CHERD-1708; No.

of Pages 16
ARTICLE IN PRESS
chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx

Contents lists available at ScienceDirect

Chemical Engineering Research and Design

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

Conceptual design of unit operations to separate

aromatic hydrocarbons from naphtha using ionic
liquids. COSMO-based process simulations with
multi-component “real” mixture feed

V.R. Ferro ∗ , J. de Riva, D. Sanchez, E. Ruiz, J. Palomar

Sección Ingeniería Química, Universidad Autónoma de Madrid, 28049 Madrid, Spain

a b s t r a c t

COSMO-based process simulations using Aspen Plus and Aspen HYSYS were systematically applied to the conceptual
design of the two main unit operations commonly proposed to separate aromatic and aliphatic hydrocarbons with
ionic liquids (ILs) as extracting solvents; the extraction itself and the vacuum distillation for regenerating the ionic liq-
uid. By the first time, multi-component (up to 28 components) “real” mixture feeds were taken into account to model
the naphtha in the process design. Binary model (n-hexane + benzene, n-heptane + toluene, n-octane + ethylbenzene,
n-octane + m-xylene) mixture feeds were also considered to validate the computational procedure. Nine differ-
ent ionic liquids and mixtures of them, (IL–IL) mixtures, were selected as extracting solvents. Ionic liquids were
introduced in the process simulations as (pseudo)components and the COSMOSAC property model was used for
estimating the activity coefficients of the individual components in the mixtures. The information needed to both
create the non-data bank ionic liquid (pseudo)components and to specify the COSMOSAC property model was gath-
ered from COSMO-RS calculations. COSMO-based models exhibited a reasonably good predictability of both the
thermo-physical properties of the pure (hydrocarbons and ionic liquids) components and the LL and VL equilibria of
their mixtures. The performances of extraction and regeneration individual operations were analyzed at different
operating conditions, including the nature of the IL-based extracting agent, the solvent-to-feed ratio, and the hydro-
carbon mixture composition. The present results suggest that COSMO-supported process simulations are capable
of confidently dealing with complex multicomponent mixtures of hydrocarbons and ionic liquids. This opens new
perspectives to improved developments of this process based on ionic liquids and their mixtures.
© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Keywords: Aromatic–aliphatic separation; Ionic liquids; Process simulation; Aspen Plus; COSMO models

1. Introduction
Separation of aromatics and aliphatic compounds from
petrochemical feedstocks, having a relevant economical
and practical interest (Meindersma and de Haan, 2008;
Meindersma et al., 2010), is probably one of the most exten-
sively studied separation processes using ionic liquids (ILs) as
an alternative to organic solvents. The conventional processes
used to remove the aromatics from naphtha depend on the
aromatics content being the extraction suitable for the range
of 20–65 wt% (Meindersma and de Haan, 2008; Meindersma
et al., 2010). Several polar organic solvents and mixtures of
them have been evaluated as possible extracting agents in
this process: sulfolane, N-methyl pyrrolidone, N-formyl mor-
pholine, ethylene glycols, propylene carbonate, furfural and
others (Gaile et al., 2007; Hamid and Ali, 1996; Kumar and
Mohan, 2013) but sulfolane, as a rule, exhibits higher per-
formances than the remaining organic solvents evaluated.

∗
Corresponding author. Tel.: +34 91 497 7607.
E-mail address: victor.ferro@uam.es (V.R. Ferro).
Received 31 May 2014; Received in revised form 17 August 2014; Accepted 5 October 2014
http://dx.doi.org/10.1016/j.cherd.2014.10.001
0263-8762/© 2014 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
CHERD-1708; No. of Pages 16
ARTICLE IN PRESS
2 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx
Fig. 1 – Simplified conceptual diagram of the process to separate aromatic hydrocarbons from naphtha using ionic liquids
as extracting solvents.
Hence, UOP has developed an industrial process to separate
aromatics from naphtha using this solvent (Asselin, 1984).
Nevertheless, extraction with conventional organic solvents
(including sulfolane) seems not to be a definitive option since
additional separation operations are required to separate the
extraction solvent from both the extract and the raffinate
phases and to purify the solvent, resulting in additional invest-
ments and energy consumption (Meindersma and de Haan,
2008; Meindersma et al., 2010). Application of ILs as solvents
for extraction operations in the current and other indus-
trial processes is widely accepted as promising since, due
to their negligible vapor pressure, it is expected to require
fewer process steps and less energy consumption than extrac-
tion with conventional solvents. In particular, solvent recovery
seems to be relatively easy (Meindersma and de Haan, 2008;
Meindersma et al., 2010). Several ILs have been investigated as
extracting solvents in this process: imidazolium, pyridinium,
pyrrolidinium, etc. A complete review of the ILs investigated
in this role over the past 10 years can be found in Meindersma
et al. (2010). More recently, low-viscous ILs based on the
cyano-anions have been proposed for the aromatic extraction
(Hansmeier et al., 2010; Meindersma and de Haan, 2012). In
addition, mixtures of mutually miscible (Garcia et al., 2012b;
Potdar et al., 2012) and even immiscible (Arce et al., 2008a)
ILs have also been studied in order to improve the extracting
properties in respect to the individual ILs.
Separation of aromatic compounds from naphtha with ILs
has been the subject not only of basic thermodynamic studies
devoted to elucidate the equilibrium conditions of the process
(see for example references Arce et al., 2007a,b, 2008a,b, 2009;
Calvar et al., 2011; Corderi et al., 2012; Garcia et al., 2011a,b,
2012a; Gonzalez et al., 2010; Meindersma et al., 2005, 2006a,c,
2010; Pereiro and Rodriguez, 2010 and references therein), but
also of process developments (Meindersma, 2005; Meindersma
and de Haan, 2008; Meindersma et al., 2006b) including pilot
plant scaled experiments (Meindersma, 2005; Meindersma
et al., 2012). In all the conceptual designs (in spite of their com-
plexities) developed so far for this and other similar processes
(Arce et al., 2007c; Meindersma, 2005; Meindersma and de
Haan, 2008; Meindersma et al., 2006b; Pereiro and Rodriguez,
2009, 2010; Seiler et al., 2004; Shiflett et al., 2011; Shiflett and
Yokozeki, 2006) two main operations are considered (Fig. 1):
(i) aromatic hydrocarbons are separated from their mixtures
with aliphatic ones by liquid–liquid extraction using ILs as
extracting solvents and (ii) further, ILs are regenerated from
Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
their mixtures with the aromatic hydrocarbons (to be recy-
cled at the beginning of the process) by vacuum distillation.
Stripping with air has also been proposed as an alternative to
IL regeneration (Meindersma, 2005; Meindersma et al., 2010).
Other schemes developed for recovering styrene monomer
from 4-mebupyBF4 IL (Jongmans et al., 2013) could also be
appropriate to regenerate the ILs in processes devoted to sep-
arate aromatic hydrocarbons from naphtha.
Most of the conceptual designs cited above are supported
by process simulations which, in general, reveal significant
computational difficulties. In these and other related works
either the conceptual design of the processes is merely out-
lined and/or simulations of the individual operations (usually
LL-extraction) are carried out. Complex flowsheets have been,
as a rule, not calculated. In particular, the IL regeneration after
the primary separation with ILs is not simulated or simply
mass balances are performed specifying the IL recovery but
without solving the phase equilibrium for the corresponding
VL operation. Only a few works simulate the IL regeneration
with one-stage VL separators, shortcut or rigorous distillation
columns (Arce et al., 2007c; Jongmans et al., 2013; Pereiro and
Rodriguez, 2009, 2010; Seiler et al., 2004; Shiflett et al., 2011;
Shiflett and Yokozeki, 2006). Regarding the conceptual designs
of the aromatic separation from naphtha and the correspond-
ing process simulations, another distinctive feature should be
emphasized: they are habitually limited to the use of binary
(aromatic + aliphatic) mixtures to model the real feed. Multi-
component more “real” mixtures are not considered. The most
frequent difficulties found in process simulations with ILs in
general and in this process in particular are related to severe
errors occurring in the flowsheet calculations (Meindersma,
2005) and also to the absence of reliable information on the
VL equilibrium, the heat capacities of the ILs and their mix-
tures with conventional organic solvents (Arce et al., 2007c),
etc. This second issue hinders the complete specification of
the simulation. Generally speaking, two conflicting problems
are recognizable in the simulations referred here:
(i) Since ionic liquids are not present in the process simula-
tors’ databanks (frequently Aspen Plus and/or Aspen HYSYS),
the values of parameters for several physical properties of
the ionic liquids are estimated, guessed or simply left out
(Meindersma, 2005). To include ILs in process simulations,
users are forced to “create” them as non-databank compo-
nents. This is especially complex because the models and
computational routes implemented in the process simulators
CHERD-1708; No. of Pages 16
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to estimate the properties of pure components have not been
developed for this particular class of compounds. Conse-
quently, the simulation crashes if the non-supply or non-
consistently estimated information of the pure components is
demanded in any critical calculation step. For “creating” non-
databank IL components two alternatives have been explored
using Aspen Plus and/or Aspen HYSYS: ILs are introduced
(a) as conventional components (see a good example in Ref.
Shiflett et al., 2010), or (b) as pseudo-components (Bedia et al.,
2013; Ferro et al., 2012a; Ruiz et al., 2014). In the first one, as a
rule, a huge amount of data should be supplied to the program
because the property methods and models for estimating the
unknown properties of the new components fail when work-
ing with ILs. In most cases these data are not available or they
are hardly obtainable. The second way allows working with
much less experimental information (in the current situation,
only Andrade’s equation parameters to model IL viscosity)
since it uses the a priori COSMO-based methods to estimate
the required pure solvent and mixture properties (see below).
(ii) NRTL and UNIQUAC activity models are often used
to calculate the activity coefficients of the components in
the mixtures of ILs and organic compounds, their binary
interaction parameters being correlated from experimental
equilibrium data (see, for example, Refs. Arce et al., 2007c;
Garcia et al., 2012b; Kato and Gmehling, 2005; Pereiro and
Rodriguez, 2010; Seiler et al., 2004; Shiflett and Yokozeki,
2006 and other related ones). However, these models exhibit
a strong system- and equilibrium-dependent character, i.e.
the interaction parameters obtained by correlation of the
LLE data for a specific system could hardly be used to solve
either the VL equilibrium of the same system or the LL
equilibrium of other mixtures. Furthermore, VLL equilib-
rium data are extremely scarce in multi-component mixtures
including ILs. Additionally, it should be taken into account
that creating new IL components and NRTL/UNIQUAC prop-
erty packages for multi-component (aliphatic + aromatic + ILs)
process simulations by using experimental data repre-
sents a considerable amount of previous work to be done
because the corresponding binary interaction parameters
for all the component pairs considered have to be deter-
mined. This is almost experimentally and economically
unaffordable. Hence, as it was previously mentioned, pro-
cess simulations on the aromatic and aliphatic hydrocarbon
separation with ILs model the “real” feed mixtures as
simply binaries (n-hexane + benzene), (n-heptane + toluene),
(n-octane + ethylbenzene), (n-octane + m-xylene), etc.
Recently, the most significant achievements on molecular
thermodynamics of fluid phase equilibria as well as several
other theoretical and empirical approaches have been suc-
cessfully applied to reproduce the experimental data on the
thermodynamic properties of pure ILs and mixtures that con-
tain them (Paduszynski and Domanska, 2012; Vega et al., 2010).
For example, the electrolyte-NRTL (eNRTL) (Simoni et al., 2008)
and the NRTL-SAC (Chen et al., 2008) models have been used
to correlate values of infinite-dilution activity coefficients for
organic compounds in ionic liquids and further to predict
the LL and VL phase behavior of the corresponding mixtures.
Likewise, the statistical associating fluid theory (SAFT)-based
models have been strongly recommended due to their phys-
ical background (Ji et al., 2012; Paduszynski and Domanska,
2012) and used to model SL, LL, VL and GL equilibria in systems
containing ILs (Ji et al., 2012; Kroon et al., 2006; Paduszynski
and Domanska, 2012; Rahmati-Rostami et al., 2011). These
models provide a realistic description of the thermodynamic
Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
3
properties of pure ILs and their mixtures with conventional
compounds. Nevertheless, the elevated number and/or the
system-specific character of the parameters required limit
their application with a priori and extensive character in the
search and design of ILs with optimized properties for a given
application. Moreover, they are not implemented (or not con-
veniently implemented) in commercial process simulators to
model processes with ILs. This restricts their use in tasks nor-
mally addressed by the conceptual design of new processes
using ILs.
COSMO-RS model (Klamt, 2005; Klamt et al., 2010), needing
only few general (no system-dependent) adjustable param-
eters, has shown to yield good qualitative and satisfying
quantitative predictions for the activity coefficients of neu-
tral compounds in ionic liquids and for binary mixtures of
ionic liquids and neutral solvents (Diedenhofen and Klamt,
2010). Therefore, COSMO-RS has become a widely used effi-
cient tool for the screening/selection/design of ILs with desired
properties for specific applications (Ab Manan et al., 2009;
Gutierrez et al., 2012; Palomar et al., 2008, 2009). COSMO-RS
has been applied with reasonable success to predict densi-
ties (Palomar et al., 2007), vapor pressures and vaporization
enthalpies (Diedenhofen et al., 2007; Schröder and Coutinho,
2014) of pure ILs. It has also turned out well in predicting:
(i) the activity coefficients at infinite dilutions (Banerjee and
Khanna, 2006; Diedenhofen et al., 2003; Gonzalez-Miquel et al.,
2012; Liu et al., 2014) in mixtures of hydrocarbons, alcohols and
polar organics in several ILs, (ii) gas solubilities in ILs and the
corresponding Henry’s law constants (Ab Manan et al., 2009;
Bedia et al., 2013; Fallanza et al., 2013; Gonzalez-Miquel et al.,
2011, 2012; Liu et al., 2014; Palomar et al., 2011a,b), (iii) the
LL equilibria of binary, ternary and quaternary mixtures of
organic compounds and ILs (Banerjee et al., 2008; Domanska
et al., 2006; Ferreira et al., 2011, 2012; Freire et al., 2007, 2008;
Potdar et al., 2012) and, (iv) the VL equilibria of binary mix-
tures of conventional organic solvents and ILs (Banerjee et al.,
2006, 2008; Ferro et al., 2012a; Freire et al., 2007, 2008; Kato and
Gmehling, 2005; Ruiz et al., 2014). Additionally, COSMO-based
models (Klamt, 1995; Lin and Sandler, 2002; Mathias et al.,
2002) have been wholly implemented in Aspen Plus since its
version 12.1 under the general denomination of COSMOSAC
property model (Aspen Technology, 2003). Taking advantage
from this development, we have fruitfully used the COSMO-
based calculations with the Aspen Technology programs for
carrying out different tasks directly related to the concep-
tual design of several processes involving organic compounds
(Ferro et al., 2012b) and ILs (Bedia et al., 2013; Ferro et al., 2012b;
Ruiz et al., 2014). Based on the technical, energy and eco-
nomic analysis derived from these results the selection/design
of optimized ILs for specific uses is improved. Certainly, the
integration of the COSMO-based results into Aspen Plus has
been developed by other authors (Cadoret et al., 2009; Tian
et al., 2010) avoiding the direct use of the COSMOSAC property
model already implemented in the process simulator. How-
ever, the direct integration seems to be more efficient and less
time-consuming.
In this work, the conceptual design of the individual unit
operations (Fig. 1) used to remove aromatic hydrocarbons from
naphtha was performed with the support of Aspen Plus and
Aspen HYSYS process simulations by using the COSMOSAC
property model. The operating conditions at both the extrac-
tion and the flash distillation process units were explored as a
function of the IL and hydrocarbons nature. The hydrocarbon
mixture composition was also taken into account. Here,
CHERD-1708; No. of Pages 16
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4 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx
for the first time, multi-component (aliphatic + aromatic)
mixtures (up to 28 components) were used to model the “real”
naphtha fed to the process. Multi-component hydrocarbon
mixtures were composed by C4 –C10 aliphatic hydrocarbons,
cycloalkanes, and by benzene, toluene, ethylbenzene and
xylenes. Binary (aromatic + aliphatic) mixtures were also
considered in order to validate the results obtained for
multi-component (aromatic + aliphatic) mixtures with those
obtained in previous conceptual designs and thermodynamic
studies carried out on simpler binary mixtures. Ongoing from
binary to multi-component (aromatic + aliphatic) mixtures
had the primary intention to give a more real description of
the process, and consequently, a more realistic conceptual
design. On the other hand, nine individual ILs with different
cations and anions as well as from binary to quaternary
(IL–IL) systems were used as extracting solvent in the pro-
cess. The ILs selected to the present study were composed
by cations: 1-alkyl-3-methylimidazolium (Cn mim+ , being
C1 ≡ methyl(m), C2 ≡ ethyl(e), C4 ≡ butyl(b), C6 ≡ hexyl(h)
and C8 ≡ octyl(o)) and anions: triflates (CF3 SO3 − , shortly
TfO− ) and bistriflamides (N(CF3 SO2 )2 − , shortly NTf2 − ). 3-
Methyl-N-butylpyridinium dicyanamide (3-mebypyDCN) and
4-methyl-N-butylpyridinium tetrafluoroborate (4-mebupyBF4 )
were also considered.
The paper is organized into two main parts: Firstly,
the information required to generate non-databank IL
(pseudo)components and to specify the COSMOSAC property
model in the Aspen Plus basis environment was derived with
the COSMO-RS method. Then, it was evaluated and validated
the capacity of the COSMOSAC property model (as specified
in this work) to predict the properties of the individual ILs
selected, the component activity coefficients in binary mix-
tures of organic components and ILs and, finally, the LL and
VL equilibria in Aspen Plus and Aspen HYSYS. Secondly, the
individual extraction and distillation (Fig. 1) unit operations
were conceptually designed for the cases of both binary and
multi-component (aromatic + aliphatic) mixtures feed. The
performances of the individual operations were evaluated in
terms of parameters commonly used in Process Engineer-
ing (see Section 2). The results presentation evolves stepwise
from the simplest separation of binary (aromatic + aliphatic)
mixtures with single IL to multi-component hydrocarbon mix-
tures with binary to quaternary (IL–IL) mixtures. At the end of
this paper, an example of how the results of the conceptual
design of the individual unit operations enrich the selection
of the best IL-based extracting agent was discussed.
2. Computational details
2.1. Quantum chemical calculations
In COSMO and COSMO-RS calculations (Klamt, 2005; Klamt
et al., 2010) the molecular structure of the selected ILs was
described by the ion-paired (molecular-like) model. These
structures were obtained by geometry optimization at BP-
TZVP computational level considering solvent effects through
the COSMO continuum solvation model (Andzelm et al., 1995;
Klamt, 1995). Vibrational frequency calculations to confirm the
presence of an energy minimum were performed. After opti-
mization, a file with extension.cosmo, containing the ideal
screening charges on the molecular surface computed by the
COSMO methodology was generated. It was used in further
COSMO-RS calculations of the thermo-physical properties
Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
of the fluid. The TURBOMOLE suit (TmoleX version 3.1) of
programs (Schäfer et al., 2000) and the program package
COSMOthermX, version C30 1201 (Diedenhofen et al., 2012)
were used, respectively, in all the quantum chemical and
COSMO-RS calculations. The COSMOthermX calculations use
the implicit BP TZVP C30 1201 parametrization.
2.2. Creating the property package
IL (non-databank) components were introduced in the Aspen
Plus process simulations as pseudo-components. Following
the procedure implemented in the program, their molecu-
lar weights, normal boiling temperatures and densities were
specified by the user. The remaining unknown properties of
the pseudo-components were estimated by the methods and
models used implicitly in Aspen Plus (Aspen Technology, 2011)
for this class of components by performing a Property Estima-
tion calculation (at the basis environment of the simulator).
Additionally, the coefficients of the Andrade’s equation for the
viscosity-to-temperature dependency were also specified by
the user. These coefficients were obtained by regression of vis-
cosity vs. temperature experimental data (de Riva et al., 2014).
The aromatic and aliphatic hydrocarbons were selected as
conventional components from the Aspen Plus database. The
COSMO-SAC (Lin and Sandler, 2002) equation as implemented
by default in Aspen Plus (under the general denomination
COSMOSAC) was selected to estimate the activity coefficients
of the components in the mixtures. Original parametrization
of the COSMO-SAC model (Lin and Sandler, 2002) was used.
The molecular volumes and ␴-profiles needed to specify the
COSMOSAC property model for the ILs were provided by the
user, whereas those corresponding to the organic solvents
were directly taken from the database of Aspen Plus. The infor-
mation used for specifying both the IL pseudo-components
and the COSMOSAC property model were attained from the
previous COSMO-RS calculations. The property package cre-
ated in Aspen Plus was imported from Aspen HYSYS which
supports some of the process simulations performed in this
work. The version 8.4 of the Aspen ONE program package was
used.
2.3. Validating the property system created
In order to evaluate the predictive capacity of the current
computational procedure, several simulations (flowsheet
run type at the simulation environment of the simula-
tor) focused calculating some selected properties of the
pure ILs (density, viscosity, heat capacity and heat of
vaporization) and their mixtures with aromatic and/or
aliphatic hydrocarbons (component activity coefficients at
infinite solutions, VL and LL equilibria) were performed.
LLE diagrams of ternary (aromatic + aliphatic + IL) and
quaternary (aromatic + aliphatic + IL1 + IL2 ) mixtures were
calculated. Ternary mixtures consist of (n-hexane + benzene),
(n-heptane + toluene), (n-octane + ethylbenzene) and (n-
octane + m-xylene) with 3-mebupyDCN, 4-mebupyBF4 ,
C2,4 mimNTf2 and emimTfO ILs. The LL equilib-
rium of a single quaternary mixture composed by
(n-hexane + benzene + emimMeSO4 + emimEtSO4 ) was cal-
culated. VLE diagrams of (benzene + C1,2,4 mimNTf2 ILs) and
(toluene + C1,2,4,6,8 mimTfO) were also predicted. The obtained
results, when possible, were compared to the experimental
data published elsewhere (see below for references). Two
statistics were employed for quantifying the goodness of
CHERD-1708; No. of Pages 16
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chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx 5

the predictions in respect to the experimental values: (i) the

Table 1 – Composition of the multi-component
relative absolute average deviation (RAAD) (also known as (aliphatic + aromatic) mixtures used in this work for
average absolute relative deviation) and (ii) the root mean modeling the “real” naphtha feed to the process to
square deviation (RMSD). They are defined as follows: remove aromatic hydrocarbons.

100  |xi
Calc
− xi
Exp
| Component wt%
RAAD (%) = ·
n Exp
xi Mixture 1a
i
Benzene 1.8
where x is any variable considered and n is the number of Toluene 3.3
values to be compared. Ethylbenzene 2.0
m-Xylene 2.9
⎛  Exp 2
⎞1/2 n-Hexane 43.2
Calc
(xilm − xilm )
⎜ ⎟ n-Heptane 15.8
RMSD (%) = 100 · ⎜ ⎟
i l m
n-Octane 31.0
⎝ 6·k ⎠
Mixture 2b
n-Butane 1.5
where x is the mole fraction and the subscripts i, l and m desig- i-Pentane 4.2
nate, respectively, the components, phases and tie lines. The n-Pentane 10.3
Cyclopentane 1.5
value k designates the number of tie lines considered and 6
2,3-Dimethylbutane 0.8
refers to the number of compositional variables per tie line. 2-Methylpentane 6.0
3-Methylpentane 4.0
2.4. Process simulations n-Hexane 8.6
Methylcyclopentane 4.1
300 ton/h of an (aliphatic + aromatic) mixture containing c.a. Benzene 1.8
Cyclohexane 2.8
10 wt% of aromatic(s) hydrocarbon(s) was always fed to the
2-Methylhexane 2.8
extraction column. Calculation of the extractive unit operation
3-Methylhexane 3.8
with binary (aliphatic + aromatic) mixture feeds were carried n-Heptane 4.4
out only with the aim to: (i) validate the computational pro- Methylcyclohexane 4.8
cedure, since the majority of the experimental information Toluene 3.0
on the current process has been obtained for this kind of 2-Methylheptane 2.4
systems and (ii) gain support to further interpret the results 1,3-Dimethylcyclohexane 7.0
n-Octane 5.4
obtained with real multi-component mixtures. Indeed, binary
Ethylcyclohexane 2.0
mixtures do not have practical significance in potential real 2,6-Dimethylheptane 1.9
processes. Two multi-component mixtures (1 and 2) with the Ethylbenzene 2.0
compositions given in Table 1 were used in this work as fresh p-Xylene 1.9
feed to the separation process. Multi-component mixture 1 (7 3-Methyloctane 2.9
components) is composed by some representative aromatic o-Xylene 1.0
n-Nonane 2.6
and aliphatic hydrocarbons which allows more realistic mod-
n-Decane 3.0
eling of the process than the binary (aromatic + aliphatic)
i-Decanes 4.0
ones while avoiding several complexities related to the pres-
ence of the lighter (C4 - and C5 -) hydrocarbons (see further). a
Meindersma (2005).
b
Multi-component mixture 2 (28 components) has a FCC-like Meindersma and de Haan (2008).
composition.
The extractor was simulated by the rigorous model of
the counter-current liquid–liquid extraction (Extract) in Aspen (aliphatic + aromatic) mixtures using individual ILs as extract-
Plus. Operating temperature and pressure were always set to ing solvents, (ii) multi-component (aliphatic + aromatic) mix-
40 ◦ C and 1 atm. In all the simulations the extractor was calcu- tures (1 and 2) with individual ILs and finally, (iii) multi-
lated considering a 98.0% of aromatic hydrocarbon(s) recovery component (aliphatic + aromatic) mixtures (1 and 2) with
through the extract (design specification). In order to primar- binary to quaternary (IL–IL) mixtures as extracting agents.
ily evaluate the extractive unit operation, the (S/F) molar ratios The two-outlet VL flash model in Aspen Plus (Flash2)
needed to reach the target recovery were computed for differ- was used for modeling the IL regenerator. The operating
ent numbers of equilibrium stages (N). Based on these data, temperature at the regenerator was selected in order to
the (S/F) molar ratio for N → ∞ ((S/F)min. ) was determined for avoid the thermal decomposition of the regenerated IL(s). 3-
the systems assessed. Afterwards, the operation performance mebupyDCN and 4-mebupyBF4 begin to decompose at c.a.
was detailed evaluated for the most promising studied ILs in 230–250 ◦ C, whereas NTf2 and TfO ILs decompose at 320–330 ◦ C
a 12 equilibrium stages column. This allows the direct com- (Crosthwaite et al., 2005; Fredlake et al., 2004; MacFarlane
parison of the present results with those published elsewhere et al., 2002; Meindersma and de Haan, 2012). In all the process
(Meindersma, 2005; Meindersma and de Haan, 2008). Perfor- simulations of the IL regenerator, the following design spec-
mances of the extractive unit operation with different ILs were ifications were set: (i) the IL recovered was 99.0 mol% pure,
evaluated in terms of solvent consumption, (S/F), and prod- (ii) the mixture to be separated was fed at the bubble point
uct recoveries and/or purities (aromatics in the extract and temperature for the corresponding operating pressure, and (iii)
aliphatics in the raffinate). Recoveries or purities were used operating temperature was fixed to 230 ◦ C for 3-mebupyDCN
casuistically depending on the relationship studied. Analysis and 4-mebupyBF4 ILs or 320 ◦ C for TfO- and NTf2 -ILs. The next
of the extractive process operation was conducted sequen- two process variables were used to evaluate the IL regenera-
tially throughout the following systems: (i) binary model tion process operation: (i) the operating (equilibrium) pressure

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
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at which the target separation was reached for the specified

temperature and (ii) the calculated heat duty (in kJ per kg
of IL regenerated) of the operation. This treatment is simi-
lar to the one employed in our previous study (Ferro et al.,
2012a). Four different situations were studied in relation to
the IL regeneration: (i) individual ILs were regenerated from
their binary mixtures with different aromatic hydrocarbons.
This is a hypothetical circumstance because it essentially
assumes a perfect separation in the extractor. However, it
can give a general outlook about the influence of the IL and
aromatic nature on the operating conditions and energetic
requirements of the IL regeneration. 15 wt% aromatic mixtures
were supposed every time, (ii) individual ILs were regener-
ated from their ternary mixtures with (aromatic + aliphatic)
hydrocarbons. The presence of aliphatic hydrocarbons in the
extract is not desirable not only because it reduces their
recovery through the raffinate and the aromatic purity in the
extract, but also because it represents an extra energetic load
in the IL regeneration (see below). However, it is unavoidable
when multi-component “real” (aromatic + aliphatic) mixtures
are fed to the process because the previous extraction does
not completely separate aromatic and aliphatic hydrocar-
bons. Hence, the consequence of the aliphatic hydrocarbon
presence in the mixture feed to the IL regeneration on both
the operating conditions and the energetic needs of the IL
recovery were analyzed previously to discuss the IL regener-
ation from multi-component (aromatic + aliphatic) mixtures.
In these studies, 2 wt% of n-hexane, n-heptane or n-octane
was always added to mixtures of different ILs and aromatic
hydrocarbons (benzene, toluene, ethylbenzene and m-xylene).
Aliphatic addition was made in such a way that the flows of the
remaining components of the mixture (aromatic and IL) were
kept constant; (iii) individual ILs were regenerated from the
extract resulting from the extraction of multi-component real
mixtures 1 and 2, and (iv) (IL–IL) mixtures were regenerated
from the real extracts (as in the previous situation).
3. Results and discussion
3.1. Property prediction of pure ILs and their mixtures
with the organic compounds
Densities, viscosities, heat capacities and heats of vaporiza-
tion predicted by Aspen Plus and Aspen HYSYS simulations
Heat vaporiz. n=6
Heat capac. n=9
Viscosity n = 11
Density n=8
0 2 4 6 8 10
RAAD, %
Fig. 2 – Relative absolute average deviation (RAAD) of some
selected thermo-physical and transport properties for the
pure ILs considered in the present work. The number of
pure ILs taken for the statistical analysis is shown inside
the bars.
here were similar to those obtained by Banerjee et al.
(2008) with COSMO-RS model for ternary and quater-
nary systems containing ethanol, hexane, hexene and
hxmimBF4 and/or emimEtSO4 ILs. They were also similar
to those obtained by Shah and Yadav (2012) for (aro-
matic + aliphatic + IL) ternary mixtures using the COSMO-SAC
model and Potdar et al. (2012) for ternary and quaternary (aro-
matic + aliphatic + IL(s)) mixtures. Predicted LLE diagrams for
the ternary (hexane + benzene + C(2,4,6,8,10) mimNTf2 ILs) suc-
cessfully reproduced the increase, experimentally observed,
of the mutual solubility of both hydrocarbons and the ILs
as the length of the alkyl chain becomes longer (Arce et al.,
2007b), however, the region of mutual solubility was some-
what overestimated in respect to the experiments. This result
can be understood from the previous ones reported here on
the estimation of the activity coefficients of the individual
components in binary mixtures with ILs. At the same time,
they were responsible for certain inaccuracies obtained (see
next paragraphs) in the estimation of the aromatic purities
6
Aliphatic
5 Aromatic
Cyclic aliphatic
Experimental ln(γ)

(with the COSMOSAC property model) for the pure ILs used
4
in this work agree reasonably well (Fig. 2) with experimental
reported data. Computed RAADs (in %) for all the ILs included
3
in this work are 2.4, 5.0, 9.8 and 8.7, respectively, for the
mentioned properties. These accuracies are similar to those
2
obtained by us in other related works where a similar com-
putational procedure was used (Bedia et al., 2013; Ferro et al.,
1
2012a; Ruiz et al., 2014).
Current calculations also predicted reasonably well (Fig. 3) 0
the component activity coefficients at infinite dilution
in binary (aliphatic or aromatic hydrocarbons + ILs) mix- 0 1 2 3 4 5 6
tures as derived by comparison with experimental data Calculated ln(γ)
(Domanska and Marciniak, 2008). Nevertheless, activity coef-
ficients of the aromatic and aliphatic hydrocarbons are Fig. 3 – Experimental vs. calculated activity coefficients at
slightly under- and over-estimated, respectively. Relatively infinite dilution for the organic component in binary
small errors were also obtained in the prediction of the (organic + IL) mixtures. Results are given in logarithmic
LL equilibria in ternary (aromatic + aliphatic + IL) and quater- scale. T = 308 K.
nary (aromatic + aliphatic + IL1 + IL2 ) mixtures (Figs. 4 and 5 Experimental data were taken from Domanska and
and Table 2). The accuracies of the predictions reached Marciniak (2008).

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
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0.00 0.00
1.00 1.00
A Experimental
Calculated
0.25 0.25
0.75 0.75

e
an

Be
e

ex
n

To

nz
pta

n-H
lu

en
0.50
e

0.50

en
0.50
n-H

0.50

e
e
0.75
0.25 0.75
0.25

1.00
0.00 1.00
0.00 0.25 0.50 0.75 1.00 0.00
0.00 0.25 0.50 0.75 1.00
emimTfO
(emimMeSO4+emimEtSO4)

Fig. 5 – Experimental (solid line) and Aspen Plus (dotted

0.00 line) calculated (with COSMOSAC property model) LL
1.00 mmim
B emim equilibria (wt%) of the quaternary mixtures
(n-hexane + benzene + emimMeSO4 + emimEtSO4 ).
bmim
hxmim Experimental data were taken from Ref. Potdar et al. (2012).
e

0.25
IL mixture contains 80 mol% emimEtSO4 . T = 298.15 K.
t an

0.75 omim
To
ep

lue
n-H

ne

containing aromatic hydrocarbons and ILs, the main compo-

0.50 nents of the mixtures to be treated in the IL-regenerator, were
0.50
satisfactorily well described for the characteristic composi-
tions considered in this work. However, for certain individual
0.75 (hydrocarbon + IL) systems and hydrocarbon molar fractions
0.25
above 0.5 some disagreements with experimental data have
been observed (Ferro et al., 2012a).

1.00
0.00 0.25 0.50 0.75
CnmimTfO
Fig. 4 – (A) Experimental and Aspen Plus calculated (with
COSMOSAC property model) LL equilibria (wt%) for the
ternary mixture (n-heptane + toluene + emimTfO IL).
Experimental data were taken from Garcia et al. (2011a). (B)
Predicted LLE of ternary mixtures
(n-heptane + toluene + C(1,2,4,6,8)mimTfO ILs). T = 313.15 K.
in the extract. The increase of the miscibility region with the
length of the alkyl chain of the cation was also predicted for
Cn mimTfO ILs (Fig. 4B) while preserving a high immiscible
region even for the ILs with the longest alkyl chains.
Predicted VLE for binary mixtures (ben-
zene + C(1,2,4) mimNTf2 ILs) also matched reasonably well
with the experimental ones (Fig. 6A) for all the composi-
tion interval. The computed MRDs between calculated and
experimental values were, respectively, 4.8%, 5.4% and 5.4%.
Fig. 6B shows the predicted VLE of the binary mixtures
(toluene + C(1,2,4,6,8) mimTfO ILs) in the region of toluene molar
fractions below 0.25. It is interesting to note that, in both the
cases shown in Fig. 6, the vapor pressure of the mixtures
for any composition decreased as the length of the cation
alkyl chain becomes longer. The accuracies reached in these
predictions are similar to those obtained previously (Banerjee
et al., 2006, 2008; Ferro et al., 2012a; Freire et al., 2007, 2008;
Kato and Gmehling, 2005; Ruiz et al., 2014). From the present
results it could be concluded that VLE behavior of mixtures
0.00 3.2. Simulation of the extracting unit operation
1.00
Separation of binary (aromatic + aliphatic) mixtures with indi-
vidual ILs
In order to recover 98.0% of the aromatic hydrocarbon from
the binary (aromatic + aliphatic) mixtures with different indi-
vidual ILs (Fig. 7, Table 3), (S/F)min. in the interval from 0.6 to
4.2 were required. A reasonable low number of 4–6 equilib-
rium stages also guarantied the target separation but using
considerably higher solvent flows (Fig. 7). Taking into consider-
ation the elevated prices of the ILs (Meindersma and de Haan,
2008), the (S/F) factor has noticeable significance in the selec-
tion of the extracting solvent being desirable to operate as
near as possible to (S/F)min. condition. This is viable, for exam-
ple, in a 12-stage column which represent, simultaneously,
a reasonably small equipment. Under any condition where
the aromatic target recovery was achieved, aliphatic hydro-
carbons were always separated throughout the raffinate with
purities over 99.7–99.8 wt% and recoveries higher than 80.0%
(Table 3). Moreover, the aromatic (free-of-solvent) purity in
the extract was about 35–65 wt% for all the systems consid-
ered. Loses of IL through the raffinate were always lower than
0.001%. For example, in toluene separation from its mixtures
with n-heptane using 4-mebupyBF4 as extracting agent in a 12-
stage LL extractor, an (S/F)min. molar ratio of 2.64 guarantees a
toluene recovery of 98.0% in the extract and a heptane purity of
99.8 wt% in the raffinate. This results are very similar to those
obtained by Meindersma (2005) who modeled the extraction
with NRTL activity model the binary interaction parame-
ters being regressed from experimental LL equilibrium data.

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
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Table 2 – RMSD between experimental and Aspen Plus/Aspen HYSYS (with COSMOSAC property model) calculated LLE
diagrams of some ternary and quaternary (aliphatic + aromatic + IL(s)) mixtures studied in the present work.
Hydrocarbon mixture IL T (K) No. tie lines RMSD (%)

313.2 8 3.86
4-mebupyBF4 a
333.2 8 3.44
298.15 7 6.53
(n-Hexane + benzene) emimNTf2 b
333.15 7 6.79
bmimNTf2 c 298.15 7 8.20
emimMeSO4 + emimEtSO4 d 298.15 8 4.80

3-mebupyDCNe 313.15 6 2.88

f
313.2 14 4.09
4-mebupyBF4
(n-Heptane + toluene) 348.2 13 2.62
emimTfOg 313.2 11 1.22
emimNTf2 h 298.15 7 26.6

4-mebupyBF4 a 313.2 8 1.95

(n-Octane + ethylbenzene)
4-mebupyBF4 a 348.2 8 1.34

313.2 10 2.49
(n-Octane + m-xylene) 4-mebupyBF4 a
348.2 10 2.55

Experimental data for comparison are taken from references:

a
Meindersma et al. (2006a).
b
Arce et al. (2007a).
c
Arce et al. (2007b).
d
Potdar et al. (2012). (IL–IL) mixture has 80 mol% of emimEtSO4 .
e
Hansmeier et al. (2010).
f
Meindersma et al. (2006c).
g
Garcia et al. (2011a).
h
Arce et al. (2008b).

However, the toluene purity obtained here (49.5 wt%) was
lower than that one reported by Meindersma (82.3 wt%). This
later could be explained by the quality of the activity coeffi-
cient predictions discussed in the previous paragraph.
(S/F)min. molar ratios calculated in this paper showed
an inverse trend respect to the partition coefficients
obtained in laboratory experimental determinations of the
LLE (Arce et al., 2007b; Garcia et al., 2011a; Meindersma
et al., 2006a) for series of both the IL and the (aro-
matic + aliphatic) mixtures. Thus, recovering 98.0% of
the aromatic from its mixtures with the aliphatic hydro-
carbons needed an increase in solvent flows in the
sequence (n-hexane + benzene) < (n-heptane + toluene) < (n-
octane + ethylbenzene) ≈ (n-octane + m-xylene) for any IL
used as extracting solvent (Table 3). On the other hand,
(S/F)min. molar ratio decreases as the length of the alkyl chain
bonded to the imidazolium cation increases. It correlated
well with the partition coefficients obtained in experimental
determinations of the LLE for the Cn mimNTf2 (n = 2, 4, 6, 8) IL
series (Arce et al., 2007b) (Table 3). Furthermore, the aliphatic
recovery in the raffinate (and correspondingly, the aromatic
free-of-solvent purity in the extract) decreased as the length
of the alkyl chain increased. Similar results were obtained for
(n-octane + ethylbenzene) and (n-octane + m-xylene) binary
mixtures with different ILs.
mixtures (Table 3) as reflected in the following evidences: (i)
the (S/F)min. ratio decreased in the sequence: mmimTfO > 4-
mebupyBF4 > mmimNTf2 ≈ 3-mebupyDCN (Table 4) similarly
to the individual binary mixtures (Table 3), (ii) for a spe-
cific extracting solvent, 4-mebupyBF4 for instance, aliphatic
hydrocarbons in the raffinate yielded 98.8 wt% purity and
85.8% recovery, whereas the overall aromatic free-of-solvent
purity was 72.9% when aromatics were separated from multi-
component mixture 1 (Table 4). This result was also similar to
the results obtained for binary mixtures (n-heptane + toluene),
for example, using the same IL flow (Table 3), (iii) individual
aromatic recoveries (in the extract) from multi-component
mixture 1, using a (S4-mebupyBF4 /F) molar ratio 3.5 in a 12-
stage column follow the sequence: benzene (100%) > toluene
(99.9%) > ethylbenzene (97.7%) > m-xylene (93.2%), which is
comparable to that one obtained for binary mixtures con-
taining the same aromatics. When multi-component mixture
2 was fed to the extraction column, calculated (S/F)min.
molar ratios and aliphatic recoveries were very similar to
those obtained for multi-component mixture 1. However, the
free-of-solvent purity of the aromatic fraction was signifi-
cantly reduced (Table 4) for all the ILs evaluated because the
relatively high contents in light aliphatic hydrocarbons of the
feed respect to mixture 1.

3.4. Separation of (aromatic + aliphatic)

3.3. Separation of multi-component
(aromatic + aliphatic) mixtures with individual ILs
Results (Table 4) of the aromatic and aliphatic separation
with some individual ILs when multi-component mixtures
1 and 2 were fed to a 12-stage extraction column (fixing
overall 98.0% recovery for the aromatics) were consistent
with the results obtained for the corresponding binary
multi-component mixtures with (IL–IL) mixtures
Separation of aliphatic and aromatic hydrocarbons from
the multi-component mixture 1 with (IL–IL) mixtures of
the ILs 4-mebupyBF4 , mmimTfO, and mmimNTf2 showed
different behaviors depending on the ILs combined (Fig. 8).
Binary (IL–IL) mixture (mmimTfO(1) + mmimNTf2 (2)) and
reciprocal (IL–IL) binary (4-mebupyBF4 (1) + mmimTfO(2))

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
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Table 3 – Results of the Aspen Plus simulations (with COSMOSAC property model) in the conceptual design of the
extraction unit operation for (aliphatic + aromatic) binary mixtures with ionic liquids.a Design specification in the all
simulations: to recover 98.0% of the aromatic component in the extract. Feed: 10 wt%-aromatic mixture. Extractor
operating conditions: P = 1 atm, T = 40 ◦ C.
Hydrocarbon mixture IL (S/F)min. (M)b Aliphatic recoveryc,d (wt%)

3-mebupyDCN 0.88 87.0

4-mebupyBF4 1.33 90.0
mmimNTf2 0.72 88.7
emimNTf2 0.63 86.4
n-Hexane benzene
mmimTfO 1.37 92.2
emimTfO 1.23 91.2
bmimTfO 0.85 88.1
hxmimTfO 0.73 84.8
omimTfO 0.55 81.3

3-mebupyDCN 1.49 86.5

4-mebupyBF4 2.41 88.9
mmimNTf2 1.26 88.7
emimNTf2 1.05 86.5
n-Heptane toluene mmimTfO 3.58 93.2
emimTfO 2.65 91.5
bmimTfO 1.51 87.4
hxmimTfO 1.23 84.2
omimTfO 0.90 81.0

3-mebupyDCN 2.17 87.4

4-mebupyBF4 3.79 89.0
mmimNTf2 1.93 89.0
emimNTf2 1.58 87.5
n-Octane ethylbenzene mmimTfO 6.20 93.4
emimTfO 4.37 91.7
bmimTfO 2.34 87.9
hxmimTfO 1.84 85.0
omimTfO 1.32 81.8

3-mebupyDCN 2.35 86.4

4-mebupyBF4 4.18 87.9
mmimNTf2 2.12 88.7
emimNTf2 1.73 86.5
n-Octane m-xylene mmimTfO 6.91 92.8
emimTfO 4.85 90.9
bmimTfO 2.56 86.9
hxmimTfO 2.00 83.7
omimTfO 1.43 80.6

a
In all the cases studied the aliphatic purity in the raffinate is 99.7–99.8 wt%, the aromatic (free-of-solvent) purity in the extract lies in the
interval 35.0–65.0 wt% and the IL loss through the raffinate is lower than 0.001%.
b
For N → ∞, see Fig. 9.
c
Aliphatic recovery in the raffinate.
d
In a 12-staged column.

mixture disclosed quasi-linear performance ((S/F)min. and
aliphatic recovery in the raffinate, in this case) of the extrac-
tion with the IL2 mass percentage in the (IL–IL) mixture
(Fig. 8). In contrast, the (4-mebupyBF4 (1) + mmimNTf2 (2))
mixture showed a non-ideal behavior for the extraction,
with (S/F)min. and aliphatic recovery values larger than
those obtained with the respective pure ILs (Fig. 8). A
quaternary (4-mebupyBF4 + mmimTfO + mmimNTf2 ) mix-
ture having equi-mass fraction composition gave molar
(S/F)min. ratio, aliphatic hydrocarbons purity (wt%) and

Table 4 – Results of the Aspen Plus simulations (with COSMOSAC property model) in the conceptual design of the unit
operation to remove aromatic hydrocarbons from (aromatic + aliphatic) mixtures by extraction with ionic liquids.
Multi-component mixtures 1 and 2 were fed to the extractor. 12-Staged extraction column operating at atmospheric
pressure and T = 40.0 ◦ C was used. Design specification: an overall 98.0% aromatic recovery in the extract. Aliphatics were
separated in the raffinate.
Ionic liquid Multi-component mixture 1 Multi-component mixture 2

Molar (S/F) Aliphatic Aliphatic Molar (S/F) Aliphatic Aliphatic

purity (wt%) recovery (%) purity (wt%) recovery (%)

3-mebupyDCN 1.9 99.7 81.0 1.8 99.7 74.9

4-mebupyBF4 3.9 99.7 80.7 3.8 99.8 72.5
mmimNTf2 1.8 99.7 82.1 1.8 99.8 75.2
mmimTfO 5.9 99.7 85.9 5.7 99.7 79.6

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
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mmimTfO
binary (15 wt% aromatic + IL) mixtures with some selected aromatics. Mixtures are feed to the regenerator at the corresponding bubble point temperature. Regenerator operating

362
334
311
308
Table 5 – Results of the Aspen Plus simulations (with COSMOSAC property model) in the conceptual design of the individual IL regeneration by vacuum distillation from their

mmimNTf2
QIL-Regener. (kJ/kg-IL-regenerated)

325
303
285
282
4-mebupyBF4

453
418
389
385
3-mebupyDCN

459
424
395
391
mmimTfO

55.1
44.5
36.5
36.7
Fig. 6 – (A) Experimental (solid line) and Aspen Plus
calculated (dashed line) VL equilibria (using COSMOSAC
property package) for the binary mixtures of benzene with
mmim (), emim () and, bmim () NTf2 ILs. Insert shows
mmimNTf2

the (benzene + mmimNTf2 ) VLE for all composition

28.1
20.1
14.9
14.9

intervals. Experimental data were taken from Ref. Kato

Equilibrium pressure (kPa)
temperature was 230.0 ◦ C. Purity of the IL regenerated was 99.0 mol%.

et al. (2004). (B) Predicted VLEs of the binary mixtures

(toluene + C(1,2,4,6,8) mimTfO ILs). T = 353.15 K.
4-mebupyBF4

aliphatic hydrocarbons recovery (%) 4.2, 99.7 and 84.0 when

the multi-component (aromatic + aliphatic) mixture 1 was
51.7
40.6
32.5
32.9

fed to a 12-stage extractor. The multinary equi-mass (3-

mebupyDCN + 4-mebupyBF4 + mmimTfO + mmimNTf2 ) (IL–IL)
mixture ILs gave values 3.4, 99.7 and 83.3 for the same
variables.

4. Simulation of the IL regeneration

3-mebupyDCN

4.1. Regeneration of individual ILs from (aromatic + IL)

33.3
23.8
17.6
17.6

binary mixtures

IL regeneration from their binary (15 wt% aromatic + IL) mix-

tures needed reduced pressures in the range 15–60 kPa when
an operating temperature of 230 ◦ C was set (Table 5). Vac-
Ethylbenzene

uum requirements of the process increased in the sequence:

Aromatic

benzene < toluene < ethylbenzene ≈ m-xylene for all the ILs
m-Xylene
Benzene
Toluene

evaluated in this work (Table 5). Moreover, the heat duties

(QIL-Regener. ) required to regenerate the ILs from their mix-
tures with aromatics under the same conditions are in the

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
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A A
6
6 (n-Hexane + Benzene)
(n-Heptane + Toluene)
5

(S/F), molar
4
(S/F)

3
2

0 5 10 15 20 0 20 40 60 80 100
Number of stages IL(2), wt%
B
10
B
86
(n-Octane + Ethylbenzene)
(n-Octane + m-Xylene) 85

Aliphatic recovery, %
8
(S/F)

84

6 83

82

4
81

5 10 15 20
0 20 40 60 80 100
Number of stages
IL(2), wt%
Fig. 7 – (S/F) vs. number of theoretical separation stages for
Fig. 8 – Results of the aromatic separation from
LL extraction of the aromatics from their binary mixtures
(aromatic + aliphatic) mixtures as a function of the
with aliphatic hydrocarbons using 4-mebupyBF4 IL as
composition of the (IL–IL) mixture used as extracting
extracting solvent. T = 313.15 K. (A) Benzene and toluene
solvent. (A) (S/F) molar ratio and (B) aliphatic recovery in the
from their respective mixtures with n-hexane and
raffinate. () 4-mebupyBF4 (1) + mmimNTf2 (2), ()
n-heptane. (B) Ethylbenzene and m-xylene from their
mmimTfO(1) + mmimNTf2 (2), ()
mixtures with n-octane. Profiles shown here were
4-mebupyBF4 (1) + mmimTfO(2). Multi-component mixture
analogous to those obtained for all the other ILs studied in
model 1 was fed to the extractor. A 12-staged extractor was
this work with the same binary (aromatic + aliphatic)
used operating at 40 ◦ C and atmospheric pressure. Similar
mixtures.
profiles were obtained for other variables like aliphatic
purities and recoveries.

range 300–450 kJ/kg-IL-regenerated (Table 5), following the
opposite tendency in respect to the operating pressures for
the aromatic hydrocarbons. Similar results were obtained
when heat duties were given in kJ/kg-aromatic-removed.
For NTf2 and TfO ILs, setting the operating temperature
at the IL regenerator to 320 ◦ C (see Section 2), allowed the
process to operate at higher pressures even near to the atmo-
spheric one when TfO ILs were used as extracting solvents
(Fig. 9A). Increases of the equilibrium pressure computed for
(15 wt% aromatic + mmimNTf2 ) mixtures under temperature
growths from 230 to 320 ◦ C were 51.9, 40.4, 31.8 and 33.1
with benzene, toluene, ethylbenzene and m-xylene, respec-
tively. Nevertheless, the increase of the operating temperature
simultaneously had a negative energetic effect since the
heating requirements of the aromatic removal from their
binary mixtures with ILs increased (Fig. 9B) approximately 1.4
times (115–125 kJ/kg-IL-regenerated) for all the studied (15 wt%
aromatics + mmimTfO or mmimNTf2 ) mixtures in the temper-
ature interval 230–320 ◦ C.
4.2. Regeneration of individual ILs from ternary
(aliphatic + aromatic + IL) mixtures
An extra (2 wt%) aliphatic (n-hexane, n-heptane or n-octane)
load in the (aromatic + IL) mixtures increased the operat-
ing pressure making the IL regeneration possible under
weaker vacuum conditions. However, simultaneously the
heat requirements of the regeneration increased (Fig. 10).
Average increments (at 230 ◦ C) were approx. 25% for the
equilibrium pressure and approx. 20% for the heat duties
for the mmimTfO regeneration, respect to the values shown
in Table 5. These increases were moderated regenerating
mmimNTf2 (average growths: 10.6% and 13.1% for pressure
and QIL-Regener. ) and 4-mebupyBF4 (average growths: 10.5%
and 14.3% for pressure and QIL-Regener. ) ILs but, they were more
acute when 3-mebupyDCN was regenerated (average growths:
235.5% and 57.3% for pressure and QIL-Regener. ). On the other
hand, additional loads of n-hexane in the IL-regenerator
feed gave the highest growths (respect to the other aliphatic

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
CHERD-1708; No. of Pages 16
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12 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx

A A
150 60
Benzene
Toluene
Ethylbenzene 56
120 Benzene
m-Xylene
Toluene

Pressure, kPa
Pressure, kPa

52

90
48

Ethylbenzene
60 44 m-Xylene

40
30 n-Hexane n-Heptane n-Octane
225 250 275 300 325
Aliphatic
Temperature, ºC

B 405 B
440 Benzene

QIL-Regener., kJ/kg-IL-regenerated
QIL-Regener., kJ/kg-IL-regenerated

Toluene
Ethylbenzene 390
400 m-Xylene

375
360
Benzene
360 Toluene
320 Ethylbenzene
m-Xylene
345
280
n-Hexane n-Heptane n-Octane
225 250 275 300 325 Apliphatic
Temperature, ºC
Fig. 10 – Behavior of (A) the operating pressure and (B) the
Fig. 9 – (A) Operating pressure and (B) heat duties of the IL heat duties of the IL regeneration for binary mixtures
regeneration as a function of the operating temperature for (aromatic + mmimTfO) when an extra 2 wt% load of
binary mixture (15 wt% aromatic + mmimTfO). The purity of aliphatic hydrocarbons was added to the feed (see text for
the IL regenerated was 99.0 mol%. more details). See Table 5 for comparison with binary
(aromatic + IL) mixtures. T = 230.0 ◦ C. The purity of the IL
regenerated was 99.0 mol%.
studied in this work) on both the equilibrium pressures (at
230.0 ◦ C) and heat duties for all the ILs evaluated here.
were 259.4 and 111.8 kPa; 361 and 369 kJ/kg-IL-regenerated.
4.3. Regeneration of individual ILs from These results also suggest that effects of the considered vari-
multi-component (aromatics + aliphatics + IL) mixtures ables are additionally interrelated.

The main tendencies depicted in the two previous paragraphs
were revealed at once when multi-component mixtures 1
and 2 were fed to the extractor and the individual ILs were
recovered from the corresponding extracts (Tables 5 and 6).
The following conclusions were attained: (i) equilibrium pres-
sures and QIL-Regener. exhibited similar behaviors as a function
of the IL nature, (ii) computed equilibrium pressures and
QIL-Regener. (Table 6) were always higher than those obtained
for any binary (aromatic + IL) mixture (Table 5) due to the pres-
ence of aliphatics in the extract, (iii) they were even higher
in multi-component mixture 2 than in mixture 1 (Table 6),
corresponding with the higher concentration of aliphatic
hydrocarbons in mixture 2 respect to mixture 1 (Table 1), (iv) an
increase of the regenerator operating temperature caused an
increase of both the equilibrium pressures and the QIL-Regener
In fact, recovering mmimTfO and mmimNTf2 ILs at 320.0 ◦ C
from the extract corresponding to mixture 1 required equilib-
rium pressures over 246 and 107 kPa and heat duties of 297 and
324 kJ/kg-IL-regenerated. When the extract resulted from the
mixture 2, the equilibrium pressures and heat duties needed
4.4. Regeneration of (IL–IL) mixtures from
multi-component (aromatics + aliphatics + ILs) mixtures
The regeneration of (IL–IL) mixtures essentially behaved like
the regeneration of individual ILs for the studied systems,
obtaining in this case an almost linear dependence of the oper-
ating conditions and heat duties with the composition of the
IL mixture (Fig. 11) for the multi-component mixture 1. This
seems to be a differentiating feature in respect to the oper-
ation at the extractor where non-ideal behaviors have been
previously described.
5. General outlook
Examining of the altogether results related to both the extrac-
tion and the IL regeneration (Fig. 12) suggests that selection
of the IL-based extracting agent for (aromatic + aliphatic) sep-
aration processes is not a straightforward task. This was
previously discussed (Ferro et al., 2012a) from the point of
view of the IL regeneration. Two main conclusions can be

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
CHERD-1708; No. of Pages 16
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chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx 13

Table 6 – Results of the Aspen Plus simulations (with COSMOSAC property model) in the conceptual design of the
individual IL regeneration by vacuum distillation from the multi-component extract (in aromatic + aliphatic separation
process). Mixtures are feed to the regenerator at the corresponding bubble point temperature. Regenerator operating
temperature was 230.0 ◦ C. Purity of the IL regenerated was 99.0 mol%. Composition of the mixtures fed to the regenerator
is also provided.
Variable/ionic liquid 3-mebupyDCN 4-mebupyBF4 mmimNTf2 mmimTfO

Real model mixture 1

Aromatics in extract (wt%) 3.7 1.1 2.1 0.70
Equilibrium pressure (kPa) 47.2 88.6 37.3 94.8
QIL-Regener. (kJ/kg-IL-regenerated) 579 413 226 209

Real model mixture 2

Aromatics in extract (wt%) 4.9 2.4 3.0 1.2
Equilibrium pressure (kPa) 53.2 104.2 40.3 103.2
QIL-Regener. (kJ/kg-IL-regenerated) 439 363 262 255

A → A 86

90 60

Aliphatic recovery, %
(S/F) x 10, molar
84
75 45
Pressure, kPa

60 82
30

45
15 80

30 CN yBF4 NTf2 mTfO re (1) re (2) re (3) re (4)

yD p i u
0 20 40 60 80 100 bup mebu mmi
m
mm mixt ixtu ixtu ixtu
3-m
e
4- IL IL m IL m IL m
IL(2), wt%
B
450
B 60
QIL-Regener., kJ/kg-IL-Regenerated

QIL-Regener.x0.1,kJ/kg-IL-regenerated
90
400
Equilibrium pressure, kPa

50
350 75

40
300 60

30
250 45

200 20
30

CN yBF4 NTf2 mTfO re (1) re (2) re (3) re (4)

0 20 40 60 80 100 yD p i tu
bup m ebu m m i
m
m m mi x i x tu i x tu ixtu
3 -m
e
4- IL IL m IL m IL m
IL(2), wt%

Fig. 11 – (A) Operating pressures and (B) heat duties of the
regenerator when (IL–IL) mixtures were used as extracting
solvents. ILs were regenerated from the extracts
corresponding to the multi-component mixture 1.
Operating temperature at the regenerator was 230.0 ◦ C. ()
(4-mebupyBF4 (1) + mmimNTf2 (2)), ()
(mmimTfO(1) + mmimNTf2 (2)), ()
(4-mebupyBF4 (1) + mmimTfO(2)).
Fig. 12 – Result summary for the (A) extracting operation
and (B) solvent regeneration for the ILs (and their mixtures)
studied in this work. Multi-component mixture 1 was fed
to the extractor. (IL–IL) mixtures (1), (2), (3) and (4) are,
respectively, equi-mass mixtures of
(4-mebupyBF4 + mmimNTf2 ), (mmimTfO + mmimNTf2 ),
(4-mebupyBF4 + mmimTfO) and
(4-mebupyBF4 + mmimNTf2 + mmimTfO).

derived from the present results: (i) none of the IL-based mixtures exhibit better performances than the individual
extracting agents evaluated here have simultaneously the ILs.
best performances for all the response variables analyzed.
This makes process optimizations on complete flow dia- 5.1. Concluding remarks
grams necessary to select IL-based extracting solvents with
optimized properties for separating aromatics from their mix- Separation of near-to-real multi-component (aro-
tures with aliphatic hydrocarbons. (ii) as a rule, the (IL–IL) matic + aliphatic) mixtures using ionic liquids substantially

Please cite this article in press as: Ferro, V.R., et al., Conceptual design of unit operations to separate aromatic hydrocarbons from
naphtha using ionic liquids. COSMO-based process simulations with multi-component “real” mixture feed. Chem. Eng. Res. Des. (2014),
http://dx.doi.org/10.1016/j.cherd.2014.10.001
CHERD-1708; No. of Pages 16
ARTICLE IN PRESS
14 chemical engineering research and design x x x ( 2 0 1 4 ) xxx–xxx
differed from the scheme consolidated from the binary
model (aromatic + aliphatic) mixtures ordinarily employed to
study this process. A more realistic design of the individual
operations involved was achieved in this work by using
COSMO-based process simulations with mixtures of complex
composition. This allowed new insights in both the technolog-
ical and the economical features of this process. Thus, feeding
multi-component (aromatic + aliphatic) mixtures directly to
the extraction column reduces the purity of the aromatics
in the extract due to the presence of aliphatic hydrocarbons
which additionally represent an extra energetic load to the IL
regeneration. This demands new design solutions respect to
the simplified flow diagram shown in Fig. 1 of this paper.
(IL–IL) mixtures seemed to be good extracting solvents
for separating aromatic and aliphatic hydrocarbons. The
present results suggest that process performance could be
conveniently tailored by modifying the composition of the IL-
mixture. This is a way to improve the extracting capacity of the
solvent and, consequently, to reduce the solvent consumption.
All in all, current results validated the integration of
the COSMO-based models to Aspen Plus and Aspen HYSYS
process simulators for accomplishing conceptual designs
of the operations involved in the process to separate
(aromatic + aliphatic) hydrocarbon mixtures using ILs as
extracting solvents. They particularly revealed the capac-
ity of COSMO-supported process simulations for confidently
dealing with complex multi-component mixtures of hydrocar-
bons and ILs which is absolutely indispensable for extending
the use of computational tools in the creation of new pro-
cesses for removing aromatics from naphtha using ILs as
extracting solvents (including the selection of IL-based sys-
tems with optimized properties to this application). Even, the
contradictions addressed in this paper respect to both the
experimental results and the NRTL-based process simulations
(i.e. the under estimated purity of toluene in extraction with
4-mebupyBF4 ) of the aromatic extraction with ILs define a pro-
ductive contribution of the COSMO-based process simulations
to the creation of new processes focused to the separation
of (aromatic + aliphatic) mixtures with ILs. In fact, the pre-
dictive capacity of this methodology could be exploited for
both proposing and evaluating (including the screening of IL-
based systems with extracting improved properties) as most
as possible design alternatives. Finally, on the basis of these
results, the most promising alternatives could be selected
and submitted to the further engineering developments (Basic
Engineering, for example) where more accurate predictions
are needed. This approach ensure an economical procedure
as the experimental data needed to regress the adjustable
parameters of the NRTL model should be generated only for
the most promising systems.
Acknowledgments
The authors are grateful to Comunidad de Madrid (project
S2013-MAE-2800) and to Ministerio de Ciencia e Innovación
of Spain (Project CTQ2011-26758) for financial support. We are
very grateful to “Centro de Computación Científica de la Uni-
versidad Autónoma de Madrid” for computational facilities.
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