Chemical Engineering Science 135 (2015) 166178

Contents lists available at ScienceDirect

Chemical Engineering Science

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

Design/optimization of energy-saving extractive distillation process

by combining preconcentration column and extractive
distillation column
Yi An, Weisong Li, Ye Li, Shanyuan Huang, Jian Ma, Changlin Shen, Chunjian Xu n
State Key Laboratory of Chemical Engineering, Co-innovation Center of Chemistry and Chemical Engineering, Tianjin University, Tianjin 300072, China

H I G H L I G H T S

G R A P H I C A L

A B S T R A C T

An innovative two-column extractive distillation process was developed.

The new process is energy efcient
with lower capital investment.

Two systems were investigated to
verify the energy and economic
advantages.
Path from conventional setup to energy-saving new process.

art ic l e i nf o

a b s t r a c t

Article history:
Received 29 January 2015
Received in revised form
25 April 2015
Accepted 2 May 2015
Available online 9 May 2015

In extractive distillation, the addition of entrainer may reverse the relative volatility of the feed
components causing the component with higher-boiling point to be removed as the distillate from the
extractive column. In this study, the energy saving possibility of a three-column extractive distillation
system was studied when this phenomenon occurred. Based on a three-column conventional extractive
distillation system, an innovative energy-saving extractive distillation process with lower capital
investment was developed by combining preconcentration column and extractive distillation column.
Two important case studies were investigated to verify the above-mentioned energy and economic
advantages: the separation of n-propanol-water using N-methyl-2-pyrrolidone (NMP) as entrainer and
the separation of ethyl acetateethanol using furfural as entrainer. In order to separate these two
mixtures, rst a three-column extractive distillation sequence including a preconcentration column was
applied to diluted fresh feedstock. Then, based on this three-column conventional extractive distillation
system, an innovative energy-saving distillation process was developed. For the two separated mixtures,
based on the method of global economic optimization, a scheme with optimum design variables was
developed for both of the conventional distillation and the new proposed distillation processes. Results
revealed that the new process offered 22.76% and 17.25% energy-savings respectively. Similar percentage
of reduction in total annual costs (TAC) can also be obtained when compared to the conventional
distillation process.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
Extractive distillation
Energy-saving
Process design

1. Introduction
Distillation is by far the most important separation process in
chemical engineering, and it exploits the relative volatility

Corresponding author. Tel./fax: 86 22 27404440.

E-mail address: cjxu@tju.edu.cn (C. Xu).

http://dx.doi.org/10.1016/j.ces.2015.05.003
0009-2509/& 2015 Elsevier Ltd. All rights reserved.

difference of the components to achieve desired separation.

However, for systems with close boiling point or azeotropic
systems, a separation by conventional distillation process becomes
difcult or even impossible. For these systems, several nonconventional techniques such as heterogeneous azeotropic distillation,
pressure-swing distillation, and extractive distillation have been
proposed (Doherty and Malone, 2001; Seader and Henley, 1998).
However, the pressure-swing option is not economically feasible if

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

the azeotropic composition is not sufciently sensitive to pressure, and some complexities of dealing heterogeneous azeotropic
distillation, such as multiple steady states, parametric sensitivity
that were clearly illustrated by many authors which consequently
make the design and control challenging (Doherty and Malone,
2001; Seader and Henley, 1998; Widagdo and Seider, 1996).
Extractive distillation is the most widely used form of homogeneous azeotropic distillation due to the low energy consumption
and exible selection of the possible entrainers (Lei et al., 2003;
Sucksmith, 1982). In extractive distillation, a heavier entrainer that
has different interaction with the azeotropic components is added
to alter the relative volatility of the components, thereby effectively breaking the azeotrope. Nowadays, extractive distillation
with ionic liquids or the mixture of ionic liquids and solid
inorganic salt as entrainers attracted more and more attention
(Lei et al., 2014a, 2014b).
An important and special aspect of extractive distillation is that
we are not free to pick which of the components in the feed will be
the distillate from the extractive column. For a given entrainer, one
and only one of the feed components can be recovered in the
distillate from the extractive column, and it is not always the
component with the lowest boiling point. For example, the separation of methanol and acetone using chlorobenzene causes higherboiling methanol to be recovered as the distillate from the extractive
column, and the lower-boiling acetone to leave in the bottom stream
with chlorobenzene. Other entrainers, such as water, dimethyl
sulfoxide (DMSO) causes acetone to be recovered as the distillate
from the extractive column (Kossack et al., 2008; Luyben, 2008a,
2008b; Kotai et al., 2007; Modla and Lang, 2012, 2011; Langston et
al., 2005; Gil et al., 2009). It is important to know which of the feed
components will appear in the distillate stream from the extractive
column in order to design the equipment. Isovolatility curve and
pseudo-binary (entrainer-free) equilibrium diagram are reliable
ways. (Doherty and Malone, 2001; Hsu et al., 2010).
Extractive distillation is widely used in a number of processes
(Lladosa et al., 2011; Pacheco-Basulto et al., 2012; Arin and Chien,
2008; Abushwireb et al., 2007; Wang et al., 2012; Gil et al., 2012; Xu
and Wang, 2006; Hsu et al., 2010), but it is still energy intensive,
different methods to overcome the drawback of energy intensive
have been reported. Process integration is a useful option and it has
been proven that the process integration leads to a signicant
reduction in energy consumption compared to conventional process
with no integration. Doherty et al. (Knapp and Doherty, 1990)
developed thermally-integrated extractive distillation sequences for
the separation of ethanol from water using ethylene glycol as

167

entrainer and methanol from acetone using water as entrainer,

results showed that thermally-integrated extractive distillation system greatly reduced the energy consumption. Abushwireb et al.
(2007) investigated the recovery of aromatics from pyrolysis gasoline using N-methylpyrolidone as entrainer, the results presented in
their report proved that the heat-integrated extractive distillation
system was the best candidate. Luyben (2008b) also studied the
heat-integrated extractive distillation system for the separation of
acetonemethanol using water as entrainer, 27% reboiler duty was
saved as compared to the two-column sequence without thermal
integration. In recent years, the use of dividing wall columns has
drawn considerable attention. Kiss and Suszwalak (2012) studied
bioethanol dehydration by extractive dividing-wall column (E-DWC)
system, which led to 10% energy savings. In our previous study, the
E-DWC system was used to separate methylalmethanol mixture,
results showed that 8% reboiler duty could be saved (Xia et al., 2012).
Wu et al. (2013) made a critical assessment of the energy-saving
potential of E-DWC, they found that the energy-saving potential of
E-DWC was limited.
Although the methods mentioned above are energy efcient,
they have some defects along the way. For example, heat-integrated
extractive distillation systems lead to high investment cost (Knapp
and Doherty, 1990). E-DWC has not been widely used in industry yet
due to the complexities of design and control. As stated by Errico
et al. (2013a, 2013b, 2013c), many studies just focus on extractive
distillation column and entrainer recovery column without considering the preconcentration column. The preconcentration column of
the process, which in fact is commonly used in extractive distillation
system especially for diluted fresh feed should also be considered
since they are also energy intensive.
This paper intends to investigate the energy-saving possibility of
extractive distillation system when the adding of the high-boiling
solvent reverse relative volatility of feed components. Based on a
three-column conventional extractive distillation system, an innovative extractive distillation process will be developed. Two case
studies will be used as demonstrating examples to verify the energy
and economic advantages of the new process. In the studies, based
on global economic optimization procedure, an optimum design for
both conventional and innovative process will be investigated.

2. Problem statement and process synthesis procedure

In general, for diluted two-component mixtures, the extractive
distillation process is made up of three columns: preconcentration

MAKEUP
S

D1

D2

D3

F
A+B

B1

B2

B3

B
Preconcentration
column

Extractive distillation
column

Fig. 1. Sketch of conventional extractive distillation process.

Entrainer recovery
column

168

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

distillation column (PDC), extractive distillation column (EDC) and

entrainer recovery column (ERC). The process ow diagram of the
extractive distillation process is presented in Fig. 1. The diluted
mixture AB is fed into the PDC to separate a pure B (higherboiling point) as bottom product and a near-azeotropic composition mixture of AB as distillate product. Then, the distillate
product taken from the PDC is sent afterward to the second
column (EDC). In the EDC unit, the extractive entrainer S is added
near the top of the EDC. Due to the addition of entrainer the
relative volatility of A and B is changed, thereby causing the
component having the greater volatility, not necessarily the
component with the lowest boiling point, is taken overhead as a
pure distillate. The other feed component and S are recovered in
the bottom of the extractive distillation column and then fed to
the ERC. The heavy entrainer S is separated from the remaining
component in ERC and then recycled to the EDC. A small makeup
stream of entrainer is added to balance tiny entrainer losses in
both distillate streams.
As shown in Fig. 1, it is worth noting that two pure B streams
are obtained from the bottom of the PDC and the top of the EDC
respectively, which is an opportunity to improve the energy
efciency. Instead of cooling the overhead vapor of the EDC to
serve as the liquid reux ow, the vapor ow can be directly fed to
the bottom of the PDC, which provides part of the vapor required
for the PDC, thereby causing the vapor ow generated by the
reboiler of the PDC to be reduced. Due to the reduction of the
vapor ow provided by the reboiler of the PDC, the reboiler heat
duty and heat transfer area can then be signicantly decreased.
Part of liquid B stream can be directly fed on the top of the EDC,
thus serving as the liquid-phase ow.
The process ow diagram of the new sequence is presented in
Fig. 2 including two distillation units: combined preconcentration/
extractive distillation column, entrainer recovery column. The rst
column in the sequence can be divided into two sections: the
preconcentration section and extractive distillation section. Its
function corresponds to that of the preconcentration column and

the extractive distillation column in the conventional extractive

distillation system. The preconcentration section and extractive
distillation section is in fact acting as the PDC and EDC unit of the
conventional sequence respectively.
The diluted mixture AB is fed into the preconcentration
section, and a near-azeotropic composition mixture of AB is
removed as distillate. Then, the distillate product taken from the
preconcentration section is sent afterward to the extractive
distillation section. The feed component A and S are recovered in
the bottom of the rst column and then fed to the ERC. The heavy
entrainer S is separated from component A in ERC and then
recycled to the rst column. As shown in Fig. 2, there is only one
product B stream rather than two products B stream in Fig. 1, and
it is removed as liquid side stream of the rst column. It is worth
noting that the intermediate heat exchange is an option. If the
vapor ow provided by the extractive distillation section is not
sufcient, a sidestream reboiler has to be installed to return the
required amount of vapor ow to the preconcentration section.
Otherwise, the sidestream reboiler is not required.
Hence, a two-column extractive distillation system is generated
by combining preconcentration/extractive distillation columns
which is energy efcient as well as has lower capital investment.
In this paper, two case studies are studied to testify the abovementioned energy and economic advantages: the separation of npropanol/water using N-methyl-2-pyrrolidone (NMP) as entrainer,
and the separation of ethyl acetate/ethanol using furfural as
entrainer.

3. Process design and economical optimization

The new process is more complicated when compared with the
conventional extractive distillation process. Also from the analysis
above, the conventional extractive distillation process can be
directly retrotted to the new process. Therefore, the steady state
design begins from the conventional extractive distillation system.

F
A+B

Preconcentration
section

D1

D2
A

B
MAKEUP
S

Extractive
distillation
section

B1

B2

A+S

Combined
preconcentration/extractive
column

Entrainer
recovery
column

Fig. 2. Sketch of combined preconcentration/extractive distillation process.

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

For the new process, the rst column is a special column with
complex conguration. From Figs. 1 and 2 the path from conventional process to the new process, it is clear to know that when the
combined preconcentration/extractive distillation column is
decomposed, it should be exactly the PDC and EDC in the
conventional extractive distillation system. Thus, after we get the
optimal design variables of the conventional extractive distillation
system, the optimum design variables of the conventional extractive distillation system can be directly applied to the new process.
Therefore, the original optimal congurations are all kept the same
in the new process (Errico et al., 2014a, 2014b).
3.1. Process design
In this work, the commercial software Aspen Plus V7.1 was
used in the steady state simulations. The desired product quality
requirements were achieved by the Design Spec/Vary feature in
Aspen Plus. In all cases, the reux ratio and distillate rate were
used as the operation variables of each column.
The PDC and the ERC are all simple columns with one feed
stream and two product streams. It's easy to design these two
columns. The EDC with two feed streams and two product streams,
it is more complicated. There are some very simple and reliable
tools can be used. Residue curve maps that allow us to determine
whether the entrainer is feasible and they can be used as simple
method to analysis and design feasible extractive distillation
sequence (Doherty and Malone, 2001; Doherty and Caldarola,
1985). It is important to know which of the feed components will
appear in the distillate stream from the extractive column in order
to design the equipment. Isovolatility curve is a reliable way, plot the
isovolatility curve on the composition triangle. If the curve intersects the A-S edge, then component A will be the distillate from the
extractive column, otherwise component B will appear in the
distillate stream (Doherty and Malone, 2001; Hsu et al., 2010). A
relative volatility at various feed ratios plot is a useful tool to
demonstrate the effectiveness of the entrainer. The feed ratio is a
very important design variable. In fact, there is a minimum value of
feed ratio where the minimum and maximum reux ratios occur
simultaneously. Below this value, we are unable to get the desired
purity of the product. With the sensitivity analysis tool in Aspen
Plus, it can clearly show the feasible range of feed ratio and reux
ratio. It can help us choose the appropriate feed ratio and reux
ratio to meet the product specications.
3.2. Economical optimization
Once a base-case design is developed, the next step is to
optimize the design variables. It is conventional to use the total
annual cost (TAC) as the objective function to be minimized to
screen process candidates, which including annualized capital
costs and operating costs (Douglas, 1988; Muoz et al., 2006;
Kraemer et al., 2009; Harwardt and Marquardt, 2012). The following objective function was used to carry out a global economic
optimization.


TAC 103 $=year C v ir  FCI
1
Table 1
Utility prices.
Utility

Price ($/GJ)

High pressure steam (41 barg)

17.7
Medium pressure steam (10 barg) 14.19
Low pressure steam (5 barg)
13.28
Cooling water
0.354

169

where FCI is the xed capital investment. In this paper, just major
pieces of equipment were concerned, which are the three distillation column vessels (including column internals), three reboilers,
and four condensers. The tray sizing function in Aspen Plus was
used to calculate the diameter of column vessels and sieve plate is
selected in all columns. An overall heat transfer coefcient and a
differential temperature driving force in each heat exchange were
used to calculate the required heat transfer area. Here the overall
heat transfer coefcient and differential temperature for the
condenser and reboiler were all taken from Luyben (2006). A cost
estimation program CAPCOST of Turton was used to estimate all
the major equipment costs (Turton et al., 2009). ir is the xed
capital recovery rate, it is assumed to be 0.3. Cv is the operating
cost, which includes mostly utilities consumption (steam, cooling
water). The utilities consumption costs can be calculated from the
heat duties of reboilers and condensers. High pressure steam with
pressure of 41 barg (254 1C), medium pressure steam with pressure of 10 barg (184 1C) and low pressure steam with pressure of
5 barg (160 1C) and cooling water with temperature of 30 1C are
supposed to be available in the plant. The utility prices taken from
CAPCOST are listed in Table 1 (Turton et al., 2009).
The design variables need to be optimized in the conventional
process include the total stages of the PDC (NT1), the EDC (NT2),
and the ERC (NT3), fresh stream feeding location of the PDC (NF1),
entrainer and fresh streams feeding locations (NFE and NF2) of the
EDC, and the feeding location of the ERC (NF3) and the entrainer
ow rate (S). As so many design variables need to be optimized, a
calculation sequence was established to facilitate the optimization.
Such sequential iterative optimization procedure is clearly demonstrated in Fig. 3 (Liang et al., 2014).

4. Case study: N-propanol and water separation

N-propanol is widely used as solvent or as important ne
chemical in the chemical and pharmaceutical production process.
It is impossible to separate n-propanol from water through
conventional distillation because of the existence of a binary
azeotrope. The n-propanol/water mixture has a minimum azeotrope with composition of about 42.5 mol% n-propanol at 1 atm.
Traditional separation method for the system include heterogeneous azeotropic distillation using cyclohexane or diisopropyl
ether (DIPE) as entrainer (Lee and Shen, 2003; Pienaar et al.,
2013). There is little report about separating this system through
extractive distillation. In this section, conventional extractive
distillation is studied for the separation of this system. The new
combined preconcentration/extractive distillation column setup is
applied to investigate the energy-saving possibility of this extractive distillation system.
4.1. Conventional three-column process
4.1.1. Steady state design analysis
The thermal condition specications of the feed, products, and
recycle solvent streams are listed in Table 2. In all the alternatives
proposed the amount of product is always the same. The RADFRAC
distillation routine was used to design and simulate the processes.
The operating pressure was set at 1 atm for each column at both
the conventional and the new process. The NRTL thermodynamic
model was selected to predict the physical properties in the
simulation and built-in binary interaction parameters was used.
Table 3 shows the binary interaction parameters for the NRTL
model. The tray spacing for each column in the conventional and
the new process was specied as 0.4 m. In this work, we chose
N-methyl-2-pyrrolidone (NMP) as the heavy entrainer. From
Fig. 4a, it is observed that NMP is a feasible entrainer for the

170

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

Fig. 3. Sequential iterative optimization procedure for the conventional extractive distillation system.

Table 2
Specications for streams.
Stream

Conditions

Feed
n-Propanol product
H2O product
NMP entrainer recycle

Saturated liquid
Saturated liquid
Saturated liquid
90.0 1C

Table 3
The binary interaction parameters for the Aspen plus NRTL model.
Binary parameters

n-Propanol (i)
H2O(j)

n-Propanol (i)
NMP(j)

H2O(i)
NMP(j)

Aij
Aji
Bij/K
Bji/K
Cij

0.0
0.0
181.2160
927.9748
0.4687

0.0
0.0
 234.2208
 205.8249
0.3000

0.0
0.0
 120.5810
288.7615
0.3055

separation of n-propanol-water system. That is because the

entrainer NMP does not form any azeotropes with the original
components, and is completely miscible with them in all proportions. The residue curve map has the optimal conguration-the
minimum boiling n-propanol-water azeotrope is the unstable
node, the entrainer NMP is the stable node, and the two components of n-propanol and water are both saddles. From Fig. 4a, it is
observed that isovolatility curve intercepts the water-NMP edge of
the triangle. This observation determines that the overhead
product removed from the EDC should be water (the higherboiling component) and not n-propanol (the lower-boiling component). It is worth mentioning that, in an extractive distillation
system, the component with lower-boiling point cannot

automatically be assumed to be the distillate product removed

from the EDC. From Fig. 4b, it is observed that NMP is an effective
entrainer, causing an increase in the relative volatility of the water
and n-propanol, thus effectively breaking the azeotrope.
Beginning the design process from the PDC, the distillate
composition was specied to be 40.0 mol% n-propanol, a nearazeotropic composition mixture of n-propanol-water. The bottom
composition was specied to be 99.9 mol% water to reduce the
n-propanol loss.
The EDC, its more complicated. The ow rate of the entrainer is
an important design variable. Without appropriate entrainer ow
rate and reux ratio, we are unable to get the desired purity of the
product. With the sensitivity analysis tool in Aspen Plus, several
case studies were made to investigate the effects of changing the
ow rate of entrainer and reux ratio on the product compositions
of the distillate stream from the EDC, which is the water product.
In each case, the number of theoretical plates (NT2), the distillate
rate with different S and RR2 were xed. Fig. 5a shows the effects
of changing the ow rate of NMP and RR2 on the water product of
the EDC with NT2 58. Fig. 5a shows that at any value of the
entrainer ow rate, there is a minimum reux ratio and also a
maximum reux ratio, RRmin and RRmax get closer as we add less
entrainer. At small values of entrainer ow rate there will be a
narrow range of RR2 over which the desired separation is possible.
For a given entrainer ow rate S, there is an optimum reux ratio,
which gives the desired water purity. It is critical to choose the
feasible range of the entrainer ow rate and reux ratio to meet
the water purity. To achieve the desired 99.9 mol% water purity,
the entrainer ow rate must be above 290 kmol/h, and the reux
ratio RR2 is about 0.75. Below this value, the separation is not
possible. Fig. 5b shows the effects of changing the ow rate of
NMP and RR2 on the impurity of n-propanol of the EDC.
Similar with the PDC, the ERC is a simple column. The bottom
composition of NMP purity was specied to be 99.999 mol%, the
reason for the ultra-high purity in NMP is because the impurity in

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

H2O (100.02 C)

Ternary Map (Mole Basis)

2.5

Relative Volatility

0.9
0.8
0.7

87.65 C

0.6
0.5
0.4
0.3
0.2

NMP

2.0

1.5

1.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0

0.1
(203.99 C)

171

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

NMP/Azeotrope Feed Ratio

C3H8O-01
(97.20 C)

XD(mole frac of H2O)

1.000
0.999
S=310kmol/h
0.998

S=300kmol/h

0.997

S=290kmol/h

0.996
0.995

S=280kmol/h
0.8

1.0

1.2

1.4

1.6

1.8

2.0

XD(mole frac of n-propanol)

Fig. 4. (a) Residue curve map with isovolatility curves for the N-propanol-H2O-NMP system at 1 atm. (b) Relative volatility at various feed ratios.

0.005
0.004

S=280kmol/h
S=290kmol/h

0.003

S=300kmol/h
0.002

S=310kmol/h

0.001
0

0.8

1.0

1.2

RR2

1.4

1.6

1.8

2.0

RR2

Fig. 5. (a) Effect of RR2 and entrainer ow rate S in extractive column (NT2 58) on H2O purity. (b) Effect of RR2 and entrainer ow rate S in extractive column (NT2 58) on
impurity of n-propanol.

4.1.2. Economical optimization

Fig. 6 shows the results of the optimization runs for the PDC
with NT1 and NF1 as the design variables. From this plot, the best
NT1 is stage 9 and the best NF1 is stage 6.
Fig. 7a shows the summary of the TAC plots at each entrainer
ow rate for the EDC, it can be observed that the optimal entrainer
ow rate is 330 kmol/h. Fig. 7c shows the results for varying NT2
with the entrainer ow rate xed at 330 kmol/h. From Fig. 7c, the
optimal NT2 is 58. Fig. 7b shows the results of the optimization
runs for varying NF2 and NFE with NT2 xed at 58 and the entrainer
ow rate xed at 330 kmol/h. QR2 is chosen as the objective
function instead of using TAC to investigate the effect of changing
NF2 and NFE. From Fig. 7b, the optimal NFE is stage 6 and the
optimal NF2 is stage 44. The nal optimal design variables for the
EDC are S 330 kmol/h, NT2 58, NFE 6 and NF2 44.
Fig. 8 shows the summary of the TAC plots for the ERC. From
the gure, the optimal NT3 is stage 27 and the optimal NF3 is
stage 8.
4.2. New two-column process
After the optimal design variables of the conventional extractive distillation system are determined, the optimal design

998.0

TAC(x1000$/year)

the NMP will have a very bad inuence on the water purity. A heat
exchanger must be placed between the EDC and the ERC to cool
the NMP temperature. In this case, the temperature of the
entrainer NMP was cooled to be 90.0 1C. This is because Knight
and Doherty (1989) suggested that the entrainer feed temperature
to the EDC should be 515 1C below the boiling temperature of the
distillate product from the EDC.

997.5
997.0
NT1=9 with the
optimum NF1=6

996.5
996.0
995.5
995.0
994.5

10

11

NT1
Fig. 6. TAC vs NT1 with the optimum NF1 plot for the PDC.

variables of the conventional extractive distillation system can

be directly applied to the new process. Thus, the original optimal
congurations are all kept the same in the new process. The
optimal design variables for the PDC and the EDC can be directly
applied to the preconcentration section and extractive section for
the rst column of the new process respectively. The nal
optimum process ow diagrams for the conventional extractive
distillation system and the new process are shown in Fig. 9.
4.3. Process comparison
In this section, heat duty, TAC of the above two processes will
be compared. Table 4 shows the heat duty and the minimized TAC
results for the optimal conventional extractive distillation system
and the new combined preconcentration/extractive column system. It is shown that the total reboiler duty of the new process is

172

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

3340
NFE=5
NFE=6
NFE=7

2371.5
3335
2371.0

QR2/kW

TAC(x1000$/year)

2372.0

2370.5
2370.0

3330
3325

2369.5
2369.0
320

330

340

350

3320
43

44

45

S-solvent flow rate(kmol/h)

46

NF2

TAC(x1000$/year)

2375
2374
2373
2372
2371
2370
2369
54

56

58

60

NT2

TAC(x1000$/year)

Fig. 7. (a) TAC plot at various entrainer ow rate S for the EDC. (b) QR2 vs NFE and NF2 for S 330 kmol/h, NT2 58 plots for the EDC. (c) TAC vs NT2 for S 330 kmol/h plot for
the EDC.

1302

5. Case study: Ethyl acetate and ethanol separation

1301

Ethyl acetate (EA) is an important environmental friendly

solvent, and is industrially used in a wide range of applications.
In the synthetic processes for ethyl acetate, ethyl acetate/ethanol
mixture is commonly obtained. It is impossible to achieve the
separation of ethyl acetate/ethanol mixture by conventional distillation, because the ethyl acetate/ethanol mixture forms a minimum azeotrope with composition of about 46.55 mol% ethanol at
1 atm. The purication techniques for ethyl acetate have been
investigated, such as azeotropic distillation, extractive distillation,
and membrane separation (Berg, 1999; Zhang et al., 2008; Sato
et al., 2008). In this section, conventional extractive distillation is
studied for the separation of this system. The new process is also
applied to investigate the energy-saving possibility of this extractive distillation system.

1300

NT3=27 with the

optimum NF3=8

1299
1298
1297
25

26

27

28

29

30

NT3
Fig. 8. TAC vs NT3 with the optimum NF3 plot for the ERC.

less than that of the conventional design by about 1575.9 kW,

which is about 22.76% saving in total reboiler energy consumption.
The reason is that part of the vapor ow required for the
preconcentration section is provided by the extractive section,
thereby causing the vapor ow provided by the intermediated
reboiler to be reduced. From the economical data, it is observed
that the separation using the new process leads to 15.63% reduction in total capital investment cost, that is because the new
process saves one condenser and the side stream reboiler is much
smaller compared to that of the conventional conguraion. There
is also a signicant reduction in operating cost. The total operating
cost for the conventional process is 3371.4 (103 $/year) while the
new process costs 2752.4 (103 $/year). This represents a reduction
of 18.36% of the cost of the energy, that is mainly because the new
process leads to 22.76% saving in total reboiler energy consumption. The TAC of the new process is 3918.0.0 (103 $/year), this can
be directly compared to the TAC of the conventional process. Thus,
the separation using the optimum new two-column desgin leads
to the reduction in total annual cost as much as 17.57%.

5.1. Conventional three-column process

5.1.1. Steady state design analysis
Table 5 shows the thermal condition specications for the feed,
products, and solvent recycle stream. In all the alternatives
proposed the amount of product is always the same. The RADFRAC
distillation routine was used to design and simulate the processes.
The operating pressure was set at 1 atm for each column at both
the conventional and the new process. The NRTL thermodynamic
model was selected to predict the physical properties in the
simulation and built-in binary interaction parameters was used.
Table 6 shows the binary interaction parameters for the NRTL
model. The tray spacing for each column in the conventional and
the new process was specied as 0.4 m. In this work, we chose
furfural as the heavy entrainer for its low price. From Fig. 10a, it is
observed that furfural is a feasible entrainer for the separation of
ethyl acetate/ethanol mixture. From Fig. 10a, it is observed that
ethanol (the higher-boiling component) is the distillate of the EDC.
From Fig. 10b, it is observed that furfural is an effective entrainer,

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

173

Fig. 9. (a) The optimum process ow diagram for the new combined preconcentration/ extractive column system. (b) The optimum process ow diagram for the
conventional extractive distillation system.

Table 4
Comparision between the optimum conventional design and corresponding new
two-column design.
Conventional process
Heat duty
QRT (kW)
QCT(kW)
Economical data
TIC (103 $)
TOC (103 $/year)
TAC (103 $/year)

New process

Table 5
Specications for streams.
Stream

Conditions

Feed
Ethyl acetate product
Ethanol product
Furfural entrainer recycle

Saturated liquid
Saturated liquid
Saturated liquid
70.0 1C

(%) Difference

6925.3
6876.9

5349.4
5301.0

 22.76
 22.92

4605.3
3371.4
4753.0

3885.3
2752.4
3918.0

 15.63
 18.36
 17.57

causing an increase in the relative volatility of the ethyl acetate

and ethanol, thus effectively breaking the azeotrope.
At the beginning of the design process from the PDC, the
distillate composition was specied to be 45.0 mol% ethyl acetate,

a near-azeotropic composition mixture of ethyl acetate/ethanol.

For column 2, Fig. 11a shows the effects of changing the ow rate
of furfural and RR2 on the ethanol product of the EDC with
NT2 46. To achieve the desired 99.5 mol% ethanol purity, the
furfural ow rate must be set above 390 kmol/h at a reux ratio of
about 1.25. The feed ratio is about 2.36, which is much larger than
the feed ratio 1.94 in case 1 indicating that furfural to the ethyl

174

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

section for the rst column of the new process respectively. The
nal optimum process ow diagram for the conventional extractive distillation system design and the new process design is
shown in Fig. 15.

acetate/ethanol system is less effective than NMP to the npropanol/water system. Fig. 11b shows the effects of changing
the ow rate of furfural and RR2 on the impurity of ethyl acetate
of the EDC. The bottom composition of the ERC was set at
99.999 mol% furfural. A heat exchanger must be placed between
the ERC and the EDC. In this case, the temperature of the entrainer
furfural was cooled to be 70.0 1C.

5.3. Process comparison

In this section, heat duty, TAC of the above two processes for
the separation of ethyl acetate/ethanol were compared. Table 7
shows the heat duty and the minimized TAC results for the
optimal conventional extractive distillation system and the new
combined preconcentration/ extractive column system. It is shown
that the total reboiler duty of the new process is less than that of
the conventional design by about 1495.9 kW, which is about
17.25% saving in total reboiler energy consumption. From the
economical data, it is observed that the separation using the
new process leads to 14.10% reduction in total capital investment
cost. There is also a signicant reduction in operating cost. The
total operating cost for the conventional process is 3748.7 (103 $/
year) while the new process cost is 3163.2 (103 $/year). This
represents a reduction of 15.62% of the cost of the energy, that is
mainly because the new process leads to 17.25% saving in total
reboiler energy consumption. The TAC of the new process is 4567.2
(103 $/year), this can be directly compared with the TAC of the
conventional process. Thus, the separation using the optimum
new two-column desgin leads to the reduction in total annual cost
by as much as 15.16%.

5.1.2. Economical optimization

Fig. 12 shows the results of the optimization runs for the PDC.
From this plot, the best NT1 is stage 27 and the best NF1 is stage 11.
The result shows that the separation of ethyl acetate/ethanol
system is much more difcult than the separation of n-propanol/
water system.
Fig. 13a shows the summary of the TAC plots at each entrainer
ow rate for the EDC, it can be observed that the optimal entrainer
ow rate is 540 kmol/h. The result also indicates that the entrainer
furfural to the ethyl acetate-ethanol system is less effective than
NMP to the n-propanol-water system. Fig. 13c shows the results
for varying NT2 with the entrainer ow rate xed at 540 kmol/h.
From Fig. 13c, the optimal NT2 is 46. Fig. 13b shows the results of
the optimization runs for varying NF2 and NFE with NT2 xed at 46
and the entrainer ow rate xed at 540 kmol/h. From Fig. 13b, the
optimal NFE is stage 8 and the optimal NF2 is stage 31. The nal
optimal design variables for the EDC are S 540 kmol/h, NT2 46,
NFE 8 and NF2 31.
Fig. 14 shows the summary of the TAC plots for the ERC. From
Fig. 14, the optimal NT3 is stage 25 and the optimal NF3 is stage 11.
5.2. New two-column process

6. Summary and conclusion

Similar to case 1, after the optimal design variables of the

conventional extractive distillation system are determined, the
optimal design variables of the conventional extractive distillation
system can be directly applied to the new process. Thus, the
original optimal congurations are all kept the same in the new
process. The optimal design variables for the PDC and the EDC can
be directly applied to the preconcentration section and extractive

In the extractive distillation process, the adding of high-boiling

entrainer (organic solvent, ionic liquids) may reverse the relative
volatility of the feed components causing the component with
higher-boiling point be removed as the distillate from the extractive column. The energy-saving possibility of extractive distillation
system was investigated when this phenomenon occurred. Based
on a three-column conventional extractive distillation system, an
innovative process by combining preconcentration column and
extractive distillation column was proposed. The new process is
energy efcient with lower capital investment. The main reason is
that part of the vapor ow required for the preconcentration
section is provided by the extractive section, thereby causing the
vapor ow provided by the intermediated reboiler to be reduced.
The new process is not limited to the studied systems which can
also be used to separate other azeotropic and in systems with close
boiling point as long as the bottom product removed from the
preconcentration column and the distillate product removed from
the extractive distillation column have the same composition

Table 6
The binary interaction parameters for the Aspen plus NRTL model.
Binary parameters

Ethanol (i)
Ethyl acetate (j)

Ethanol (i)
Furfural (j)

Ethyl acetate (i)

Furfural (j)

Aij
Aji
Bij/K
Bji/K
Cij

0.0
0.0
216.3048
95.0457
0.3000

0.0
0.0
139.6013
425.8981
0.30000

0.0
0.0
548.0231
 257.2865
0.30000

ETHANOL (78.31 C) Ternary Map (Mole Basis)

Relative Volatility

0.9
0.8
0.7
0.6

72.14 C

0.5
0.4
0.3
0.2
0.1
FURFURAL
(161.35 C)

0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9

C4H8O-01
(77.20 C)

2.8
2.6
2.4
2.2
2.0
1.8
1.6
1.4
1.2
1.0
0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Furfural/Azeptrope Feed Ratio

Fig. 10. (a) Residue curve map with isovolatility curves for the ethanol-ethyl acetate-furfural system at 1 atm. (b) Relative volatility at various feed ratios.

0.998

175

0.010

0.997

XD(mole frac of EA)

XD(mole frac of Ethanol)

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

0.996
S=410kmol/h

0.995
0.994

S=400kmol/h

0.993

S=390kmol/h

0.992
S=380kmol/h

0.991

0.009
0.008

S=380kmol/h

0.007

S=390kmol/h

0.006

S=400kmol/h

0.005
0.004

S=410kmol/h

0.003
0.002
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0

0.990
1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0

RR2

RR2

Fig. 11. (a) Effect of RR2 and entrainer ow rate S in extractive column (NT2 46) on ethanol purity. (b) Effect of RR2 and entrainer ow rate S in extractive column (NT2 46)
on impurity of ethyl acetate.

1457

TAC(x1000$/year)

TAC(x1000$/year)

1911
1910
1909

NT1=27 with the

optimum NF1=11

1908
1907
1906
25

26

27

28

29

30

1456
NT3=25 with the
optimum NF3=11
1455

1454
24

31

25

1927.0

3250

1926.5

3248

QR2/kW

TAC(x1000$/year)

27

Fig. 14. TAC vs NT3 with the optimum NF3 plot for the ERC.

Fig. 12. TAC vs NT1 with the optimum NF1 plot for the PDC.

1926.0
1925.5
1925.0
1924.5
525

26

NT3

NT1

NFE=7
NFE=8
NFE=9

3246
3244
3242
3240

530

535

540

545

550

3238
30

555

31

S-solvent flow rate(kmol/h)

32

33

NF2

TAC(x1000$/year)

1932
1930
1928
1926
1924
42

44

46

48

NT2
Fig. 13. (a)TAC plot at various entrainer ow rate S for the EDC. (b) QR2 vs NFE and NF2 for S 540 kmol/h, NT2 46 plots for the EDC. (c) TAC vs NT2 for S 540 kmol/h plot for
the EDC.

176

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

F
300.000 kmol/hr
0.750 Ethanol
0.250 EA

S MAKEUP

0.100 kmol/hr
1.000 Furfural

2415.6 kW

2
11

26

225.758kmol/hr
1908.4 kW 0.995Ethanol
0.00454 EA
0.000460Furfural

56

B2
536.721kmol/hr
1.2334E-16 Ethanol
1E-05 EA
0.99999 Furfural

S
1atm
3391.8 kW MAKEUP

RR1=1.066

11

26

Preconcentration
column

2028.3 kW

1atm
1481.4kW

1atm
1344.6kW

RR2=0.507

31

45
B1
134.831kmol/hr
0.995 Ethanol
0.005 EA

3399.6kW

2
8

0.1kmol/hr
1.000 Furfural
D1
165.169 kmol/hr
0.550 Ethanol
0.450 EA

24

Entrainer recovery
column

Combined preconcentration/extractive
column

D2
74.347 kmol/hr
0.00499 Ethanol
0.995 EA
0.00001 Furfural

11

D1
165.169kmol/hr
0.550Ethanol
0.450 EA
5.0696E-21Furfural

33

B1
611.068kmol/hr
0.000607Ethanol
3239.9kW 0.121 EA
0.878Furfural

300.000 kmol/hr
0.750 Ethanol
0.250 EA

RR2=1.012

RR1=1.068

70

1atm
1340.9kW

1atm
3395.5kW

3239.2 kW

D2
90.926 kmol/hr
0.995 Ethanol
0.004 EA
0.001 Furfural

B2
614.248 kmol/hr
0.000604 Ethanol
0.120 EA
0.879 Furfural

RR3=1.018

11

24

2033.7kW

Extractive distillation
column

D3
74.342 kmol/hr
0.00499 Ethanol
0.995 EA
0.00001 Furfural

B3
539.906kmol/hr
1.226E-16 Ethanol
1E-05 EA
0.99999 Furfural

2429.9kW

Entrainer recovery
column

Fig. 15. (a) The optimum process ow diagram for the new combined preconcentration/ extractive column system. (b) The optimum process ow diagram for the
conventional extractive distillation system.

specication. Two important systems were used to verify the

energy and economic advantages: the separation of n-propanol/
water and the separation of ethyl acetate/ethanol. Using these two
systems as examples, important observations of this paper are
summarized as below:
1. The separation of n-propanol/water using N-methyl-2-pyrrolidone (NMP) as entrainer and the separation of ethyl acetate/
ethanol using furfural as entrainer causing the component with
higher-boiling point be removed as the distillate from the
extractive column, which are water and ethanol respectively
in these two case studies.
2. The new process is a useful technology to save energy and
lower the capital investment. The optimal design of the

conventional extractive distillation process and the new process were presented. For the two case studies-the separation of
n-propanol/water and ethyl acetate/ethanol, the results show
that the new process leads to energy savings of 22.76% and
17.25% respectively and a similar reduction in capital investment and the total annual costs. In the new process, an
intermediate reboiler was used to meet the energy requirement in the preconcentration section.

Conict of interest
The authors declare no competing nancial interest.

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

Table 7
Comparision between the optimum conventional design and corresponding new
two-column design.

Heat duty
QRT (kW)
QCT(kW)
Economical data
TIC (103 $)
TOC (103 $/year)
TAC (103 $/year)

Conventional process

New process

(%) Difference

8672.5
8647.8

7176.6
7151.9

 17.25
 17.30

5448.0
3748.7
5383.1

4680.0
3163.2
4567.2

 14.10
 15.62
 15.16

Nomenclature
NRTL
E-DWC
PDC
EDC
ERC
NF1
NFE
NF2
NF3
NTn
QCn
QRn
QCT
QRT
NMP
EA
RRn
TAC
TIC
TOC

non-random two liquid

extractive dividing-wall column
preconcentration distillation column
extractive distillation column
entrainer recovery column
feeding location for the fresh feed
feeding location for the entrainer
feeding location for the feed to column EDC
feeding location for the feed to column ERC
number of theoretical plates for column n
condenser duty for column n (kW)
reboiler duty for column n (kW)
total condenser heat duty (kW)
total reboiler heat duty (kW)
N-methyl-2-pyrrolidone
ethyl acetate
reux ratio for column n
total annual costs
total investment costs
total operating costs

Acknowledgment
The authors thank for the support by the Programme of
Introducing Talents of Discipline to Universities (No: B06006)
and the assistance from the staffs in the State Key Laboratories
of Chemical Engineering (Tianjin University).
References
Abushwireb, F., Elakrami, H., Emtir, M., 2007. Recovery of aromatics from pyrolysis
gasoline by conventional and energy-integrated extractive distillation. Comput.
Aided. Chem. Eng. 24, 10711076.
Arin, S., Chien, I., 2008. Design and control of an isopropyl alcohol dehydration
process via extractive distillation using dimethyl dulfoxide as an entrainer. Ind.
Eng. Chem. Res. 47, 790803.
Berg, L., 1999. Separation of Ethyl Acetate from Ethanol by Azeotropic Distillation,
US Patent 5993610.
Doherty, M.F., Caldarola, G.A., 1985. Design and synthesis of homogeneous
azeotropic distillations. 3. The sequencing of columns for azeotropic and
extractive distillations. Ind. Eng. Chem. Fundam 24, 474485.
Doherty, M.F., Malone, M.F., 2001. Conceptual Design of Distillation Systems, rst
ed. McGraw Hill, New York.
Douglas, J.M., 1988. Conceptual Design of Chemical Processes. McGraw-Hill,
New York.
Errico, M., Rong, B.-G., Tola, G., Spano, M., 2013a. Optimal synthesis of distillation
systems for bioethanol separation. Part 1: Extractive distillation with simple
columns. Ind. Eng. Chem. Res. 52, 16121619.
Errico, M., Rong, B.-G., Tola, G., Spano, M., 2013b. Optimal synthesis of distillation
systems for bioethanol separation. Part 2: Extractive distillation with complex
columns. Ind. Eng. Chem. Res. 52, 16201626.
Errico, M., Rong, B.-G., Tola, G., 2013c. Optimal synthesis and design of extractive
distillation systems for bioethanol separation: from simple to complex columns. Comput. Aided. Chem. Eng. 32, 373378.

177

Errico, M., Pirellas, P., Torres-Ortega, C.E., Rong, B.-G., Segovia-Hernandez, J.G.,
2014a. A combined method for the design and optimization of intensied
distillation systems. Chem. Eng. Process. 85, 6976.
Errico, M., Rong, B.-G., Torres-Ortega, C.E., Segovia-Hernandez, J.G., 2014b. The
importance of the sequential synthesis methodology in the optimal distillation
sequences design. Comput. Chem. Eng. 62, 19.
Muoz, R., Montn, J.B., Burguet, M.C., Torre, J., 2006. Separation of isobutyl alcohol
and isobutyl acetate by extractive distillation and pressure-swing distillation:
simulation and optimization. Sep. Purif. Technol. 50, 175183.
Luyben, W.L., 2006. Distillation Design and Control Using AspenTM Simulation, rst
ed. John Wiley & Sons, New Jersey.
Gil, I.D., Boti, D.C., Ortiz, P., Sanchez, O.F., 2009. Extractive distillation of acetone/
methanol mixture using water as entrainer. Ind. Eng. Chem. Res. 48,
48584865.
Gil, I.D., Gomez, J.M., Rodrguez, G., 2012. Control of an extractive distillation
process to dehydrate ethanol using glycerol as entrainer. Comput. Chem. Eng.
39, 129142.
Harwardt, A., Marquardt, W., 2012. Heat-integrated distillation columns: vapor
recompression or internal heat integration? AIChE J. 58, 37403750.
Hsu, K.Y., Hsiao, Y.C., Chien, I.L., 2010. Design and control of dimethyl carbonatemethanol separation via extractive distillation in the dimethyl carbonate
reactive-distillation process. Ind. Eng. Chem. Res. 49, 735749.
Kiss, A.A., Suszwalak, D., 2012. Enhanced bioethanol dehydration by extractive and
azeotropic distillation in dividing-wall columns. Sep. Purif. Technol. 86, 7078.
Knapp, J.P., Doherty, M.F., 1990. Thermal integration of homogeneous azeotropic
distillation sequences. AIChE J 36, 969984.
Knight, J.R., Doherty, M.F., 1989. Optimal design and synthesis of homogeneous
azeotropic distillation sequences. Ind. Eng. Chem. Res. 28, 564572.
Kossack, S., Kramer, K., Gani, R., Marquardt, W., 2008. A systematic synthesis
framework for extractive distillation processes. Chem. Eng. Res. Des. 86,
781792.
Kotai, B., Lang, P., Modla, G., 2007. Batch extractive distillation as a hybrid process:
separation of minimum boiling azeotropes. Chem. Eng. Sci. 62, 68166826.
Kraemer, K., Kossack, S., Marquardt, W., 2009. Efcient optimization-based design
of distillation processes for homogeneous azeotropic mixtures. Ind. Eng. Chem.
Res. 48, 67496764.
Langston, P., Hilal, N., Shingeld, S., Webb, S., 2005. Simulation and optimization of
extractive distillation with water as solvent. Chem. Eng. Proc 44, 345351.
Lee, L., Shen, H., 2003. Azeotropic behavior of a water n-propanol cyclohexane
mixture using cyclohexane as an entrainer for separating the water nproponal mixture at 760 mmHg. Ind. Eng. Chem. Res. 42, 59055914.
Lei, Z.G., Li, C.Y., Chen, B.H., 2003. Extractive distillation: a review. Sep. Purif. Rev.
32, 121213.
Lei, Z.G., Dai, C.N., Zhu, J.Q., Chen, B.H., 2014a. Extractive distillation with ionic
liquids: a review. AIChE J 60, 33123329.
Lei, Z.G., Xi, X.M., Dai, C.N., Zhu, J.Q., Chen, B.H., 2014b. Extractive distillation with
the mixture of ionic liquids and solid inorganic salt as entrainers. AIChE J 60,
29943004.
Liang, K., Li, W., Luo, H., Xia, M., Xu, C., 2014. Energy-efcient extractive distillation
process by combining preconcentration column and entrainer recovery column.
Ind. Eng. Chem. Res. 53, 71217131.
Lladosa, E., Monton, J.B., Cruz Burguet, M., 2011. Separation of di-n-propyl ether and
n-propyl alcohol by extractive distillation and pressure swing distillation:
computer simulation and economic optimization. Chem. Eng. Process. 50,
12661274.
Luyben, W.L., 2008a. Effect of solvent on controllability in extractive distillation.
Ind. Eng. Chem. Res. 47, 44254439.
Luyben, W.L., 2008b. Comparison of extractive distillation and pressure-swing
distillation for acetone methanol separation. Ind. Eng. Chem. Res. 47,
26962707.
Modla, G., Lang, P., 2012. Removal and recovery of organic solvents from aqueous
waste mixtures by extractive and pressure swing distillation. Ind. Eng. Chem.
Res. 51, 1147311481.
Modla, G., Lang, P., 2011. Comparison of extractive and pressure-swing batch
distillation for acetone-methanol separation. Comput. Aided. Chem. Eng. 29,
382386.
Pacheco-Basulto, J.A., Hernndez-McConville, D., Barroso-Muoz, F.O., Hernndez,
S., Segovia-Hernndez, J.G., Castro-Montoya, A.J., Bonilla-Petriciolet, A., 2012.
Purication of bioethanol using extractive batch distillation: simulation and
experimental studies. Chem. Eng. Process. 61, 3035.
Pienaar, C., Schiwarz, C.E., Knoetze, J.H., Burger, A.J., 2013. Vaporliquidliquid
equilibria measurements for the dehydration of ethanol, isopropanol, and
n-propanol via azeotropic distillation using DIPE and isooctane as entrainers.
J. Chem. Eng. Data. 58, 537550.
Sato, K., Sugimoto, K., Nakane, T., 2008. Separation of ethanol/ethyl acetate mixture
by pervaporation at 100  130 1C through NaY zeolite membrane for industrial
purpose. Micropor. Mesopor. Mater 115, 170175.
Seader, J.D., Henley, E.J., 1998. Separation Process Principles, rst ed. John Wiley &
Sons, New Jersey.
Sucksmith, I., 1982. Extractive distillation saves energy. Chem. Eng. 28, 9195.
Turton, R., Bailie, R.C., Whiting, W.B., Shaeiwitz, J.A., 2009. Analysis, Synthesis and
Design of Chemical Processes, third ed. Prentice Hall, New Jersey.
Wang, Q., Yu, B., Xu, C., 2012. Design and control of distillation system for methylal/
methanol separation: Part 1: Extractive distillation using DMF as an entrainer.
Ind. Eng. Chem. Res. 51, 12811292.
Widagdo, S., Seider, W.D., 1996. Azeotropic distillation. AIChE J 42, 96130.

178

Y. An et al. / Chemical Engineering Science 135 (2015) 166178

Wu, Y.C., Hsu, P.H.C., Chien, I.L., 2013. Critical assessment of the energy-saving
potential of an extractive dividing-wall column. Ind. Eng. Chem. Res. 52,
53845399.
Xia, M., Yu, B., Wang, Q., Jiao, H., Xu, C., 2012. Design and control of extractive
dividing-wall column for separating methylal-methanol mixture. Ind. Eng.
Chem. Res. 51, 1601616033.

Xu, S.L., Wang, H.Y., 2006. A new entrainer for separation of tetrahydrofuranwater
azeotropic mixture by extractive distillation. Chem. Eng. Process. 45, 954958.
Zhang, D.L., Deng, Y.F., Li, C.B., Chen, J., 2008. Separation of ethyl acetate-ethanol
azeotropic mixture using hydrophilic ionic liquids. Ind. Eng. Chem. Res. 47,
19952001.