Article

pubs.acs.org/IECR

Improving the Performance of Extractive Dividing-Wall Columns

with Intermediate Heating
Jieping Yu,† San-Jang Wang,‡ Kejin Huang,*,† Yang Yuan,† Haisheng Chen,† and Li Shi†
†
College of Information Science and Technology, Beijing University of Chemical Technology, Beijing 100029, P. R. China
‡
Center for Energy and Environmental Research, National Tsing Hua University, Hsinchu 300, Taiwan

ABSTRACT: In spite of the fact that using extractive dividing-wall columns (EDWCs) lead to a considerably reduced reboiler
heat duty in comparison with conventional extractive distillation column (CEDC) flowsheets, the involvement of a heavy
entrainer frequently requires a relatively high-pressure steam for process heating and incurs consequently adverse steady-state
economics. To address the potential deficiency, we proposed, in the present study, to facilitate the EDWC with intermediate
heating because the great boiling-point difference between the components in the azeotropic mixture and entrainer results in
steep temperature profiles and allows effectively recovering sensible heat from the recycled entrainer and using relatively low-
pressure steam. When the extractive separation operation dominates the EDWC, intermediate heating should be arranged in the
left side of the dividing wall and feed preheating is frequently the most favorable option. On the other hand, when the entrainer
recovery operation dominates the EDWC, intermediate heating should be arranged below the lower end of the dividing wall, i.e.,
in the stripping section, and an intermediate reboiler is the favorable option. Under both circumstances, the heat recovery from
the recycled entrainer should be considered prior to the use of available utilities, thereby permitting great improvement in the
steady-state economics. The strategy features simplicity in principle and requires a relatively small number of trial and error
searches. It is evaluated in terms of extractive separations of two binary azeotropic mixtures: dimethyl carbonate and methanol
(with aniline as the entrainer) and acetone and methanol (with dimethyl sulfoxide as the entrainer). It is found that intermediate
heating could substantially enhance the performance of the EDWC with the resultant steady-state economics overwhelmingly
above that of the CEDC flowsheet. Even compared with the CEDC flowsheet reinforced with intermediate heating, the EDWC is
still likely to yield comparable steady-state economics. These outcomes indicate that intermediate heating should be taken into
account in the synthesis and design of the EDWC and the EDWC with intermediate heating should be regarded as a potential
option for the extractive separations of binary azeotropic mixtures.

1. INTRODUCTION low-grade utility as in the CEDC flowsheet, and this represents

As one of the most promising technologies for ternary mixture
separations, dividing-wall columns (DWCs) can be much more
thermodynamically efficient and cost-effective than their
conventional alternatives (e.g., the frequently adopted direct
and indirect separation sequences).1−6 However, when the
DWC is employed to the extractive separation of binary
azeotropic mixtures (the process is termed the EDWC,
hereafter, in the current work), in spite of the fact that reboiler
heat duty can still be considerably reduced in comparison with
that of conventional extractive distillation column (CEDC)
flowsheets, the situation is actually twofold: (i) the EDWC is
still more thermodynamically efficient and cost-effective than
the CEDC flowsheet, and (ii) the EDWC is more
thermodynamically efficient but less cost-effective than the
CEDC flowsheet. Although many design and operating
variables affect the steady-state performance of the EDWC,
the occurrences of the second situation are aroused mainly by
the necessity of exclusive utilizations of relatively high-grade
utilities for reboiler heating (In contrast, in the CEDC
flowsheet as shown in Figure 1a although the entrainer
recovery distillation column requires relatively high-grade
utilities, the extractive distillation column uses frequently low-
grade utilities). It is the mass and thermal coupling between the
extractive separation operation and entrainer recovery oper-
ation involved in the EDWC that precludes the use of relatively
definitely a kind of potential drawback of process intensifica-
tion, posing essentially a severe limitation to process
applicability and flexibility.
Recently, the EDWC has received increasing attention in the
separation of binary azeotropic mixtures.7−15 Chien and his co-
workers assessed the performance of the EDWC in terms of the
separations of three binary azeotropic mixtures, including
isopropyl alcohol and water (with dimethyl sulfoxide (DMSO)
as the entrainer), dimethyl carbonate and methanol (with
aniline as the entrainer), and acetone and methanol (with water
or DMSO as the entrainer).16 Although the EDWC led to
reduced total reboiler heat duty for all the three systems studied
in comparison with the corresponding CEDC flowsheets, only
did the one separating the mixture of acetone and methanol
secure a reduction in the total reboiler heat duty and total
annual cost (TAC) simultaneously (because low-pressure
steam could be used as the hot utility for both the CEDC
flowsheet and EDWC in this system). The increases in the
TACs in the other two systems revealed the potentially adverse
effect of mass and thermal coupling between the extractive
Received: August 6, 2014
Revised: December 9, 2014
Accepted: February 24, 2015
Published: February 24, 2015

© 2015 American Chemical Society 2709 DOI: 10.1021/ie503148t

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Industrial & Engineering Chemistry Research
Figure 1. CEDC flowsheet versus EDWC: (a) CEDC flowsheet and
(b) EDWC.
separation operation and entrainer recovery operation involved.
Lately, Sun et al. studied the separation of an azeotropic
mixture of benzene and cyclohexane with furfural as the
entrainer.17 They found that the EDWC was not only more
thermodynamically efficient but also more cost-effective than
the corresponding CEDC flowsheet. Due to the exclusive use of
medium-pressure steam in the EDWC (while the correspond-
ing CEDC flowsheet used low-and medium-pressure steams in
the extractive and entrainer recovery distillation columns,
respectively), the degree of the reduction in the TAC was
substantially smaller than that of the reduction in total reboiler
heat duty, implying again the adverse effect of mass and thermal
coupling between the extractive separation operation and
entrainer recovery operation involved. Similar tendencies were
also reported by some other researchers.10,18,19 Since an
entrainer is chosen based on the thermodynamic properties
of the azeotropic mixture separated (e.g., the elevation of the
relative volatility between the two components contained and
easy separation from them), its inclusion is quite likely to make
infeasible the use of the relatively low-grade utility in the
EDWC as in the CEDC flowsheet. This explains why the
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EDWC, although favored with relatively high thermodynamic
efficiency, appears frequently to be less cost-effective than the
corresponding CEDC flowsheet. To overcome the drawback,
one has therefore to find a way to use effectively low-grade
utility in the EDWC as in the CEDC flowsheet.
In the current work, we attempt to alleviate or even remove
completely the drawback of the EDWC indicated above and
our major objective is to extend its applicability and flexibility as
per its operation characteristics. In the next section, a
systematic strategy is proposed to enhance the steady-state
economics of the EDWC with intermediate heating, followed
by the evaluation studies in terms of the extractive separations
of two binary azeotropic mixtures of dimethyl carbonate and
methanol and acetone and methanol. In-depth comparisons are
conducted between the EDWC and CEDC flowsheet with and
without intermediate heating and the salient features of
intermediate heating are analyzed. Some concluding remarks
are finally given in the last section.
2. IMPROVING THE STEADY-STATE PERFORMANCE
OF THE EDWC WITH INTERMEDIATE HEATING
2.1. Operating Characteristics of the EDWC. In the
CEDC flowsheet as shown in Figure 1a, two distillation
columns are included. One is an extractive distillation column
(EDC), separating the light component from the top and the
heavy component compounded with the entrainer from the
bottom. The other is an entrainer recovery column (ERC),
separating the heavy component from the top and the entrainer
from the bottom. The entrainer recovered is then recycled to
the EDC. Since the CEDC flowsheet deals actually with the
separations of three components and includes two distillation
columns to accomplish a given task, the DWC technique is
then applied to introduce mass and thermal coupling between
the two distillation columns involved and the attempt gives rise
to the configuration of the EDWC as shown in Figure 1b. It is
noted that the dividing wall runs from the top to a certain stage
in the middle and generates two rectifying sections for
purifying, respectively, the two components involved in the
binary azeotropic mixture separated. Two condensers are
needed at the top, serving to provide liquid flows for the two
sections along the dividing wall. In terms of the vapor split
ratio, defined by βV = V1/(V1 + V2), the operation of the
EDWC can be categorized into three typical modes: (i) When
βV > βU, the EDWC is dominated actually by the extractive
separation operation in the left side of the dividing wall because
most of utility is consumed in the purification of the light
component. (ii) When βV < βL, the EDWC is dominated
actually by the entrainer recovery operation in the right side of
the dividing wall because most of utility is consumed in the
purification of the heavy component. (iii) When βL < βV < βU,
the EDWC works in a rather balanced mode between i and ii.
Here, βU and βL are two characteristic parameters for the
EDWC. Usually, setting βU = 0.8 and βL = 0.2 can yield
reasonable results for process design and analysis. Since the
vapor split ratio βV holds approximately an inequality
relationship with feed composition as shown in eq 1, feed
composition can sometimes be used as a rough index to
determine the operation mode of the EDWC, especially at the
early stage of process synthesis and design.
DOI: 10.1021/ie503148t
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βV = V1/(V1 + V2)

≈ D1(1 + R1)/(D1(1 + R1) + D2(1 + R 2))

(if constant vapor flow rates are applicable, then V1
≈ D1(1 + R1) and V2 ≈ D2(1 + R 2))

> D1/⎛⎝D1 + D2⎞⎠ (since R1 > R 2 because the extractive

separation operation is generally more difficult than the
entrainer recovery operation under the framework of the
EDWC)
= Z1
(1)

Since the entrainer should be easily separated from the two

components of the binary azeotropic mixture processed, it
generally exhibits a much higher boiling-point than those of the
two components and this characteristic leads to the formation
of two steep temperature profiles in the extractive separation
operation and entrainer recovery operation involved in the
EDWC. These steep temperature profiles allow using effectively
intermediate heating with the available low-grade steam as the
hot utility, thereby being likely to reduce the operating cost of
the EDWC. Moreover, the sensible heat of the entrainer
recycled from the bottom of the EDWC should also be used as
a heat source for intermediate heating and this represents
essentially the major thrust for the enhancement of steady-state
economics. Many studies already indicated the efficacy of this
kind of heat integration in the various extractive separation
operations.20,21
2.2. Improving the Performance of the EDWC with
Intermediate Heating. As per the thermodynamic inter-
pretation of distillation operation, intermediate heating should
be arranged somewhere in the stripping section.22−25 For the
EDWC, there exist actually two stripping sections, respectively,
in the extractive separation operation and entrainer recovery
operation involved although they share quite a large common
section at the bottom. While the former has its stripping section
from the bottom to the feed stage, the latter from the bottom to
the lower end of the dividing wall. It is straightforward to Figure 2. Configurations for the EDWC with intermediate heating:
understand that intermediate heating should be arranged to (a) EDWC−FPH and (b) EDWC−IR.
favor simultaneously both the extractive separation operation
and entrainer recovery operation involved. In order to driving forces between feed and the entrainer recovered from
maximize the effect of intermediate heating (as a result, the the bottom and between feed and the available low-grade
consumption of relatively high-grade utilities can be reduced in utility. Because of the heat exchange with the feed (whose
the reboiler), one needs to determine with great caution the temperature is usually low), the recovered entrainer can, in
location of intermediate reboiler and this can be facilitated as general, be directly recycled into the top of the left side of the
per the operation characteristics of the EDWC outlined in the dividing wall, and the employment of a cooler to cool it is, in
preceding subsection. For the EDWC operated in the first most cases, no longer necessary (as opposed to the CEDC
mode (i.e., βV > βU), it is preferable to arrange the intermediate flowsheet and EDWC shown in Figures 1a and b, respectively).
reboiler near the feed (in the left side of the dividing wall) and It is noted that the feed is now divided into two portions (i.e., a
this can alleviate the negative effect of a potential feed pinch- vapor and a liquid ones) and fed onto different stages of the left
point. In this situation, the intermediate reboiler needs not to side of the dividing wall. This delicate arrangement not only
affect directly the entrainer recovery operation (in the right side enhances the vapor−liquid phase mass transfer in the extractive
of the dividing wall) because only a small amount of utility is separation operation but also entails an additional degree of
consumed there (note that the vapor split ratio can be adjusted freedom for process synthesis and design.26 For the EDWC
to play a role in this aspect). The extreme situation happens operated in the rest modes (i.e., βL < βV < βU and βV < βL), it is
when the intermediate reboiler is installed on the feed pipeline preferable to arrange the intermediate reboiler near the lower
and the intermediate reboiler functions actually as a feed end of the dividing wall. Figure 2b sketches such a
preheater. Figure 2a sketches such a configuration for the configuration for the EDWC with an intermediate reboiler
EDWC with a feed preheater (EDWC−FPH). Here, the two (EDWC−IR). Here, the two intermediate reboilers are
feed preheaters are indicated with bold lines with the recycled indicated again with bold lines with the recycled entrainer
entrainer and low-pressure steam as hot utilities, respectively. and low-pressure steam as hot utilities, respectively. The
The EDWC−FPH is characterized by the greatest temperature intermediate reboiler can affect both the extractive separation
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Figure 3. Systematic strategy for the development of the EDWC with intermediate heating.

operation and entrainer recovery operation involved with the
vapor split ratio βV as an effective adjusting parameter in
process synthesis and design. In comparison with the EDWC−
FPH, its temperature driving forces could be severely confined
between the liquid withdrawn from the common stripping
2712
section (i.e., the section below the dividing wall) and the
entrainer recovered from the bottom and between the liquid
withdrawn from the common stripping section (i.e., the section
below the dividing wall) and the available low-grade utility.
Hence, it is sometimes beneficial to arrange further a feed
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preheater in the EDWC−IR especially when βV or feed 3. EXAMPLE I: SEPARATING A BINARY AZEOTROPIC
composition is around 0.5, because in these situations the great MIXTURE OF DIMETHYL CARBONATE (DMC) AND
temperature driving force between feed and the entrainer from METHANOL (MEOH) WITH ANILINE AS THE
the intermediate reboiler can still justify the recovery of sensible ENTRAINER
heat. 3.1. Problem Description. As shown in Figure 4a, DMC
2.3. Systematic Strategy for Developing the EDWC and MEOH form an azeotrope at 13.52 mol % DMC under the
with Intermediate Heating. The unique operating character- atmospheric pressure. Figure 4 parts b and c describe,
istics of the EDWC outlined above remind us of the possibility respectively, the VLE behaviors of MEOH/ANILINE and
that the process could be reinforced with intermediate heating
no matter whether it is cost-effective or not as compared with
the corresponding CEDC flowsheet. To enhance its steady-
state economics, the designer should make full use of the
sensible heat of the entrainer recovered from the bottom prior
to using the available low-grade utility. A systematic strategy is
thus derived for the synthesis and design of the EDWC−FPH/
EDWC−IR as shown in Figure 3. As can be seen, it consists
generally of three main steps (indicated here by three curves
with end arrows). In the first step, the discrimination is made
between the EDWC−FPH and EDWC−IR and this can be
conducted as per eq 1 with reference to the given operating
conditions and product specifications. It should be indicated
here that the early determination of process configuration
favors greatly the search of optimum process design, leading to
not only an easy-to-understand procedure but also a dramatic
reduction in problem complexity and computational require-
ment in trial and error searches. In the second step, an initial
design of the EDWC−FPH or EDWC−IR is generated and
serves as a starting-point for process optimization. No special
requirements are posed actually on this process design as long
as it meets the given specifications on the two top and one
bottom products through the adjustments of two reflux flow
rates and reboiler heat duty. It helps to confine all the structural
and operating variables in their feasible regions and thus
improves the trial and error search efficiency. In the third step,
the adjustment of the initial design of the EDWC−FPH or
EDWC−IR is performed with the aim to minimize the TAC.
Since many structural design variables are involved and they are
in nature discontinuous, the employment of a multivariable
search method will no doubt lead to a complicated procedure
for process synthesis and design. To avoid the difficulty, in the
current work we adopt instead the commonly use grid-search
method. Despite the strategy appears to be quite cumbersome,
it can locate the optimum solution fairly easily and quickly
because of the simplicity of single variable based search method
and the heuristics gained in the previous rounds of iterations.
In the present study, the TAC, a summation of operating
cost and annualized capital investment by a payback period of 3
years, is taken as the objective function for process develop-
ment. While the operating cost includes steam cost, cooling
water cost, and entrainer makeup cost, the annualized capital
cost consists of column shells cost, column stages cost,
intermediate and bottom reboiler cost, top condenser cost,
and cooler cost. The prices of steam and cooling water are
taken from the work fo Seider et al.,27 and the formulas for cost
estimations are adopted from the work of Douglas (c.f.,
Appendix A).28 In particular, the dividing wall cost is assumed
to be negligible as compared with the other equipment costs,
and the EDWC shell cost is calculated with the method by
Chien and his co-workers.16 The M&S index is assigned a value Figure 4. T−x−y diagrams for binary mixtures in example I at 1 atm:
of 1536.5 in the current work. (a) DMC/MEOH, (b) MEOH/aniline, (c) DMC/aniline.

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DMC/ANILINE, and they show clearly the inclusion of

ANILINE could favor the separation of DMC and MEOH. The
operating conditions and design specifications are the same as
in the work of Chien and his co-workers and reproduced here
in Table 1 for quick reference.16 The normal boiling points of

Table 1. Operating Conditions and Design Specifications of

Example I
parameter value
condenser pressure (atm) 1
stage pressure drop (atm) 0.0068
feed flow rate (kmol/h) 170.50
feed temperature (°C) 63.73
feed composition (mole fraction) DMC 0.1467
MEOH 0.8533
product specification (mole fraction) DMC 0.998
MEOH 0.9999
aniline 0.99999

DMC, MEOH, and aniline are 90.22, 64.53, and 183.88 °C,
respectively. One can readily note that a great temperature
difference exists between the boiling points of the two
components in the azeotropic mixture and entrainer, implying
that intermediate heating can be an effective means to improve
the steady-state economics of the EDWC. The commercial
software ASPEN PLUS is employed to predict system
performance and the UNIQ-RK thermodynamic model to
represent vapor−liquid equilibrium relationship. All the
relevant parameters are taken from the work of Hsu et al.29
3.2. CEDC Flowsheet. Hsu et al. once studied the
extractive separation of a binary azeotropic mixture of DMC
and MEOH via a CEDC flowsheet with aniline as the
entrainer.29 With the same steady-state operating conditions
and product specifications, we reproduce their optimum
process design here as shown in Figure 5a. The reboiler heat
duties are 3165.13 and 949.43 kW, respectively, for the
extractive distillation column (CEDC−EDC) and entrainer
recovery column (CEDC−ERC), resulting in a sum of 4114.56
kW. The temperature profiles of the CEDC−EDC and
CEDC−ERC are shown in Figure 6a and b, respectively.
While the bottom temperature of the CEDC−EDC is 163.79
°C, the bottom temperature of the CEDC−ERC rises to 188.06
°C. For the maintenance of a minimum temperature driving
force (i.e., ≥10 °C) in the two reboilers, medium-pressure
steam ($4.8/1000 lb) and high-pressure steam ($6.6/1000 lb)
must be employed, respectively, as hot utilities in the CEDC−
EDC and CEDC−ERC.
3.3. EDWC with and without Intermediate Heating.
The initial design of the EDWC can simply be constructed in
terms of the thermodynamic equivalent structure of the CEDC
flowsheet obtained above. Namely, while the bottom section
below the lower end of the dividing wall is assumed to have the
same number of stages as in the stripping section of the
CEDC−ERC, the two rectifying sections share the same
number of stages as in the rectifying section of the CEDC− Figure 5. Optimum designs for example I: (a) CEDC flowsheet, (b)
EDC. Optimization of this initial process design is then EDWC, (c) EDWC−FPH.
conducted, and this leads to the optimum EDWC as shown in
Figure 5b. The reboiler heat duty is 3538.54 kW, which is and
much lower than the total reboiler heat duty of the CEDC the extractive separation operation (EDWC−EDC) and
flowsheet, implying a great enhancement in thermodynamic entrainer recovery operation (EDWC−ERC) involved are
efficiency by mass and thermal coupling between the CEDC− also shown in Figure 6a and b, respectively. Since the bottom
EDC and CEDC−ERC. The resultant temperature profiles of temperature of the EDWC rises now to 193.40 °C, it only
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for the former, and ΔT1, EDWC = 193.40 − 78.34 = 115.06 °C

Figure 6. Temperature profiles of the CEDC flowsheet and EDWC
for example I: (a) CEDC−EDC versus EDWC−EDC, (b) CEDC−
ERC versus EDWC−ERC.
permits the use of high-pressure steam ($6.6/1000 lb) for
reboiler heating, lowering inevitably the steady-state economics
as compared with the CEDC flowsheet. While the EDWC−
ERC displays a slightly greater temperature span than the
CEDC−ERC, the EDWC−EDC exhibits a much greater one
than the CEDC−EDC (it is essentially closely related to the
mass and thermal coupling between the extractive separation
operation and entrainer recovery operation involved). In
particular, both the CEDC flowsheet and EDWC feature
quite steep temperature profiles in their two stripping sections.
The detailed temperature differences are ΔT1, CEDC = 163.79 −
79.82 = 83.97 °C and ΔT2, CEDC = 188.06 − 166.27 = 21.79 °C
and ΔT2, EDWC = 193.40 − 115.15 = 78.25 °C for the latter.
These characteristics imply the possibilities of improving their
performance with intermediate heating.
Since the vapor split ratio, βV = 0.9069 > Z1 = 0.8533 > 0.8, it
is reasonable to conclude that the extractive separation
operation dominates essentially the EDWC and intermediate
heating should be included into process synthesis and design in
the form of the EDWC−FPH. The initial process design is
assumed to be the EDWC obtained above with the addition of
a feed preheater. According to the systematic strategy proposed
in section 2, the synthesis and design of the EDWDC−FPH is
performed and the resultant optimum process design is
sketched in Figure 5c. The feed preheater only uses the
sensible heat of the entrainer recovered from the bottom of the
EDWDC−FPH and the bottom reboiler heat duty turns to be
2316.20 kW. Which is considerably lower than that of the
EDWC, implying a great enhancement in thermodynamic
efficiency by intermediate heating.
3.4. CEDC Flowsheet versus EDWC with and without
Intermediate Heating. The summary of all the process
designs studied are presented in Table 2. In comparison with
the CEDC flowsheet, although the EDWC achieves a 14.00%
reduction in the total reboiler heat duty, the exclusively using of
high-pressure steam results in a 17.88% increase in steam cost
and consequently brings about a 5.41% increase in the TAC.
With the consideration of intermediate heating, the EDWC−
FPH becomes not only much more thermodynamic efficient
but also more cost-effective than the CEDC flowsheet, securing,
respectively, a reduction in the total reboiler heat duty, steam
cost, and TAC by 43.71%, 22.84%, and 17.94%.
4. EXAMPLE II: SEPARATING A BINARY AZEOTROPIC
MIXTURE OF ACETONE (ACE) AND METHANOL
(MEOH) WITH DMSO AS THE ENTRAINER
4.1. Problem Description. As shown in Figure 7a, ACE
and MEOH give an azeotrope at 22.74 mol % MEOH under
the atmospheric pressure. Figure 7 parts b and c describe,
respectively, the VLE behaviors of MEOH/DMSO and ACE/
DMSO and show clearly that the inclusion of DMSO can favor
the separation of ACE and MEOH. The example is adopted
again from Chien and his co-workers, and the operating
conditions and product specifications are reproduced here in
Table 3 for quick reference.16 The normal boiling points of the
ACE, MEOH, and DMSO are found in the database of ASPEN
PLUS and are 56.25, 64.48, and 190.74 °C, respectively. Again,

Table 2. Summary of All Process Designs Studied for Example I

configurations CEDC EDWC EDWC−FPH CEDC−FPH

TAC for column (103 $/y) 434.89 495.44 419.68 353.31
TAC for reboiler (103 $/y) 166.52 88.56 68.52 132.59
TAC for condenser (103 $/y) 145.00 124.52 125.14 144.95
TAC for cooler (103 $/y) 80.39 80.29 0.00 0.00
TAC for IR (103 $/y) 0.00 0.00 107.54 100.61
capital cost (103 $/y) 826.80 788.81 720.88 731.46
steam cost (103 $/y) 720.03 (0.00%) 848.75 (+17.88%) 555.56 (−22.84%) 531.98 (−26.12%)
cooling water cost (103 $/y) 13.67 11.75 7.67 9.64
entrainer cost (103 $/y) 4.75 0.66 0.34 4.80
operating cost (103 $/y) 738.44 861.15 563.57 546.42
reboiler heat duty (kW) 4114.56 (0.00%) 3538.54 (−14.00%) 2316.20 (−43.71%) 2906.24 (−29.37%)
total TAC (103 $/y) 1565.24 (0.00%) 1649.96 (+5.41%) 1284.45 (−17.94%) 1277.88 (−18.36%)

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Figure 7. T−x−y diagrams for binary mixtures in example II at 1 atm:
(a) MEOH/ACE, (b) MEOH/DMSO, (c) ACE/DMSO.
a great temperature difference exists between the boiling points
of the two components in the azeotropic mixture and entrainer,
implying the possibility that intermediate heating can be an
effective means to enhance the steady-state economics of the
EDWC. The commercial software ASPEN PLUS is used to
simulate the processes and the UNIQUAC model to describe
the vapor−liquid phase behaviors.
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Table 3. Operating Conditions and Design Specifications of
Example II
parameter value
condenser pressure (atm) 1
stage pressure drop (atm) 0.0068
feed flow rate (kmol/h) 540
feed temperature (°C) 46.85
feed composition (mole fraction) ACE 0.5
MEOH 0.5
product specification (mole fraction) ACE 0.994
MEOH 0.995
DMSO 0.9999
4.2. CEDC Flowsheet. The optimum design of the CEDC
flowsheet is shown in Figure 8a. The reboiler heat duties are
6871.95 and 5332.90 kW, respectively, for the CEDC−EDC
and CEDC−ERC, summing into 12204.85 kW. Figure 9a and b
depict the steady-state temperature profiles of the CEDC−
EDC and the CEDC−ERC. Since their bottom temperatures
are 124.39 and 194.72 °C, respectively, low-pressure steam
($3.0/1000 lb) should be used in the former and high-pressure
steam ($6.6/1000 lb) in the latter, thereby being able to
maintain a minimum temperature driving force of 10 °C in
these two reboilers.
4.3. EDWC with and without Intermediate Heating.
The initial process design is again constructed based on the
thermodynamic equivalent structure of the obtained CEDC
flowsheet and the resultant optimum EDWC is sketched in
Figure 8b. The reboiler heat duty is 12009.34 kW and only
slightly lower than the total reboiler heat duty of the CEDC
flowsheet, implying a marginal enhancement in thermodynamic
efficiency by mass and thermal coupling between the CEDC−
EDC and CEDC−ERC. The steady-state temperature profiles
of the EDWC−EDC and EDWC−ERC involved are also
shown in Figure 9a and b, respectively. Note that the bottom
temperature becomes now 199.56 °C, so only can high-
pressure steam be used here as a hot utility. Steep temperature
profiles are still found in the two stripping sections of the
CEDC flowsheet and EDWC. While the former exhibits
temperature differences ΔT1,CEDC = 124.39 − 79.29 = 45.10 °C
and ΔT2,CEDC = 194.72 − 120.50 = 74.22 °C, the latter
ΔT1,EDWC = 199.56 − 78.15 = 121.41 °C and ΔT2,EDWC =
199.56 − 96.66 = 102.9 °C (Note also the fact that it is the
mass and thermal coupling between the extractive separation
operation and entrainer recovery operation involved that
enables the ΔT1,EDWC to be much greater than the ΔT1,CEDC).
It is thus reasonable to improve their performance with
intermediate heating during process synthesis and design.
Since the vapor split ratio of the resultant EDWC is 0.2 < 0.5
= Z1 < βV = 0.6788 < 0.8, it is reasonable to interpret that the
EDWC works in a balanced mode between the extractive
separation operation and entrainer recovery operation involved.
Intermediate heating should therefore be included into process
synthesis and design in the form of the EDWC−IR and the
optimum process design is sketched in Figure 8c. Two
intermediate reboilers (IR−I and IR−II) are installed between
the 39th and 40th stages with the entrainer recovered from the
bottom and low-pressure steam as hot utilities, respectively.
Although the addition of the intermediate reboilers increases
somehow capital cost, it leads to a considerable reduction of
reboiler heat duty. The heat duty of bottom reboiler and IR−II
sums now to 9626.62 kW, and it is much lower than that of the
DOI: 10.1021/ie503148t
Ind. Eng. Chem. Res. 2015, 54, 2709−2723
Industrial & Engineering Chemistry Research
Figure 8. Optimum designs for example II: (a) CEDC flowsheet, (b)
EDWC, (c) EDWC−IR.
EDWC, implying again a great enhancement in thermodynamic
efficiency by intermediate heating.
4.4. CEDC Flowsheet versus EDWC with and without
Intermediate Heating. The summary of all the process
2717
Article
Figure 9. Temperature profiles of the CEDC flowsheet and EDWC
for example II: (a) CEDC−EDC versus EDWC−EDC, (b) CEDC−
ERC versus EDWC−ERC.
designs studied are presented in Table 4. While the EDWC
leads to a 1.60% smaller reboiler heat duty than the CEDC
flowsheet, the former requires 51.03% more steam cost than the
latter. The increased steam cost makes finally the former exhibit
a 21.34% larger TAC than the latter. As far as the EDWC−IR is
concerned, it achieves simultaneously a reduction in reboiler
heat duty, steam cost, and TAC by 21.12%, 29.48%, and
15.49%, respectively.
5. DISCUSSION
For the extractive separation of binary azeotropic mixtures,
while the great difference in the boiling point temperatures
between the two components in the azeotropic mixture and
entrainer is a prerequisite for the selection of entrainer, it is also
the primary reason for the EDWC to frequently have a higher
TAC than the CEDC flowsheet, thereby restricting its
applicability and flexibility. The steep temperature profile in
the stripping sections is thus an inherent operating character-
istic of the EDWC and allows using effectively intermediate
heating to enhance its thermodynamic efficiency. It is also due
to the same reason that the sensible heat of the entrainer
recovered from the bottom of the EDWC should, prior to the
other available utilities, be used as a hot utility for intermediate
heating. This design strategy permits to fully tap the potential
of intermediate heating and is likely to yield great enhancement
of steady-state economics. The two examples studied in the
current work have demonstrated clearly the feasibility and
effectiveness of the systematic strategy proposed in the current
work. Even compared with the CEDC flowsheets with
intermediate heating (i.e., the CEDC−FPH/CEDC−IR as
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Ind. Eng. Chem. Res. 2015, 54, 2709−2723
Industrial & Engineering Chemistry Research Article

shown in Figure 10a and b), the EDWC−FPH/EDWC−IR

(−46.92%)

(−28.69%)
(−23.61%)
CEDC−IR−FPH
may not be inferior in steady-state economics. As shown in
Table 2, the EDWC−FPH really presents a comparable TAC
with the CEDC−FPH for example I. For example II, although
the EDWC−IR appears to be slightly inferior to the CEDC−IR
flowsheet (c.f., Table 4), it is mainly because the sensible heat
771.13
187.14
420.51
0.00
396.76
1775.54
1012.30
28.37
3.65
1044.31
8703.38
2819.85
of the entrainer recovered from the bottom has not been used
to its fullest extent (for example, to further preheat the feed
where a great temperature driving force is available there). If
feed preheating is allowed in both processes, they are
(−44.86%)

(−27.69%)
(−22.81%)
considered to have comparable steady-state economics. Figure
EDWC−IR−FPH

11a and b sketch the resultant optimum designs of the

EDWC−IR−FPH and the CEDC−IR−FPH, respectively. As
shown in Table 4, the EDWC−IR−FPH gives a rather
comparable TAC with the CEDC−IR−FPH.
1.33
909.91
61.65
425.99

370.09
1767.65
1051.64
28.78

1081.74
8824.79
2849.39

It is worthwhile to compare here the effect of arranging

0

intermediate heating to the CEDC flowsheet and EDWC. For

example I, while the CEDC−FPH flowsheet cuts the TAC by
18.36% as compared with the CEDC flowsheet, the EDWC−
(−38.33%)

(−14.24%)
(−19.29%)

FPH by 22.15% as compared with the EDWC. Similarly, for

example II, while the CEDC−IR and the CEDC−IR−FPH
CEDC−IR

flowsheets cut the TACs by 19.29%, and 23.61%, respectively,

as compared with the CEDC flowsheet, the EDWC−IR and the
EDWC−IR−FPH by 30.36%, and 36.39%, respectively, as
730.97
214.39
399.41
158.65
261.68

34.25
3.65
1765.11
1176.14

1214.03
10466.47
2979.14

compared with the EDWC. It appears to be more advantageous

to consider intermediate heating in the EDWC than in the
CEDC flowsheet. The phenomenon stems from the fact that
intermediate heating reduces the consumption of relatively
(−29.48%)

(−21.12%)
(−15.49%)

high-grade utility in the former but low-grade and relatively

high-grade utilities in the latter.
EDWC−IR

It is worth mentioning here an interesting phenomenon

observed in the current study that different designs of the
extractive separation process lead to different entrainer recycle
880.99
92.79
418.15
112.75
238.03
1742.70
1344.96
31.45
0.29
1376.70
9626.62
3119.41

flow rates from the extractive separation operations to the

entrainer recovery operations involved. It can clearly be
identified from the comparison of process designs shown in
Figures 5, 8, 10, and 11. For instance, in example II, the
(−1.60%)
(+51.03%)

(+21.34%)

entrainer recycle flow rates of the CEDC−IR and EDWC−IR

are obviously smaller than those of the CEDC flowsheet and
Table 4. Summary of All Process Designs Studied for Example II
EDWC

EDWC, respectively (c.f., Figures 8 and 10). The phenomenon

also gives rise to different entrainer makeup flow rates between
0.00

0.73
767.08
216.36
355.08
220.09

1558.62
2880.53
39.39

2920.65
12009.34
4479.27

the process designs presented in the current work. It is

considered here that the strong interactions between the
extractive separation operation and entrainer recovery oper-
ation involved and the high degree of nonlinearity in the
thermodynamic properties of the binary azeotropic mixture
(0.00%)

(0.00%)
(0.00%)

separated should be responsible for the occurrence of such a

unique phenomenon.
CEDC

It is no doubt that the effectiveness of intermediate heating

depends heavily on the relative cost between the low-grade and
0.00

3.66
830.30
326.84
362.79
220.46

1740.39
1907.28
40.04

1950.98
12204.84
3691.37

high-grade steams used (which varies accordingly to the

changes in plant locations). In the case that the price difference
between the low-grade and high-grade steams is great enough,
it is certainly advantageous to enhance the steady-state
TAC for condenser (103 $/y)

cooling water cost (103 $/y)

performance of the EDWC−FPH and EDWC−IR with

TAC for reboiler (103 $/y)
TAC for column (10 $/y)

TAC for cooler (103 $/y)

intermediate heating (as shown in the current work). Even in

operating cost (103 $/y)
entrainer cost (103 $/y)

reboiler heat duty (kW)

TAC for IR (103 $/y)
3
configurations

capital cost (103 $/y)

the case that the price difference is fairly small, intermediate

steam cost (103 $/y)

total TAC (103 $/y)

heating can still be effective provided that a steep temperature

profile is available in the stripping section of the EDWC.
However, only should heat recovery from the recycled entrainer
be considered in this situation.
It should be borne in mind that intermediate heating can
only be applied to the cases that the chosen entrainers make the
2718 DOI: 10.1021/ie503148t
Ind. Eng. Chem. Res. 2015, 54, 2709−2723
Industrial & Engineering Chemistry Research
Figure 10. Optimum designs of the CEDC−FPH and CEDC−IR for examples I and II, respectively: (a) CEDC−FPH, (b) CEDC−IR.
EDWC less competitive than the CEDC flowsheet. For those
situations that the chosen entrainers do not make the EDWC
less competitive than the CEDC flowsheet, it cannot be used
because there may be no steep temperature profiles to permit
heat recovery from the recycled entrainers and use of relatively
low-grade utility. Although intermediate heating makes the
resultant EDWC−FPH and EDWC−IR (EDWC−IR−FPH)
have more complicated structures than the CEDC flowsheet, it
never means that they have inevitably complicated process
dynamics and operation difficulties. Therefore, if operationally
feasible, they should be preferred to the CEDC flowsheet with
and without intermediate heating because at least the space
needed to accommodate them is likely to be considerably
reduced. The dynamics and control of the EDWC−FPH and
2719
Article
EDWC−IR (EDWC−IR−FPH) remain, therefore, to be an
important issue to be addressed in the future.
6. CONCLUSIONS
For the extractive separations of binary azeotropic mixtures,
although the EDWC can be more thermodynamic efficient than
the CEDC flowsheet, the chosen entrainers can frequently
enable the former to be less economically favorable than the
latter. In terms of the operating characteristics of the EDWC,
i.e., the existence of steep temperature profiles, intermediate
heating is proposed to enhance the steady-state economics of
the EDWC and a systematic strategy is thus devised to facilitate
process synthesis and design. In case that the EDWC is
dominated by the extractive separation operation, intermediate
heating should be arranged as a feed preheater because the
DOI: 10.1021/ie503148t
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Industrial & Engineering Chemistry Research
Figure 11. Optimum designs of the EDWC−IR−FPH and CEDC−IR−FPH for example II: (a) EDWC−IR−FPH, (b) CEDC−IR−FPH.
greatest temperature driving forces are reached with the
entrainer recovered from the bottom and the available utilities.
In case that the EDWC is dominated by the entrainer recovery
operation or operates in a balanced mode between these two
situations, intermediate heating should be arranged below the
lower end of the dividing wall. Under both circumstances, the
sensible heat recovered from the recycled entrainer and the
energy supplied by low-grade utility can be maximized,
permitting consequently great improvement in steady-state
economics. Provided that a steep temperature profile is
available in the stripping section of the EDWC, the strategy
2720
Article
can be used and effective irrespective of the relative cost
between the low-grade and high-grade steams employed.
In terms of the two example systems separating, respectively,
two azeotropic mixtures of DMC and MEOH and MEOH and
ACE, the feasibility and effectiveness of the systematic strategy
proposed have been confirmed. It has been demonstrated that
the steady-state economics of the EDWC can be substantially
enhanced with intermediate heating. The EDWC with
intermediate heating is not only much more thermodynamically
efficient but also more cost-effective than the CEDC flowsheet.
It can even yield comparable steady-state economics with the
CEDC flowsheet reinforced also with intermediate heating. The
DOI: 10.1021/ie503148t
Ind. Eng. Chem. Res. 2015, 54, 2709−2723
Industrial & Engineering Chemistry Research Article

striking outcome reminds us of the fact that two schemes have where M&S indicates the Marshall & Swift Equipment Cost
essentially the same minimum utility requirement because the Index and FC = FmFp = 3.67.
extremely different process configurations do not alter their The stage cost is given by
separation routines. ⎛ M&S ⎞ 1.55
The systematic strategy proposed in the current work is stage cost [$] = ⎜ ⎟4.7D LCFC
considered to be of great significance to the synthesis and ⎝ 280 ⎠ C
(A.7)
design of the EDWC. Future work will be centered on the where FC = Fs + Ft + Fm = 1 + 0 + 1.7 = 2.7.
dynamics and operation of the EDWC with intermediate The heat exchanger cost is given by
heating.

■
⎛ M&S ⎞ 0.65
heat exchanger cost [$] = ⎜ ⎟101.3A (2.29 + FC)
APPENDIX A: TAC ESTIMATIONS FOR THE CEDC ⎝ 280 ⎠
FLOWSHEET AND EDWC (A.8)
The TAC is given by where FC = (Fd + Fp)Fm = (1.35 + 0) × 3.75 for reboiler or
intermediate reboiler, and FC = (Fd + Fp)Fm = (1 + 0) × 3.75
CC for condenser or cooler.
TAC = OC +
β (A.1) The steam cost is given by
where OC is the total operating cost; CC, the total installed ⎡$⎤ Cs ⎛ Q R ⎞⎛ h⎞
capital cost; and β, the payback period. steam cost ⎢ ⎥ = ⎜ ⎟⎜8150 ⎟
⎣ y ⎦ 1000 lb ⎝ λV ⎠⎝ y⎠ (A.9)
The equipment is sized as follows:
(1) The heat-transfer area for reboiler or intermediate where Cs ($) is the saturated steam price, and λV (Btu/lb), the
reboiler (AR) is given by latent heat of steam.
QR The cooling water cost is given by
AR [ft2] = ⎡$⎤
UR ΔTR (A.2)
cooling water cost ⎢ ⎥
⎣y⎦
where QR (Btu/h) is the heat duty of reboiler or intermediate
reboiler, ΔTR (°F), the temperature driving force, and UR, the $0.03 ⎛ 1 gal ⎞⎛ Q C ⎞⎛ h⎞
overall heat-transfer coefficient, which is assumed to be 250 = ⎜ ⎟⎜ ⎟⎜8150 ⎟
1000 gal ⎝ 8.314 lb ⎠⎝ 30 ⎠⎝ y⎠ (A.10)
Btu/(h·ft2·°F) for heating steams and 50 Btu/(h·ft2·°F) for the
recycled entrainer. The entrainer cost is given by
(2) The heat-transfer area for condenser or cooler (AC) is
given by ⎡$⎤ ⎛ kmol ⎟⎞⎛ h ⎞⎛ $ ⎞⎟
entrainer cost ⎢ ⎥ = ⎜FEM ⎜8150 ⎟⎜price
QC ⎣y⎦ ⎝ h ⎠⎝ y ⎠⎝ kmol ⎠
A C[ft2] = (A.11)
UCΔTC (A.3)
Notation
where QC (Btu/h) is the heat duty of condenser or cooler, ΔTC A = hypothetical component or heat-transfer area, ft2
(°F), the log-mean temperature driving force, and UC, the B = hypothetical component or bottom product, kmol/h
overall heat-transfer coefficient, which is assumed to be 150 C = hypothetical component
Btu/(h·ft2·°F) for the former and 50 Btu/(h·ft2·°F) for the C1 = section of the EDWC, EDWC−FPH, or EDWC−IR
latter. C2 = section of the EDWC, EDWC−FPH, or EDWC−IR
(3) The column length (LC) is given by C3 = section of the EDWC, EDWC−FPH, or EDWC−IR
⎛N ⎞ Cs = saturated steam price, $
LC[ft] = 2.4⎜ T ⎟ D = diameter, m or distillate product, kmol/h
⎝ 0.5 ⎠ (A.4) F = feed flow rate, kmol/h
where NT is the total number of stages. FL = liquid phase feed flow rate, kmol/h
(4) Whereas the diameter of the column shell below the FV = vapor phase feed flow rate, kmol/h
lower end of the dividing wall can be directly estimated with L = liquid flow rate, kmol/h
ASPEN PLUS, the equivalent diameter (De) of the column LC = column length, ft
shell above the top part of the dividing wall is back-calculated as NT = total number of stages
follows QC = condenser heat duty or cooler heat duty, kW
Qcon = condenser heat duty, kW
De = D12 + D2 2 Qcoo = cooler heat duty, kW
(A.5)
QIR = intermediate reboiler heat duty, kW
where D1 and D2 are the diameters of the left and right sides of Qreb = reboiler heat duty, kW
the dividing wall. QR = reboiler heat duty or intermediate reboiler heat duty,
The capital and operating costs are calculated according to kW
the following expressions: R = reflux ratio
The column cost is given by T = temperature, K
Tbot = temperature at bottom, K
⎛ M&S ⎞ 1.066 ΔT = temperature difference, K
column cost [$] = ⎜ ⎟101.9D LC 0.802(2.18 + FC)
⎝ 280 ⎠ C
ΔTC = temperature driving force, K
(A.6) ΔTR = temperature driving force, K
2721 DOI: 10.1021/ie503148t
Ind. Eng. Chem. Res. 2015, 54, 2709−2723
Industrial & Engineering Chemistry Research Article

UC = overall heat-transfer coefficient, Btu/(h·ft2·°F) Programs Foundation of Ministry of Education of China

UR = overall heat-transfer coefficient, Btu/(h·ft2·°F) (20100010110008), and Ministry of Science and Technology of
V = vapor flow rate, kmol/h Taiwan under Grant No. MOST 103-2221-E-233-005.

■
Z = feed composition
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