Article

Cite This: Ind. Eng. Chem. Res. 2018, 57, 11050−11060 pubs.acs.org/IECR

Extractive Distillation Optimization Using Simulated Annealing and

a Process Simulation Automation Server
Xiao-Ling Yang and Jeffrey D. Ward*
Department of Chemical Engineering, National Taiwan University, Taipei 106-07, Taiwan
*
S Supporting Information
Downloaded from pubs.acs.org by UNIV DE LOS ANDES UNIANDES on 03/27/19. For personal use only.

ABSTRACT: In this work, continuous extractive distillation processes were optimized using simulated annealing (SA). The
processes were modeled in Aspen Plus and the simulated-annealing optimization algorithm was implemented in MATLAB. For
the separation of acetone and methanol, the TAC of the process for each entrainer considered was lower than the initial
Ind. Eng. Chem. Res. 2018.57:11050-11060.

condition taken from the literature. For the separation of n-hexane and ethyl acetate,we considered NMP, 2-methylpyridine, 3-
methylpyridine, DMF, and pyrrole as possible entrainers. The results show that DMF offers the best performance and economic
benefit. For the separation of n-hexane and tetrahydrofuran, the candidate entrainers were DMF, NMP, and 2-methylpyridine.
DMF was again found to be the most suitable entrainer. The results show that the SA algorithm has the advantage of running
automatically and has a high probability to obtain a design near the global optimum.

1. INTRODUCTION reviewed MINLP optimization algorithms for extractive

Separation of homogeneous azeotropic mixtures is a
challenging problem in the chemical industry.1 One of the
most common ways to separate such mixtures is by extractive
distillation.2−7 Widagdo and Seider8 reviewed the column
performance of homogeneous and heterogeneous towers. They
presented an algorithm for heterogeneous azeotropic dis-
tillation design including both steady-state and dynamic
simulation. Andersen9 focused on the effect of design on the
steady-state operation and the control properties of homoge-
neous azeotropic distillation. Heat-integrated distillation
sequences were studied by Knapp and Doherty.10
For a two-component system, separation using a heavy
entrainer is accomplished with two columns: an extractive
distillation column and an entrainer recovery column. As is
shown in Figure 1, high-purity components A and B can be
collected from the tops of the two columns. The entrainer can
also be recovered in the entrainer recovery column and
recycled. There are six design variables to be determined: the
entrainer flow rate (FE), the total number of stages in the
extractive distillation column (N1), the solvent and fresh feed
tray locations (NFE and NFF), the total number of stages in the
solvent recovery column (N2) and feed tray location of the
solvent recovery column (NF2). The extractive column can be
divided into three parts: the rectifying section (NR), the
extractive section (NE), and the stripping section (NS); N1,
NFE, and NFF can be expressed in terms of NR, NE, and NS.
The extractive distillation process has both discrete and
continuous variables, so the optimization problem is a mixed
integer nonlinear programming problem. Kossack et al.11,12
distillation flowsheets and applied the method of combining
shortcut calculation and rigorous MINLP optimization. This
approach gave good performance even without user
intervention. Many researchers have proposed global opti-
mization techniques13 including simulated annealing, genetic
algorithm, Tabu search,14 and particle swarm optimization.
Simulated annealing has been applied to many chemical
process optimization problems, for example in the optimal
design of reactive distillation systems,15 pressure-swing
distillation systems16 and heat integrated distillation sequen-
ces.17 However, in most of these cases, shortcut process design
methods (e.g., the Fenske−Underwood−Gilliland equations)
are used for column design. We are only aware of a single
report of the design of an extractive distillation process using
simulated annealing18 and in that work a rigorous process
simulator was not used for the process modeling. In this
research, the simulated annealing method is applied to obtain
the optimal design of three extractive distillation processes that
are used for separating minimum-boiling binary azeotropes.
The simulated annealing code interfaces with a rigorous
process simulator (Aspen Plus) via an automation server.
Received: February 12, 2018
Revised: July 9, 2018
Accepted: July 18, 2018
Published: July 18, 2018

© 2018 American Chemical Society 11050 DOI: 10.1021/acs.iecr.8b00711

Ind. Eng. Chem. Res. 2018, 57, 11050−11060
Industrial & Engineering Chemistry Research Article

Figure 1. Two-column process for extractive distillation.

2. METHODS
2.1. Simulated Annealing. The simulated annealing
method was originally proposed by Kirkpatrick19 based on
the work of Metropolis et al.20 Suman and Kumar21 presented
a comprehensive review of simulated annealing (SA)-based
optimization algorithms for single-objective and multiobjective
problems. The method is based on the concept of annealing in
metalwork. Initially, molecules of melts are disordered at high
temperature. As the metal cools, at each temperature, the
molecules are assumed to be in thermodynamic equilibrium.
Also new random values of variables are generated and the
system may change to another energy state. For optimization,
the energy state is the variable to be minimized, in this work,
the total annual cost of the process. If the new state has lower
energy, this move is accepted. However, if the new state has a
higher energy, the move is accepted when the acceptance
probability is greater than a random value generated over a
uniform distribution (eq 1). According to the Metropolis

ÄÅ ÉÑ
ÅÅÅ Enew − Eold ÑÑÑ
criteria, the acceptance probability is defined as follows:
i ΔE yz
= expÅÅÅ− ÑÑ = expjjj− zz
Ñ
ÅÅÇ ÑÑÖ k T {
P{Enew }
Pacc =
P{Eold} KbT
(1)
where ΔE is the difference of the normalized energy between Figure 2. Flowchart for SA algorithm.
the new and the old states. The optimization ends when the
temperature reaches the freezing temperature. (6) Decrease the temperature according to the cooling
The procedure for the simulated annealing algorithm is schedule. Then reset i = 1 and repeat steps 2−5 until the
illustrated in Figure 2: final temperature is reached.
(1) Start with a given initial temperature, final temperature Parameter settings for the SA algorithm have an important
and solution space. impact on the results of the optimization process. Many people
(2) Perturb di in the neighborhood to generate a new including Aarts and Krosr,22 Patel et al.,23 and Painton and
solution vector dnew. Diwekar24 discussed parameter selection. Parameter selection
(3) Reevaluate the objection function E(dnew) and calculate in this work is described in detail in the Supporting
ΔE = E(dnew) − E(di). Information.
(4) If ΔE ≤ 0, then accept the new value dnew by setting di+1 2.2. Implementation of the SA Algorithm. The Aspen
= dnew. If exp(−ΔE/T) ≥ U(0,1), also accept di+1. Plus ActiveX Automation Server enables external Windows
U(0,1) is a random number between 0 and 1. Otherwise programs to transfer data to and from Aspen Plus.25 Input
set di+1=di. variables and results in an Aspen Plus simulation are organized
(5) Return to step 3 until the system reaches thermody- in a tree structure. Most of the properties of simulation can be
namic equilibrium at temperature T. accessed through the automation server, but some properties
11051 DOI: 10.1021/acs.iecr.8b00711
Ind. Eng. Chem. Res. 2018, 57, 11050−11060
Industrial & Engineering Chemistry Research
of the simulation are read-only. Most important operations
such as changing input variables, connecting blocks in the
flowsheet, running a simulation and retrieving results can all be
accomplished via the automation server. Matlab can also
function as an automation client.26
While running the SA algorithm, one of two special cases
may arise that must be handled by the code. One is that the
Aspen Plus flowsheet fails to converge, and the other is that the
Aspen Plus program crashes. To recover from these cases
automatically, an improved simulated annealing algorithm was
developed. If the flowsheet fails to converge, the algorithm
rejects that point and tries another point. The rejected point
does not count toward the equilibrium detection. To handle
the case where Aspen Plus crashes, a second instance of Matlab
is run in the background. The code running in this instance
checks periodically to determine if Aspen Plus has stopped
responding (crashed). If Aspen Plus has crashed, the Aspen
Plus task is killed (using the Windows command taskkill),
Aspen Plus is restarted, and the optimization continues from
the last successful point.
It was observed that the basic SA algorithm sometimes failed
to approach the global minimum after a single run. Therefore,
the procedure was modified as shown in Figure 3 so that the
Figure 3. Optimization procedure.
SA algorithm was run several times, each time starting with the
ending point from the previous run (or turn). The same
optimization parameters (temperature trajectory, etc.) were
used for each turn. The procedure is run until no significant
change (0.01% for the acetone-methanol separation, 0.1% for
the other cases) in the TAC is detected after five turns.
3. CASE STUDIES
3.1. Separation of Acetone and Methanol. Acetone
and methanol have similar normal boiling points (329.2 and
337.5 K) and a minimum-boiling azeotrope. Luyben and
Chien1 studied three candidate entrainers for the separation:
DMSO, water, and chlorobenzene. They studied both steady-
state economics and dynamic control of the processes and
presented a comparison of the three solvents. The designs that
they presented are used as the starting point (initial condition)
for the optimization performed in this work.
11052
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Figure 4. Txy diagram for acetone and methanol at 1 atm.
Figure 5. Relative volatility curve.
The Txy diagram for mixtures of aceteone and methanol as
predicted using the UNIQUAC model is shown in Figure 4.
The model predicts that the minimum-boiling azeotrope at 1
atm occurs at 77.6 mol % acetone and 328.4 K. Figure 5 shows
the relative volatility curve for the three candidate solvents
calculated using a flash unit in Aspen Plus. For the column
design, the solvent feed temperature is 320 K and the mixture
feed flow rate of all the cases is assumed to be 540 kmol/h of
50/50 mol % acetone-methanol mixture at 320 K. All columns
are designed to operate at atmospheric pressure. The purities
of the overhead and bottom compositions are achieved by
manipulating the reflux ratio and the reboiler duty using the
“Design Spec/Vary” feature in Aspen Plus. To facilitate
comparison with the work of Luyben and co-workers,1,27 for
the separation of acetone and methanol, we performed all TAC
calculations using economic basis 1 described in the
Supporting Information. Figure 6 shows the actual process
flowsheet, and Figure 7 shows the process flowsheet as it is
simulated in Aspen Plus, with a torn recycle stream.
3.1.1. Water as an Entrainer. On the basis of sensitivity
tests in Aspen Plus, the constraints on the design variables
were specified as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤
N2 ≤ 60, 2 ≤ NF2 ≤ N2−1, 500 ≤ FE ≤ 1500. The TAC given
by Luyben for their extractive system is $3 750 000/year for
the same purity of products. The results of the annealing
process are shown in Figure 8. Figure 8a shows the results after
the first run of the SA algorithm. The results indicate that the
TAC decreases while temperature decreases and finally a point
near the global minimum TAC is obtained. The minimum
point from the first run is taken as the starting point of the
second run. Figure 8b shows the annealing result of the second
run. The optimal design results for each turn are shown in
DOI: 10.1021/acs.iecr.8b00711
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Industrial & Engineering Chemistry Research
Figure 6. Proposed design flowsheet of acetone and methanol mixture.
Figure 7. Flowsheet simulated in Aspen Plus
Figure 8. Annealing processes for the system: (a) result of 1st turn, (b) result of 2nd turn.
Table 1. For the following 5 turns, the optimal result remains
nearly the same as $3 264 600/year, which is a decrease of
12.94% compared with the initial condition ($3 750 000/year).
Because these results were carried out in the Aspen Plus
using a flowsheet with a torn recycle stream (as shown in
Figure 7), a validation of the results was conducted. All of the
11053
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parameters from the SA procedure results were specified
manually in Aspen Plus. The results, which are shown in Table
2, indicate a deviation in the TAC of 2.1%. The difference is
probably due to impurity in the recycle stream.
3.1.2. DMSO as an Entrainer. DMSO has much higher
boiling point than both of the components to be separated.
DOI: 10.1021/acs.iecr.8b00711
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Table 1. Optimal Design Result of SA Algorithm in Each The acetone product and the methanol product are held to be
Turn Using Water Solvent 99.95 mol %, which is slightly higher than the case when water
is used as solvent, because the solvent is more effective so a
SA (first SA (second
conventional turn) turn) higher purity product can more easily be obtained. The same
NR 24 39 39
values of parameters for the SA algorithm were used. The
NS 17 15 15
constraints on the design variables are specified as 0 ≤ NR ≤
NE 15 30 30 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤ N2 ≤ 60, 2 ≤ NF2 ≤ N2−1,
N2 26 31 31 100 ≤ FE ≤ 1000.
NF2 14 21 21 The optimum design and economics are shown in Table 3.
entrainer 1100 850 842 The TAC decreases to $2 422 900/year, which is a decrease of
capital cost ($ × 106) 3.03 3.28 3.29 12.53% compared to the starting point. A comparison of the
energy cost ($ × 106/year) 2.72 2.18 2.17 results between the flowchart with the torn recycle stream and
TAC ($ × 106/year) 3.75 3.27 3.27 the complete flowchart is shown in Table 4. There is a 0.29%
deviation between the results.
Table 2. Comparison of Results before and after Joining 3.1.3. Chlorobenzene as an Entrainer. In this system,
Stream Using Water Solvent methanol is collected overhead in the extractive distillation
column and acetone is collected overhead in the solvent
results before results after recovery column. The same values of parameters for the SA
joining stream joining stream
algorithm were used and the constraints on the design variables
C1 ID(m) 2.40 2.45
were specified as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤
QR(MW) 8.78 9.11
N2 ≤ 60, 2 ≤ NF2 ≤ N2−1, 500 ≤ FE ≤ 2500. The TAC
QC(MW) 7.63 7.96
decreases to $3 216 600/year as shown in Table 5, which
C2 ID(m) 1.68 1.68
represents a decrease of 34.75% compared with the starting
QR(MW) 5.90 5.91
QC(MW) 5.80 5.80
point ($4 930 000/year).
cooler QHX(MW) 1.08 1.08
Table 6 shows the deviation of 2% between the flowsheet
total total capital ($ × 3.29 3.33
with the torn recycle stream and the complete flowsheet. For
system 106) this case, to connect the recycle stream in Aspen Plus using the
total energy ($ × 2.17 2.23 same parameters from SA results, the constraint on the
106/year) composition of chlorobenzene in the recycle stream was
TAC ($ × 106/year) 3.27 3.34 increased from 99.90 mol % to 99.99 mol %. Therefore, the
energy consumption in the second column increased slightly
Table 3. Optimal Design Result of SA Algorithm in Each compared to the former systems.
Turn Using DMSO Solvent 3.2. Separation of N-Hexane and Ethyl Acetate. N-
SA (first SA (second hexane and ethyl acetate are used as organic solvents in
conventional turn) turn) pharmaceutical industry and form a homogeneous minimum-
NR 3 3 3 boiling azeotrope. According to Acosta et al.,28 the azeotropic
NS 13 18 18 mixture boils at 338 K with a mole fraction of n-hexane equal
NE 20 29 30 to 0.657. Figure 9 shows the Txy diagram for mixtures of n-
N2 17 11 11 hexane and ethyl acetate at 1 atm using the UNIQUAC
NF2 8 5 5 equation with, which indicates an azeotrope with a
entrainer 750 471 459 composition of 66 mol % n-hexane at 338.3K. Figure 10
capital cost ($ × 106) 2.08 2.2644 2.2896 shows the relative volatility curve for different solvents. It can
energy cost ($ × 106/year) 2.08 1.6698 1.6597 be seen from the figure that the relative volatility with the
TAC ($ × 106/year) 2.77 2.4246 2.4229 solvent DMF is larger than that with NMP, 2-methylpyridine,
3-methylpyridine, and pyrrole. Pyrrole has the worst perform-
Table 4. Comparison of Results before and after Joining ance, so the others are taken as the candidate solvents. For the
Stream Using DMSO Solvent simulation, the feed is taken to be 100 kmol/h of 66.87 mol %
results before results after
n-hexane and 33.13 mol % ethyl acetate. For this separation, all
joining stream joining stream TAC calculations are performed using economics basis 2 as
C1 ID(m) 2.01 2.05 described in the Supporting Information.
QR(MW) 6.83 6.86 3.2.1. DMF as an Entrainer. DMF is the most effective
QC(MW) 5.11 5.14 entrainer considered for this mixture and high product purities
C2 ID(m) 1.69 1.69 can be achieved using this entrainer. The n-hexane and ethyl
QR(MW) 4.37 4.37 acetate products are specified to be 99.5 mol % pure, and this
QC(MW) 3.02 3.02 is achieved in part by holding the bottoms composition in the
cooler QHX(MW) 2.90 2.90 extractive column of 0.1 mol % n-hexane. The range of the
total total capital ($ × 2.28 2.29 design variables was determined based on sensitivity analysis in
system 106) Aspen Plus as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤ N2
total energy ($ × 1.66 1.67 ≤ 60, 2 ≤ NF2 ≤ N2−1, 50 ≤ FE ≤ 250.
106/year)
Then a SA-based optimization was performed. The results
TAC ($× 106/year) 2.42 2.43
after each turn are shown in Table 7. In this study, the TAC of
all the overall process with DMF solvent using extractive
11054 DOI: 10.1021/acs.iecr.8b00711
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Industrial & Engineering Chemistry Research Article

Table 5. Optimal Design Result of SA Algorithm in Each Turn Using Chlorobenzene Solvent
conventional SA (1st turn) SA (2nd turn) SA (3rd turn) SA (4th turn) SA (5th turn) SA (6th turn)
NR 16 32 31 26 30 32 30
NS 12 11 16 16 15 16 16
NE 16 21 28 32 31 32 31
N2 18 18 18 20 21 20 19
NF2 10 7 7 8 9 8 7
entrainer 1900 1252 1029 1001 1001 993 994
capital cost ($ × 106) 3.48 3.3666 3.3162 3.3132 3.3429 3.3651 3.3240
energy cost ($ × 106/year) 3.78 2.3392 2.1390 2.1252 2.1142 2.0960 2.1086
TAC ($ × 106/year) 4.93 3.4614 3.2444 3.2296 3.2285 3.2177 3.2166

Table 6. Comparison of Results before and after Joining Table 7. Optimal Design Result of SA Algorithm in Each
Stream Using Chlorobenzene Solvent Turn Using DMF Solvent
results before results after 1st turn 2nd turn 3rd turn 4th turn
joining stream joining stream
NR 23 17 17 22
C1 ID (m) 2.79 2.80 NS 17 12 18 8
QR (MW) 10.27 10.33 NE 12 8 11 21
QC (MW) 5.88 5.95 N2 16 16 14 13
C2 ID (m) 2.05 2.12 NF2 10 10 8 7
QR (MW) 3.96 4.25 entrainer 198 173 102 71
QC (MW) 4.08 4.35 column cost ($ × 105) 9.5087 8.8768 8.0291 7.4141
cooler QHX (MW) 4.10 4.10 make-up entrainer cost 2.0463 2.0079 1.7350 1.6416
total total capital ($ × 3.32 3.36 ($ × 105)
system 106) cooler cost104 $) 2.7332 2.4635 1.6432 1.2502
total energy ($ × 2.11 2.16 TAC($105/year) 11.8280 11.1310 9.9285 9.1808
106/year)
D1(n-hexane) 0.9950 0.9950 0.9950 0.9950
TAC ($ × 106/year) 3.22 3.28
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990

mol % pure. Higher purities are selected because the solvent is

Figure 9. Txy diagram for n-hexane and ethyl acetate at 1 atm.
Figure 10. Relative volatility curve.
distillation is $918 080/year. The computation time was about
4 hours.
3.2.2. NMP as an Entrainer. Yuan et al.29 considered NMP
as an entrainer and presented an optimum design with the
mass fraction of the light component (n-hexane) in this
mixture reaching 99.00%. In our research, the n-hexane
product and ethyl acetate product are specified to be 99.50
11055
so effective that the purities can be obtained with little increase
in energy cost. The parameters for the SA process were the
same as before and the constraints on the design variables were
specified as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤ N2 ≤
60, 2 ≤ NF2 ≤ N2−1, 50 ≤ FE ≤ 300.
The values of the design variables after each turn are shown
in Table 8. The values fluctuate from turn to turn as the
solvent concentration in the recycle stream changes (ranging
from 99.90 mol % to almost 100%). However, higher solvent
composition in the recycle stream increases the energy
consumption and cost of the second column. So in the
optimum design, the solvent composition is set to be 99.90
mol %. After eight turns of SA, the TAC decreases to
$1 032 600/year, a 12.30% decrease from the initial result of
$1 177 300/kmol. The computing time was almost 9 h, which
is significantly higher than the case using DMF solvent.
3.2.3. 2-Methylpyridine as an Entrainer. 2-Methylpyridine
is a less effective solvent, so achieving 99.50 mol % purity for
each product requires a greater solvent flow rate. As before, the
bottoms composition in the extractive column is fixed at 0.01
mol % n-hexane. The parameters of the SA algorithm are set
the same as before and the constraints on the design variables
were specified as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤
N2 ≤ 60, 2 ≤ NF2 ≤ N2−1, 50 ≤ FE ≤ 300.
We were unable to find a reliable value for the cost of this
entrainer in the open literature, therefore the design was
optimized for two different values of the entrainer cost: $50/
kmol and $300/kmol. When solvent cost is set at 50$/kmol,
the values of all the design parameters after each turn are listed
in Table 9. After six turns of the SA procedure, the optimized
TAC is $1 265 200/year, which is a decrease of 17.46%
DOI: 10.1021/acs.iecr.8b00711
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Table 8. Optimal Design Result of SA Algorithm in Each Turn Using NMP Solvent
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn 7th turn 8th turn
NR 5 5 9 8 11 12 8 7
NS 5 7 6 8 10 9 9 8
NE 6 7 7 9 9 11 10 11
N2 39 40 38 31 26 19 9 10
NF2 11 8 5 5 7 11 4 5
entrainer 157 150 150 117 121 116 106 100
column cost ($ × 105 ) 9.0211 8.7508 8.5218 7.5384 7.5771 7.3195 6.8955 6.7787
make-up entrainer cost ($ × 105) 2.4183 2.4989 2.5618 3.0471 2.9584 3.0471 3.2145 3.3202
cooler cost ($ × 104 ) 3.3385 3.2227 3.2161 2.6229 2.6792 2.5720 2.3693 2.2665
TAC ($ × 106/year) 1.1773 1.1572 1.1405 1.0848 1.0803 1.0614 1.0347 1.0326
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 9. Optimal Design Result of SA Algorithm in Each Turn Using Solvent Cost $50/kmol
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn
NR 11 9 14 11 9 10
NS 39 32 33 24 13 14
NE 29 25 29 31 43 38
N2 31 10 37 51 32 25
NF2 11 9 9 20 10 10
entrainer 211 213 219 198 181 181
column cost ($ × 106 ) 1.4457 1.2804 1.2723 1.2481 1.1793 1.1799
make-up entrainer cost ($ × 104) 6.0103 6.6533 5.6109 5.9325 6.7374 6.1429
cooler cost ($ × 104 ) 2.7038 2.7610 2.8078 2.6531 2.4096 2.3832
TAC ($ × 106/yearr) 1.5328 1.3746 1.3565 1.3340 1.2708 1.2652
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 10. Optimal Design Result of SA Algorithm in Each Turn Using Solvent Cost $300/kmol
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn
NR 22 31 33 31 14 13
NS 32 22 21 15 22 18
NE 21 23 26 35 46 43
N2 35 42 36 32 32 24
NF2 24 24 20 21 14 8
entrainer 247 246 223 208 174 187
column cost $ × (106 ) 1.4670 1.3468 1.3196 1.2996 1.2203 1.1934
make-up entrainer cost ($ × 105 ) 3.9253 3.2562 3.3142 3.3521 3.4552 3.4585
cooler cost ($ × 104 ) 3.0690 3.0926 2.8452 2.6787 2.3389 2.4389
TAC ($ × 106/year) 1.8903 1.7033 1.6794 1.6616 1.5892 1.5636
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

compared to the result after the first turn. The optimum
solvent flow rate is 181 kmol/h. When the solvent cost is set as
$300/kmol, the design results after each turn, presented in
Table 10, show that the TAC decreases to $1 563 600/year.
The optimum solvent flow rate in this case is 187 kmol/h,
which is very close to the result when the solvent cost is $50/
kmol.
3.2.4. 3-Methylpyridine As an Entrainer. When 3-
methylpyridine is used to separate the mixture, an even greater
solvent flow rate is required to achieve the desired 99.50 mol %
n-hexane purity and 99.50 mol % ethyl acetate purity. To
implement the SA procedure, we adopted the same SA
11056
parameters and design variable constraints used for the 2-
methylpyridine case.
Again we were unable to find a reliable value for the cost of
this entrainer in the open literature; therefore, the design was
optimized for two different values of the entrainer cost: $50/
kmol and $300/kmol. The results using an entrainer cost of
$50/kmol are shown in Table 11, and the results using solvent
cost of $300/kmol are shown in Table 12. The optimal solvent
flow rate is similar for both cases.
3.3. Separation of N-Hexane and Tetrahydrofuran. N-
Hexane and tetrahydrofuran are widely used as solvents in
industry and the boiling points are very close (339.1 K for
THF, 341.4 K for n-hexane). Vapor−liquid equilibrium data
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Table 11. Optimal Design Result of SA Algorithm in Each Turn Using Solvent Cost $50/kmol
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn 7th turn
NR 10 6 7 6 7 7 6
NS 35 42 20 16 16 16 15
NE 20 22 30 43 53 51 50
N2 40 34 32 22 22 21 22
NF2 13 10 15 8 8 8 8
entrainer 448 435 413 302 284 285 289
column cost ($ × 106) 1.7300 1.6873 1.5369 1.4037 1.4042 1.4042 1.3995
make-up entrainer cost ($ × 104) 4.5841 5.6174 5.3438 5.6479 5.3870 5.3720 5.6708
cooler cost ($ × 104) 5.4399 5.2671 5.0398 3.8804 3.6989 3.7033 3.7495
TAC ($ × 106/year) 1.8303 1.7962 1.6407 1.4990 1.4951 1.4949 1.4937
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 12. Optimal Design Result of SA Algorithm in Each Turn Using Solvent Cost $300/kmol
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn 7th turn 8th turn
NR 11 10 10 9 8 8 8 8
NS 28 23 20 15 16 19 16 16
NE 24 22 25 30 34 34 50 44
N2 35 28 29 32 31 31 22 22
NF2 14 12 7 14 11 11 8 8
entrainer 421 439 423 384 362 342 292 304
column cost ($ × 106 ) 1.6160 1.6080 1.5692 1.5041 1.4703 1.4607 1.4107 1.4100
make-up entrainer cost ($ × 105) 2.8168 2.7755 2.8179 2.9231 3.0101 3.0459 3.1601 3.1003
cooler cost ($ × 104) 5.1402 5.2572 5.1128 4.7581 4.5351 4.3369 3.7799 3.9006
TAC ($ × 106/year) 1.9490 1.9381 1.9022 1.8440 1.8167 1.8086 1.7609 1.7591
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 13. Optimal Design Result of SA Algorithm Using

NMP Solvent in Each Turn
1st turn 2nd turn 3rd turn
NR 5 5 5
NS 15 16 16
NE 16 17 16
N2 18 8 8
NF2 6 4 4
entrainer 105 92 94
column cost ($ × 105) 7.4536 7.1771 7.1751
make-up entrainer cost ($ × 105) 9.8422 9.8812 9.8777
Figure 11. Txy diagram for n-hexane-THF at 1 atm. cooler cost ($ × 104) 2.3719 2.1149 2.1507
TAC ($ × 106/year) 1.7533 1.7273 1.7268
D1 (n-hexane) 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990

a temperature of 336.17 K at 100 kPa was reported, which is

Figure 12. Relative volatility curve.
for the binary mixture n-hexane-THF have been reported in
the literature.30 A minimum boiling temperature azeotrope
with an average mass fraction of n-hexane equal to 0.4309 and
11057
very close to the results using the UNIQUAC model for this
system. Figure 11 gives the Txy diagram for the binary system.
Yuan et al.29 proposed four candidate entrainers according
to the polarity principle. The dielectric constant of
tetrahydrofuran is higher than that of n-hexane. N,N-
Dimethylformamide(DMF), N-methyl-2-pyrrolidone(NMP),
2-methylpyridine, and 3-methylpyridine were chosen as
potential entrainers because their dielectric constant is higher
than that of tetrahydrofuran. Figure 12 shows the relative
volatility curve between n-hexane and tetrahydrofuran after
adding different entrainers. From this figure, it is clear that
DOI: 10.1021/acs.iecr.8b00711
Ind. Eng. Chem. Res. 2018, 57, 11050−11060
Industrial & Engineering Chemistry Research Article

Table 14. Optimal Design Result of SA Algorithm Using DMF Solvent in Each Turn
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn
NR 17 17 13 13 18 24
NS 9 11 13 15 18 22
NE 44 46 46 41 36 20
N2 31 12 12 11 11 11
NF2 25 8 7 7 7 7
entrainer 295 207 184 176 131 121
column cost ($ × 105) 10.3460 8.8285 8.3443 8.1710 7.9666 7.8154
make-up entrainer cost ($ × 105) 1.3772 1.2802 1.6184 1.6358 1.2217 1.0936
cooler cost ($ × 104) 3.7782 2.7971 2.5538 2.4643 1.9680 1.8533
TAC ($ × 105/year) 12.1020 10.3880 10.2180 10.053. 9.3851 9.0944
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 15. Optimal Design Result of SA Algorithm in Each Turn Using Solvent Cost $50/kmol
1st turn 2nd turn 3rd turn 4th turn 5th turn 6th turn 7th turn
NR 8 11 8 9 9 9 8
NS 17 16 21 20 25 23 19
NE 37 36 42 56 56 53 23
N2 41 35 35 30 20 20 21
NF2 13 11 10 11 8 8 9
entrainer 433 442 418 355 366 353 370
column cost ($ × 106) 1.6021 1.6012 1.5501 1.5054 1.5016 1.4971 1.4917
make-up entrainer cost ($ × 104) 0.9727 0.2111 1.4626 2.4787 2.2497 2.5165 2.4417
cooler cost ($ × 104) 4.7859 4.8168 4.6107 4.0261 4.0518 3.9397 4.0933
TAC($106/year) 1.6597 1.6514 1.6109 1.5704 1.5646 1.5616 1.5571
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 16. Optimal Design Result of SA Algorithm in Each Table 17. Design Results with Different Solvents
Turn Using Solvent Cost $300/kmol
water DMSO chlorobenzene
2nd C1 NR 39 3 30
1st turn turn 3rd turn 4th turn
NS 15 18 16
NR 14 14 10 10 NE 30 30 31
NS 19 28 32 15 ID (m) 2.45 2.05 2.80
NE 45 44 40 43 QR (MW) 9.11 6.86 10.33
N2 28 23 22 22 QC (MW) 7.96 5.14 5.95
NF2 18 10 9 10 C2 N2 31 11 19
entrainer 410 400 421 401 NF2 21 5 7
column cost ($ × 106) 1.5691 1.5344 1.5522 1.5185 ID (m) 1.68 1.69 2.12
make-up entrainer cost ($ × 5.6621 7.1136 4.9176 7.6819 QR (MW) 5.91 4.37 4.25
104)
QC (MW) 5.80 3.02 4.35
cooler cost ($ × 104) 4.4886 4.3648 4.5342 4.3655
cooler QHX (MW) 1.08 2.90 4.10
TAC ($ × 106/year) 1.6706 1.6491 1.6467 1.6390
entrainer 842 459 994
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950
total capital cost (× 106$) 3.33 2.29 3.36
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 system energy cost ($ × 106/ 2.23 1.67 2.16
B2 (entrainer) 0.9990 0.9990 0.9990 0.9990 year)
TAC ($ × 106/year) 3.34 2.43 3.28

NMP is the most effective entrainer and 3-methylpyridine is

the least effective entrainer. In order to enhance the relative
volatility between the mixture components, only NMP, DMF,
and 2-methylpyridine were considered in this work. The feed
flow rate was taken to be 100 kmol/h with a composition of
38.41 mol % n-hexane, which is close to the mixture azeotropic
point at 1 atm. The design flowsheet was shown by Yuan et
al.29 N-hexane is produced at high purity in the top of the
extractive distillation column and tetrahydrofuran is collected
at high purity in the distillate of entrainer recovery column.
11058
The n-hexane product is specified to be 99.50 mol % pure,
whereas tetrahydrofuran product is held greater than or equal
to 99.50 mol % to make the simulation converge more easily.
For this separation, TAC calculations were performed using
economic basis 2 as described in the Supporting Information.
3.3.1. NMP as an Entrainer. NMP has a much higher
boiling point than either DMF or 2-methylpyridine and should
be the most effective solvent based on the relative volatility
calculations. Yuan et al.29 present an optimized design of an
DOI: 10.1021/acs.iecr.8b00711
Ind. Eng. Chem. Res. 2018, 57, 11050−11060
Industrial & Engineering Chemistry Research Article

Table 18. Design Results of n-Hexane and Ethyl Acetate System with Different Solvents
DMF NMP 2-methylpyridine 2-methylpyridine 3-methylpyridine 3-methylpyridine
NR 22 7 10 13 6 8
NS 8 8 14 18 15 16
NE 21 11 38 43 50 44
N2 13 10 25 24 22 22
NF2 7 5 10 8 8 8
entrainer 71 100 181 187 289 304
entrainer cost 53.489 421.90 50 300 50 300
column cost ($ × 105) 7.4141 6.7787 11.799 11.934 13.995 14.100
make-up entrainer cost ($ × 105) 1.6416 3.3202 0.6143 3.4585 0.5671 3.1003
cooler cost ($ × 104) 1.2502 2.2665 2.3832 2.4389 3.7495 3.9006
TAC ($ × 105/year) 9.1808 10.3260 12.6520 15.6360 14.9370 17.5910
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B1 (n-hexane) 0.0001 0.0005 0.0001 0.0001 0.0001 0.0001
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 0.9950 0.9950
B2 (recycled entrainer) 0.9990 0.9990 0.9990 0.9990 0.9990 0.9990

Table 19. Design Results of n-Hexane-THF System with obtained by the SA procedure is $909 440/year, which is a
Different Solvents decrease of 24.85% compared with the results of the first turn.
3.3.3. 2-Methylpyridine as an Entrainer. The parameters of
2- 2-
DMF NMP methylpyridine methylpyridine SA optimization were set the same with the other cases, and
the constraints on design variables are specified as 0 ≤ NR ≤
NR 24 5 8 10
50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤ N2 ≤ 60, 2 ≤ NF2 ≤ N2−1,
NS 22 16 19 15
NE 20 16 23 43
250 ≤ FE ≤ 500.
N2 11 8 21 22
The annealing process and results using solvent cost of $50/
NF2 7 4 9 10
kmol are shown in Table 15. Another comparison using
entrainer 121 94 370 401
solvent cost of $300/kmol is presented in Table 16. The
entrainer cost 53.489 421.90 50 300
optimum values of the design variables using 2-methylpyridine
column cost ($ × 7.8154 7.1751 14.9170 15.1850
solvent are substantially larger than those using NMP and
105) DMF solvents, because the required solvent flow rate is
make-up entrainer 1.0936 9.8777 0.2441 0.7682 relatively high.
cost ($ × 105) 3.4. Results and Discussion. The separation of methanol-
cooler cost ($ × 1.8533 2.1507 4.0933 0.4366 acetone system using extractive distillation was optimized by
104)
the improved SA method. The results using three different
TAC($ × 105/ 9.0944 17.2680 15.5710 16.390
yearr) solvents are compared with base-case designs presented in the
D1 (n-hexane) 0.9950 0.9950 0.9950 0.9950 literature. A 12.94% decrease is achieved using water, a 12.53%
D2 (ethyl acetate) 0.9950 0.9950 0.9950 0.9950 decrease is achieved using DMSO, and a 34.75% decrease is
B2 (recycled 0.9990 0.9990 0.9990 0.9990 achieved using chlorobenzene. Table 17 shows the comparison
entrainer) of the new results. DMSO is found to be the best entrainer for
the system, consistent with the previous research.
Similarly, the other two azeotropic mixtures are separated
using extractive distillation processes designed using the same
extractive distillation process which produced n-hexane with a SA method. The initial points are randomly chosen and the
purity of 99.10%. They also provided the number of stages in total optimization procedure takes approximately 5−6 h. For n-
each column, the feed stage locations and solvent-to-feed ratio. hexane-ethyl acetate system as shown in Table 18, using DMF
In this work, their results were used as a starting point. The as the solvent results in lower cost compared with other
range of variable settings are shown as 0 ≤ NR ≤ 50, 0 ≤ NS ≤ solvents when n-hexane and ethyl acetate products are
50, 2 ≤ NE ≤ 50, 5 ≤ N2 ≤ 60, 2 ≤ NF2 ≤ N2−1, 50 ≤ FE ≤ specified to be 99.95 mol % pure. For the n-hexane-
500. tetrahydrofuran system as shown in Table 19, minimum
Table 13 gives the detailed results for each turn. The TAC obtained using DMF solvent is $909 440/year, which is
minimum TAC obtained by SA procedure is $1 726 800/year, much lower than for other solvents.
which is a decrease of 1.51% compared with the initial result.
3.3.2. DMF as an Entrainer. DMF has the same effect on
the n-hexane-tetrahydrofuran system: n-hexane is driven 4. CONCLUSION
overhead in the extractive column and tetrahydrofuran can The design of several extractive distillation processes using
be captured by the solvent and later separated in the entrainer Aspen Plus as an automation server was studied in this work. A
recovery column. The same SA parameters are used for this simulated annealing algorithm was written in MATLAB, which
case and constraints on the design variables are specified as 0 ≤ functioned as the automation client. For each case, suitable
NR ≤ 50, 0 ≤ NS ≤ 50, 2 ≤ NE ≤ 50, 5 ≤ N2 ≤ 60, 2 ≤ NF2 ≤ parameters for the optimization algorithm and suitable ranges
N2−1, 50 ≤ FE ≤ 350. for the design variables were determined. Three separations
The design variable parameters and economics of the were studied: acetone and methanol, n-hexane and ethyl
optimum results are shown in Table14. The minimum TAC acetate, and n-hexane and tetrahydrofuran. The results show
11059 DOI: 10.1021/acs.iecr.8b00711
Ind. Eng. Chem. Res. 2018, 57, 11050−11060
Industrial & Engineering Chemistry Research
that the proposed method is quite suitable for the design of
different extractive distillation processes. The method can be
programmed automatically and saves considerable time
compared to manual optimization by sequential iteration.
Simulated annealing with multiple turns can be used to
determine if there is a better solution in the neighborhood of
the solution found after the first turn. Starting the algorithm
from different initial conditions increases the likelihood that
the global optimal result is obtained. The n-hexane-ethyl
acetate case and n-hexane-tetrahydrofuran case demonstrate
that the relative volatility and the price of each entrainer are
important factors for choosing the best entrainer.
■
ASSOCIATED CONTENT
* Supporting Information
S Chem. Eng. 1995, 19 (5), 551−566.
This material is available free of charge via the Internet at
http://pubs.acs.org/. The Supporting Information is available
free of charge on the ACS Publications website at DOI:
10.1021/acs.iecr.8b00711.
Additional information about the economic calculations,
parameters used in the simulated annealing algorithm,
and detailed representative results for the design of one
two-column process (PDF)
■
AUTHOR INFORMATION
Corresponding Author
*E-mail: jeffward@ntu.edu.tw.
ORCID
Jeffrey D. Ward: 0000-0003-0727-7689
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was funded by the Taiwan Ministry of Science and
Technology under grant 105-2221-E-002-208-MY2.
■
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