive column connected with
one or more external side reactors that is the so-called side reactor
configuration (SRC) [23–32]. In such a manner, the reaction and the
separation are conducted in different apparatuses, and thus the condi-
tions for the reaction and the separation operations can be set in-
dependently [25–27]. Meanwhile, the reaction holdup within the re-
actor is not limited to such an extent [28,29]. The SRC technique has
been successfully applied in systems such as production of ethylbenzene
[27], methyl acetate [28], TAME [30], and butyl acetate [31], etc.,
displaying its attractive competitiveness to RD.
In the current work, an alternative process for EG preparation based
on the side reactor concept is presented. The combinations of the re-
actors and the column are cautiously investigated. A preliminary ana-
lysis of key design variables, such as the operating conditions for the
reaction and separation, the configuration parameters (e.g., side stream
location, side stream rate), are conducted, so as to generate their ef-
fective values or ranges for further optimization.
2. Process studied
The hydration of ethylene oxide (EO) is a typical consecutive exo-
thermic reaction system. While in the proposed intensified SRC process,
only the preparation of EG and DEG are considered and they can be
expressed in Eqs. (1) and (2). The side reaction of TEG production from
DEG and EO is ignored due to the observed excessive low concentration
of DEG in the reaction zone with little possibility to react with EO
[8,11].
Main reaction: C2H4O (EO)+H2O→C2H6O2 (EG) (1)
Side reaction: C2H4O (EO) + C2H6O2 (EG)→C4H10O3 (DEG) (2)
The reaction rates can be written as
r1 = k1 xEO x H2O (3)
r2 = k2 xEO xEG (4)
where k1, k2 are the respective reaction rate constants. The specific re-
action kinetics data, taken from the work of Ciric and Gu [11], are listed
in Table 1. Clearly, a relatively high selectivity can be obtained by
maintaining a high concentration of water and a low concentration of
EG in the reaction system. While this can be achieved in an integrated
reaction and separation process, owing to the obvious differences in the
2
Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx
LC Column length, m
LR Reactor height, m
TAC Total annual cost, $/yr
x Liquid mole fraction
z Liquid mole fraction in the reactor
φ Fractional conversion of water
ω Rate-constants ratio
boiling points between the pure components. The boiling points of the
components in the reaction system at atmospheric pressure are ranked,
in ascending order, as follows: EO (10.5 °C) < H2O (100 °C) < EG
(197.3 °C) < DEG (244.8 °C).
In the current work, the intensified SRC technique will be adopted
in the EG reaction system. Several parallel isothermal continuous
stirred tank reactors are to be connected to a non-reactive column. In
the side reactors, the reactor feeds are withdrawn from the distillation
column and the reactor effluents are returned back to the same column
for separation. In the column, due to the distillation, water would move
towards the top, while the produced heavier EG will flow down to the
bottoms. This will contribute to suppress the side reaction of EO with
EG in the reactors, thereby improving the reaction selectivity. However,
the fullest advantage in SRC cannot be simply achieved with an arbi-
trary combination of the reactors and the column. The objective of this
work is to investigate the design of the SRC process for EG preparation
and to discover the effect of the operating conditions and the config-
urations on the system performance and economics.
3. Process specifications and design procedure
The design objective is to convert 99.9 % of EO in the side reactors
and keep the molar purity of EG in the bottoms at 0.95. The feed rates
of water and EO in stoichiometric ratio are set to 26.3 and 27.53 kmol/
h, respectively. Fresh water is fed on the top stage in the column, while
EO is split and distributed to the external reactors. Cooling water is
used as the cooling utility and steam is used as a heating media. The
design variables involve the operating conditions of the reactors and the
column (pressure, temperature), the number of reactors, the side stream
rates and locations, the number of separation stages, etc. The optimi-
zation objective is to minimize the total annual cost (TAC), which in-
cludes the energy cost and capital cost for the reaction operation and
that for the separation operation. The detail calculation of TAC is in-
cluded in in the subsequent section.
To reduce the complexity of the design, a preliminary analysis of the
key design variables, such as the operating conditions for the reactors
and column and the configuration parameters (e.g., side stream rate,
side stream location) are conducted, aiming to generate effective values
or ranges for their further optimization. On the basis, a sequential grid-
search procedure is followed to determine the ultimate optimum values.
The effect of important variables on the economics and the trade-off
between the reaction cost and the separation cost would also be de-
scribed in detail. Fig. 1 illustrates the overall design procedure of the
SRC process for EG preparation.
Process simulation and design are carried out based on the Aspen
Plus platform. To account for the non-ideal vapor liquid equilibrium
(VLE), the Wilson model is used to calculate the activity coefficients.
RadFrac model is used to represent the column and the RStoic module is
employed to calculate the reactors. In the RStoic model, the fractional
Table 1
Reaction Data.
Reaction k (kmol·m−3·s-1) ΔH(kJ·mol−1)
Main reaction (1) 3.15 × 1012exp[-9547/T] −80.0
Side reaction (2) 6.3 × 1012exp[-9547/T] −13.1
L. Ding, et al. Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

220 °C, to allow condensation with cooling water of 25 °C and boiling

using normal steam. This creates a pressure interval between 38 and
191 kPa (area 1).

4.2. Evaluation of SRC configurations

An initial simulation is performed to evaluate the effect of the side

stream flow rates in addition to their locations on product purity, in
order to obtain possible effective SRC configurations. For the process
involving a single reactor, the impacts of the side stream flow rate and
the return stage on the product purity are presented in Fig. 3.
In the pre-simulation, the total number of stages in the column,
counted from top to bottom, is fixed at 7 (including the bottom reboiler)
and the liquid withdrawn stage is set to 3. In addition, the column
pressure is 101 kPa, the reaction temperature is 160 °C, the reboiler
duty is 12 MW and the distributed ratios of EO to the reactors are 0.34,
0.33 and 0.33 from top to bottom. Therefore, different side stream re-
turn stages would constitute different SRC configurations, such as the
co-current SRC configuration and the counter-current SRC configura-
tion, etc., as presented by Baur [28].
As illustrated in Fig. 3, the counter-current SRC configuration (a), in
which the recycling stage is set at the upper stage of the withdrawn, is
not found to be beneficial for high selectivity in general. This is because
the remixing of products into the internal flows in the intermediate
stages would then promote the side reaction in the reactors, resulting in
poor selectivity and low product purity.
In addition, the co-current side reactor configurations (b)∼(d) in
Fig. 3 appear to be more attractive than the counter-current config-
urations. For the co-current side reactor configuration, when the re-
cycling rates are restricted to a comparable low range (i.e., < 700
kmol/h), there is a rapid rise in product purity with the increasing
reactor throughput due to increasing content of water, while increasing
bypassing stages (b→d) in the recycling loop has an ignorable effect on
the improvement of the process performance. However, for comparable
large side flow rates (i.e. > 700 kmol/h), more bypassing stages (b→d)
result in lower product purity. This occurs because for the process with
the fixed column stages, the descending return stage of the reactor ef-
fluent would lead to a decrease in the stripping stages, resulting in in-
Fig. 1. Flowchart for SRC design for EG synthesis. sufficient separation and poor system performance. Consequently, it is
preferable to reduce the number of intermediate stages when recycling
conversions of EO in the main reaction and side reaction, denoted by φ1 flow rates are large. Therefore, the limiting case of the re-
and φ2, are provided with Fortran subroutines based on their re- actor–separation unit (e), wherein the total liquid leaving the trap-out
lationship with the rate-constants ratio (Eq. (5)) [32]. The required stage is rerouted through an external reactor and fed back to the stage
reactive holdup can be determined by the desired extent of reaction below, is found to be more advantageous for product purity and se-
with the reaction kinetics. lectivity.
For the specific reactor–separation unit (e), the flow rate of the side
φ1 ωz H2O − zEG stream hits the maximum limit and large holdup will be required.
=
φ2 zEG (5) However, Fig. 4 indicates that for a fixed desired product purity of 0.95,

where z H2O and zEG represent the liquid mole fractions of water and EG
within the reactor, respectively.

4. Preliminary analysis of design variables

4.1. Decision of operation conditions ranges

Fig. 2 presents the vapor pressure of water and EG and the deli-
neated area of the distillation operation (area marked with 1) and the
reaction operation (area 2) in the EG process via SRC described in this
study. Water and EG are chosen due to their nearly pure compositions
in the top condensation and bottom products [11,15,22].
A common reaction temperature range of 150−200 °C is considered
due to the acceptable reaction rate [6,8], while the pressure for the
reaction must be held sufficient high that allow a liquid operation.
These limits are shown in Fig. 2 by the Reaction area 2. For the dis- Fig. 2. Vapor pressures of water, EG and the delineated areas of the distillation
tillation operation, the temperature interval is limited between 75 and operation (area 1) and the reaction operation (area 2) in the SRC process.

3
L. Ding, et al.
Fig. 3. Effect of side stream flow rate and side stream return stage on the
product purity.
Fig. 4. Effect of side stream flow rate on the heat duties of the reboiler and the
condenser at a product purity of 0.95 in SRC configurations (b) and (e).
an increase in the side stream rate will result in a rapid reduction in the
energy consumption in the separator, thus minimum energy require-
ment is found in configuration (e). Therefore, the reactor-separation
unit will be used in the later design.
In practice, more than one side reactors may be required to enhance
the system performance. To determine the relative locations of the
external reactors, the influence of the number of stages between ad-
jacent trap-out stages in the column on the product purity is in-
vestigated. Note that the top reactor will be linked to the upmost stage
and it accepts the total condensation from the condenser, which con-
tains nearly pure water. The results revealed that, the increase in this
number has a minor effect on the combined performance at the constant
number of stripping stages and reboiler duty, as illustrated in Fig. 5.
Therefore, the number of intermediate stages between the adjacent
trap-out stages is fixed at 1 in the subsequent process optimization.
Fig. 6 depicts a typical SRC flowsheet that employs three side re-
actors for EG synthesis based on the effective reactor–separation unit
configuration. In the figure, R1, R2, and R3 represent the external side
reactors from top to bottom.
5. Process optimization and economic analysis
5.1. TAC calculation and optimization procedure
Based on the suggested reactor–separation SRC configuration (fea-
tured by a total liquid trap-out and recycling back to the stage below)
and the operation windows, the decisive variables are to be further
optimized by minimizing the TAC value. Here, the decisive variables
include the reaction temperature, column pressure, number of stripping
stages, number of reactors, and distributed ratios of EO to the reactors.
The TAC value consists of the reaction cost and separation cost, as
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Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx
given in Table 2. Further, the detailed reaction cost includes the reactor
investment and the energy cost for heating the external reactors. The
separation cost includes the capital investments of the column, reboiler
and condenser, as well as the energy cost for separation. Evaluation of
the equipment cost follows the procedure of Douglas [33] and a M&S
index of 1536.5, published in the Chemical Engineering magazine, is
applied in the calculation. Furthermore, the following costs for heating
and cooling are taken into account: $14.50/1000 kg for the high-pres-
sure steam, $10.50/1000 kg for the medium-pressure steam and $0.02/
m3 for cooling water, which is modified after one prepared by Busche
and is recommended to be used for early estimates [34]. The equipment
sizing, cost basis and TAC calculation are summarized in Table 2. A
payback period of 3 years and an annual operating time of 7200 h are
assumed in the calculation.
A sequential optimization procedure, where the variables are
changed one at a time, is adopted in the process optimization. Fig. 7
shows the optimization procedure for the SRC process for EG synthesis.
Fig. 8 shows how the distributed ratio of EO to the reactors affects the
TAC value at the constant product purity of 0.95 for the given case.
That is the column pressure is 101 kPa, the reaction temperature is
160 °C, the number of reactors is 3, the number of stripping stages is 4,
the number of stages between adjacent trap-out stages is 1. It can be
found that, there exist the optimal values of the distributed ratios of EO
matching the minimum TAC. Hence, in the following design, the dis-
tributed ratios of EO will be optimized under any combinations of the
reactors and column. Note that the number of stages between adjacent
trap-out stages has been suggested to be 1.
5.2. Results and discussion
5.2.1. Effect of reaction temperature
Fig. 9(a), (b) show the effect of reaction temperature on TAC, and
the trade-off between reaction cost and separation cost under the given
process conditions, respectively. Detailed optimization results are listed
in Table S1 of the supplementary material.
A high reaction temperature will increase the reaction rates and
thus reduce the reactor cost. However, increasing the reaction tem-
perature, indicating more external energy supply to the reactors, leads
to a drastic rise in the energy cost and thus the overall cost for reaction,
as presented in Fig. 9(b) and (c). On the other hand, as the reaction
temperature increases, the energy cost in the separation operation is
obviously decreased (Fig. 9(d)). This is because the external energy
added to the reactors will be eventually transferred to the column and
hence favors the separation. Therefore, an increase in the reaction
temperature leads to lower reboiler duty, decreasing the energy cost for
separation and even the overall separation cost. Consequently, as can be
seen from Fig. 9(b), there is a trade-off between the reaction cost and
Fig. 5. Effect of number of stages between adjacent trap-out stages on the
product purity for reactor-separation unit configuration (e).
L. Ding, et al. Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

results in a higher overall separation cost, as shown in Fig. 10(b).

On the other hand, for the reaction unit, higher column pressure
means higher feed temperature and thus less energy supplied to the
reactors. As a result, there is a rapid decrease in the reaction cost,
displayed in Fig. 10(b) and (c). Therefore, the TAC value initially de-
creases with the increasing column pressure. However, at some point,
the increasing separation cost becomes more dominant and the TAC
begins to increase. As revealed in Fig. 10(a), for the given process
conditions that is the reaction temperature is 150 °C, the number of
stripping stages is 4, and the number of reactors is 3, the column
pressure of 124 kPa corresponds to the minimum TAC.

5.2.3. Effect of number of stripping stages

Fig. 6. A typical schematic of the SRC process employing three reactors for EG
production based on reactor-separation configuration.
the separation cost with the varying reaction temperature. Under the
given reaction temperature range, since the increase of reaction cost
plays more important role in TAC than the decrease of the separation
cost, hence, the TAC value increases with the increasing reaction tem-
perature. The final reaction temperature is suggested to be 150 °C.
5.2.2. Effect of column pressure
Generally, higher distillation pressure results in higher column
temperature and more expensive heat source would be required.
Moreover, higher column pressure in the EG system causes the increase
in the reboiler duty, which can be seen in Table S2 of the supplemen-
tary material. These contribute to the increase in the energy cost for
separation, as revealed in Fig. 10(d). However, the competing effects
owing to the increase in column pressure, i.e., the reductions in the
condenser area due to higher condensing temperature and the column
diameter because of increased vapor density, give rise to the decrease in
capital investment for separation (Fig. 10(d)). Since the effect of in-
creased the energy cost is significantly larger than the effect of a de-
crease in the capital cost for the separation unit, higher column pressure
A higher number of stripping stages increases the column height and
results in a higher column investment. However, the energy cost and
the corresponding capital investment in the heat exchangers can be
reduced, as seen in Fig. 11(d). The result is that there is a minimum in
the separation cost.
Furthermore, an initial increase in the number of stripping stages,
benefit for the separation operation, helps to strengthen the reaction
performance. Thus, there is reduction in the reaction cost firstly.
However, beyond a certain point, the reaction cost reaches a nearly
constant value because of the weak impact of the excess number of
stripping stages on the separation performance (Fig. 11(c)). Overall, the
TAC value initially decreases due to the obvious reduction in the energy
cost but then turns to increase due to the continuous increase in the
column investment (Fig. 11(a)). Table S3 of the supplementary material
summaries the detailed information for the equipment sizing and eco-
nomics. For the given process conditions that is the reaction tempera-
ture is 150 °C, the column pressure is 124 kPa, and the number of re-
actors is 3, the optimum number of stripping stages is determined to be
4.
5.2.4. Effect of number of side reactors
Undoubtedly, an increase in the number of reactors would increase
the reactor investment and the energy cost due to the additional reactor
heating requirements (Fig. 12(c)). In contrast, as shown in Fig. 12(b),
the separation cost shows a decreasing tendency with the increasing
number of reactors. This is attributed to the fact that the improved
reaction performance while using more reactors is more favorable for
the system performance and thus less energy will be needed for

Table 2
Equipment Sizing and Economics Basis.
Column diameter, DC (m) Aspen tray sizing

Length, LC (m) 0.61 m spacing plus 20 % extra length

Condensers area, Ac(m2) Heat-transfer coefficient = 3000 W/(K·m2)
Reboiler area, Ar (m2) Heat-transfer coefficient = 1600 W/(K·m2)
ΔT = 20 °C
Reactor diameter, DR (m); LR/DR = 2
reactor height, LR (m)
Energy cost MP Steam= $10.50/1000 kg (temperature level: 147∼ 185 °C)
HP steam=$14.50/1000 kg (temperature level:186∼240 °C)
Cooling water= $0.02/m3
Capital costs($)
Column shell 30100DC1.066LC0.802
Column trays 1441 DC1.55LC
condenser 13779 Ac 0.65
reboiler 19152 A r0.65
reactors 31043 DR1.066LR0.802 (150∼160 °C)
32932 DR1.066LR0.802 (161∼190 °C)
33876 DR1.066LR0.802 (191∼200 °C)
TAC TAC= reaction cost+ separation cost
reactor cost
reaction cost= + energy cost for reactors
payback period
(column +reboiler+condenser) cost
Separation cost= + energy cost for separation
payback period
payback period = 3 years

5
L. Ding, et al.
Fig. 7. Optimization procedure for SRC process for EG synethsis.
Fig. 8. Effect of distributed ratios of EO to reactor R1 and R3 on the TAC value.
separation. Consequently, there is a drastic decrease in the energy cost
in the separation unit and hence the corresponding investments in the
heat exchangers. This leads to sharp drop in TAC when the number of
6
Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx
reactors is increased from 1 to 3 (Fig. 12(a)). While further increase of
the number of reactors leads to a relatively small reduction in TAC and
this is because the increase of the reaction cost turns to get more im-
portant.
For the specified process parameters, the SRC with 5 reactors ap-
pears to be more advantageous in the economics. However, the SRC
with the moderate number of side reactors of 3 is ultimately re-
commended due to its simplicity and marginally higher TAC than that
of the SRC with 5 reactors.
5.3. Optimization results of SRC
Table 3 details the generated final optimization results for the
proposed SRC process for EG preparation. The profiles of liquid com-
positions and temperature in the generated optimal SRC design are
shown in Fig. 13(a), (b), respectively. As shown in Table 3, in the
generated optimal SRC design, the temperatures within the reactors are
set to 150 °C under sufficient pressures of 467, 461, 455 kPa, respec-
tively, from top to bottom. The optimal pressure for distillation is
124 kPa, with a temperature range of 106∼204 °C (Fig. 13(b)).
As shown in Fig. 13(a), the mole fraction of water in the liquid
phase in the column section coupled with side reactors is close to unity
(EO is considerably more volatile than water). Excessive high surplus of
L. Ding, et al. Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

Fig. 9. Effect of reaction temperature on (a) TAC, (b) the trade-off between reaction cost and separation cost, (c) the detailed reaction cost and (d) the detailed
separation cost. (The column pressure is 124 kPa, the number of stripping stages is 4 and the number of reactors is 3).

Fig. 10. Effect of column pressure on (a) TAC, (b) the trade-off between reaction cost and separation cost, (c) the detailed reaction cost and (d) the detailed
separation cost. (The reaction temperature is 150 °C, the number of stripping stages is 4 and the number of reactors is 3).

7
L. Ding, et al. Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

Fig. 11. Effect of number of stripping stages on (a) TAC, (b) the trade-off between reaction cost and separation cost, (c) the detailed reaction cost and (d) the detailed
separation cost. (The reaction temperature is 150 °C, the column pressure is 124 kPa and the number of reactors is 3).

Fig. 12. Effect of number of reactors on (a) TAC, (b) the trade-off between reaction cost and separation cost, (c) the detailed reaction cost and (d) the detailed
separation cost. (The reaction temperature is 150 °C, the column pressure is 124 kPa, and the number of stripping stages is 4).

8
L. Ding, et al. Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx

Table 3
Design Results for the SRC Process and Comparisons with RD processes.
Parameter SRC RD-I RD-II

Column pressure/kpa 124 101.3 1520

Reaction temperature/ oC 150,150,150 ∼100 ∼200
Reaction pressure/kPa 467, 461, 455 101.3 1520
Feeding location of water 1 (top stage) 1 (top stage) 1 (top stage)
Feeding location of EO R1,R2,R3 1-6 6
Number of reactors/reactive stages 3 6 6
Total number of stages (excluding condenser, including reboiler) 9 11 11
Locations of reactors/ reactive stages condensation→R1→stage 1 1-6 1-6
stage 2→R2→stage 3
stage 4→R2→stage 5
Feeding ratio of EO 0.40,0.36, 0.24 0.29,0.01,0.18, 0,0,0,
0.17,0.17,0.18 0,0,1
Reaction holdup/m3 0.444,0.411,0.368 0.012,1.467,0.371, 0.100,0.100,0.100,
0.448,0.482,0.551 0.100,0.100,0.100
Bottom molar purity of EG 0.95 0.95 0.948
Condenser duty/MW 9.10 7.31 7.4
Reboiler duty/MW 6.82 6.7 6.9
Reactor heating duty/MW 0.58,0.56,0.57 — —
Reboiler temperature/°C 204 197 320

SRC process through the manipulation of the composition profiles in the

Fig. 13. (a) Liquid compositions and (b) temperature profiles in the column in
the optimized SRC design.
water to EO in the liquid withdrawn will greatly help the suppression of
the reaction of EO with EG in the reactors. Similar simulation results of
the composition profiles have also been presented in a RD column,
reported by Ciric and Gu [11], Cardoso et al. [15], and Al-Arfaj and
Luyben [22].
5.4. Comparison between RD and SRC process for EG synthesis
For the preparation of EG from EO, an excessive surplus of water to
EO and a relatively satisfactory selectivity can be obtained in a RD or
column, even though the fresh oxide and water are fed in a nearly 1:1
ratio. In the process intensification, the large consumption of fresh
water is thus avoided, and the need for the apparatus to separate and
evaporate the extra water can hence be eliminated in comparison to the
conventional serial process. By using the SRC concept, the distinct ad-
vantages of improved process efficiency, simplified process units and
reduced consumption of raw materials can be achieved. Comparisons
between the obtained SRC design and the representative RD schemes
are also performed in this work.
One of the most fundamental differences between RD and SRC is the
selection of operating conditions. In the SRC approach, the reaction
temperature can be set at any expected value with a proper heat ex-
changer. The pressure in a normal column is generally adjusted to get
the highest possibility to use the available inexpensive heat source with
a moderate distillation temperature range. However, this is not the case
in a RD column. RD is only feasible when the distillation condition
overlaps the reaction condition. The limited overlapping window of the
operating conditions may increase the difficulties in balancing the
trade-off between the reaction and the separation for the systems with a
mismatch between the reaction temperature and separation tempera-
ture. Table 3 also presents two representative RD schemes in the
synthesis of EG, namely RD-I, RD-II, which were retrieved from the
works of Ciric and Gu [11] and Al-Arfaj and Luyben [22], respectively.
In these three processes, the feed rates are kept the same with the nearly
identical product purity.
For the RD-I flowsheet, the operating pressure is designated as at-
mosphere pressure, which gives a proper distillation temperature range
where available cooling water and steam are used as the heat mediums
[11]. However, a lower reaction temperature of about 100 °C can also
be obtained and larger holdup and excessive tray height are thus re-
quired [14,22]. This may increase the difficulty in the development and
operation of the process in practice. To overcome the reaction space
limitation, Okasinski and Doherty [14] proposed the operation of a RD
column at 1520 kPa (15 atm) with the reaction temperature up to about
200 °C, which was later used by Cardoso, et al. [15], and Al-Arfaj and
Luyben [22]. Similarly, Parker [8] described an EG reactive distillation
column which operated under pressures between 14 and 34 atm. A
more realistic holdup of 0.1 m3 was used in the RD-II process [22].
However, high column temperature would at the same time bring about
an excessive reboiler temperature (320 °C), a large amount of high-
grade energy would be required.
While the problem in the process conditions mismatch has been
solved in the proposed SRC design, in which the reaction temperature

9
L. Ding, et al.
Table 4
Economical Comparisons between the Designed SRC and RD-II Processes.
Parameter SRC RD-II
4
Cooling water/(10 ton/yr) 563.87 458.43
Steam for reboiler/(104ton/yr) 9.61 17.78
Steam for reactors/(104ton/yr) 2.15 —
Reaction cost/(104$/yr)
Energy cost for reaction 22.60 — ment of the catalyst deactivation or replacement. However, little in-
Reactor cost 2.34 — formation is currently available for the commercial operation of SRC.
Total 24.94 — Development of the appropriate design tools is necessary to speed up
Separation cost/(104$/yr)
Energy cost for separation 150.59 267.03
Column cost 8.64 7.68
Condenser cost 5.04 2.68
Reboiler cost 20.91 20.99
Total 185.19 298.38
TAC/(104$/yr) 210.12 298.38
and distillation temperature have been adjusted at their optimal states.
In such a manner, additional expenditures on the capital investment for
the reactors and energy consumption in the reaction operation
(1.71 MW) will simultaneously be generated. However, Table 4 shows
that the SRC design still demonstrates its distinct economic superiority
due to its obviously less requirement for the energy consuming in the
reboiler, as compared with the RD-II process. Despite the close reboiler
duties in the RD-II and SRC processes (Table 3), excessively higher
reboiler temperature (320 °C) in the RD-II process would lead to ob-
vious increase in the utilization of steam due to its decreasing latent
heat at the elevated condensing temperature. It should be noted that,
the pressure for the steam used in the RD-II system would become very
high (14.6 MPa). Other heat media at the temperatures above 340 °C
(e.g., Dowtherm A) might be more appropriate, while which may lead
to further increase in the energy cost due to the utilization of more
costly heat transfer fluid [34]. The results reveal that better system
performance has been achieved in the SRC process.
6. Conclusions
In this work, the side reactor concept is proposed to intensify the
hydration of EO to produce EG. Process simulation, analysis, and design
have been conducted in the Aspen Plus software. The preliminary
analysis of operating conditions for the reaction and separation are
systematically performed, and the evaluation of the SRC configurations
of different side stream rates and side stream locations are carried out.
On the basis of the suggested values or scopes for the design variables,
the SRC process is optimized using a sequential design approach. The
results show that the specific SRC configuration, configured with a total
liquid withdrawn and recycled back to the column stage below, gives
better performance. Furthermore, the process with a reaction tem-
perature of 150 °C and a distillation temperature range of 106 ∼204 °C
(124 kPa) demonstrates better economic performance. The reaction
temperature and separation temperature have been set under their
optimal states in the SRC process, solving the process conditions mis-
match problems encountered in conventional RD processes.
In principle, the SRC technique, as an extension of the conventional
reactive distillation technology, can be extended to various kinds of
consecutive reactions (e.g., chlorination, alkylation of aromatic hy-
drocarbon, hydration of olefin oxides, etc.) and equilibrium-limited
reactions (e.g., esterification, etherification, hydrolysis of esters, etc.) in
the chemical industry. This concept is particularly attractive for the
systems with obvious differences in the conditions for reaction and
separation (e.g., high-pressure reaction and vacuum separation, low-
temperature reaction and high-temperature separation). For example,
in the industrial application of SRC for the production of benzal
chloride, energy saving can be achieved in the combination of the high-
pressure reaction and vacuum-distillation, which resulted in reduced
10
Chemical Engineering & Processing: Process Intensification xxx (xxxx) xxxx
reboiler temperature [35]. The production of silanes is another poten-
tial reaction system for SRC. A maximum reaction temperature of
100 °C on the specified catalyst would generate a pressure of ∼5 atm in
the RD column, and thereby, an extremely low condensing temperature
(∼-78 °C) is obtained [36]. SRC may also be used and the distillation
temperature can be independently improved. Furthermore, the SRC
technique is also effective for the catalytic reactions with easier treat-
the commercialization of SRC technologies.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
We gratefully acknowledge the financial support for this work from
the Key Research and Development Program of Jiangsu Province (No.
BE2018718) and the Natural Science Foundation of Jiangsu Province
(No.BK20161481).
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.cep.2019.107744.
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