Journal of Cleaner Production 218 (2019) 212e224

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Journal of Cleaner Production

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

Design optimization and operating pressure effects in the separation

of acetonitrile/methanol/water mixture by ternary extractive
distillation
Yinglong Wang a, Guangle Bu a, Xueli Geng a, Zhaoyou Zhu a, Peizhe Cui a, *, Zuwei Liao b
a
College of Chemical Engineering, Qingdao University of Science and Technology, 53 Zhengzhou Road, Qingdao, 266042, China
b
State Key Laboratory of Chemical Engineering, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, 310027, China

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

Article history: Ternary extractive distillation is a green and sustainable separation process for the treatment of phar-
Received 19 November 2018 maceutical wastewater containing methanol/acetonitrile and acetonitrile/water azeotropes that achieves
Received in revised form the recovery of the acetonitrile and methanol solvents. A novel sequential iterative optimization
27 January 2019
methodology is proposed and the isovolatility curves of systems at different pressures are analyzed in
Accepted 30 January 2019
Available online 2 February 2019
this work to investigate the effect of the operating pressure on the ternary extractive distillation process.
Four optimization procedures with different conditions of pressure and limits for the use of cold utilities
were carried out. The optimization results showed that the optimal pressures of the first column and the
Keywords:
Ternary extractive distillation
third column are related to the top vapor that can be condensed by chiller water and cooling water,
Sequential iterative optimization respectively, and the pressure of the second column is related to the effect of preheating on the third
Azeotrope column. The ternary extractive distillation process with optimal operating pressure shows 60.1% energy
Pressure cost savings and 47.0% total annual cost savings compared with the optimal process operating at at-
Isovolatility curve mospheric pressure. The proposed optimization method has the advantages of automatic optimization
with a smaller number of simulator runs, providing a new solution for the simulator-based process
optimization. The investigation of the operating pressure effect provides additional insight for the design
and optimization of ternary extractive distillation.
© 2019 Elsevier Ltd. All rights reserved.

1. Introduction the advantages of cleaner production and environmental protec-

It is well known that acetonitrile (ACN) and methanol (MeOH)
are two critical chemical raw materials and solvents. Due to their
ability to dissolve in most organics and their relatively low toxicity
and chemical reactivity, they are widely used as solvents in the
chemical and pharmaceutical industry manufacturing. Acetonitrile,
methanol, water and their mixtures are widely used as analytical
settings and a large amount of the acetonitrile/methanol/water
mixtures is produced after analysis (Cesas, 2012; Tavazzi et al.,
2018). Furthermore, large amounts of pharmaceutical wastewater
containing acetonitrile and methanol are generated in the pro-
duction of peptide drugs (Hintzen et al., 2014; Yuan et al., 2009).
The separation of methanol/acetonitrile/water not only achieves
the recycling of the acetonitrile and methanol solvents but also has
* Corresponding author.
E-mail address: cpzmagic@qust.edu.cn (P. Cui).
tion. However, it is difficult to separate acetonitrile/methanol/water
effectively by conventional distillation due to the presence of
azeotropes of acetonitrile/water and methanol/ acetonitrile. Many
azeotrope separation processes such as azeotropic distillation
(Cesas, 2012), pressure-swing distillation (Repke et al., 2005), and
extractive distillation (You et al., 2018; Zhang, Zhu et al., 2018a)
have been investigated. Generally, the separation of acetonitrile/
methanol/water can be achieved by combining the separation
processes for these two azeotropes. Compared with other combi-
nation separation processes, the ternary extractive distillation
(TED) process has the advantage of recycling the entrainer using a
column.
For almost a century, many scientists have focused on the
research and development of azeotropic separation technology. The
recent progress in this field can be summarized as follows. Mahdi
et al. (2014) classified azeotropic separation techniques into three
categories, namely, the enhancement of distillation processes, the
membrane processes and processes intensification. Enhancement

https://doi.org/10.1016/j.jclepro.2019.01.324
0959-6526/© 2019 Elsevier Ltd. All rights reserved.
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
Nomenclature
ACN acetonitrile
C1,C2,C3 the first column, the second column, the third
column
ED extractive distillation
MeOH methanol
i the index of decision variables
MPCHW minimum pressure for chilled water pressure
MPCW minimum pressure for cooling water
MTCHW minimum temperature for chilled water
MTCW minimum temperature for cooling water
NF1, NF2, NF3 feed stage location of the column C1, C2, C3
NREC recycle stage location of the column T1
NT1, NT2, NT3 total stage of the column C1, C2, C3
P1, P2, P3 pressure of the column C1, C2, C3
RR1, RR2, RR3 reflux ratio of the column C1, C2, C3
S/F solvent to feed flow rate ratio
TAC total annual cost, $/y
TAC(Ximin) the current minimum value of TAC, $/y
TED ternary extractive distillation
VB Visual Basic
Ximin the current optimum value of the decision variable
of distillation processes includes azeotropic distillation (Zhao, Li
et al., 2017), pressure-swing distillation (Liang et al., 2017; Xia
et al., 2017) and extractive distillation (ED) (Navarro et al., 2018;
Tututi-Avila et al., 2017) which are widely used in industry as the
developed mature distillation technology. Extractive distillation is
achieved by adding a third component known as an entrainer to
increase the relative volatility and alter the vapor liquid equilibrium
data of the components that must be separated. Extractive distil-
lation has been extensively investigated for separating binary
azeotropic mixtures in a wide variety of studies ranging from the
examination of vapor-liquid equilibrium data (Zhang, Zhu et al.,
2018), solvent screening (Dong et al., 2018; Zhu et al., 2018), en-
ergy saving and processes intensification (Han et al., 2015; Tututi-
Avila et al., 2017), optimization and design (Dong et al., 2018;
Wang, Q. et al., 2018; You et al., 2018), to the dynamic control
scheme (Feng et al., 2018; Luyben, 2018; Yi et al., 2018). In recent
years, these ED investigations have been extended to the separation
of ternary azeotropic mixtures and have attracted considerable
attention. Wang et al. (2018a) proposed ten novel thermally
coupled extractive distillation sequences for the separation of
acetonitrile/benzene/methanol mixture. Wang et al. (2018b; 2018c)
further studied the solvent screening and dynamic control scheme
of the conventional and intensified extractive distillation. Y. Zhao
Lyu, et al. (2017); Zhao Zhao, et al. (2017) carried out a compari-
son of heterogeneous azeotropic distillation and ED for the sepa-
ration of the ethanol/toluene/water mixture and observed that ED
provided a 39.3% reduction in the total annual cost (TAC) compared
to partially heat-integrated heterogeneous azeotropic distillation.
In our previous works (Zhao et al., 2018; Zhao, You et al., 2017), the
ternary extractive distillation (TED) process for the separation of
tetrahydrofuran/ethanol/water mixture was investigated. In most
of these studies, the separation processes are optimization by
convenient sequential iterative optimization procedures on the
basis of minimized TAC.
Since the azeotropes involved in the acetonitrile/methanol/
water system are pressure-sensitive, the effects of the operating
pressure in each column of TED on the energy consumption and
TAC are complicated and significant. In this paper, a novel
213
sequential iterative optimization methodology is proposed to
investigate the operating pressure effects on the TED process in
detail.
2. Methods
2.1. Simulator-based optimization methodology
The optimization methodology based on a simulator has the
advantage of running automatically and saving computational time
and is widely applied in the ED process optimization (Silva et al.,
2018). Yang and Ward (2018) investigated the design and optimi-
zation of ED using simulated annealing. You et al. (2018) explored a
multi-objective genetic algorithm to optimize the pre-
concentration ED process with multiple objectives. Torres-Ortega
et al. (2013) developed a multi-objective stochastic optimization
procedure to optimize ED. In addition to optimization of extractive
distillation, they have expanded the simulator-based optimization
methodology to other topics such as distillation (Quiroz-Ramírez
et al., 2017), reactive distillation (Santaella et al., 2017), heat
exchanger networks, divided wall columns and multicomponent
distillation column (Segovia-Herna
ndez and Go
mez-Castro, 2017).
These works are insightful and meaningful compared with the
conventional sequential iterative optimization methodology, but
the algorithm appears to be quite difficult for the optimization of
complex process with more decision variables, particularly for the
problems involving pressure which is a continuous variable. In our
previous works (Wang et al., 2016), we proposed a two-column
pressure-swing distillation optimization method based on the
simulated annealing algorithm using an Aspen Plus simulator in-
tegrated with Visual Basic (VB). The optimization of pressure was so
difficult that we optimized it independently using a new procedure
based on the optimum design of other variables. This is not a rare
problem. It was reported that the CPU time for the optimizations of
the complex reactive distillation process (Santaella et al., 2017) and
the complex pre-concentration ED process (You et al., 2018) were
12 days and 200 h, respectively. The optimization problem based on
the simulator is different from the convenient simulation optimi-
zation problem based on mathematical modeling. For the
simulator-based optimization methodology, the CPU time
requirement of each step executed by the Aspen Plus simulator is
very high due to the long convergence time required by the Aspen
Plus simulator (Kiss et al., 2012). Therefore, the decrease in the
number of steps carried out by the Aspen Plus simulator is crucial
for reduce the CPU time of the optimization. The conventional
sequential iterative optimization methodology has the advantage
of effective convergence with a suitable number or run steps of
Aspen Plus simulator and is widely used for ED optimization.
Therefore, two simulator-based sequential iterative optimization
methods were developed combining the advantages of the con-
ventional sequential iterative optimization methodology and the
simulator-based optimization methodology; these method were
studied and illustrated systematically using the optimization of the
TED process.
2.2. Semiautomatic sequential iterative optimization methodology
To the best of our knowledge, the sequential iterative optimi-
zation method was first reported and applied in the optimization of
reactive distillation (Tang et al., 2005). Currently, this method has
been extensively used in the design and optimization of ED,
pressure-swing distillation, azeotropic distillation and divided wall
columns. The theory of sequential iterative optimization method is
based on the single factor optimization method implemented by
iterative optimization of each decision variable and finding the
214 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
optimum values of the decision variables sequentially. The optimal
value of the decision variable is related to the minimum TAC that is
obtained by changing the decision variable to be optimized while
keeping the other decision variables constant. The procedure for
the TED process was established as shown in Fig. 1. We can
decompose this procedure into two parts. The first is the outer full
sequential iterative optimization procedure that control the opti-
mization sequence of the decision variables. The second is the inner
decision variables optimization procedure. The inner decision var-
iables optimization procedure can be executed automatically using
simulator-based optimization methodology.
The inner decision variables optimization procedure of the
conventional sequential iterative optimization method consists of
several procedures as follows: (1) Change the value of decision
variables in the Aspen Plus simulator input fields; (2) Execute the
reinitialization and running of Aspen Plus simulator; (3) Copy the
result data of column diameter, distillate temperature, bottom
temperature, condenser heat duty and reboiler heat duty to Excel;
(4) The TAC is calculated automatically according to the formula set
in the Excel; (5) Save the data to a new data line in Excel. In this
procedure, (1) and (3) are tedious and time-consuming and are
crucial for the efficiency of this optimization methodology. To
change the decision variables automatically, active links are created
for the value of decision variables from Excel to Aspen Plus simu-
lator input fields. Similarly, the result data can be saved to Excel
automatically by creating active links from the Aspen Plus simu-
lator into Excel. The other procedures can be executed automati-
cally by a VBA program. Based on the above analysis, a
semiautomatic optimization methodology can be developed by
Excel VBA integrated with Aspen Plus simulator using COM pro-
gramming technology and ActiveX server technology.
This method represents a considerable improvement relative to
Fig. 1. Sequential iterative optimization procedures of the TED process.
the convention sequential iterative optimization method. Never-
theless, there are some obstacles for this methodology such as need
to execute the outer entire sequential iterative optimization pro-
cedure manually, the manual change of the decision variables in
Excel and the need to establish active links between Aspen and
Excel for different Aspen Plus files. Therefore, a novel sequential
iterative optimization methodology was developed.
2.3. Novel sequential iterative optimization methodology
The novel sequential iterative optimization methodology was
implemented using the software developed with VB. The devel-
oped software integrates Aspen Plus simulator and Excel using
ActiveX technology and Object Linking and Embedding (OLE)
automation server technology (Kiss et al., 2012), respectively. The
input data and output data connection and control of the simulator
are applied in VB. The decision variable, optimization result, capital
investment, energy consumption and TAC data are saved in Excel.
As shown in Fig. 2, the main software interface was designed in
which the necessary parameters of ED, path of Aspen Plus and Excel
and optimization sequence can be specified. As shown in Fig. 3, a
“Total Annual Cost Model” interface was designed in which the TAC
model can be specified.
The optimization procedure for the novel sequential iterative
optimization methodology is shown in Fig. 4 and consists of the
following steps.
(1) Establish a convergence process using the simulator. Letter i
denote the index of the decision variables. Set the initial
value (Xi), step length (DXi), number (Ni) for each of the
decision variables according to the value of specified by the
simulator. Set an optimization sequence of the decision
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
Fig. 2. Main interface of the novel sequential iterative optimization software.
Fig. 3. “Total Annual Cost Model” interface of the novel sequential iterative optimi-
zation software.
variables (Sque) based on the sequential iterative optimiza-
tion procedure of TED illustrated in Fig. 1.
Sque ¼ S1, S2, S3 … Sj … Sjmax, i ¼ Sj, Sj through the value of i
control the optimization sequence of the decision variables.
Take the optimization of the decision variable Xi as an example
to illustrate the optimization procedure for each design variable.
(2). Generate a series of numbers according to the following
generator rules:
Generator rules: generate 2Niþ1 numbers according to the
arithmetic progression with a central number of Xi and step length
215
Fig. 4. Flowchart of the novel sequential iterative optimization methodology.
of Dxi.
Generated numbers: Xi-Ni  DXi, Xi-(Ni-1)  DXi, Xi-(N-2)  DXi …
Xi-DXi, Xi, XiþDXi, …Xiþ(Ni-2)  DXi, Xiþ(Ni-1)  DXi, Xi þ N  DXi
Where Xih ¼ Xi-Ni  DXiþ(h-1)  DXi, h ¼ 1, 2, 3 … ihmax,
ihmax ¼ 2Niþ1.where Ni denotes the amount of the numbers
generated from Xi in the direction of increase or decrease, ihmax
denotes the amount of the generated numbers, Xih is the generated
number of the decision variable Xi.
(3). Replace the value of the decision variable Xi in the simulator
with the generated number Xih.
(4). Reinitialize and run the simulator.
(5). Return the simulation results data to VB programming and
calculate TAC of Xih based on the TAC model.
(6). Compare the TAC value of Ximin with the TAC value of Xih, and
update the values of Ximin and TAC (Ximin).
Where TAC (Ximin) and Ximin are the current minimum value of
TAC and the corresponding current optimum value of the decision
variable, respectively.
(7). Save the data for the decision variables, the results, TAC,
Ximin, TAC (Ximin), etc. to Excel.
216 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
(8). Go back to (3) with a new generated number until all of the
generated numbers of Xi are calculated. An optimum value of
Ximin will be obtained with minimized TAC.
(9). Update the value of Xi with Ximin and go back to (4). The loop
end with the value of Ximin is equal to Xi and an optimum
value of the decision variable Xi is obtained.
(10). All of the decision variables are iteratively optimized ac-
cording to this sequence until the optimum design is
obtained.
The condition for the end of the optimization procedure is that
the optimal values of all of the decision variables are the same as
the values in the previous outer entire sequential iterative opti-
mization procedure. The optimum design can be obtained because
the TAC of TED often shows a distinct trend of increasing or
decreasing before or after the optimum of the decision variables.
The novel sequential iterative optimization method includes some
innovations. First, the configuration of the optimization sequence
of decision variables enabled the automatic execution of optimi-
zation procedure. Second, the proposed generate rules provide a
solution for the automatic change of decision variables. Third, the
current optimum of design variables can be found via the proposed
evaluation of current minimum TAC. It is important to note that the
novel sequential iterative optimization methodology proposed
here is universally applicable and can be used for the optimization
of the processes simulated by the simulator such as reactive
distillation, divided wall columns, azeotropic distillation, pressure-
swing distillation, extractive reactive distillation, multicomponent
distillation column. The application of this optimization method-
ology to additional processes will be explored in future work.
The search space of the TED optimization problem depends on
the feasible solution of the TED process. The search space increases
exponentially with the increase in the number of the decision
variables. In the optimization procedure of intelligent optimization
algorithms optimization methodology, at each steps of the simu-
lator execution, all of the decision variables can be changed in a
large search space. By contrast, only one decision variable can be
changed for the novel sequential iterative optimization method-
ology in a small search space. Therefore, the novel sequential iter-
ative optimization methodology shows better convergence ability
than the intelligent optimization algorithms optimization meth-
odology. In addition, no parameters must be determined for the
proposed methodology. By contrast, many algorithm parameters
must be changed according to different optimization processes or
different azeotropes for the intelligent optimization algorithms
optimization methodology.
3. Process design and economic basis
3.1. Process design of ternary extractive distillation
The ternary azeotrope acetonitrile/methanol/water mixture
contains azeotrope acetonitrile/water and methanol/acetonitrile.
Therefore, the selection entrainer for this system should have the
ability of breaking these two azeotropes. At atmospheric pressure,
the boiling points of methanol, acetonitrile, water are 337.85,
354.75 and 373.15 K, respectively. In the normal design for this TED,
methanol, acetonitrile and water are separated in the first column
(C1), the second column (C2) and the third column (C3) as the
distillates, respectively. Here, there is a contradiction that the
selected entrainer needs to reduce the relative volatility of the
heavy component acetonitrile in C1 while increasing the relative
volatility of the light component acetonitrile in C2. Raeva and
Sazonova (2015) selected glycerol as the entrainer to separate the
heavy acetonitrile component of the methanol/acetonitrile
azeotrope as distillate in C1. In these conditions, the above
contradiction is solved because acetonitrile is separated in C1 as the
distillate. In addition, the methanol, water, and glycerol mixture of
the bottom mixture of C1 can be easily separated in C2 and C3 due
to their lack of azeotropes. However, the authors do not optimize
the decision variables of the processes.
In this study, we further investigated the design and optimiza-
tion of this process. The process was simulated using the com-
mercial Aspen Plus 7.2 software. The nonrandom two liquid (NRTL)
model with built-in binary interaction parameters (see Table A1)
was used to describe the phase behavior of this system. The feed
flow rate was set to 100 kmol/h with the composition of 30 mol%
acetonitrile, 20 mol% methanol, and 50 mol% water. The purity of
the acetonitrile product in the distillate of C1 was set to 99.95%,
which should be sufficient high so that the required purity of
methanol can be achieved according to the material balance of
acetonitrile. The purity of the methanol in the distillate of C2 was
set to 99.90 mol%. The purity of the recycling entrainer in the bot-
tom of C3 is specified as 99.99 mol%.
As shown in Fig. 5, the reflux ratios for these columns are
specified relative to the purity of the products and recycling
entrainer. While the reflux ratios are specified, eleven decision
variables must be optimized, namely, the solvent to feed flow rate
ratio (S/F), the number of stages (NT1), feed stage location (NF1),
recycle stage location (NREC), and the operating pressure (P1) of C1,
the number of stages (NT2), feed stage location (NF2) and the
operating pressure (P2) of C2, the number of stages (NT3), feed stage
location (NF3) and the operating pressure (P3) of the C3. Among
these, S/F, P1, P2 and P3 are continuous variables and the others are
discrete variables. The operating pressure of extractive distillation
can be set to 1 atm and not to be optimized and therefore can be
seen as an additional decision variable in order to distinguish it
from other decision variables. The optimization of the TED process
is a mixed integer nonlinear programming problem (MINLP)
referring to an objective function. In this work, the objective
function is the total annual cost (TAC) and the constraint condition
is the purity of the products and recycling entrainer that are shown
as Eqs. (1)e(4).
objective function ¼ TAC (1)
constraints : Xacetonitrile;  0:9995 (2)
D1
Xmethanol; D2  0:999 (3)
Xrecycling entrainer; B3  0:9999 (4)
3.2. Economic basis
The total annual cost (TAC) is widely used as an objective
function to evaluate the economics of the process design and in-
cludes both the operating cost and the capital cost (Silva et al.,
2017). It can be described by Eq. (5).
TAC ð$=yrÞ ¼ annual operating cost þ annual capital cost
(5)
The annual operating costs include the costs of steam and
cooling water (see Eq. (6)). The annual capital cost (see Eq. (7)) is
often related to the capital investment and a payback period. In this
work, a payback period of 3 years is assumed.
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224 217

Table 1
Basis of economic and equipment design.

Column vessel cost ¼ 17640  D1:066  H0:802 where units of D and H are meters:

Colum height (H) ¼ NT trays with 2 ft spacing plus 20% extra height;
Colum diameter (D) is calculated by Aspen tray sizing.
Heat exchanges costs ¼ 7296  A0:65
Q
Area of heat exchanges ðAÞ ¼
Dt  k
Q is the duty of heat exchanger, (kW);
△t is temperature difference, (K); k is heat transfer coefficient, 0.568 (kW/ (K$m2)) for reboilers and 0.852 (kW/ (K$m2)) for condensers.
Temperature difference between hot utilities and material steam be heated  20 K
Temperature difference between cold utilities outlet temperature and the condensed material stream inlet temperature  7 K
Annual energy costs ¼ Cs  QR
QR is reboiler duty (GJ); Cs is the price of hot utilities ($/GJ)
Annual cold utilities costs ¼ CW  QC
QC is condenser duty (GJ); Cw is the price of cold utilities ($/GJ)
Hot utilities price Low-pressure steam (433 K) ¼ $7.78/GJ
Medium-pressure steam (457 K) ¼ $8.22/GJ
High-pressure steam (527 K) ¼ $9.88/GJ
Higher-pressure steam (597 K) ¼ $11.54/GJ
Cold utilities price Cooling water (304 Ke316 K) ¼ $0.354/GJ
Chilled water (278.15K-288.15 K) ¼ $4.43/GJ
Refrigerant at 20  C ¼ $7.89/GJ
Capital investment
TAC ¼ þ Annual energy costs þ Annual cooler costs
payback period

condensers.

4. Results

4.1. Effect of operating pressure on the binary azeotropes

The optimization of the operating pressure for the ED process is

Fig. 5. Scheme of the TED process.
Annual operating cost ¼ Annual energy cost
þ Annual cooler cost
Annual capital cost ¼ capital investment = payback period
The economic basis, setting of parameters, and relationship of
the design and sizing for the ED process are summarized in Table 1.
The capital investment mainly depends on the cost of the column
vessels and heat exchanges. The cost of equipment such as liquid
delivery pumps, pipes, and valves is neglected. The cost of extra
pumps for the vacuum system and the electricity for these pumps is
also neglected (You et al., 2018). The cost of cooling water, chilled
water, refrigerant and steam at different temperatures are taken
from Luyben's book (2012). The cost of higher-pressure steam
(597 K) is estimate as $11.54/GJ (9.88 þ (9.88 - 8.22) ¼ 11.54) based
on the temperature difference (527 - 457) and cost difference (9.88
- 8.22) between the medium-pressure steam and high-pressure
steam. The cooling water inlet temperature and the outlet tem-
perature are assumed to be 304 K and 316 K, respectively, and are
used to calculate the log-mean temperature driving forces in the
a systematic and complex problem that was considered and
investigated by many studies reported in the literature ranging
from the separation of binary azeotropes to the separation of
ternary azeotropes (Gu et al., 2018; Li et al., 2017; You et al., 2017).
For the extractive distillation column of C1, two pressure-sensitivity
azeotropes of acetonitrile/water and methanol/acetonitrile must be
separated. For the separation of pressure-sensitivity azeotrope, the
VLE data and azeotropic composition of the separating system
changes with the changes in the operating pressure in the ED col-
umn, resulting in the change of the ED separation performance. The
acetonitrile content in the acetonitrile-water and methanol-
acetonitrile azeotropes at different pressures varying from
0.05 atm to 1.0 atm are shown in Fig. 6 (Table A2). An examination
of Fig. 6 shows that the acetonitrile content in the methanol/
(6) acetonitrile and acetonitrile/water azeotropes increases with
decreasing pressure. This means that less entrainer can be used
with a lower operating pressure if the effect of the pressure on the
(7) entrainer is not taken into account. In fact, the effect of the pressure
on the separation performance of the entrainers is complex and can
be analyzed using the isovolatility curves (Zhang Li, et al., 2018;
Zhang Yang, et al., 2018).
The isovolatility curve is a special equivolatility curve such that
a0 ¼ 1. The equivolatility curve (also known as univolatility curve)
of components A and B is the set of points where the relative vol-
atilities of A and B are equal to a0 as described by Eq. (8) (Laroche
et al., 1991).
a AB ¼ ðYA =YB Þ=ðXA =XB Þ ¼ a0 (8)
The isovolatility curves of acetonitrile (A) and methanol (B) with
heavy entrainer glycerol (E) at different pressures are shown in
Fig. 7. The isovolatility curves of acetonitrile (A) and water (B) with
heavy entrainer glycerol (E) at different pressures are shown in
Fig. 8. The acetonitrile/water and methanol/acetonitrile azeotropes
218 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224

approximately equal demonstrating that the pressure has almost

no effect on the entrainer. The changes of the isovolatility curves
with varying pressures for these two systems are consistent. As the
pressure decreases, the intersection point Xp moves closer to A, and
less entrainer is required. However, if the operating pressure is
lower than the minimum pressure so that top vapor can be
condensed by cooling water, an expensive cold utility chilled water
or refrigerant is used.

4.2. TED process with specified pressure

To investigate the effect of the operating pressure on the TED

Fig. 6. Boiling point and proportion of acetonitrile in the azeotropes at different
pressures: (a) acetonitrile/water (b) methanol/acetonitrile.
are minimum boiling azeotropes and the ABE ternary mixture
belongs to the Serafimov's class 1.0-1a (Kiva et al., 2003). The
intersection point of the isovolatility curve at the AB side is the
azeotropic point with the azeotropic composition of A and B. The
intersection point Xp of the isovolatility curve at AE describes the
minimal amount of the entrainer for breaking the azeotrope. The
slopes of the isovolatility curves at different pressures are
process, the novel sequential iterative optimization procedure for
the TED process with the pressure set at 1 atm is executed first. As
shown in Fig. 9(a), many attractive trends that are consistent with
the optimization procedure of the conventional sequential iterative
optimization methodology are observed. First, although the TAC is
fluctuating, the current minimum value of TAC TAC(Ximin) decreases
with the increasing number of the execution steps of the simulator.
Second, the rate of TAC(Ximin) decrease decreases with the
increasing number of the execution steps of the simulator. Third,
there are many short steps that show decreases to TAC(Ximin) or
increases from TAC(Ximin) that are caused by the value of the deci-
sion variable decreasing to Xim or increasing from Ximin, respec-
tively. The optimum design is obtained within 618 steps of the
simulator execution, as presented in the Case 1 of Table 2.
In the optimum design of Case 1, the temperatures at the bot-
toms of C1, C2, C3 are 416.00 K, 475.69 K, and 564.8 K, respectively,
correspondingly requiring the use of medium-pressure steam
(457 K, $8.22 per GJ), high-pressure steam (527 K, $9.88 per GJ), and
higher-pressure steam (597 K, $11.54 per GJ). Based on section 4.1,
we can conclude that the separation performance of C1 is beneficial
for the decrease in the operating pressure. In addition, by setting a
low operating pressure for C1, C2 and C3, the temperature of the
bottom can be decreased and cheaper steam can be used.
For a distillation column, there is a temperature related to the
minimum temperature that necessitates the use of cooling water
and an operating pressure corresponding to that temperature that
are defined as the minimum temperature for cooling water
(MTCW) and the minimum pressure for cooling water (MPCW).
Similarly, the minimum temperature for chilled water (MTCHW)
and minimum pressure for chilled water (MPCHW) were defined
relative to the chilled water. For the cold utilities used in this paper,
323 K and 295.15 K were selected as the MTCW and MTCHW,
respectively, according to the study by Luyben (2016). For most of

Table 2
Optimum design of the TED process with the specified pressure. Case 1: pressure fixed at 1 atm; Case 2: pressure fixed at MPCW.

Case 1 Case 2

C1 C2 C3 C1 C2 C3

P (atm) 1 1 1 0.34 0.55 0.13

NT/NF/NREC 52/35/3 38/30 18/10 62/45/6 33/24 9/5
S/F 2.51 1.12 (-55.4%)
RR 0.0034 1.046 0.178 0.978 0.988 0.290
ID (m) 0.790 0.581 1.015 0.792 0.538 1.310
QC (KW) 252.83 399.56 667.83 525.06 (þ107.7%) 398.76 (-0.2%) 625.43 (-6.3%)
QR (KW) 2205.03 1441.08 2154.76 1005.20 (-54.4%) 775.73 (-46.2%) 1169.64 (-45.7%)
Distillate temperature (K) 354.58 337.68 373.15 323.20 (-8.8%) 323.20 (-4.3%) 324.43 (-13.1%)
Bottom temperature (K) 416.00 475.69 564.80 359.80 (-13.5%) 408.60 (-14.1%) 497.58 (-11.9%)
Cold utilities cost (103 $/yr) 2.58 4.07 6.81 5.35 (þ107.7%) 4.07 (-0.2%) 6.38 (-6.4%)
Energy cost (103 $/yr) 522.01 410.05 716.14 223.49 (-57.2%) 172.47 (-57.9%) 332.81 (-53.5%)
Operating cost (103 $/yr) 524.59 414.13 722.95 228.85 (-56.4%) 176.54 (-57.4%) 339.19 (-53.1%)
Capital cost (103 $/yr) 411.60 274.72 321.90 436.68 (þ6.1%) 289.11 (þ5.2%) 295.16 (-8.3%)
Annual operating cost (103 $/yr) 1661.66 744.57 (-55.2%)
Annual capital cost (103 $/yr) 336.07 340.32 (þ1.3%)
Annual energy cost (103 $/yr) 1648.20 728.78 (-55.8%)
TAC (103 $/yr) 1997.73 1084.89 (-45.7%)
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
Fig. 7. Isovolatility curves of the acetonitrile/methanol/glycerol mixture at different pressures.
the ED processes with varying pressure, the optimum pressure in
the column is related to the use of cooling water, and the optimum
pressure in the distillation column is selected according to MPCW
or to be slightly higher than MPCW. For the TED process for
acetonitrile/methanol/water separation, the MPCW values for C1,
C2 and C3 were 0.34 atm, 0.55 atm and 0.13 atm. For this low
operating pressure column, the pressure drop per tray was
assumed in the present work to be 0.002 atm as given in Luyben's
study.
As shown in Fig. 9(b), an optimization procedure based on the
novel sequential iterative optimization methodology was executed
to investigate the effect of MPCW on the performance of this pro-
cess. The optimum design is presented in the Case 2 of Table 2.
Compared with the optimum TED process with the pressure set to
1 atm (Case 1), the annual operating cost, annual energy cost, and
TAC of Case 2 show the reductions of 55.2%, 55.8% and 45.7%,
respectively. The solvent to feed flow rate ratio was decreased by
55.4% from 2.51 to 1.12. The decrease of the entrainer recycled in
these columns leads to a dramatic improvement in the decrease of
the reboiler duty of C1, C2 and C3. In addition, the temperature of
the bottom decreased and it is possible that cheaper steam can be
used at the MPCW pressure. We note that the temperature differ-
ence between the top temperature and bottom temperature of C1
decreased by 40.4% from 61.4 K to 36.6 K, leading to the increase in
the number of stages and the cost of columns. Even though the
capital cost of C1, C2 and the cold utilities cost of C1 increased, the
increased cost makes only a slight impact on TAC.
4.3. TED process with pressure optimization
To further optimize the operating pressure, a novel sequential
219
iterative optimization procedure with pressure optimization was
executed as shown in Fig. 10(a). In this optimization procedure,
there is a constraint that the operating pressure in the columns
should be not less than MPCW and the cold utilities for the
condenser are limited to the use of the cooling water. Case 3 in
Table 3 describes this optimum design. The optimum pressure in C1
and C3 are the MPCW, which is the same as for Case 2, but the
optimum pressure for C2 increased from 0.55 to 0.82. The value of
other decision variables also changed with the optimization of the
pressure of C2. The decision variables, capital investment, energy
consumption and TAC of Case 3 were analyzed and compared to the
results obtained for Case 2. For case 3, the steam cost of C2
increased by 15.4% and the steam cost of C3 decreased by 6.6% due
to the increased pressure. The bottom temperature of C2 is 416.15 K
and the medium-pressure steam (457 K at $8.22 per GJ) instead of
the low-pressure steam (433 K) in the reboiler is used. However,
the use of medium-pressure steam C2 is equivalent to the effect of
the preheat feed materials stream of C3 with a cheaper steam
which leads to the annual operating cost increase of only 0.7%. The
cost of the reboiler and condenser of C2 decreased because the
temperature difference of heating and cooling increased, account-
ing for most of the increase of the annual capital cost and TAC.
According to the optimization procedure described above, the
TAC and energy consumption can be reduced with the pressure
equal to MPCW in C1 and C3. If the pressure in C1 and C3 decreased
to a value lower than MPCW, the cost of cold utilities increased due
to the use of an expensive chilled water or refrigerant. Hence, there
is a trade-off between the cost of the stream and cold utilities. Is it
possibile that the cost increase due to the introduction of chilled
water or refrigerant is lower than the TAC reduction by the opti-
mization of the pressure? To study this problem, an optimization
220 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224

Fig. 8. Isovolatility curves of the acetonitrile/water/glycerol mixture at different pressures.

Fig. 9. TAC values at different steps of the simulator: (a) Pressure specified as 1 atm (b) Pressure specified as MPCW.

procedure with pressure optimization and no limit to the use of
cold utilities was executed (Fig. 10(b)). The optimum design is ob-
tained using 620 steps executed by the simulator, as presented in
the Case 4 of Table 3. The design and economics of Case 4 are
analyzed and compared with those of Case 2. The optimization
results show that the annual operating cost, annual capital cost,
annual energy cost and TAC are reduced by 1.8%, 3.8%, 11.6% and
2.5%, respectively. With the optimal pressure of C1 chaning from
0.34 atm to 0.13 atm, the S/F decreased by 27.7% from 1.12 to 0.81.
The reduction of the entrainer mainly accounts for the reduction of
the energy cost and TAC of Case 4. We note that the cold utilities
cost of C1 increased to 76.31  103 $/yr from 5.51  103 $/yr and is
compensated by the reduction in the energy cost. The optimum
pressures of C1 and C3 are the MPCHW and MPCW, respectively.
The optimal pressures of C3 is MPCW due to the vapor in C3 flowing
at a considerable rate that must be condensed and the sharp in-
crease in the price of the cold utility. The flowsheet and liquid
composition profiles of Case 4 are shown in Figs. 11 and 12.
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224 221

Fig. 10. Value of TAC at different steps of the simulator: (a) cold utilities limited to the use of the cooling water (b) no limit for the use of cold utilities.

Table 3
Optimum design of the TED process with pressure optimization. Case3: cold utilities limited to the use of the cooling water; Case 4: no limit for the use of cold utilities.

Case 3 Case 4

C1 C2 C3 C1 C2 C3

P (atm) 0.34 0.71 0.13 0.13 0.75 0.13

NT/NF/NREC 62/45/4 33/25 8/5 48/33/4 34/25 8/5
S/F 1.09 (-2.7%) 0.81 (-27.7%)
RR 1.035 1.029 0.055 1.176 1.003 0.049
ID (m) 0.800 0.525 1.195 1.074 0.526 1.136
QC (KW) 540.31 (þ2.9%) 402.58 (þ1.0%) 628.54 (-0.5%) 598.09 (þ13.9%) 396.39 (-0.6%) 623.83 (-0.3%)
QR (KW) 1006.12 (þ0.1%) 841.07 (þ8.4%) 1092.49 (-6.6%) 797.54 (-20.7%) 835.97 (þ7.8%) 987.66 (-15.6%)
Distillate temperature (K) 323.22 (þ0.0%) 329.22 (þ1.9%) 324.43 (þ0.0%) 299.92 (-7.2%) 330.54 (þ2.3%) 324.43 (þ0.0%)
Bottom temperature (K) 359.28 (-0.1%) 416.15 (þ1.8%) 497.58 (þ0.0%) 335.63 (-6.7%) 407.80 (-0.2%) 497.19 (-0.1%)
Cold utilities cost (103 $/yr) 5.51 (þ2.9%) 4.10 (þ1.0%) 6.41 (þ0.5%) 76.31 (þ1325.5%) 4.04 (-0.6%) 6.36 (-0.3%)
Energy cost (103 $/yr) 223.70 (þ0.1%) 199.11 (þ15.4%) 310.86 (-6.6%) 177.32 (-20.7%) 185.87 (þ7.8%) 281.03 (-15.6%)
Operating cost (103 $/yr) 229.20 (þ0.2%) 203.22 (þ15.1%) 317.27 (-6.5%) 253.63 (þ10.8%) 189.91 (þ7.6%) 287.39 (-15.3%)
Capital cost (103 $/yr) 441.26 (þ1.0%) 243.44 (-15.8%) 287.52 (-2.6%) 445.06 (þ1.9%) 270.68 (-6.4%) 266.25 (-9.8%)
Annual operating cost (103 $/yr) 749.69 (þ0.7%) 730.93 (-1.8%)
Annual capital cost (103 $/yr) 324.07 (-4.8%) 327.33 (-3.8%)
Annual energy cost (103 $/yr) 733.67 (þ0.7%) 644.22 (-11.6%)
TAC (103 $/yr) 1073.76 (-1.0%) 1058.26 (-2.5%)

5. Discussion pressure (Case 1).

The optimization procedures of Section 4 demonstrated that the
optimal pressure of the TED process is a systematic problem that
does not always depend on MPCW. On the one hand, for a normal
distillation column, the top temperature, bottom temperature, and
temperature difference between them are changed at different
pressures, leading to the corresponding changes in the cost of the
condenser, reboiler and column. On the other hand, for a pressure-
sensitivity azeotrope, the extent of decreases or increases of the
required S/F are different with variation in the pressure. Therefore,
for an extractive distillation column separating the pressure-
sensitivity azeotropes, the effect of the pressure on the composi-
tion profiles of the column and the S/F for all of the azeotropes must
be considered systematically. For the TED process for the acetoni-
trile/methanol/water mixture, the optimization results show that
the annual operating cost, annual energy cost and TAC for Case 4
decrease 56.0% by, 60.1% and 47.0%, respectively, relative to those
for Case 1. The economics and performance of the optimum design
with pressure optimization (Case 4) improves dramatically
compared with the optimum design operating at atmospheric
The CPU time for the proposed novel sequential iterative opti-
mization method depends mainly on the number of steps carried
out by the Aspen Plus simulator and the time for each step. The
number of the steps executed by the Aspen Plus simulator depends
on the convergence performance of the sequential iterative opti-
mization method which is affected by the initial values set for the
decision variables. The numbers of steps for cases 1e4 is 618, 645,
309, and 620, respectively. The CPU time for the Aspen Plus simu-
lator execution mainly depends on the computer environment. The
CPU time required for TED with pressure optimization in this work
is several hours (Microprocessor: Intel Core i7-3770 CPU @
3.40 GHz), representing a dramatic improvement compared with
the intelligent optimization algorithms optimization method
(Wang et al., 2016; Santaella et al., 2017; You et al., 2018).
6. Conclusions
A novel sequential iterative optimization method was imple-
mented using the software developed based on the proposed novel
flowchart and simulator-based optimization technology, which
222 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224

Fig. 11. Optimal flowsheet of Case 4.

Fig. 12. Liquid composition profiles of Case 4: (a) C1 (b) C2 (c) C3.
 Y. Wang et al. / Journal of Cleaner Production 218 (2019) 212e224
provided a new solution for the simulator-based process optimi-
zation. Compared with intelligent optimization algorithms opti-
mization method, the proposed method shows better convergence
ability with fewer simulator execution steps and no need for
changing algorithm parameters for different optimization
problems.
The effects of the design, optimization and operating pressure
on the separation of acetonitrile/methanol/water mixture by TED
were explored. The optimum design with operating pressure
optimization (Case 4) shows 56.0% savings in annual operating cost,
60.1% savings in energy cost and 47.0% savings in TAC relative to the
optimum design operating at atmospheric pressure (Case 1). The S/
F shows a 67.7% reduction from 2.51 to 0.81 with the optimum
pressure of C1 changing from 1.0 atm to 0.13 atm. The dramatic
reduction in the entrainer mainly accounts for the improvement
and energy savings of Case 4. The optimization results of Case 4
show that the pressures of C1, and C3 are the MPCHW and MPCW,
respectively, and the pressure of C2 is related to the effect of pre-
heating on C3. The optimization results show that the optimization
of the operating pressure in the columns of TED processes is a
systematic problem that depends on the use of cold utilities and
other factors.
Acknowledgements
This work is supported by the National Natural Science Foun-
dation of China (21808117& 21776145& 21822809), the National
Science Fund for Distinguished Young Scholars (21525627) are
gratefully acknowledged.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jclepro.2019.01.324.
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