Separation and Purification Technology 50 (2006) 175–183

Separation of isobutyl alcohol and isobutyl acetate by

extractive distillation and pressure-swing distillation:
Simulation and optimization
R. Muñoz ∗ , J.B. Montón, M.C. Burguet, J. de la Torre
Departamento de Ingenierı́a Quı́mica, Escuela Técnica Superior de Ingenierı́a, Universitat de València,
Dr. Moliner, 50, 46100 Burjassot, Valencia, Spain
Received 21 September 2005; received in revised form 22 November 2005; accepted 22 November 2005

Abstract
We have studied, simulated and evaluated economically two separation alternatives of a mixture made up of 52 mole% of isobutyl alcohol and
48 mole% of isobutyl acetate by means of a practical case of a plant to treat 12,000 Tm/year of the original mixture. The simulation has been
carried out satisfactorily by means of a package of commercial software (Aspen HYSYS® ) using the thermodynamic model UNIQUAC with binary
parameters obtained experimentally by us.
The two processes evaluated (extractive distillation using n-butyl propionate as a solvent and pressure-swing distillation) have been optimized
independently from each other and the best configurations have been evaluated economically. The simulation and economic evaluation of the
two separation alternatives that we have considered allow us to conclude that, for a 12,000 Tm/year plant, the pressure-swing distillation is more
attractive than the extractive distillation using n-butyl propionate as an entrainer.
© 2005 Elsevier B.V. All rights reserved.

Keywords: Extractive distillation; Pressure-swing distillation; Simulation; Isobutyl alcohol; Isobutyl acetate; n-Butyl propionate

1. Introduction overcome by several techniques including azeotropic and extrac-

Isobutyl acetate (IBAc) is a solvent widely used in Chem-
ical Industry. It is used alone or in solvent blends in applica-
tions including coatings, inks, adhesives, industrial cleaners and
degreasers. The IBAc is produced by estherification of acetic
acid with isobutyl alcohol (IBA). Final purification of acetate
by traditional technologies is a relatively complex procedure
due to the existence of a minimum boiling point azeotrope in
the IBA + IBAc mixture at atmospheric pressure.
Azeotropes are non-ideal mixtures whose components are
very difficult and, hence, expensive to separate. This can be
Abbreviations: BUP, butyl propionate; DMF, dimethylformamide; EC,
extractive column; ED, extractive distillation; FCI, fixed capital investment
(D 103 ); HPC, high pressure column; IBA, isobutyl alcohol; IBAc, isobutyl
acetate; LPC, low pressure column; PSD, pressure-swing distillation; RHD,
reboiler heat duty (MJ/h); SRC, solvent recovery column; TAC, total annual
costs (D 103 /year); VLE, vapour–liquid equilibrium
∗ Corresponding author. Tel.: +34 963544319; fax: +34 963544898.
E-mail address: rosa.munoz@uv.es (R. Muñoz).
tive distillation [1–3], reactive distillation [4,5], liquid–liquid
extraction [6], adsorption [7], membrane pervaporation [8], salt
addition [9] and pressure-swing distillation [10]. In this work,
only extractive distillation (ED) and pressure-swing distillation
(PSD) will be considered.
ED can be used to separate the components of an azeotropic
mixture adding an agent (entrainer) that modifies the relative
volatility of the mixture. Also, PSD can be used to recover
pure components with a simple change in pressure, a fact which
results in a change of the azeotropic composition, provided that
it is pressure-sensitive.
Laboratory experiments in either extractive distillation or
pressure-swing distillation are time-consuming and expensive
because of the large number of parameters involved. It would be
desirable to predict the experimental data with the help of avail-
able simulation programs. Computer simulations using commer-
cial process simulators have been used with success as an aid
for process development. They were used to set up the guide-
lines for further pilot experiments and moreover, to optimize the
operating parameters governing the process at steady-state.

1383-5866/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.seppur.2005.11.022
176 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183

the IBA + IBAc separation by extractive distillation with BUP

Nomenclature as entrainer and by swing-pressure distillation, with the help of
a commercial simulator (Aspen HYSYS® v3.2 of Aspen Tech-
A UNIQUAC binary interaction parameters
nology Inc.). Finally, we have chosen the best alternative for
(cal/mol)
the separation of the azeotropic mixture under study from the
C costs (D 103 /year)
economic point of view.
im minimum acceptable rate of return
ir fixed capital recovery rate (depreciation rate)
K vapour–liquid equilibrium constant 2. Simulation

Greek letter 2.1. Problem definition

α relative volatility
The two alternatives considered in this study (ED and PSD)
Subscripts were simulated with the same basic data. The feed is a mix-
f fixed ture made up of 52 mole% of isobutyl alcohol and 48 mole% of
i, j primitive mixture components isobutyl acetate, with a flow rate of 12,000 Tm/year; we took
S solvent (entrainer) 8000 working hours per year, that is a mass flow of 1500 kg/h.
v variable
2.2. Property package
Superscript
Computer simulation using commercial process simulators is
∞ infinite dilution
a useful tool to predict qualitatively the influence of the operating
variables on the column performance, provided that the interac-
tion binary parameters for the studied mixture are available in
The synthesis and design of extractive distillation processes
their own data-bank. The accuracy of the simulated results is
take place in two steps [11]. The first one involves the selection
strongly dependent on the quality of the binary parameters for
of one or more candidate solvents (which facilitate the separa-
the liquid-phase activity coefficient models.
tion by changing the relative volatilities in the mixture through
In this paper, the simulation was undertaken with HYSYS and
physical or chemical interactions with the original components),
DISTIL. UNIQUAC activity model was chosen because it was
and the choice of one or more column configurations. The sec-
the most suitable, but unfortunately, no data exist in their own
ond step, process design, involves the search for optimal process
library to cover all possible interactions between the components
parameter values. The success of the second step depends on the
studied in this work, so we have used the binary interaction
solutions obtained for the first one because efficiency in extrac-
parameters published by us in previous papers [14–17]. The
tive distillation is largely determined by the choice of a suitable
parameters used are listed in Table 1.
entrainer.
In this work, based on the guidelines for the solvent screening, 2.3. Extractive distillation
we have chosen three solvents: N,N-dimethylformamide (DMF),
1-hexanol and butyl propionate (BUP). DMF was recommended 2.3.1. Solvent selection
as a potential entrainer for alcohol–acetate azeotropic mixtures Since the solvent is the core of extractive distillation, more
because of its high polarity [12] and 1-hexanol and BUP have attention should be paid on the selection of potential solvents.
been chosen because they are, respectively, in the same homol- Of all possible entrainers that can be used for the separation
ogous series with one of the key-components [13]. Therefore, in of IBA and IBAc azeotrope mixture we have chosen three:
order to be able to select the best solvent among them, we have N,N-dimethylformamide, 1-hexanol and butyl propionate. DMF
carried out simulations with Aspen HYSYS® v3.2 of Aspen was recommended as a potential entrainer for alcohol–acetate
Technology Inc., using the binary interaction parameters corre- azeotropic mixtures because of its high polarity and 1-hexanol
lated from experimental data obtained for all binaries involved and BUP have been chosen because they are, respectively, in the
[14–17]. According to the results obtained, the best solvent same homologous series with one of the key-components.
seems to be butyl propionate. Once the solvent has been selected,
we have designed the separation sequence and optimized the Table 1
operating parameters. UNIQUAC binary interaction parameters
On the other hand, to investigate how the pressure-swing dis- Component i Component j Aij (cal/mol) Aji (cal/mol)
tillation works with the IBA + IBAc azeotropic system, we have
done a simulation of the vapour–liquid equilibrium using DIS- IBA IBAc 116.17–0.53Ta 361.90–0.45Ta
IBA DMF 56.603 −155.920
TIL v5.0 of Hyprotech Ltd. at different pressures with the inter- IBA 1-Hexanol 461.869 −340.476
action parameters obtained from experimental VLE data [14]. IBA BUP 35.346 49.224
Based on these results we have decided to carry out the design IBAc DMF 551.320 −281.210
and optimization of the pressure-swing distillation process. IBAc 1-Hexanol 316.172 −227.902
The aim of this work is to study the influence of the operation IBAc BUP 131.014 −128.309
variable values and column configuration on the performance of a T is the temperature in Kelvin.
 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183
Fig. 1. VLE data plotted on a solvent free basis for the system IBA (1) + IBAc
(2) + solvent (3) at 101.3 kPa. Continuous line for x3 = 0; dashed lines simulated
with UNIQUAC model with parameters given in Table 1 for x3 = 0.7: (- · · -)
BUP, (- - -) 1-hexanol and (- · -) DMF.
In order to verify the effect of the aforementioned solvents,
the VLE of the ternary mixtures, on a solvent free basis, was
simulated and plotted in Fig. 1. It may be observed that DMF
reverses the volatility of the original mixture, that is, enhances
the relative volatility of IBAc with regard to IBA in such a way
that IBAc would be obtained as the overhead product in the
extractive column, IBA and DMF being the bottom products. On
the contrary, 1-hexanol and BUP enhance the relative volatility
of IBA with regard to IBAc, both in the natural way, that is, IBA
would be obtained as the overhead product and IBAc together
with the solvent (1-hexanol or BUP) would be obtained as the
bottom product. This figure confirms that BUP brings about a
larger enhancement of the relative volatility, so that BUP is the
best promising entrainer for the separation of IBA and IBAc
azeotropic mixture by extractive distillation.
Another criterion for solvent selection is through the relative
volatility in presence of a solvent [18–20], defined as:
∞
Ki,S
αSi,j = ∞ (1)
Kj,S
∞ is the infinite dilution K-value for trace of species i in
where Ki,S
the solvent and Kj,S∞ is the infinite dilution K-value for trace of
species j in the solvent. Table 2 lists the K-values at infinite dilu-
Table 2
K-values at infinite dilution and relative volatility in presence of a solventa
∞ ∞
Solvent Ki,S Kj,S
DMF 2.8 6.0
1-Hexanol 5.2 3.7
BUP 4.4 2.1
a Simulated values with DISTIL using UNIQUAC model.
177
tion and the relative volatility. The greater the relative volatility
value, the easier the separation.
In Table 2, it can be seen that DMF reverses the volatility of
the primitive mixture (αSi,j < 1). 1-Hexanol alters only slightly
the activity coefficients of the components to be separated, BUP
being the best entrainer since it shows a higher relative volatility
and therefore it will allow a separation sequence not too expen-
sive.
2.3.2. Sequencing of the extractive distillation process
After the entrainer has been selected, in this work we have
chosen the butyl propionate, attention is directed to the sequence
of the distillation towers. The process configuration is shown in
Fig. 2, in which the solvent is added at the top trays of the extrac-
tive column (EC). In this column, BUP increases the volatility
of IBA with respect to IBAc and thus makes the separation eas-
ier. Since BUP is much less volatile than either IBA or IBAc, it
flows down the column to leave with the bottom product.
The solvent recovery column (SRC) removes IBAc from
BUP. This is an easy separation because the solvent is much less
volatile than IBAc. The lean solvent is then cooled and recycled
back to the extractive column. A low impurity solvent is needed
for the recycling, so as not to adversely affect the performance
of the extractive column. If the recovery of the solvent is high
a very small amount of solvent make-up is required to maintain
the solvent-to-feed ratio constant.
2.3.3. Optimization
2.3.3.1. Partial optimization based on the total reboiler heat
duty as a reference variable. In order to select the best con-
ditions to carry out the global economic optimization, we start
with a partial optimization specifying some variables and using
the total reboiler duty as a reference variable.
The variables chosen to be specified can be characterized as
either design variables or optimization variables. Design vari-
ables are those whose values are set by market demands or
physical conditions. In our study we specified the temperature,
pressure, flow rate and composition of binary feed. We also spec-
ified distillate purity and recovery of IBA in the first column,
and distillate purity of IBAc and bottom purity of solvent in the
second column. Finally, solvent make-up was chosen as a pure
component at ambient conditions. All the previously mentioned
variables are taken as design variables in this problem and the
selected values are shown in Table 3. Once design variables
have been specified, their values remain constant throughout the
optimization procedure. On the contrary, optimization variables
are those that must arbitrarily be assigned a value. The values
are subject to change as we proceed from the base case to the
optimal design. In this problem, the solvent-to-feed ratio in the
extractive column and the number of trays in each column are
optimization variables.
The optimization procedure using HYSYS requires setting
αSi,j
the number of trays in both columns. With the short-cut design
0.46 facility of HYSYS we did a case study analyzing the variation
1.40 of stage number and reboiler heat duty (RHD) as a function of
2.10 the reflux ratio, in order to set the number of ideal trays and feed
position of the solvent recovery column. Fig. 3 shows the results
178 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183

Fig. 2. HYSYS process flow diagram (PFD) of extractive distillation.

and it looks like a good decision to set the number of ideal trays
for this column at 30 (feed entry at stage number 13).
In the extractive column we cannot use the short-cut design
facility, so we have studied five cases varying the number of ideal
trays from 35 to 70 (fewer than 35 do not converge whatever
the solvent-to-feed ratio is; more than 70 is not reasonable),
selecting in each case the best solvent and feed entry stage. In
Table 4 the five cases are specified.
With the specifications showed in Table 3 and for the cases
specified in Table 4, the columns were then established with the
rigorous steady-state column facility of HYSYS. From previous
simulation runs, it was found that the solvent-to-feed ratio is

Table 3
Specifications of design variables in the extractive distillation process
Streams Variable Specification
Fig. 3. Solvent recovery column case study in the extractive distillation process.
Feed streams
Solid line: stage number vs. reflux ratio. Dashed line: reboiler heat duty vs. reflux
Binary feed Temperature (◦ C) 100
ratio.
Pressure (kPa) 110
Molar flow (kmol/h) 15.91 (1500 kg/h)
Molar composition 48% IBAc
Solvent make-up Temperature (◦ C) 25 Table 4
Pure component Number of ideal trays in the extractive column for each case
Extractive column Case
Distillate Purity of IBA 98.5%
Recovery of IBA 99.75% EC-1 EC-2 EC-3 EC-4 EC-5
Solvent recovery column Ideal trays number 35 40 50 60 70
Distillate Purity of IBAc 99.5% Solvent entry stage (optimum) 7 7 8 9 10
Bottom Purity of recycled solvent 99.5% Feed entry stage (optimum) 24 30 35 42 50
 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183
Fig. 4. Total reboiler heat duty vs. solvent-to-feed ratio in the extractive distil-
lation process (case EC-3).
very critical, having a significant effect on the reflux flow rate
in both columns, and therefore on the total reboiler heat duty,
so the partial optimization was made over this variable. In each
case, the solvent-to-feed ratio was then adjusted to minimize the
total RHD needed for the process. As an example (EC-3), Fig. 4
shows this effect. This procedure was applied successfully for all
five cases. Table 5 shows a summary of the partial optimization
based on total reboiler heat duty as a reference variable.
2.3.3.2. Global economic optimization. As it can be seen in
Table 5 the minor reboiler heat duty corresponds to EC-5. How-
ever, this case requires a big number of stages in the extractive
column; so, it would be an expensive column. Therefore, to
determine the best of these five alternatives it is necessary to
carry out an economic evaluation based on the minimum total
annual costs (TAC), using the following objective function [21]:
TAC (D 103 /year) = Cv + Cf + (ir + im ) · FCI
where Cv is the process variable cost, mostly annual utility
consumption (steam, cooling water and electrical power) and
BUP make-up cost; Cf the annual fixed costs, i.e. maintenance
and wages; FCI the fixed capital investment; ir the fixed cap-
ital recovery rate applied to FCI (depreciation rate); im is the
minimum acceptable rate of return on FCI.
Table 5
Optimum solvent-to-feed ratio in the extractive column for each case
Case Solvent-to-feed ratio Total reboiler heat
duty (RHD) (MJ/h)
EC-1 3.00 5646
EC-2 2.00 4562
EC-3 1.33 3350
EC-4 1.00 3094
EC-5 0.90 2823
179
Table 6
European utility prices [23] (Chemical Engineering Plant Cost Index (CEPCI-
2004) ≡ 444.2 and project life 10 years)
Capital cost
Utility Price
Low-pressure steam (D /t) 17
Cooling water (D /m3 ) 0.04
Electricity (D /kWh) 0.041
Solvent (BUP) (D /kg) 1.40
In this optimization Cf was assumed to be 10% of FCI, and
ir + im was supposed to be 20% of FCI; hence, Eq. (2) could be
rewritten as:
TAC (D 103 /year) = Cv + 0.30 · FCI (3)
Fixed capital investment (FCI) was estimated using the costs
estimation program CAPCOST of Turton et al. [22] with an
updated Chemical Engineering Plant Cost Index [23]. A 10-year
project life is selected (ir = 10%). Variable costs were obtained
applying the unitary costs from Table 6 [24].
Fig. 5 shows the calculated TAC data for the five cases at
different solvent-to-feed ratios (Table 4). As it can be observed,
there is a minimum for case EC-3 (solvent-to-feed ratio = 1.33).
Table 7 lists details of extractive and solvent recovery columns
needed to meet the design objectives together with the total
annual cost for this optimum. In Appendix A are listed the esti-
mated capital investment of each individual unit.
2.4. Pressure-swing distillation
It is well-known that, in some cases, changing the system
pressure can affect the vapour–liquid equilibrium (VLE) of a
mixture. This effect can be exploited to separate a binary mix-
ture containing a minimum boiling azeotrope [2], provided that
(2)
Fig. 5. Total annual cost (TAC) vs. solvent-to-feed ratio in the extractive distil-
lation process.
180 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183

Table 7 Table 8
Global economic optimum for extractive distillation process (EC-3) Specifications of the design variables in the pressure-swing distillation process
Design parameters Extractive Solvent recovery Variable Specification
column (EC) column (SRC)
Binary feed Temperature (◦ C) 100
Number of stages 50 30 Molar flow (kmol/h) 15.91 (1500 kg/h)
Molar composition 48% IBAc
Feed (top down stage number) 8 (solvent) 13
35 (binary feed) High pressure column (HPC) Pressure (kPa) 101.3
Purity of IBAc (bottom) 99.5%
Assumed tray efficiency (%) 70 70
Number of trays 72 43 Low pressure column (LPC) Pressure (kPa) 20
Reflux ratio 3.91 3.67 Purity of IBA (bottom) 98.5%
Reflux rate (kg/h) 2453.0 3221.5
RHD (MJ/h) 2102 1248
Total annual costs (TAC) ≡ D 1.33 million per year Fig. 7 shows the pressure-swing sequence for the separation
of IBA from IBAc. The feed enters the high pressure distilla-
tion column at 101.3 kPa and the distillate of this column has a
this mixture significantly changes composition over a moderate
composition that approaches the high pressure azeotrope. This
pressure range.
distillate is the feed stream to the low pressure column at 20 kPa,
2.4.1. Operating pressures selection and distillate has a composition that approaches the low pressure
To investigate the pressure sensitivity of IBA + IBAc azeotrope. This distillate has a composition that is similar to the
azeotropic mixture, we begin with a simulation of the VLE by feed composition and it is recycled to mix with the feed to HPC.
DISTILL at different pressures, using UNIQUAC thermody- High purity IBAc (99.5 mole%) is produced as a bottom stream
namic model with the parameters listed in Table 1. In Fig. 6, the from the HPC and IBA (98.5 mole%) is produced as a bottom
IBAc mole fraction and temperature of the azeotrope are plotted stream from the LPC that will be recycled to the estherification
as a function of pressure. We can observe a significant pressure reactor.
influence on the azeotropic composition. In order that the comparison of this process with the ED may
The operating pressure should be chosen within such a range be effective, we have considered the same degrees of purity for
that water can be used as coolant for the overhead condenser both processes.
and steam can be used as a heating medium for the reboiler.
According to that, the low pressure column (LPC) will work 2.4.3. Optimization
at 20 kPa and the high pressure column (HPC) at atmospheric We begin the procedure with a local optimization, specifying
pressure (101.3 kPa). some design variables and using the total reboiler heat duty as
an objective function, following a procedure similar to that used
2.4.2. Sequencing of the pressure-swing distillation process in ED.
For a binary mixture presenting a pressure-sensitive mini- The design variables selected in this study are the flow rate,
mum boiling point azeotrope, the separation sequence is formed composition and temperature of binary feed, the operating col-
by two columns operating at different pressures [2]. umn pressures and the purities of the bottom streams in both
columns. Table 8 shows the specification chosen for all the pre-
viously mentioned variables. On the other hand, the optimization
variables are the number of trays in each column, the recycle flow
rate and the HPC distillate composition.
Like in extractive distillation, the rigorous steady-state col-
umn facility of HYSYS requires to set the number of trays in
both columns. Therefore, with the short-cut column design facil-
ity we did a preliminary optimization (case study) of the number
of trays and feed position for both columns. From the results of
these case studies we selected 30 ideal trays (feed entry at stage
8) for the HPC and 16 ideal trays (feed entry at stage 4) for the
LPC.
With the design variable specifications showed in Table 8 and
once the number of trays was fixed, the system then converged
successfully in the rigorous facility of HYSYS. To carry out
the optimization, we studied six cases varying the HPC distil-
late composition from 0.675 to 0.800, selecting in each case the
best recycle flow rate that minimizes the total reboiler heat duty
Fig. 6. IBAc mole fraction and temperature of the azeotrope as a function of needed for the PSD process. The variation range of this opti-
pressure. Solid line: azeotrope composition (IBAc) vs. pressure. Dashed line: mization variable was established to produce reasonable results.
azeotrope temperature vs. pressure. This variable presents a maximum interval of variation which
 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183 181

Fig. 7. HYSYS process flow diagram (PFD) of pressure-swing distillation.

corresponds to the values of the azeotropic compositions at both the columns for PSD process together with the total annual costs
pressures. But when the value approaches either of both com- for this case are listed in Table 10. In Appendix B are listed the
positions, the design is critical, or the system does not converge estimated capital investment of each individual unit.
or it requires very high reflux ratios in one of the two columns. As can be seen in Tables 7 and 10, the annual costs estimated
In any case, the design becomes not feasible technically or eco- for the PSD process are quite lower than the ones corresponding
nomically. Table 9 shows the minimum reboiler heat duty for to the ED process (D 0.99 million against D 1.33 million) both
each specified case. obtained using the same criteria and evaluation procedures. This
As it can be seen in Fig. 8 and Table 9 the global optimum result may seem surprising, since usually the ED is a separa-
for the PSD process corresponds to PSD-4. This optimum is tion process more attractive than PSD process, provided that an
based on the minimum reboiler heat duty but it coincides with
the global economic optimum, since, having previously fixed the
number of stages in each column, the operation costs (mainly
the total reboiler heat duty) dominate the total costs.
In order to compare this alternative with the other alternative
of separation (ED), which was previously studied, it will be
necessary to evaluate economically the PSD optimum, using an
objective function similar to the one considered previously (Eqs.
(2) and (3)), with the utility costs shown in Table 6. Details of

Table 9
Optimum values of the optimization variables in the pressure-swing distillation
(PSD) process

Case HPCa distillate Recycle flow Total RHDb

composition (IBA) rate (kg/h) (MJ/h)

PSD-1 0.675 3300 5629

PSD-2 0.700 2400 5079
PSD-3 0.725 1900 4729
PSD-4 0.750 1500 4594
PSD-5 0.775 1100 4791
PSD-6 0.800 850 5871
Fig. 8. Total reboiler heat duty vs. recycle flow rate in the pressure-swing dis-
a High pressure column. tillation process: () PSD-1; () PSD-2; (䊉) PSD-3; (
) PSD-4; () PSD-5;
b Reboiler heat duty. () PSD-6. Solid line: minimum envelope.
182 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183

Table 10 the cots associated with the investment grow much more slowly,
Global economic optimum for PSD process (PSD-4) and therefore the total costs of both alternatives are much closer.
Design parameters High pressure Low pressure We have to keep in mind, however, that when we increase the
column (HPC) column (LPC) size of the plant significantly the costs of the make-up solvent
Number of stages 30 16 grow in the same proportion, if we maintain the specification of
Feed (top down stage number) 8 4 purity and recovery.
Assumed tray efficiency (%) 70 70
Number of trays 43 –
Packed height (m) – 9.29 3. Conclusions
Reflux ratio 1.86 1.33
Reflux rate (kg/h) 3952.5 1995.0
The simulation of processes with a commercial software pro-
RHD (MJ/h) 3119 1475
gram (HYSYS) used appropriately is a very powerful tool to
Total annual costs (TAC) ≡ D 0.99 million per year analyze the separation alternatives. When applied to the study
of the separation of IBA + IBAc azeotropic mixture, using UNI-
QUAC model with the values of the binary parameters obtained
by us, it has produced satisfactory results.
appropriate solvent is used in the extractive column and that it The simulation and economic evaluation of the two separa-
becomes easy to recover. tion alternatives that we have considered allow us to conclude
We will analyze the structure of the total annual costs more that for a 12,000 Tm/year plant, the PSD is more attractive than
carefully. In Table 11 we can see more precisely the details of the the ED using BUP as an entrainer.
annual costs for each separation alternative. The first thing that Probably for larger plants (100,000 Tm/year), the ED option
calls our attention in Table 11 is the big difference of the capital will be more attractive, but by a narrow margin in any case, since
investment value between both alternatives, because of the big with this entrainer the distillation columns necessary to carry
size of the columns in the ED process (see Table 7) needed to out the ED and the further recovery of solvent are very large and
obtain the desired purity of the products and recover the sol- therefore the necessary investment is much higher than in the
vent efficiently. This big difference of FCI leads to an important PSD process.
difference of the costs associated with the capital investment
(mainly fixed capital recovery and minimum acceptable rate of
return). In the end, these costs determine the difference between Acknowledgement
both alternatives. By lowering these costs the difference between
them would be less although the PSD process would always be The authors acknowledge the financial support from the Min-
favourable. On the other hand, the cost of the steam for the isterio de Ciencia y Tecnologı́a of Spain, through Project No.
reboilers is, by far, the most important of the utility costs, which CTQ2004-04477/PPQ.
fully justifies the decisions previous to carrying out the local
optimization (in those cases in which there is no FCI variation)
Appendix A
only based on these costs. As it can be seen, the cost of steam is
clearly higher in the PSD process than in the ED process, because
Estimated capital investment of each individual unit in the
the reflux rates are higher in the first case (Tables 7 and 10).
extractive distillation (ED) process
All these results have been obtained for a practical case based
on a plant for the treatment of 12,000 Tm/year of an IBA + IBAc D 103
mixture. If we consider larger plants, the difference between
both alternatives becomes less and less, precisely because the Extractive column (EC)
Tower + trays 1995.44
steam costs grow almost proportionally to the flow rate, while Reboiler 108.71
Condenser 31.95
Reflux pump 42.21
Reflux vessel 37.68
Table 11
Summary of economic results Total 2215.99
Process Extractive Pressure-swing Solvent recovery column (SRC)
distillation distillation Tower + trays 1016.65
Reboiler 92.98
Fixed capital investment (D 103 ) 3460.83 2197.50 Condenser 25.14
Cost proportional to FCI (D 103 /year)a 1038.25 659.25 Reflux pump 39.83
Steam (D 103 /year) 219.08 300.38 Reflux vessel 43.17
Cooling water (D 103 /year) 16.85 23.62 Total 1217.77
Electric power (D 103 /year) 9.70 7.56
Solvent make-up (D 103 /year) 46.07 – Cooler 6.60
Recycled pump 20.47
Total annual costs (D 103 /year) 1329.95 990.81
Fixed capital investment for ED process 3640.83
a Cost proportional to FCI = Cf + (ir + im ) · FCI.
 R. Muñoz et al. / Separation and Purification Technology 50 (2006) 175–183 183

Appendix B [3] M.F. Doherty, M.F. Malone, Conceptual Design of Distillation Systems,
McGraw-Hill, New York, 2001.
[4] M.F. Doherty, G. Buzad, Chem. Eng. Res. Des. 70 (1992) 448–458.
Estimated capital investment of each individual unit in the
[5] R.W. Maier, J.F. Brennecke, M.A. Stadtherr, Comput. Chem. Eng. 24
pressure-swing distillation (SPD) process (2000) 1851–1858.
[6] J.W. Drew, Chem. Eng. Prog. 71 (2) (1975) 91–99.
D 103 [7] D.R. Garg, J.P. Ausikaitis, Chem. Eng. Prog. 79 (4) (1983) 60–65.
[8] H.L. Fleming, Chem. Eng. Prog. 88 (7) (1992) 46–52.
High pressure column (HPC)
[9] W.F. Furter, Can. J. Chem. Eng. 55 (1977) 229–239.
Tower + trays 1146.52
[10] T.C. Frank, Chem. Eng. Prog. (April) (1997) 52–63.
Reboiler 105.61
[11] I. Rodriguez-Donis, V. Gerbaud, X. Joulia, Ing. Eng. Chem. Res. 40
Condenser 47.92
(2001) 2729–2741.
Reflux pump 45.05
[12] L. Berg, A. Yeh, AIChE J. 30 (1984) 871–874.
Reflux vessel 54.39
[13] E.G. Scheibel, Chem. Eng. Prog. 44 (1948) 927–936.
Total 1399.49 [14] J.B. Monton, R. Munoz, M.C. Burguet, J. de la Torre, Fluid Phase
Equilib. 227 (2005) 19–25.
Low pressure column (LPC)
[15] R. Munoz, J.B. Monton, M.C. Burguet, J. de la Torre, Fluid Phase
Tower + packing 475.46
Equilib. 232 (2005) 62–69.
Reboiler 61.37
[16] R. Munoz, J.B. Monton, M.C. Burguet, J. de la Torre, Fluid Phase
Condenser 58.72
Equilib. 235 (2005) 64–71.
Reflux pump 30.19
[17] R. Munoz, J.B. Monton, M.C. Burguet, J. de la Torre, Fluid Phase
Reflux vessel 38.47
Equilib. 238 (2005) 65–71.
Vacuum system 115.08
[18] L.T. Biegler, I.E. Grossmann, A.W. Westerberg, Systematic Methods of
Total 779.29 Chemical Process Design, Prentice Hall, New Jersey, 1997.
[19] I. Sucksmith, Chem. Eng. 89 (13) (1982) 91–95.
Recycled pump 18.72
[20] C.J. King, Separation Processes, second ed., McGraw Hill, 1980.
Fixed capital investment for PSD process 2197.50 [21] P. Langston, N. Hilal, S. Shingfield, S. Webb, Chem. Eng. Proc. 44
(2005) 345–351.
[22] R. Turton, R.C. Bailie, W.B. Whiting, J.A. Shaeiwitz, Analysis, Syn-
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