This article was downloaded by: [York University Libraries]

On: 12 August 2014, At: 08:04

Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer House,
37-41 Mortimer Street, London W1T 3JH, UK

Separation Science and Technology

Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsst20

Implementation of Ethanol Dehydration Using Dividing-

Wall Heterogeneous Azeotropic Distillation Column
a a b a
Lan-Yi Sun , Xing-Wu Chang , Cai-Xia Qi & Qing-Song Li
a
State Key Laboratory of Heavy Oil Processing, China University of Petroleum , Qingdao,
Shandong, China
b
Shandong Qilu Petrochemical Engineering Co. Ltd. , Shandong, China
Published online: 19 May 2011.

To cite this article: Lan-Yi Sun , Xing-Wu Chang , Cai-Xia Qi & Qing-Song Li (2011) Implementation of Ethanol Dehydration
Using Dividing-Wall Heterogeneous Azeotropic Distillation Column, Separation Science and Technology, 46:8, 1365-1375

To link to this article: http://dx.doi.org/10.1080/01496395.2011.556099

PLEASE SCROLL DOWN FOR ARTICLE

Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of the
Content. Any opinions and views expressed in this publication are the opinions and views of the authors, and
are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied upon and
should be independently verified with primary sources of information. Taylor and Francis shall not be liable for
any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other liabilities whatsoever
or howsoever caused arising directly or indirectly in connection with, in relation to or arising out of the use of
the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions
 Separation Science and Technology, 46: 1365–1375, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0149-6395 print=1520-5754 online
DOI: 10.1080/01496395.2011.556099
Implementation of Ethanol Dehydration Using
Dividing-Wall Heterogeneous Azeotropic
Distillation Column
Lan-Yi Sun,1 Xing-Wu Chang,1 Cai-Xia Qi,2 and Qing-Song Li1
1
State Key Laboratory of Heavy Oil Processing, China University of Petroleum, Qingdao,
Shandong, China
2
Shandong Qilu Petrochemical Engineering Co. Ltd., Shandong, China
Downloaded by [York University Libraries] at 08:04 12 August 2014
In this article, the design and optimization procedures of a
dividing-wall column for heterogeneous azeotropic distillation
(DWC-A) using cyclohexane as an entrainer for ethanol dehy-
dration are investigated. The proposed procedures can detect the
optimal values of the design variables and thereby guarantee the
minimum energy requirements, which is related to the minimum
CO2 emissions and the lowest total annual cost (TAC). Since etha-
nol and water form an azeotrope under atmosphere pressure, a con-
ventional heterogeneous azeotropic distillation sequence (CHADS),
including an azeotropic column and a recovery column, is usually
used to perform the ethanol dehydration process. However, due to
high energy requirements and equipment investments of CHADS,
the TAC is at a relatively high level. DWC-A can be used to elim-
inate the condenser of the second column and decrease the degree of
back-mixing. Both CHADS and DWC-A are simulated with Aspen
Plus1, and the results show that DWC-A has an energy saving of
42.17% and the TAC reduction of 35.18% along with higher ther-
modynamic efficiency and reduction in greenhouse gas emissions.
Keywords CO2 emissions; dividing-wall heterogeneous
azeotropic distillation; energy requirements; TAC;
thermodynamic efficiency
INTRODUCTION
Heterogeneous azeotropic distillation is commonly used
in industry to separate close boiling point mixtures and
azeotropes by using an additional entrainer to alter the
relative volatility of the components to be separated.
Ethanol-water mixture as a typical azeotropic system has
been extensively studied by many experts for its complex
characteristics of parametric sensitivity, multiple steady
states, long transient, and nonlinear dynamics. A conven-
tional heterogeneous azeotropic distillation sequence
(CHADS) for ethanol dehydration usually includes two
Received 1 September 2010; accepted 17 January 2011.
Address correspondence to Lan-Yi Sun, State Key Laboratory
of Heavy Oil Processing, China University of Petroleum,
Qingdao, Shandong 266555, China. Tel.: þ86 138 5420 8340;
Fax: 0086-532-86961711. E-mail: sunlanyi@163.com
1365
columns: an azeotropic column (C1) and a recovery col-
umn (C2) as shown in Fig. 1. Font et al. (1) measured
the consistent vapor-liquid equilibrium (VLE) and
vapor-liquid-liquid equilibrium (VLLE) data for the ter-
nary system of water-ethanol-isooctane at 101.3 kPa and
designed a two-column azeotropic distillation process to
obtain high purity ethanol using isooctane as the entrainer.
Gomis et al. (2) implemented the sensitivity analysis of the
reboiler heat duty for the process proposed by Font and
proved that the reboiler heat duty has a critical value,
which determines the ethanol purity and operation stab-
ility. Esbjerg et al. (3) studied the multiple steady states
of the direct and indirect azeotropic distillation sequences
for ethanol dehydration. As a basis, the 1=1 analysis
method, which assumed an infinite reflux rate and infinite
number of trays, was extended and applied to hetero-
geneous azeotropic distillation sequences in order to
determine steady-state bifurcation diagrams from thermo-
dynamic considerations. Luyben (4) presented a study of
the control of a two-column heterogeneous azeotropic sys-
tem separating ethanol and water using benzene as the light
entrainer. A plant-wide control structure was developed
and tested to provide effective base-level regulatory control
of this highly non-ideal system. Urdaneta et al. (5), taking
ethanol dehydration as an example, proposed a compre-
hensive study of analysis and conceptual design of ternary
heterogeneous azeotropic distillation processes. An exten-
sion to the algorithm of Pham et al. (6) for the calculation
of tray-by-tray profiles in heterogeneous systems had been
developed, which allowed the determination of multiple
heterogeneous stages.
Due to the entrainer forming ternary azeotrope (escap-
ing from the top of the azeotropic column) with ethanol
and water, the vapor load in the azeotropic column (C1)
is very high, which leads to high energy requirements of
the reboiler. Dividing-wall column (DWC, see Fig. 2a)
technology can be applied to heterogeneous azeotropic
distillation to reduce energy requirements and capital
 1366
FIG. 1. Conventional heterogeneous azeotropic distillation sequence
Downloaded by [York University Libraries] at 08:04 12 August 2014
(CHADS).
investments, as well as achieve environmental and safety
benefits. This makes DWC to something that corresponds
with the present day idea of sustainable process technology
(7). The DWC, which has been known for several decades
since it was patented by Wright (8), is equivalent in thermo-
dynamics to a fully thermally coupled distillation column
(FTCDC, see Fig. 2b) or a Petlyuk column for ternary
separations (A þ B þ C, where B is an intermediate compo-
nent) (9, 10). In addition, there are two well known ther-
mally coupled column sequences for ternary separations,
the thermally coupled distillation sequence with side
rectifier (TCDS-SR, Fig. 2c), and the thermally coupled
distillation sequence with side stripper (TCDS-SS,
Fig. 2d). FTCDC (DWC) has been described to have
higher thermodynamic efficiency for many separations (11);
however, FTCDC (DWC) is favorable only in certain
operating region (12). TCDS-SR and TCDS-SS tend to
receive special attention (13,14) and both can be imple-
mented in a single column by using a dividing-wall in prac-
tice. Several studies have shown that DWC can achieve
energy savings of around 30% compared with conventional
direct or indirect distillation sequences (15,16). Successful
FIG. 2. Thermally coupled distillation sequences for the separation of ternary mixture: (a) DWC, (b) FTCDC, (c) TCDS-SR and (d) TCDS-SS.
L.-Y. SUN ET AL.
commercial applications of DWC technology have been
reported (17,18). Hernandez et al. (19) performed steady
state and dynamic simulations of a reactive Petlyuk column
through an equivalent reactive dividing wall column and
Kiss et al. (20) developed a novel integrated design that
combines reaction and separation into a feasible reactive
DWC. Bravo-Bravo et al. (21) proposed a novel extractive
dividing wall distillation column designed using a con-
strained stochastic multiobjective optimization technique.
van Diggelen et al. (22) explored the DWC control issues
and made a comparison of various control strategies.
However, there has been no report about applying DWC
technology to the ethanol dehydration process via hetero-
geneous azeotropic distillation.
This article proposes a dividing-wall column for hetero-
geneous azeotropic distillation (DWC-A) for ethanol dehy-
dration (see Fig. 3) and cyclohexane is selected as the
entrainer because of its low cost and low toxicity (23).
The key difference between the prior work of Midori
et al. (24) and ours is the addition of a new feed (entrainer
makeup) to the decanter; as a result, the complexity of the
design and optimization procedures is increased because
new search variables are introduced, such as the flow rate
of the entrainer makeup. Although they have shown the
energy savings of DWC-A configurations as compared to
a conventional azeotropic distillation sequence, there is a
lack of study of thermodynamic efficiency, CO2 emissions
and the TAC. DWC-A is equivalent in thermodynamics
to a thermally coupled heterogeneous azeotropic distil-
lation sequence (TCHADS) as shown in Fig. 4, so the
simulation and design of DWC-A can be performed
according to TCHADS completely. DWC-A is mainly div-
ided into two sections: section T1 and section T2 (the bot-
tom of the section T2 is sealed). The section T1 of DWC-A
corresponds to the main column (T1) of TCHADS,
whereas the section T2 of DWC-A has the same function-
ality as the side stripper (T2) of TCHADS. The key differ-
ences between the previous TCDS-SS and DWC-A
(TCHADS) are the addition of a new feed (entrainer
makeup) to the decanter and the aqueous phase entering
the section T2 (side stripper). As a result, the complexity
 DESIGN AND OPTIMIZATION PROCEDURES FOR DWC-A
Downloaded by [York University Libraries] at 08:04 12 August 2014
FIG. 3. Dividing-wall heterogeneous azeotropic distillation column
(DWC-A) for ethanol dehydration.
of the design and optimization procedures is increased
because new search variables are introduced, such as the
flow rate of entrainer makeup and the inlet point of
the aqueous phase. In the present work, the design and
optimization procedures of DWC-A intended for ethanol
dehydration are elaborated and the thermodynamic perfor-
mances and economic estimation of DWC-A are studied.
The results show that an energy saving of 42.7% and
TAC reduction of 35.8% of DWC-A can be obtained com-
pared with the CHADS. In addition, the thermodynamic
efficiency of DWC-A is improved by 1.57% and emissions
reduction is cut down greatly.
FIG. 4. Thermally coupled heterogeneous azeotropic distillation
sequence (TCHADS) for ethanol dehydration.
1367
DESIGN AND SIMULATION
The design methods of DWC-A are based on CHADS.
The feed conditions, product specifications, and column
operating conditions are available from the plant or the
given examples depending upon the situation. Figure 1 is
a schematic illustration of CHADS for ethanol dehy-
dration, including an azeotropic column (C1) with 25
stages (including a total condenser and a partial reboiler,
similarly hereinafter) and a recovery column (C2) with 14
stages. The numbering of the stages is taken from the top
of the column. A feed containing 90 wt% of ethanol and
10 wt% of water enters at stage 6 of the azeotropic column
(C1) at 298.15 K. The bottom product of the azeotropic
column (C1) is an ethanol product with the required purity
and the outlet flow of the decanter (aqueous phase) is fed to
the recovery column (C2) to separate water. The distillate
of the recovery column (C2) containing ethanol and water
is recycled to the azeotropic column (C1) to mix with the
fresh feed, and waste water is withdrawn from the bottom
of the recovery column (C2). The product purities of etha-
nol and waste water are both 99.9 wt%. The feed rate is
assumed to be 1000 kg=h and the entire process is operated
at 103.3 kPa.
The simulation of CHADS is carried out using the rigor-
ous distillation module RadFrac provided by Aspen Plus1.
The Non-Random Two Liquids (NRTL) model is adopted
for the calculation of the activity coefficients in liquid phase
and the Redlich-Kwong (RK) equation of state is used to
describe the vapor phase behavior. The predicted azeo-
tropic temperatures and compositions agree well with
experimental results provided by Gmehling et al. (25).
The design and simulation of DWC-A are identical to
those of TCHADS. The specifications of feed and product
for DWC-A are the same as those for CHADS. To over-
come the complexity of the simultaneous solution of the
tray arrangement and energy requirements within a formal
optimization algorithm, the methods presented here mainly
include three steps:
a. shortcut design for finding initial estimates of variables
required for rigorous simulation,
b. rigorous simulation of TCHADS,
c. optimization of the system.
The shortcut design of TCHADS is performed accord-
ing to Carlberg and Westerberg’s suggestions (26), and it
can be obtained by exchanging liquid (L2) and vapor
streams (V2) between the main column (T1) and the side
stripper (T2) (see Fig. 4), which eliminates the condenser
from the recovery column (C2) of CHADS (see Fig. 1).
The aqueous phase is driven into the side stripper (T2)
and there is no cyclic stream present in TCHADS.
The approach for rigorous simulation involves less
number of assumptions and is more realistic than the
 1368 L.-Y. SUN ET AL.

TABLE 1
Operating parameters of CHADS and DWC-A for ethanol dehydration
CHADS DWC-A
Parameters Azeotropic column (C1) Recovery column (C2) Section T1 Section T2
Number of stages 25 14 25 14
Feed temperature (
C) 25.0 25.0
Operating pressure (kPa) 103.3 103.3
Feed stage 6 3 5 3
Feed composition (ethanol=water, wt%) 90=10 90=10
Product purity (Ethanol=Water, wt%) 99.9=99.9 99.9=99.9
Side stream location – – 3 –
Reflux ratio 1.15 0.06 1.20 –
Liquid split ratio – 4.0
Decanter outlet flow rate (kg=hr) 3988.73 – 3837.14
Entrainer makeup flow rate (kg=hr) 0.11 0.87
Downloaded by [York University Libraries] at 08:04 12 August 2014

Bottoms flow rate (kg=hr) 899.98 100.13 900.77 100.10

Fenske–Underwood–Gilliland (FUG) equations. The
RadFrac module of Aspen Plus1, a rigorous model for
simulating all types of multistage vapor-liquid fraction-
ation operations, is selected for the simulation of the
flowcharts as shown in Fig. 4. The same physical pro-
perty method (NRTL-RK) as that of CHADS is adopted
when the simulation is implemented using Aspen Plus1.
Rigorous simulation used in the present study is based
on the equilibrium-stage model, which uses mass, equilib-
rium, summation of mole fractions, and enthalpy
(MESH) equations for each stage. The equilibrium-stage
model is more common in simulators and widely used
in azeotropic distillation systems (27–29). The same stage
numbers of the main column (T1) and the side stripper
(T2) as those of the azeotropic column (C1) and the
recovery column (C2) in Fig. 1, respectively, are used in
the study to compare the performances of CHADS and
TCHADS. The numbering of the stages is taken from
the top of the column.
For the optimization process, the feed location of the
main column (T1) is determined by selecting the tray with
the composition close to feed composition, which can
efficiently decrease feed tray mixing and reduce exergy loss.
The same method is introduced to determine the feed
location of the aqueous phase to the side stripper (T2).
The side draw (L2) location is decided by selecting the tray
with the maximum water composition to minimize the
degree of back-mixing. When the feed locations and the
number of theoretical stages are fixed, there are four design
degrees of freedom: reflux ratio and bottom flow rate of the
main column (T1), bottom flow rate of the side stripper
(T2), and liquid split ratio with only two product specifica-
tions for TCHADS. Liquid split ratio (L1=L2) is specified
as the ratio of the liquid flow directed to the main column
(T1) to the flow directed to the side stripper (T2). In this
study, reflux and liquid split ratios are used as the remain-
ing degrees of freedom to minimize the reboiler duties of
TCHADS, while the other two are used to satisfy the
purity specifications. The reflux and liquid split ratios are
adjusted until the minimum reboiler duties are obtained.
When the above-mentioned three steps are completed,
the optimum TCHADS for ethanol dehydration can be
obtained. The feed ethanol solution enters at stage 5 of
the main column (T1) and the outlet flow of the decanter
(aqueous phase) enters at stage 3 of the side stripper
(T2). High-purity ethanol (99.9 wt%) is obtained at the bot-
tom of the main column (T1) and the waste water
(99.9 wt%) is withdrawn from the bottom of the side strip-
per (T2). The side liquid stream (L2) is drawn from stage 3
of the main column (T1) and the vapor stream (V2) is
returned to the same stage. The entrainer makeup flow rate
is calculated by a Fortran procedure built in Aspen Plus1,
where the entrainer makeup flow rate is defined as a vari-
able equal to the sum of the entrainer content in waste
water and ethanol product. The simulation results for the
optimized TCHADS shall be used for DWC-A as the con-
centration profiles, heat duties, and performance data for
both of them are identical. The detailed operating para-
meters of CHADS and DWC-A for ethanol dehydration
are summarized in Table 1.
The duties of reboilers and condensers and the column
diameters are obtained from the simulations and utilized
to calculate TAC of CHADS and DWC-A. The TAC is
defined as
Capital cost
Total annual cost (TAC) ¼
Plant life time
þ Annual operating cost ð1Þ
 DESIGN AND OPTIMIZATION PROCEDURES FOR DWC-A 1369

where the annual operating cost includes the cost of steam 3. Heat exchanger cost ($)
and cooling water, and the capital cost covers the cost of

M&S
the column, trays, and heat exchangers. In this work, a Heat exchanger cost ¼  474:668
plant life time of 5 years is used and the operating hours 280
of 8000 hr=year are assumed.  A0:65  ð2:29 þ Fc Þ ð6Þ
TAC calculation follows the procedure of Douglas (30)
and the specific equations of Luyben (31) and Lin et al. (32) where Fc ¼ (Fd þ Fp)Fm ¼ (1 þ 0.1)  1 ¼ 1.1 for a con-
are used. An M&S index of 1431.7 is used in the calcu- denser and Fc ¼ (Fdþ p) Fm ¼ (1.35 þ 0.1)  1 ¼ 1.45 for
lation, which is selected according to the CEPCI (Chemical a reboiler.
Engineering Plant Cost Index) (September, 2008). Suppose 4. Steam cost ($=year)
materials of construction are carbon steel. The capital cost

Cs QR
of condensers and reboilers is evaluated by considering the Steam cost ¼  8000  3600 ð7Þ
453:515 kV
heat exchange area A (33):
where Cs ($) is the saturated steam price and kV (kJ=kg)
Q is the latent heat of the steam which depends on the
A¼ ð2Þ
l  DT bottom temperature.
Downloaded by [York University Libraries] at 08:04 12 August 2014

where Q is the duty of the heat exchanger and l is the over- 5. Cooling water cost ($=year)
all heat-transfer coefficient. The values of l are calculated

0:03 QC
from field data of heat exchange area, temperatures and Cooling water cost ¼
3:785 DTW  Cp  1000
heat duties. They are assumed to equal to a value of
0.852 kW=m2  K for the condensers and 0.568 kW=m2  K  8000  3600 ð8Þ
for the reboilers, respectively. DT (K) represents the
where DTW (K) is the temperature difference between
log-mean temperature driving force depending on the
inlet and outlet cooling water and Cp (¼4.183 kJ=kg  K)
dew points and bubble points for a total condenser or
is the specific heat of water.
the temperature driving force in a reboiler depending on
the steam. Capital cost ¼ Column cost þ Tray cost
The height LC (m) of the columns is calculated as a func-
þ Heat exchanger cost ð9Þ
tion of the number of actual plates (Nactual). It is assumed
that the tray spacing is 0.6 m with 6 m disengagement and Annual operating cost ¼ Steam cost þ Tray cost
the plate efficiency is 0.75.
þ Cooling water cost
LC ¼ ðNactual  1Þ  0:6 þ 6 ð3Þ ð10Þ
The capital and operating costs are calculated according to:
1. Column cost ($) THERMODYNAMIC EFFICIENCY AND CO2 EMISSIONS
CALCULATION


M&S With the optimum design of DWC-A, thermodynamic
Column cost ¼ b   937:636 efficiency can be computed using the laws of thermody-
280
namics and compared with that of CHADS. Besides,
 D1:066  L0:802
C  ð2:18 þ Fc Þ ð4Þ
CO2 emissions are calculated to assess the environmental
benefits of DWC-A in this study. The basic theories for
where Fc ¼ Fp þ Fm ¼ 1 þ 1 ¼ 2. It is important to note
thermodynamic efficiency and CO2 emissions calculations
that the right side of Eq. (4) should be multiplied by a
are clarified as follows.
correction factor b (¼1.1) in the calculation of DWC-A
cost because a dividing wall is added, while b is equal to
Thermodynamic Efficiency
1 for the conventional distillation column. D (m) is
column diameter. Thermodynamic efficiencies can be computed using the
2. Tray cost ($) laws of thermodynamics. For this task, the equations used
are:

 First Law of thermodynamics:
M&S
Tray cost ¼  97:243  D1:55  hT  Fc ð5Þ X X
280
ðn
h þ Q þ Ws Þ  ðn
h þ Q þ Ws Þ ¼ 0
out of system into system
where Fc ¼ Fs þ Ft þ Fm ¼ 1.8 þ 0 þ 0 ¼ 1.8 and hT ¼
(Nactual  1)  0.6. ð11Þ
 1370 L.-Y. SUN ET AL.

Second Law of thermodynamics: In the distillation systems, steam is used either for heat-
X X ing purposes, indirectly in reboilers, or as a direct stripping
ðns þ Q=Ts Þ  ðns þ Q=Ts Þ ¼ DSirr ð12Þ agent in so-called steam distillations. The amount of fuel
out of system into system burnt can be calculated from
Energy balance:
QPr oc TFTB  T0
X 

T0
  QFuel ¼ ðhPr oc  419Þ ð18Þ
nEX þ Q 1  þ Ws kPr oc TFTB  TStack
into system
Ts
X 
  where kProc(kJ=kg) and hProc (kJ=kg) are the latent heat and
T0
 nEX þ Q 1  þ Ws ¼ LW ð13Þ enthalpy of steam delivered to the process, respectively,
out of system
Ts while TFTB and TStack are the flame temperature of the boi-
ler flue gases and stack temperature, respectively.
Minimum separation work: Equation (18) is obtained from a simple steam balance
X X around the boiler to relate the amount of fuel necessary
Wmin ¼ nEX  nEX ð14Þ in the boiler to provide a heat duty of QProc. The boiler feed
out of system into system
water is assumed to be at 373.15 K with an enthalpy of
Downloaded by [York University Libraries] at 08:04 12 August 2014

419 kJ=kg. The flame temperature is lower in a boiler than

Second Law efficiency:
in a furnace because the heat of combustion is removed
Wmin immediately to the steam. However, the same theoretical
g¼ ð15Þ
LW þ Wmin flame temperature of 2073 K and the stack temperature
of 433 K may be still used in the calculations.
where Ex ¼ H  T0S is the exergy function, LW ¼ T0DSirr
is the lost work in the system and g is the thermodynamic RESULTS AND DISCUSSION
efficiency. Thermodynamic properties like enthalpies and
In this study, it is important to analyze the composition
entropies of the streams of the distillation sequences are
profiles in the azeotropic distillation systems. Figures 5–6
evaluated through the use of a process simulator, Aspen
present the liquid composition profiles of the azeotropic
Plus1 (34,35).
column (C1) of CHADS and those of the section T1 of
DWC-A, respectively. As shown in Figs. 5–6, the liquid
CO2 Emissions Calculation
composition profiles of the two parts are nearly identical,
The explicit estimation of the CO2 emissions associated
but at the stages from 1 to 3, the mass fractions of water
with various energy-intensive distillation-based operations
and cyclohexane components decrease slightly with that
in process industries is carried out according to the method
of the ethanol component increasing smoothly in the azeo-
of Gadalla (36). The fuel is combusted when mixed with
tropic column (C1) of CHADS; however, the mass fraction
air, producing CO2 according to the following stoichio-
metric equation:
 y y
Cx Hy þ x þ O2 ! xCO2 þ H2 O ð16Þ
4 2

where x and y denote the number of carbon (C) and hydro-

gen (H) atoms, respectively, present in the fuel composi-
tions, and where complete oxidation of carbon is assumed.
In the combustion of fuels, air is assumed to be in excess
to ensure complete combustion, so that no carbon monox-
ide (CO) is formed. CO2 emissions, [CO2]Emiss (kg=h), are
related to the amount of fuel burnt, QFuel (kW), in a heat-
ing device as follows:



QFuel C%
½CO2 Emiss ¼ a ð17Þ
NHV 100

where a (¼3.67) is the ratio of molar masses of CO2 and C,

while NHV represents the net heating value of a fuel with a FIG. 5. Liquid composition profiles of the azeotropic column (C1) of
carbon content of C% (dimensionless). CHADS.
 DESIGN AND OPTIMIZATION PROCEDURES FOR DWC-A
Downloaded by [York University Libraries] at 08:04 12 August 2014
FIG. 6. Liquid composition profiles of the section T1 of DWC-A.
of the cyclohexane component decreases suddenly and that
of ethanol component increases sharply in the section T1 of
DWC-A. Moreover, the content of water reaches its
maximum value at stage 3 in the section T1 of DWC-A.
The above-mentioned differences are produced due to
interchanging liquid and vapor streams between the section
T1 and the section T2 for DWC-A.
Figure 7 is the liquid composition profiles of the recov-
ery column (C2) of CHADS, which shows that the mass
fraction of ethanol increases first and then decreases from
the bottom to the top of the recovery column (C2) of
CHADS, and this is the so-called back mixing, which is
the essential reason for low thermodynamic efficiency.
Figure 8 is the liquid composition profiles of the section
T2 of DWC-A, which illustrates that the mass fraction of
FIG. 7. Liquid composition profiles of the recovery column (C2) of
CHADS.
1371
FIG. 8. Liquid composition profiles of the section T2 of DWC-A.
ethanol increases gradually from bottom to top. This is
because a liquid stream with relatively high water content
is withdrawn from stage 3 of the section T1 and driven into
the section T2 of DWC-A directly, which eliminates the
back mixing. Therefore, under the same product purity
requirement, DWC-A, compared to CHADS, can save
energy and reduce exergy loss.
For DWC-A, the determination of minimum energy
requirements is conducted by varying the reflux and liquid
split ratios. Figure 9 shows the relationship between the
total reboiler duty and the two ratios when two product
specifications are set at high purities (99.9 wt%). Total
reboiler duty first decreases and then increases smoothly
with the increase of liquid split ratio at each given reflux
ratio. This illustrates that there is an optimum liquid split
ratio, which is related to feed and product conditions, col-
umn configurations, and so on. When the reflux ratio
FIG. 9. Relationship between total reboiler duty, reflux ratio and liquid
split ratio for DWC-A.
 1372 L.-Y. SUN ET AL.

becomes too low, the operation becomes infeasible and the
entrainer loss is very severe (more than 2 kg=h), hence 1.2 is
the critical value of the reflux ratio guaranteeing the speci-
fied products purities in this study. The optimal condition
with the minimum energy requirements (1967.52 kW) is
obtained with reflux and liquid split ratios equal to 1.2
and 4.0, respectively.
The thermodynamic results and TAC of CHADS and
DWC-A for ethanol dehydration are summarized in
Table 2. As can be seen from the Table 2, CHADS requires
a heat duty of 3402.30 kW. However, the heat duty which
of DWC-A required is 1967.52 kW. The corresponding
condenser duty of CHADS is higher than that of DWC-A
with the values of 3033.60 kW for CHADS and 1653.32 kW
for DWC-A, respectively. It is important to highlight that
the minimum separation work is a function of state, so
Downloaded by [York University Libraries] at 08:04 12 August 2014
specifications. The lost work of CHADS is 219.00 kW,
while that of DWC-A is 158.65 kW. As the lost work
increases, the total exergy input has to be increased to
enable the column to achieve the separation requirements,
so the total exergy input of CHADS is 229.45 kW, while
that of DWC-A is 168.99 kW. The results show that
DWC-A can save energy by 42.17% compared to CHADS
and the thermodynamic efficiency is enhanced by 1.57%.
With regard to TAC calculation, it is necessary to note
that the column diameter of DWC-A is larger than those
of the azeotropic column (C1) and recovery column (C2)
of CHADS (Table 2). That is because the vapor and liquid
loads in DWC-A are larger than those of each column of
CHADS. However, the column height of the DWADC is
equal to that of the azeotropic column (C1) of CHADS
with the value of 25.8 m due to the same stage number

the minimum separation works of the two sequences, and tray spacing. Besides, as a result of lower heat duties
10.45 kW for CHADS and 10.38 kW for DWC-A in con- of the reboilers and condensers of DWC-A compared with
sideration of the error of calculation, are approximately CHADS, the total heat transfer areas of the reboilers and
identical under the condition of the same feed and product condensers of DWC-A are less than those of CHADS

TABLE 2
Thermodynamic results and TAC of CHADS and DWC-A for ethanol dehydration
CHADS DWC-A
Parameters Azeotropic column (C1) Recovery column (C2) Section T1 Section T2
Condenser duty (kW) 1983.69 1049.91 1653.32 –
Total condenser duty (kW) 3033.60 1653.32
Condenser temperature (
C) 62.67 65.77 62.67 –
Reboiler duty (kW) 2214.39 1187.91 870.38 1097.15
Total reboiler duty (kW) 3402.30 1967.52
Reboiler temperature (
C) 78.79 100.43 78.73 100.43
Decanter temperature (
C) 25 – 25
Decanter heat loss (kW) 320.77 – 266.40
Minimum separation work (kW) 10.45 10.34
Lost work (kW) 219.00 158.65
Total exergy input (kW) 229.45 168.99
Thermodynamic efficiency (%) 4.55 6.12
Energy saving (%) 0 42.17
Column diameter (m) 1.4 0.8 1.6
Column height (m) 25.8 16.8 25.8
Reboiler heat transfer area (m2) 112.03 60.10 99.54
Total reboiler heat transfer area (m2) 172.13 99.54
Condenser heat transfer area (m2) 167.51 88.66 139.61
Total condenser heat transfer area (m2) 256.17 139.61
Column=trays=heat exchanger cost ($1000) 388.86=29.85=424.55 151.81=6.84=281.89 493.18=36.72=384.50
Capital cost ($1000) 843.26 440.54 914.40
Total capital cost ($1000) 1283.80 914.40
Annual operating cost ($1000=year) 183.15 98.23 162.53
Total operating cost ($1000=year) 281.38 162.53
Plant life time (year) 5 5
TAC ($1000=year) 538.13 345.41
 DESIGN AND OPTIMIZATION PROCEDURES FOR DWC-A 1373

content of fuels and NHV come from (37). As for DWC-A,

the reductions in CO2 emissions from the combustion of
coal, heavy fuel oil and natural gas are all about 42.17%
with the values of 732.40 kg=hr, 308.33 kg=hr and
198.67 kg=hr for the three kinds of fossil fuels, respectively.
Compared to heavy oil and coal, the natural gas can be
considered as an environmentally friendly fuel.
According to the above results, DWC-A is superior to
CHADS for ethanol dehydration. It is important to high-
light that when DWC-A is implemented in industry, poten-
tial operational and control problems associated with
flooding and operating pressure can be eliminated (38).

CONCLUSIONS
FIG. 10. Comparison of CHADS and DWC-A based on the thermo-
The separation of an azeotrope of ethanol and water
dynamic results and TAC.
was studied using CHADS and DWC-A. The results show
Downloaded by [York University Libraries] at 08:04 12 August 2014

that the proposed DWC-A can achieve significant energy

(Table 2). The total heat transfer area of the reboilers of savings that can be translated into reductions of CO2 emis-
CHADS is 172.13 m2, while that of DWC-A is 99.54 m2, sions. DWC-A can eliminate the back-mixing of ethanol
which is reduced by 42.17%. The reduction in the total heat component so that the thermodynamic efficiency is
transfer area of the condensers is about 45.5% with the improved around 1.57%. Furthermore, it is found that an
values 256.17 m2 for CHADS and 139.61 m2 for DWC-A, optimal value of liquid split ratio occurs at each given
respectively. As Table 2 shows, the total capital cost and reflux ratio. However, there is a critical value of reflux ratio
operating cost of CHADS are 1283.80 $1000 and 281.38 ensuring normal operation at less entrainer loss under the
$1000=year, and those of DWC-A are 914.40 $1000 and specified product purity requirements. Finally, savings in
162.53 $1000=year, respectively. Over a period of plant life capital costs can be expected since DWC-A needs less heat
time (5 year), the reduction in the TAC is 35.8% with the exchange devices and other subsidiary facilities (e.g., pipes
values 538.13 $1000=year and 345.41 $1000=year for and pumps), and the TAC is reduced by 35.8% compared
CHADS and DWC-A, respectively. The comparison of with CHADS.
CHADS and DWC-A based on the thermodynamic results
and TAC is shown in Fig. 10. ACKNOWLEDGEMENTS
In addition to the reduction in TAC, an energy saving The authors appreciate the support of the Promotive
certainly implies a corresponding indirect reduction of Research Fund for Excellent Young and Middle-aged
the associated CO2 emissions. Obviously, the level of CO2 Scientists of Shandong Province (BS2010NJ023) and the
emissions is strongly dependent on the nature of the fossil Fundamental Research Funds for the Central Universities
fuel used (heavy fuel oils, natural gas and coal). The CO2 (09CX04040A).
emissions of CHADS and DWC-A for ethanol dehy-
dration are summarized in Table 3. The values of carbon NOMENCLATURE
A heat-transfer area (m2)
Cp specific heat of water (kJ=kg  K)
TABLE 3 Cs saturated steam price ($)
CO2 emissions of CHADS and DWC-A for ethanol [CO2]Emiss CO2 emissions (kg=h)
dehydration D column diameter (m)
EX exergy function (kW)
Heavy Natural Fc correction factor for pressure, materials of
Coal fuel oil gas construction, etc.
Fd design type correction factor
Carbon content of 0.68 0.54 0.41
Fm material correction factor
fuels (kg=kg)
Fp pressure correction factor
NHV (kJ=kg) 22000 41500 48900
Fs tray space correction factor
CHADS (kg=hr) 1736.75 731.13 471.11
Ft tray type correction factor
DWC-A (kg=hr) 1004.35 422.81 272.44
hProc enthalpy of steam (kJ=kg)
Reduction in CO2 732.40 308.33 198.67
hT total height of trays (m)
emissions (kg=hr)
H molar enthalpy of stream (kJ=mol)
 1374 L.-Y. SUN ET AL.

LC column height (m) 5. Urdaneta, R.Y.; Bausa, J.; Brulggemannm, S.; Marquardt, W. (2002)
Analysis and conceptual design of ternary heterogeneous azeotropic
LW lost work (kW) distillation processes. Ind. Eng. Chem. Res., 41: 3849–3866.
M&S Marshall & Swift index 6. Pham, H.N.; Ryan, P.J.; Doherty, M.F. (1989) Design and minimum
Nactual actual stage numbers reflux for heterogeneous azeotropic distillation columns. AIChE J.,
NHV the net heating value of a fuel with a carbon 35: 1585–1591.
content of C% (kJ=kg) 7. Dejanovic, I.; Matijasevic, Lj.; Olujic, Z. (2010) Dividing wall column:
A breakthrough towards sustainable distilling. Chem. Eng. Process.,
Q heat transfer (kW) 49: 559–580.
QFuel the amount of heat released by fuel 8. Wright, R.O. Fractionation Apparatus. U.S. Patent 2,471,134, May
combustion (kW) 24, 1949.
QProc energy requirements of distillation process 9. Petyluk, F.B.; Platonov, V.M.; Slavinskii, D.M. (1965) Thermodyna-
(kW) mically optimal method of separating multicomponent mixtures. Int.
Chem. Eng., 5: 555–561.
S molar entropy of stream (kJ=mol  K) 10. Suphanit, B.; Bischert, A.; Narataruksa, P. (2007) Exergy loss analysis
DSirr entropy change (kJ=mol  K) of heat transfer across the wall of the dividing-wall distillation col-
T temperature (K) umn. Energy, 32: 2121–2134.
T0 temperature of the surroundings (K) 11. Rudd, H. (1992) Thermal coupling for energy efficiency. Chem. Eng.
DT temperature driving force (K) (London), 525: 14–19.
12. Agrawal, R.; Fidkowski, Z.T. (1998) Are thermally coupled distil-
Downloaded by [York University Libraries] at 08:04 12 August 2014

DTW temperature difference between inlet and lation columns always thermodynamically more efficient for ternary
outlet cooling water (K) distillations? Ind. Eng. Chem. Res., 37: 3444–3454.
TFTB the flame temperature of the boiler flue 13. Gutiérrez-Guerra, R.; Segovia-Hernández, J.G.; Hernández, S. (2009)
gases (K) Reducing energy consumption and CO2 emissions in extractive distil-
TStack stack temperature (K) lation. Chem. Eng. Res. Des., 87: 145–152.
14. Wang, S.J.; Wong, D.S.H.; Yu, S.W. (2008) Design and control of
TAC total annual cost transesterification reactive distillation with thermal coupling. Comput.
Ts temperature of the system (K) Chem. Eng., 32: 3030–3037.
W work streams (kW) 15. Annakou, O.; Mizsey, P. (1996) Rigorous comparative study of
Wmin minimum separation work (kW) energy-integrated distillation schemes. Ind. Eng. Chem. Res., 35:
Ws shaft work (kW) 1877–1885.
16. Emtir, M.; Rev, E.; Fonyo, Z. (2001) Rigorous simulation of energy
x the number of carbon atoms integrated and thermally coupled distillation schemes for ternary mix-
y the number of hydrogen atoms ture. Appl. Therm. Eng., 21: 1299–1317.
17. Becker, H.; Godorr, S.; Kreis, H. (2001) Partitioned distillation
Subscripts columns-why, when and how. Chem. Eng., 108: 68–74.
C condenser 18. Schultz, M.A.; Stewart, D.G.; Harris, J.M.; Rosenblum, S.P.; Shakur,
R reboiler M.S.; O’Brien, D.E. (2002) Reduce costs with dividing-wall columns.
Chem. Eng. Prog., 98: 64–71.
Greek Symbols 19. Hernandez, S.; Sandoval-Vergara, R.; Barroso-Munoz, F.O.;
a the ratio of molar masses of CO2 and C Murrieta-Duenas, R.; Hernandez-Escoto, H.; Segovia-Hernandez,
J.G.; Rico-Ramirez, V. (2009) Reactive dividing wall distillation col-
b correction factor for DWC-A cost
umns: Simulation and implementation in a pilot plant. Chem. Eng.
g thermodynamic efficiency (%) Process., 48: 250–258.
kProc latent heat delivered to the distillation process 20. Kiss, A.A.; Pragt, J.J.; van Strien, C.J.G. (2009) Reactive
(kJ=kg) dividing-wall columns-how to get more with less resources? Chem.
kV latent heat of the steam (kJ=kg) Eng. Commun., 196: 1366–1374.
21. Bravo-Bravo, C.; Segovia-Hernandez, J.G.; Gutierrez-Antonio, C.;
l heat-transfer coefficient (kW=m2  K)
Duran, A.L.; Bonilla-Petriciolet, A.; Briones-Ramirez, A. (2010)
Extractive dividing wall column: Design and optimization. Ind. Eng.
Chem. Res., 49: 3672–3688.
REFERENCES 22. van Diggelen, R.C.; Kiss, A.A.; Heemink, A.W. (2010) Comparison
1. Font, A.; Asensi, J.C.; Ruiz, F.; Gomis, V. (2003) Application of iso- of control strategies for dividing-wall columns. Ind. Eng. Chem.
octane to the dehydration of ethanol. Design of a column sequence to Res., 49: 288–307.
obtain absolute ethanol by heterogeneous azeotropic distillation. Ind. 23. Furzer, I.A. (1994) Synthesis of entrainers in heteroazeotropic distil-
Eng. Chem. Res., 42: 140–144. lation systems. Can. J. Chem. Eng., 72: 358–364.
2. Gomis, V.; Pedraza, R.; Francés, O.; Font, A.; Asensi, J.C. (2007) 24. Midori, S.; Zheng, S.N.; Yamada, I. (2001) Azeotropic distillation
Dehydration of ethanol using azeotropic distillation with isooctane. process with vertical divided-wall column. Kagaku Kogaku Ronbunshu,
Ind. Eng. Chem. Res., 46: 4572–4576. 27: 756–760.
3. Esbjerg, K.; Andersen, T.R.; Müller, D.; Marquardt, W.; Jørgensen, 25. Gmehling, J.; Menke, J.; Krafczyk, J.; Fischer, K. (2004) Azeotropic
S.B. (1998) Multiple steady states in heterogeneous azeotropic distil- Data, 2nd Ed.; Wiley-VCH: Weinheim, Germany.
lation sequences. Ind. Eng. Chem. Res., 37: 4434–4452. 26. Carlberg, N.A.; Westerberg, A.W. (1989) Temperature-heat diagrams
4. Luyben, W.L. (2006) Control of a multiunit heterogeneous azeotropic for complex columns. 2. Underwood’s method for side strippers and
distillation process. AIChE J., 52: 623–637. enrichers. Ind. Eng. Chem. Res., 28: 1379–1386.
 DESIGN AND OPTIMIZATION PROCEDURES FOR DWC-A
27. Chien, I.L.; Zeng, K.L.; Chao, H.Y. (2004) Design and control of a
complete heterogeneous azeotropic distillation columnsystem. Ind.
Eng. Chem. Res., 43: 2160–2174.
28. Wang, S.J.; Lee, C.J.; Jang, S.S.; Shieh, S.S. (2008) Plant-wide design
and control of acetic acid dehydration system via heterogeneous azeo-
tropic distillation and divided wall distillation. J. Process Control., 18:
45–60.
29. Arifin, S.; Chien, I.L. (2007) Combined preconcentrator=recovery col-
umn design for isopropyl alcohol dehydration process. Ind. Eng.
Chem. Res., 46: 2535–2543.
30. Douglas, J.M. (1988) Conceptual Design of Chemical Processes, 1st
Ed.; McGraw-Hill: New York, U.S.
31. Luyben, W.L. (2006) Distillation Design and Control Using AspenTM
Simulation, 1st Ed.; John Wiley & Sons: New York, U.S.
32. Lin, S.W.; Yu, C.C. (2004) Design and control for recycle plants with
heat-integrated separators. Chem. Eng. Sci., 59: 53–70.
Downloaded by [York University Libraries] at 08:04 12 August 2014
1375
33. Mascia, M.; Ferrara, F.; Vacca, A.; Tola, G.; Errico, M. (2007)
Design of heat integrated distillation systems for a light ends separ-
ation plant. Appl. Therm. Eng., 27: 1205–1211.
34. Demirel, Y. (2006) Assessment of thermodynamic performances for
distillation columns. Int. J. Exergy, 3: 345–361.
35. Seader, J.D.; Henley, E.J. (2006) Separation Process Principles, 2nd
Ed.; John Wiley & Sons: New York.
36. Gadalla, M.; Olujić, Ž.; de Rijkeb, A.; Jansens, P.J. (2006) Reducing
CO2 emissions of internally heat-integrated distillation columns for
separation of close boiling mixtures. Energy, 31: 2409–2417.
37. Wang, G.; Feng, X. (2006) CO2 emission reduction through energy
integration. Chem. Ind. Eng. Prog., 25: 2073–2081.
38. Jantes-Jaramillo, D.; Segovia-Hernández, J.G.; Hernández, S. (2008)
Reduction of energy consumption and greenhouse gas emissions in
a plant for the separation of amines. Chem. Eng. Technol., 31:
1462–1469.