Int. J. Exergy, Vol. 17, No.

3, 2015

Simultaneous optimal design and operation of a

diabatic extractive distillation column based on
exergy analysis
Arley Nova-Rincn*, Manuel A. Ramos
and Jorge M. Gmez
Grupo de Diseo de Productos y Procesos,
Departamento de Ingeniera Qumica,
Universidad de los Andes,
Carrera 1 No. 18a-10, Bogot, Colombia
Email: af.nova51@uniandes.edu.co
Email: ma.ramos43@uniandes.edu.co
Email: jorgomez@uniandes.edu.co
*Corresponding author
Abstract: The concept of diabatic distillation is applied to an extractive
distillation system of ethanol, which uses glycerol as entrainer, to study the
influence of heat flows in optimal design, operation, and thermodynamic
efficiency of such systems via exergy analysis. First, optimal operating
conditions for minimum exergy losses are computed for a diabatic column with
fixed feed locations and number of trays. Then, optimal design (feed locations,
number of trays, and heat flows along the column) and operation of the system
is calculated as a mixed integer nonlinear programming (MINLP) problem, for
an economic and economic-exergetic objective functions for two different
entrainer molar flows. It was found that the entrainer molar flow has
remarkable influence in the reduction of the exergy losses of the system.
Keywords: diabatic extractive distillation design; NLP; nonlinear
programming) optimisation; MINLP optimisation; exergy minimisation.
Reference to this paper should be made as follows: Nova-Rincn, A.,
Ramos, M.A. and Gmez, J.M. (2015) Simultaneous optimal design
and operation of a diabatic extractive distillation column based on exergy
analysis, Int. J. Exergy, Vol. 17, No. 3, pp.287312.
Biographical notes: Arley Nova-Rincn is the Programs Coordinator of the
Chemical Engineering Department at Universidad de los Andes in Bogot,
Colombia. He received a BS in Chemical Engineering from Universidad
Industrial de Santander in Bucaramanga, Colombia, and a MS in Chemical
Engineering from Universidad de los Andes. His research interests
include optimisation with integer variables and energy optimisation of process
systems.
Manuel A. Ramos received a BS and MS in Chemical Engineering from
Universidad de los Andes in Bogot, Colombia. Currently he is a PhD student
at cole Nationale Suprieure des Ingnieurs en Arts Chimiques et
Technologiques (INP-ENSIACET), Toulouse, France. His research interests
include dynamic optimisation with integer variables and energy optimisation of
process systems.

Copyright 2015 Inderscience Enterprises Ltd.

287

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A. Nova-Rincn et al.
Jorge Mario Gmez is Associate Professor and former head of the Chemical
Engineering Department at Universidad de los Andes in Bogot, Colombia.
He received a BS and MS in Chemical Engineering from Universidad Nacional
de Colombia, an MBA from Universidad de los Andes, and a PhD from
Universit de Pau et des Pays de lAdour, France. Currently, he lectures on
optimisation of chemical processes. His research interests include dynamic
optimisation with integer variables and energy optimisation of process systems.
This paper is a revised and expanded version of a paper entitled Analysis of
the influence of heat flows in optimal design and operation of multicomponent
distillation columns: extractive distillation case study presented at 2012 AIChE
Annual Meeting, Pittsburgh, PA, USA, 31 October, 2012.

Introduction

Conventional design of distillation columns is based on the concept of adiabatic

distillation with two heat exchangers located at the top (condenser) and bottom (reboiler)
of the column. Nevertheless, conventional distillation is associated with a very low
thermal efficiency (520% (Schaller, 2007)), a high exergy loss due to irreversibility
(Demirel, 2006) and hence a high degradation of energy (De Koeijer et al., 2004;
Demirel, 2004; Spasojevi et al., 2010).
Some studies have shown that the implementation of diabatic distillation (on which
heat exchange is carried out along the whole height of the column (De Koeijer et al.,
2004; Schaller, 2007)), can significantly reduce the degradation of energy (De Koeijer
et al., 2004; Jimenez et al., 2004a, 2004b; Schaller, 2007; Shu et al., 2007; Spasojevi
et al., 2010) because heat exchange in each stage lowers energy degradation along the
column and decreases the heat requirements for reboiler and condenser (Schaller, 2007;
Schaller et al., 2001). An illustrative comparison between adiabatic and diabatic
distillation columns is shown in Figure 1.
Figure 1

(a) Adiabatic distillation column and (b) diabatic distillation column (see online version
for colours)

Simultaneous optimal design and operation of a diabatic extractive distillation 289

Previous works on diabatic distillation columns (Table 1) have studied optimal operation
of binary distillation systems based mainly on entropy production, but none of them have
dealt with the problem of the optimal design and operation of diabatic distillation
columns for multi-component separations. In contrast, in the present work optimal
design and operating conditions are computed for an extractive distillation system
(multi-component separation) via MINLP, taking into account an economic and a
multi-objective objective function which includes an economic and an exergetic term.
To our knowledge, studies in simultaneous optimal design and operation (MINLP) of
multi-component distillation systems taking diabatic operation into account have not been
addressed so far.
Table 1

Previous research works on diabatic distillation systems

Year Author

2000 Rivero (2001)

Mixture to be
separated

Water Ethanol

Objective

System configuration, and analysis

Minimum
exergy losses

Adiabatic rectification and stripping

column, studied separately. Location of
maximum exergy losses. Ponchon
Savarit method is used for energy
balances. Simulation in Aspen Plus

2001 Schaller (2007)

and Schaller et al.
(2001)
2004 De Koeijer et al.
Equimolar
(2004)
mixture
2004 Jimenez et al.,
Benzene
(2004b)
Toluene

Entropy
minimisation

2007 Shu et al. (2007)

2010 Spasojevi et al.
(2010)

2012

Ghazi et al.
(2012)

2014 This research

Distillation column with sequential

heat exchangers. Optimal temperature
profiles (De Koeijer et al., 2004;
Shu et al., 2007), heat exchange area
per stage (De Koeijer et al., 2004),
temperature and heat flows of heat
exchangers utilities (Jimenez et al.,
2004b), have been computed.
Application to multicomponent systems
is mentioned (Spasojevi et al., 2010)

Adiabatic distillation column is

modelled by MESH equations and the
Water Ethanol Exergoeconomic exergy analysis is made. Cost rate of
product-ethanol is minimised. Only
column operation is analysed
Multicomponent Economic and
non-ideal
thermodynamic
mixture
(minimum
(Ethanol-water- exergy loss)
objectives are
Glycerol)
studied

Distillation column with an

independent heater/cooler at each stage
where heat load is required. Analyse
the way on which the distillation
column achieves the minimum energy
degradation (exergy loss) for optimal
design and operation

Extractive distillation: case study

The study is made for the extractive distillation system for the production of fuel grade
ethanol using glycerol as entrainer (due to its energy, availability, being economical, and
advantages against other solvents and distillation techniques), proposed by GarcaHerreros et al. (2011).

290

A. Nova-Rincn et al.

The extractive distillation system is made up of two distillation columns: the first one
for the extractive distillation process and the second for entrainer regeneration. The
mixture to be separated and an entrainer are fed into the first column to obtain a distillate
with high ethanol purity. The second column regenerates the entrainer that can be reused
in the extractive distillation column (Lei et al., 2003). The diagram of the process is
shown in Figure 2.
The present work is focused on the extractive distillation column that stands for a
multi-component separation system. This column operates at atmospheric pressure
(101.325 kPa, due to the saturation pressure of the azeotropic mixture fed, the not so
practical chemical degradation of the mixture into the column under this condition, and
the assumption that there is adequate heating media viable to carry the separation (Kister,
1992)) and produces, as distillate, ethanol with purity over 99.5 mol %.
The extractive distillation column has 17 equilibrium stages, a total condenser, and a
partial reboiler. The column is fed with 52 kmol/h of glycerol on stage 3 at 305K and
with 100 kmol/h of azeotropic mixture (ethanol: 85% mol) on stage 12 at 351K
(saturation temperature), both streams at atmospheric pressure. The aforementioned
description corresponds to the optimal design for the extractive distillation column for the
production of fuel grade ethanol, computed by Garca-Herreros et al. (2011).
Figure 2

Extractive distillation of fuel grade ethanol, using glycerol as entrainer (see online
version for colours)

Model of diabatic extractive distillation

The assumptions taken into account on this work to develop a model for the extractive
distillation column are the following:

stage dimensions are not taken into account.

heat exchange at each separation stage is taken into account

Murphree tray efficiency is assumed constant and equals to 1

Simultaneous optimal design and operation of a diabatic extractive distillation 291

mixing effect at each stage is not taken into account

vapour phase is considered as an ideal gas

the NRTL model represents the behaviour of the liquid phase

residual properties are negligible

there is not pressure drop in the column.

The process is modelled as a series of counter-current separation stages. At each stage (j),
entering and leaving liquid (Lj1, Lj) and vapour (Vj+1, Vj) flows get in contact in order to
reach thermodynamic equilibrium as shown in Figure 3. The model uses the MESH
equations, which refers to (Taylor et al., 2003):

M: material balances

E: equilibrium relations (to model the assumption that the streams leaving the stage
are in thermodynamic equilibrium)

S: mole fraction summation equations

H: enthalpy balances.

To model heat exchange on each stage, it is assumed that a series of band heaters as
used to heat liquids flowing through pipes (Chen et al., 2003) can be clamped to the
column (one per stage). This assumption is done in order to compute Qin j , Qout j and the
side heat exchanger temperature per stage. The calculation of these variables is necessary
to compute exergy losses per stage, as will be seen on the next section.
Figure 3

Scheme of an equilibrium stage, for modelling diabatic extractive distillation column

(see online version for colours)

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A. Nova-Rincn et al.

3.1 The NLP model

Let nc denote the number of components in the system and C = {1, 2, , nc} the
corresponding index in the set of components. Let nt denote the total number of stages in
the column and J = {1, 2, , nt} the corresponding index set of the stages. The subsets
COND = {1}, REB = {nt} J denote the condenser (stage 1) and the reboiler (stage nt),
respectively. Additionally, let S = {2, 3, , nt 1} J denote the subset of stages
between the condenser and the reboiler. Taking this into account, the proposed MESH
equations for stages, condenser and reboiler of the diabatic distillation column are the
equality constraints of the model, and are expressed as:
Total mass balances
Vj +1 Vj + L j 1 L j + F jL = 0, j S

(1)

Vj +1 L j 1 +
= 0,
RR

(2)

L j 1 L j Vj = 0,

j COND

j REB.

(3)

Partial mass balances

Vj +1 yi , j +1 Vj yi , j + L j 1 xi , j 1 L j xi , j + F jL = 0, i C , j S

(4)

Vj +1 yi , j +1 L j 1 +
xi , j = 0, i C , j COND
RR

(5)

L j 1 xi , j 1 L j xi , j Vj yi , j = 0, i C , j REB.

(6)

Equilibrium relationships
K ij =

yi , j
xi , j

ij Pijsat
P

K ij P Pijsat = 0, i C , j J .

(7)

Summations
nc

y
i =1

i, j

nc

xi , j = 0, i C , j J .

(8)

i =1

Enthalpy balances
Taking into account the proposed heat exchange by stage, for diabatic operation, enthalpy
balance can be described as follows:
Q in j Q out j + Vj +1 H Vj +1 Vj H Vj + L j 1 H Lj 1 L j H Lj + F jL H LF
= 0, j S
j

(9)

where Q in j and Q out j , are positive variables which represents the quantity of energy
supplied or taken out from the jth stage.
1 L 

Vj +1 H Vj +1 L j 1 +
H j Q j = 0, j COND
RR

(10)

Simultaneous optimal design and operation of a diabatic extractive distillation 293

L j 1 H Lj 1 L j H Lj Vj H Vj + Q j = 0, j REB.

(11)

The main inequality constraint of the model refers to the ethanol purity (molar fraction)
on distillate as follows:

xij 0.995, i = ethanol C , j COND.

(12)

The validity of the presented NLP model (112) on which the MINLP problem is based
was already probed and properly represents the behaviour of the extractive distillation
column (Nova-Rincn et al, 2012).
For conventional distillation with total condenser, specified operating pressure and
feed conditions, there are two degrees of freedom in the MESH model (Hanson et al.,
1962). In order to specify the distillation model, reflux ratio (RR) and reboiler heat duty
(Q nt ) of the column are considered as operating variables in this research. For diabatic
distillation, it is necessary to add a couple of additional variables Q in j and Q out j which
denote heat exchanged (entering or leaving) at each stage. It represents two additional
degrees of freedom per stage (S), giving a total of 36 degrees of freedom for the NLP
model.

3.1.1 Objective functions for NLP problem

The analysis of the influence of heat flows in the operation of multi-component
distillation is made out from two different criteria: economic and thermodynamic. The
purpose of this comparative analysis is to determine the differences in the level of the
degradation of the energy (exergy loss).

3.1.1.1 Economic criterion (P1)

The proposed economic object tive function is based on the maximisation of the net profit
(P1) for selling distillate product ( D ) at distillate cost (CD), taking into account the
energetic cost of boiling (CB) and condensing (CC).
The economic objective function is defined as follows:

max P1 = D CD Q in j CB + Q out j CC
Q in j
j J
j J

(13)

Qout j
RR

with:

CB = 2.2*103 [$/MJ] (Garca-Herreros et al., 2011), using high pressure vapour

for heating

CC = 2.125*104 [$/MJ] (Garca-Herreros et al., 2011), using water at 14C

for cooling.

The proposed optimisation problem was carried out for both adiabatic and diabatic
distillation columns. In the case of adiabatic distillation column, the terms j Q in j and
j Q out j represent only reboiler and condenser heat duties respectively. Terms of capital
cost were not taken into account.

A. Nova-Rincn et al.

294

3.1.1.2 Thermodynamic criterion (E)

As mentioned in Section 1, some researches on diabatic distillation have based their
studies on the minimisation of entropy production. Nevertheless, computing entropy
production of the system does not give enough information about how much energy is not
being effectively used (Arajo et al., 2007; Seader and Henley, 2006; Tsatsaronis, 1993).
In this work, an analysis based on the exergy loss of the system is made, considering that
exergy analysis gives information about the supplied heat conversion into separation
work and identifies the energy wastes through exergy loss (Kencse and Mizsey, 2010).
This analysis requires the calculations of the exergy loss on each separation stage and
is defined as follows (Soares Pinto et al., 2011):

 1 T0

Ex
loss j = Q j
T
j



+ Ex
streams,in j Exstreams,out j , j J

(14)

where Q j represents the heat load at stage j (Q in j or Q out j ), Tj is the side heat exchanger
temperature (temperature of condenser and reboiler utilities in the case of COND and




REB), Ex
stream, in j the exergy of the streams entering to stage j ( ExV j +1 , ExL j +1 , ExF j ),




Exstream,out j is the exergy of the streams leaving to stage j ( ExV j , ExL j ), and Exloss j is the
exergy loss of the stage due to irreversibilities of the stage.
The exergy of a stream is given by its enthalpy and entropy as:
 = H T S , j J
Ex
j
j
o j

(15)

where To is the reference temperature, set on 298 K.

With all the required terms for exergy balance defined, the objective function is
defined as the minimisation of the exergy losses along the length of the column as
follows:

min
E = Ex
loss j

Qin j
Q

(16)

jJ

out j

RR

A comparison of the results for the aforementioned optimisations is made to measure

the waste of energy that each column represents and evaluate if distillation efficiency
can be improved by diabatic operation. Besides, the analysis allows measuring the impact
(Rosen et al., 2008) and sustainability of the system. We refer to sustainability because
exergy methods can be used to improve it (Dincer and Rosen, 2007; Stougie and van der
Kooi, 2011).
The presented objective functions (13) and (16) are analysed independently and each
one of them are subject to the operational constraints (1)(12).

3.2 The MINLP model

In the MINLP problem, the discrete decision variables are related to the calculation of
number of stages and feed locations, and the continuous variables are related to the
operating conditions and energy usage involved in the separation.
In the present work, a modification of the MINLP model proposed by Viswanathan
and Grossmann (1993) is used to compute the total number of stages, feed locations,

Simultaneous optimal design and operation of a diabatic extractive distillation 295

required heat flows, and operational conditions for the diabatic extractive distillation
column. This model considers binary variables associated with the selection of a tray for
the location of reflux and feed streams.
The MINLP model uses the same notation including sets (C, J) and sub-sets
(COND, REB, S) presented for the NLP model and requires the inclusion of a new set
of feeds (glycerol and azeotropic mixture) K = {g, az}, entering to the distillation column.
For the estimation of the total number of stages, it was assumed that the distillation
column has a maximum of 55 separation stages (nt = 55), and the model will compute
where the feeds are located and how many of the nt stages really exist.
The formulation for the design of the distillation column considers solving
two situations related to discrete decisions. For the first one, the entering location
of the reboil stream is fixed (stage nt1) and the problem is to find the stage on which
reflux stream F R is fed to the column. Therefore all stages above the stage selected for
reflux are non-existing stages where vapour stream is bypassed and no liquid flow goes
downwards through them. The second situation is related to the location of feed streams
along the distillation column.
Let fjR , j S , denote the amount of reflux ( F R ) entering to tray j ( iS fjR = F R )
and z Rj , j S , be the binary variable associated with reflux location. In this way, if
z Rj = 1, all the reflux enters at stage j. On the other hand, let fjk , j S , k K , be the
amount of feed ( F k , k K ) entering to tray j ( iS f jk = F k ) and z kj , j S , k K ,
be the binary variable associated with the selection of tray j for the location of feed Fk.
In this case when z kj = 1, k K all feed F k , k K enters at stage j. A graphic idea of
the applied methodology for optimal design is shown in Figure 4.
Figure 4

Scheme and notation for optimal design of the diabatic extractive distillation column
(see online version for colours)

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A. Nova-Rincn et al.

The constraints related to the feeds locations are:

fjk = F k z kj , j S , k K

(17)

(18)

jS

= 1, k K .

k
j

Constraints related to the reflux location take into account the reflux ratio (RR) and
distillate molar flow rate ( D ), as follows:
fjR = RR D z Rj

(19)

(20)

jS

= 1.

R
j

One known condition about feeds locations in the column is the fact that for extractive
distillation, the solvent is introduced into the distillation column above the entry point of
the feed mixture to be separated (Lee, 1990). Therefore for the present case study,
glycerol must be fed above the azeotropic mixture. This can be modelled by imposing a
logical condition as shown below:
z azj z gj 0, j S .

(21)

j j

These inequalities guarantee that if z azj = 1 for one stage j S, then j j z gj = 1 and Fg
enters on or above stage j.
In the same way, reflux must be fed to the column above the feeds. It is imposed by:
z gj z Rj 0, j S .

(22)

j j

It is not necessary to define the constraint (22) for the azeotropic mixture feed because
constraint (21) states that it must be located below the feed of glycerol.
Some changes in the mass and energy balances for the separation stages with respect
to the previous NLP model are required in order to define the MINLP model, as follows:
Mass balances for the equilibrium stages equations (1) and (4) become:
Vj +1 Vj + L j 1 L j + F jk + F jR = 0, j S , k K

(23)

Vj +1 yi , j +1 Vj yi , j + L j 1 xi , j 1 L j xi , j 1 L j xi , j
K
R
+ F jk xiF + F jR xiF = 0, j C , j S , k K

(24)

where xiF = xi , j , j COND, and xiF are the mole fractions of the reflux and feeds
streams respectively.
In the same way, the enthalpy balance equation (9) is defined by:

z
j j

R
j

*(Q in j Q out j ) + Vj +1 H Vj +1 Vj H Vj + L j 1 H Lj 1 L j H Lj

K
R
+ F jk H Fj + F jR H F = 0, j S , k K

(25)

Simultaneous optimal design and operation of a diabatic extractive distillation 297

where the first term j j z ref
ensures that Q in j and Q out j will only exist in actual stages
j
R
below the selected one for reflux feeding, and the terms H F = H Lj , j COND, and
K
H Fj , j S represents the liquid molar enthalpies of the reflux and feeds streams
respectively.
Due to the formulation of the proposed MINLP problem, where a stream FR is leaving
the condenser and can be divided in nt 2 sub-streams f jk instead of a stream Lj,
j COND as was assumed for the NLP problem, the mass and enthalpy balances of the
condenser equations (2), (5) and (10) are formulated in terms of the distillate molar
flow ( D ), as follows:
Assumption L1 = 0
Vj +1 D ( RR + 1) = 0, j COND

(26)

Vj +1 yi , j +1 D ( RR + 1) xi , j = 0, i C , j COND

(27)

Vj +1 H Vj +1 D ( RR + 1) H Lj Q j = 0, i COND.

(28)

There are no changes or additional terms that affect the mass and enthalpy balances in the
reboiler, then equations that describe reboiler heat transfer keep the same form as in the
NLP model.

3.2.1 Model for dry stages, using complementary conditions

Since equilibrium stages are modelled by MESH equations, vapour liquid equilibrium
must be accomplished in all stages, even in non-existing where no mass transfer
takes place. This fact tends to cause singularity and numerical difficulties for
convergence because of the absence of liquid flow in the non-existing stages. To deal
with this situation, Gopal and Biegler (1999) developed a NLP formulation based on
complementary conditions. This approach can model the appearance and disappearance
of phases directly in phase equilibrium problems. It has been tested on benzene-toluene
as a non-ideal (UNIQUAQ) five-component system (Lang and Biegler, 2002).
MESH equations are modified by modelling the phase equilibrium as (Biegler, 2010;
Gopal and Biegler, 1999; Lang and Biegler, 2002):
yi , j j K i , j xi , j = 0, i C , j J

(29)

j 1 = s s+j , j S
j

(30)

Vj sj = 0

(31)

L j s+j = 0

(32)

where j is a corrector for the jth stage, and sj and s+j are slack (positive) variables for
the jth tray. Their values are relative to the existence of the liquid phase on each stage,
according to the following complementary conditions:
If j > 1 then sj > 0 and V j = 0

(33)

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A. Nova-Rincn et al.
If j < 1 then s+j > 0 and L j = 0.

(34)

For this work, only the absence of liquid flow is modelled because the vapour stream is
bypassed by the non-existing stages; therefore constraint (31) is not taken into account
j
and the term s is removed from constraint (30) giving:
1 j = s+j , j S .

(35)

The MINLP problem is to maximise an economic (profit) and a multi-objective

(profit-exergy losses) objective functions, subject to a set of model (MESH equations)
and an operational (xi,j 0.995, i = ethanol C, j COND) constraints. Degrees of
freedom for this problem include the calculation of 165 integer variables
( z Rj , z gj and z azj j S ) and a couple of additional variables Qin j and Qout j per each
existing stage.

3.2.2 Objective functions for the MINLP problem

The analysis of the influence of heat flows in the optimal design and operation of the
extractive distillation column is made from two different criteria: economic and
economic-exergetic. This last criterion is proposed to evaluate the influence of the
inclusion of an exergetic term into an economic objective for the optimal design and
operation of the studied system.

3.2.2.1 Economic criterion (P2)

The proposed economic objective function is based on the maximisation of the annual
profit (P) for selling distillate product ( D ). The objective function is composed by four
elements:

value of products: market value of the ethanol produced in one year of operation
(Cp(x))

operating cost: cost of the utilities required for the operation of the column in one
year (Co(x))

an electric cost was assumed for the design of the intermediate band heaters
(2.83[$/MJ] (Mara et al., 2009))

same costs of condenser and reboiler reported in Section 3.1.1.1 were used

capital cost: cost of the column, including cost of stages, condenser and reboiler
(CI(x, y))

annualising factor: factor used to annualise the infrastructure cost in a five-year

depreciation period (AF).

The economic objective function is defined as follows:

max
P2 ( x, y ) = C p ( x) Co ( x) AF CI ( x, y ).
k
zj
z Rj

(36)

Simultaneous optimal design and operation of a diabatic extractive distillation 299

Capital costs were calculated in the same manner as in the supporting information of
Garca-Herreros et al. (2011) and following the guidelines and price correlations
available in Turton et al. (2002), Seider et al. (2008), and Doherty and Malone (2001).
These infrastructure costs are function of the total number of stages, reboiler, and
condenser heat duties. All of them are variables of the optimisation problem.

3.2.2.2 Economic-exergetic criterion (EE)

In this work, an exergy analysis of the system is made, considering that exergy loss
allows determining how much energy is not being transformed into work of separation.
For the optimal operation and design of the diabatic extractive distillation column, it
is necessary to modify the exergy balance constraint (14) because there is no exergy
loss in non-existing stages. Then, the exergy loss for a stage is defined as follows:

Ex
loss j =

T
z Rj Q j 1 0
Tj
1 j j



+ Ex
streams, in j Exstreams, out j

, j J .

(37)

The multi-objective economic-exergetic function is defined by:


max
EE ( x, y ) = P( x, y ) wEx Ex
loss j .
k
zj
z Rj

(38)

jJ

wEx, is a weight factor (104) which ensures economic viability of the system as well as
minimisation of the total exergy losses of the distillation column. This parameter was
calculated iteratively (and offline), according to the following procedure:

arbitrary parameter value was chosen and the optimisation problem was solved

if the solution reports an acceptable value (based on optimisation for economic

objective function) for some variables such as distillate molar flow and profit (and
the problem converged), the parameter value chosen was valid.

Otherwise, the value was adjusted by increasing or decreasing it in an arbitrary way

according to the results obtained.
Economic and exergetic terms are combined in order to get a real and profitable
distillation system. If the objective did not include the economic term, the column would
reach the maximum number of stages (55) with few exergy losses due to the low heat
load at stages; nevertheless a low distillation flow rate is attained which represents a nonprofitable system.

Solution strategy

The NLP is based on the rigorous MESH model, composed by a set of algebraic
equations of equality constraints. This set contains equations for computing enthalpies
and entropies, and equalities to determine equilibrium constants which are function of
activity coefficients computed using the non random two liquids (NRTL) model (Renon
and Prausnitz, 1968) leading to a non-convex, NLP problem.
The MINLP problem, which is based on the NLP model, includes decision variables
related to number of stages and locations for feeds streams in the distillation column.

300

A. Nova-Rincn et al.

It was modelled using linear relationships between some of the operational variables (i.e.,
reflux ratio, distillate rate, and feeds molar flows) and a set of binary variables-related
streams locations.
The NLP and the MINLP problems were modelled in GAMS 23.8 on a quad core
Intel i5 2.7 GHz CPU with 8 GB of RAM. To solve the NLP problem, we used IPOPT
(interior point optimiser) (Wchter and Biegler, 2005). On the other hand, SBB (simple
branch and bound) was used as MINLP solver and IPOPT as NLP root-solver and subsolver for the MINLP problem.
IPOPT uses a primal-dual interior-point algorithm with a filter line-search method
(Wchter and Biegler, 2005), and is part of the open source COIN-OR (computational
infrastructure for operations research) project (Biegler, 2010). IPOPT reports advantages
for the solution of large-scale NLP problems and has shown to converge faster than other
NLP algorithms (Biegler, 2010; Wchter and Biegler, 2005).
The SBB had been developed by ARKI Consulting and Development A/S. It is
available as a commercial solver within GAMS and implements a branch-and-bound
algorithm using nonlinear relaxations for the bounding step. The NLP relaxations are
solved by one (or several) of the NLP solvers available with GAMS (Bussieck et al.,
2010) (i.e., IPOPT). SBB may perform better than other MINLP solvers (i.e., DICOPT)
on models that have fewer discrete variables but more difficult nonlinearities, and
possibly on models that are fairly non-convex (GAMS Development Corporation, 2001)
as the proposed MINLP model.
A combined strategy for search node was used for the solution of the MINLP
problem, which is made up by depth first search (DFS) and best bound or best first (BB)
strategies, and is included into the SBB options (GAMS Development Corporation,
2013).

Results and analysis

5.1 Results for NLP problem

Economic and thermodynamic optimisations were run for adiabatic and diabatic
extractive distillation columns. The optimal distillate flow rate computed for the
economic optimisation of the adiabatic column (85.427 kmol/h) is assumed as the
minimum distillate rate for remaining optimisations (for NLP problem), to study the same
separation system under different assumptions of operating conditions (adiabatic and
diabatic). Besides, it ensures the economic feasibility of the system because system profit
depends mainly on the distillate flow rate.
Table 2 summarises results for the adiabatic and diabatic distillation columns for the
proposed optimisation objectives.
From data presented in Table 2 it can be noticed that the assumption of diabatic
operation leads to the biggest profit value (economic optimisation) and the lowest exergy
losses (thermodynamic optimisation). Nevertheless the most profitable system also
represents the worst system in terms of energy efficiency (exergy loss). It can be also
noted that when the column operates with minimum exergy loss, the profit of the system
is just 0.001% lower than the maximum achieved for the system.

Simultaneous optimal design and operation of a diabatic extractive distillation 301

Table 3 shows optimal heat loads at stages for the proposed optimisation objectives,
where for the thermodynamic objective, small quantities of heat must be removed at each
stage from stages 2 to 10, and in the same way small heat duties are required from stages
11 to 18, which differs from the results of the economic one in which heat exchange was
carried out only in four stages of the column.
Table 2

Operating variables for NLP problem

Adiabatic column

Diabatic column

Initial values

[P1] and [E]

Optimisation

Initial
values

RR

0.103

0.885

0.012

0.191

0.237

D [kmol/h]

66.435

85.427

69.569

85.427

85.427

Variable

Exergy loss [GJ/h]

[E]
[P1] Optimisation Optimisation

2.972

3.902

1.2577

4.05

2.605

Profit [$/h]

1982.81

2543.776

1952.54

2548.925

2548.89

Q nt [GJ/h]

4.379

8.048

3.357

5.309

5.573

Q1 [GJ/h]

2.85

6.269

2.809

3.960

4.113

Table 3

Stages heat loads, for the diabatic distillation column. NLP problem

Diabatic column
Initial values
Heat load

Q out j [GJ/h]

Q in j [GJ/h]

[P1] Optimisation
Stage

Stage

Value

Stage

Value

0.001

0.001

0.006

0.006

0.002

0.002

0.003

0.003

0.005

0.005

0.005

0.005

0.005

0.005

12

Value

[E] Optimisation

0.604

0.004

0.004

10

0.002

10

0.002

11

0.003

11

0.003

12

0.230

12

0.230

13

0.025

13

0.025

14

0.020

15

0.018

16

0.018

17

0.019

18

0.019

4.271E-04

0.172

0.002

14

0.020

15

0.018

16

0.018

17

0.019

18

0.019

302

A. Nova-Rincn et al.

Besides, when total energy consumption (Q Total = (Q nt + Q in j ) (Q1 + Q out j )) is calculated,
a value of 1.779 GJ/h is attained for all of them. It means that the system complies with
the first law of thermodynamics. The distillation systems use the same amount of energy,
but it is being used in different ways, i.e. different locations along the column.
The main objective of the thermodynamic analysis is to evaluate whether adiabatic or
diabatic distillation system has lower total exergy losses, which represent a more efficient
use of energy in the system. Additionally the analysis estimates how much energy is
wasted with the optimal configuration achieved for the economic optimisation in contrast
with the system with the minimum exergy loss. For the mentioned analysis, exergy loss
profiles for adiabatic and diabatic distillation columns for the studied optimisations are
depicted in Figure 5.
Figure 5

Exergy losses profiles for adiabatic and diabatic distillation column, thermodynamic
and economic objectives (see online version for colours)

By inspection of the profiles presented in Figure 5, it can be noticed that the major exergy
losses for both distillation systems and optimisations are located at reboiler (stage 19),
condenser (stage 1), and at the surroundings of feed stages of the extractive distillation
column (stages 3 and 12 to 15).
Until this point and based on results on Table 2, a reduction of 33.24% in the exergy
losses of the system has been attached via diabatic operation of the extractive distillation
column.
Presented results highlight the importance of measuring the energy efficiency of the
separation systems since it is possible to get the same net profit with a lower energy
waste, when an additional exergy-based analysis is made.
Taking this into account, exergy analysis was included for the design of the
distillation column to find out if the results of the NLP problem can be extrapolated to the
MINLP problem.

Simultaneous optimal design and operation of a diabatic extractive distillation 303

5.2 Results for MINLP model

Taking into account the original feed molar flows (100 kmol/h of azeotropic mixture and
52 kmol/h of glycerol; simplified as [52G] for further reading), the design of the diabatic
distillation column is computed for the objective functions described in Section 3.2.2.
Furthermore, the MINLP problem with the two objectives was used to determine the
optimal design and operation for the molar feed flows for the optimal control of the
extractive distillation column for the production of fuel grade ethanol presented by
Ramos et al. (2013) (100 kmol/h of azeotropic mixture and 35 kmol/h of glycerol are fed;
simplified as [35G] for further reading). This is made to analyse the influence of the
entrainer molar flow in the column design as well as in the exergy losses of the system
which are related to its impact and sustainability (Stougie and van der Kooi, 2011; Rosen
et al., 2008). Molar feed flow of glycerol is not considered as continuous variable
because cost of glycerol must be included in the objective function, changing the
proposed objectives in Section 3.2.2.
Initialisation is an essential part of the successful algorithms for distillation columns
design (Barttfeld et al., 2003; Grossmann et al., 2005) due to the limitations of discrete
formulations related with its dependency on proper initialisation and bounding of the
problem (Neves et al., 2005). Therefore, initial values for both cases (52G and 35G) were
feasible solutions for the proposed MINLP cases.
Regardless of the molar feed flow of glycerol (52 or 35 kmol/h), neither the initial
value for this stream location nor the two proposed optimisation objectives, this feed
stream is located in the second stage in all of the achieved optimal designs, as shown in
Table 4.
Table 4

Design variables for economic and economic-exergetic optimisation

52G
Design variable

35G

Initial
[P2]
[EE]
Initial
[P2]
[EE]
values Optimisation Optimisation values Optimisation Optimisation

Number of stages

27

18

20

25

29

26

Location for feed g

Location for feed az

20

12

10

18

19

17

Comparing profit and exergy losses values for the proposed optimisations in Table 5, the
systems with the best profit also presents the greatest exergy losses. Besides, the system
with minimum exergy losses (35G for economic-exergetic objective) presents a reduction
of only 0.45% on its profit with respect to the most profitable (52G for economic
objective), but the reduction in exergy losses is 45.09%. It means that in order to get a
small extra-profit, great quantities of energy are being wasted (1.526GJ/h). Furthermore,
the selection of an appropriated entrainer molar flow has a significant influence in the
exergy losses of the system. Similarity in the profit value for both economic and
economicexergetic optimisations confirms the validity of the proposed exergeticeconomic objective function and the proper selection of the wEx parameter value.
From Tables 4 and 5 results, it can be observed that for a 52 kmol/h feed flow of
glycerol, achieved optimal designs present shorter columns with a very small reflux ratio,
when compared with the results for 35 kmol/h feed flow of glycerol for the proposed

304

A. Nova-Rincn et al.

optimisations. Nevertheless, similar values of the system profit were computed. To

understand the differences in columns length for the studied cases, liquid and vapour
molar flows and temperature profiles are analysed.
Profiles presented in Figures 68, shows that optimisations for the 35G feed present
lower liquid flows per stage with a lower temperature variation from the last equilibrium
stage to the reboiler than optimisations for 52G case. Furthermore, the 35G case presents
higher vapour flows per stage at a lower temperature than the 52G case, due to less
presence of glycerol in the column. Described conditions might be the cause of lower
exergy losses for the 35G designs because more liquid is being condensed (resulting in
lower total energy consumption) and the energy introduced in the reboiler is used to boil
a lighter entrainer-water mixture. For 35G cases, more energy is being transformed into
work of separation.
Table 5

Operating variables for economic and economic-exergetic optimisations

52G
Initial
values

Variable
RR
D [kmol/h]
Exergy loss [GJ/h]
Profit [$/year]

35G

[P2]
[EE]
Optimisation Optimisation

Initial
values

[P2]
[EE]
Optimisation Optimisation

0.150

0.007

0.005

0.263

0.211

0.223

85.427

85.411

85.426

85.414

85.425

85.423

3.538

3.384

2.581

2.902

2.874

1.858

14,932,445 14,970,476

14,920,755 14,935,738 14,938,756 14,902,631

Q nt [GJ/h]

5.661

5.314

5.321

5.318

5.231

5.271

Q1 [GJ/h]

3.824

3.477

3.471

4.199

4.112

4.150

Figure 6

Liquid molar flow profiles for economic and economic-exergetic optimisations

(see online version for colours)

Simultaneous optimal design and operation of a diabatic extractive distillation 305

Figure 7

Vapour molar flow profiles for economic and economic-exergetic optimisations

(see online version for colours)

Figure 8

Temperature profiles for economic and economic-exergetic optimisations (see online

version for colours)

For heat loads at stages, results for the NLP problem reported that additional heat flows
are required in the surrounding of both feed streams for the economic optimisation of the
diabatic extractive distillation column; nevertheless, when the optimal distribution of heat
loads is computed by a simultaneous strategy for operation and design, the additional heat
flows are only necessary at the neighbouring of the azeotropic mixture feed stage, as
shown in Table 6.
Figure 9 compares exergy loss profiles for economic-exergetic objective function
for the studied systems in the NLP problem and the profile achieved for a minimum
exergy loss system achieved for the NLP problem (base case).

306

A. Nova-Rincn et al.

Table 6

Heat loads for economic and economic-exergetic designs

52G
Initial
values
Heat load

[P]
[EE]
Optimisation Optimisation

Initial
values

[P]
[EE]
Optimisation Optimisation

Stage Value Stage Value Stage Value Stage Value Stage Value Stage Value

Q in j [GJ/h]

18

0.006

19

0.061

Q out j [GJ/h]

20

0.125

Figure 9

35G

11

0.061

0.052

17

0.026

18

0.031

16

0.028

12

0.127

10

0.124

18

0.083

17

0.086

17

0.084

Comparison of systems with minimum exergy loss (see online version for colours)

From exergy loss profiles in Figure 9, it can be noticed that regardless of the number of
stages and location of feeds, the major exergy losses are located at the glycerol feed stage
and the reboiler for the analysed cases. Detailed values are shown in Table 7.
The system which reported major reduction in exergy losses is the distillation column
designed for a 35 kmol/h flow of glycerol. The system 35G leads to reductions of 34.1%
and 26.82% in exergy losses with respect to the base case for the glycerol feed stage and
the reboiler respectively.
Table 8 summarises the reduction of the exergy losses of the extractive distillation
column for the production of fuel grade ethanol from the adiabatic distillation system
achieved by Garca-Herreros et al. (2011) (adiabatic case), then by the inclusion of
diabatic operation made in the NLP problem (base case), and ending with the optimal
design, taking into account the analysed molar feed flows of entrainer of the MINLP
problem.

Simultaneous optimal design and operation of a diabatic extractive distillation 307

The overall reduction of the exergy losses from the adiabatic case to the optimal
diabatic design for 35G reports a value of 52.38%, showing that the implementation of
diabatic operation into the design of a distillation system (extractive distillation for the
present study) leads to a remarkable improvement of the thermodynamic efficiency of
multi-component separation systems (De Koeijer et al., 2004; Jimenez et al., 2004b;
Rivero, 1993, 2001; Schaller et al., 2001; Shu et al., 2007).
The fact that the change of the molar flow of entrainer leads to the minimum exergy
losses for the studied system supports the statement of the significance of the selection of
a proper molar flow of entrainer to get a better performance of the extractive distillation
column in terms of thermodynamic efficiency (less exergy losses). It can be achieved by
including the molar feed flow of entrainer as a variable of the optimisation problem.
Table 7

Major exergy loss for analysed cases

Main exergy loss reductions [GJ/h]

Stage

Base case

52G

35G

Glycerol feed stage

0.793

0.852

0.522

Reboiler

1.078

1.041

0.789

Table 8

Evolution of exergy loss for the extractive distillation column

Total exergy losses

Adiabatic case
3.902

Base case

52G

35G

2.604

2.589

1.858

Conclusions

This work presents a new complete formulation and solution for the optimal design and
operation for a diabatic distillation system taking into account a multi-component mixture
(Glycerol, and ethanol-water azeotropic mixture), using an MINLP model. The proposed
model includes binary variables related to reflux and feeds locations, and an MPCC
formulation to model the vapour-liquid equilibrium in the separation stages.
For the proposed objectives and arrangements of feed flows, it was found that heat
loads along the length of the column are only necessary in the surroundings of the
azeotropic mixture feed stage. Aforementioned results differ significantly from the
computed for optimal operation achieved using a consecutive strategy.
The designs achieved for proposed economic-exergetic objective function shows that
the assumption of heat exchange into the equilibrium stages of the column can lead to a
more sustainable process ensuring also the high profit of the system.
Although the implementation of a diabatic distillation system with minimum exergy
losses as proposed in the MINLP problem has several technical limitations (band heaters
along the column), the presented study gives a first approach to the design of more
sustainable distillation columns.
In terms of process intensification, although the results for the studied system shows
an increase in the size of the column (19 to 26 separation stages) it leads to a major
reduction in exergy losses which means a more sustainable separation process.

308

A. Nova-Rincn et al.

Perspectives

The studied economic-exergetic criterion can also be applied to the design of other
energy-transforming systems associated to low thermodynamic efficiencies, taking into
account alternative strategies related to the energy usage of the system (like diabatic
distillation in the case of distillation columns).

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Nomenclature
Subscripts
B

Boiler

Distillate

Component index

Stage number index

Superscripts
az

Azeotropic mixture.

Glycerol

Feed species index

Liquid

Reflux

Vapour

Latin symbols

AF
CB

Cost of boling, $/MJ

CD

Cost of distillate, $/kmol

Cp x
CI

Value of products, $/kmol

Co x
D

Operating cost, $

Annualising factor

Capital cost, $
Distillate, kmol/h

Simultaneous optimal design and operation of a diabatic extractive distillation 311


Ex
loss j

Exergy loss on stage j, GJ/h


Ex
streams, in j

Exergy of a stream entering to stage j, GJ/h


Ex
streams, out j

Exergy of a stream leaving stage j, GJ/h

F k

Feed of species k

fjk

Amount of feed K entering to tray j, kmol/h

F jL

Liquid feed molar flow rate on stage j, kmol/h

F R

Reflux, kmol/h

f

Amount of reflux (FR) entering to tray j, kmol/h

R
j

H Lj

Molar liquid enthalpy for stage j, GJ/kmol

H LF
j

Molar liquid enthalpy for feed F on stage j, GJ/kmol

H Vj

Molar vapour enthalpy for stage j, GJ/kmol

Kij

Equilibrium constant for component i on stage j

L j

Liquid Molar Flow on stage j, kmol/h

nc

Total number of components

nt

Total number of separation stages

Total pressure of the system, set to 1 atm

Saturation pressure for component i on stage j, kPa

Q j

Duty of stage j, GJ/h

Q in j

Energy supplied to stage j, GJ/h

Q out j

Energy taken out from stage j

RR

Condenser molar reflux ratio

sat
ij

j
+

Slack variable for tray j, related to the existence of liquid phase

sj

Slack variable for tray j, related to the existence of vapour phase

Tj

Side heat exchanger temperature, K

To

Reference temperature, 298 K

Vj

Vapour molar flow on stage j, kmol/h

wEx

Weight factor for economic-exergetic criterion

xi,j

Liquid molar composition for component i on stage j

yi,j

Vapour molar composition for component i on stage j

R
j

z kj

Binary variable associated with reflux location

Binary allocation associated with feed Fk location

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A. Nova-Rincn et al.

Greek symbols

ij

Activity coefficient for specie i on stage j

Corrector for stage j, for equilibrium modification