Modeling liquidliquid and vaporliquid equilibria for the hydrocarbon

+N-formylmorpholine system using the CPA equation of state

Hossein Mahmoudjanloo
a,1
, Amir A. Izadpanah
a,n
, Shahriar Osfouri
a
,
Amir H. Mohammadi
b,c,nn
a
Department of Chemical Engineering, Faculty of Gas and Petrochemical Engineering, Persian Gulf University, Bushehr, Iran
b
Institut de Recherche en Gnie Chimique et Ptrolier (IRGCP), Paris Cedex, France
c
Thermodynamics Research Unit, School of Chemical Engineering, University of KwaZulu-Natal, Howard College Campus, King George V Avenue,
Durban 4041, South Africa
H I G H L I G H T S

LLE and VLE for the hydrocarbon+N-Formylmorpholine system are investigated.

The CPA EoS is used for the modeling purpose.

The CPA EoS parameters are obtained using vapor pressure and saturated liquid density data.

It is shown that the use of 4C association scheme for N-formylmorpholine yields satisfactory results.
a r t i c l e i n f o
Article history:
Received 1 November 2012
Received in revised form
22 March 2013
Accepted 3 April 2013
Available online 11 April 2013
Keywords:
N-formylmorpholine
Hydrocarbon
Associating uid
CPA EoS
Liquidliquid equilibrium
Vaporliquid equilibrium
a b s t r a c t
In this communication, the capability of the CPA (Cubic-Plus-Association) equation of state (EoS) for
modeling vaporliquid and liquidliquid equilibria of mixtures containing N-formylmorpholine (NFM),
alkanes and aromatics in a wide temperature range is studied. First, the CPA EoS parameters for NFM are
obtained using vapor pressure and saturated liquid density data. Then, the liquidliquid equilibrium of
binary mixtures of NFM and alkane and later the vaporliquid equilibrium for systems containing NFM
and aromatics is investigated to determine the best parameters and association scheme. It is shown that
the use of 4C association scheme for NFM yields satisfactory results.
& 2013 Elsevier Ltd. All rights reserved.
1. Introduction
Theoritical investigation of the phase and volumetric behavior
of association uids is generally complex partly because of strong
interactions between molecules. This behavior changes rapidly
with the uctuations of temperature and pressure. The properties
of association uids strongly depends on temperature i.e. a sign of
bond formation and interaction of attractions between the mole-
cules. The phase and volumetric behavior of association uids in
comparison with non-association uids considearbly differs partly
because of size and specication of clusters that form by bonds
(such as hydrogen bonding) between molecules. As a result of
association effects, association uids can be considered as a
mixture of singular molecules and formed clusters. Association
systems are one of nonideal systems for which specic equations
are required to take into account the association effects. For this
purpose, one can add equations based on association theory to the
EoS which are used for non-association systems (Prausnitz et al.,
1999).
For predicting the thermodynamic properties of association
uids, the CPA EoS presented by Kontogeorgis et al. (1996) has
been used widely in recent years. The initial framework of CPA EoS
is an equation of state that extends the capabilities of cubic EoS to
compounds with polar/hydrogen bond that covers a variety of
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Chemical Engineering Science
0009-2509/$ - see front matter & 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ces.2013.04.002
Abbreviations: Cal, calculated; %AAD, average absolute deviation; exp, experi-
mental; liq, liquid phase; vap, vapor phase; sat, saturated; c, critical; m, mixture;
mix, mixture; r, reduced; HC, hydrocarbon
n
Corresponding author.
nn
Corresponding author at: Institut de Recherche en Gnie Chimique et Ptrolier
(IRGCP), Paris Cedex, France.
E-mail addresses: izadpanah@pgu.ac.ir (A.A. Izadpanah),
a.h.m@irgcp.fr (A.H. Mohammadi).
1
Current address: Nouri Petrochemical Company, Pars Special Economic
Energy Zone, Bushehr, Iran.
Chemical Engineering Science 98 (2013) 152159
systems/compounds in petroleum industry (hydrocarbons, water,
alcohols, glycols, amines, asphaltenes, etc.). This equation is a new
concept development of equation of state, by combination of
physical effects of classic models with the contribution of associa-
tion effects. The association expression of the CPA EoS is similar to
the association expression applied in the statistical association
uid theory (SAFT) (Chapman et al., 1989, 1990).
Voutsas et al. (1997) applied the CPA EoS for investigating
the liquidliquid phase equilibrium of alcohols and hydrocarbons.
Yakoumis et al. (1998) applied this equation for predicting
the phase equilibrium of binary systems including water with
alkanes, cycloalkanes and alkenes and obtained better results
compared to the SAFT EoS. Derawi et al. (2003) applied this
equation for investigating the liquidliquid phase equilibrium of
the systems including glycols and hydrocarbons and satisfactory
results were obtained. Folas et al. (2006) applied the CPA EoS for
investigating the vaporliquid and liquidliquid phase equilibrium
in complex mixtures including alcohols, glycols and water
with aromatics and olenes. They also considered the association
effect between the aromatics and olenes with other polar
substances such as water and glycol. In a ten years study on
applications of the CPA EoS by Kontogeorgis et al. (2006a, 2006b),
they found out that this equation of state has been applied for
phase equilibrium of different systems including alkanes, glycols,
organic acids, amines, water, acid gases, validation with the
spectrometry data. Moreover, the CPA EoS has been applied for
predicting the thermodynamic properties of important industrial
substances such as sulpholane, anyline, etc. (Kontogeorgis and
Folas, 2010).
Oliveira et al. (2007) applied the CPA EoS for predicting
the mutual solubility of water in hydrocarbon and hydrocarbon
in water. Good results for solubility of aromatic and aliphatic
hydrocarbons in water and solubility of water in these hydro-
carbons were obtained in a wide range of temperature and
pressure. Kontogeorgis et al. (2007) applied the CPA EoS for
modeling the liquidliquid and vaporliquid phase equilibrium
at high pressures for mixtures conatining alcohols, mixtures
including gas hydrate inhibitors and mixtures consisting of
polar and hydrogen bonding substances for implementing this
equation in the gas and oil industries. Garrido et al. (2008) applied
the CPA EoS for modeling the liquidliquid and vaporliquid
phase equilibrium of mixtures including glycol ethers (surface
activating substances) and obtained the parameters of CPA EoS for
these substances. In 2011 Motaa et al. (2011) applied the CPA EoS
for modeling the solubility of drug-like molecules in organic
solvents.
Petrolum industry has given much attention to morpholine
derivatives such as hydroxyethylmorpholine, N-methylmorpholine,
N-formylmorpholine (NFM), N-acetylmorpholine and phenylmor-
pholine. This interest is resulted from their high efciency for the
recovery of aromatic substances specially benzene, toluene and
xylene using the morpholine derivatives from naphta, pyrolisis
gasoline and reformate streams. Extractive distillation using the
NFM solvent is a process that is used successfully for seperation of
aromatic hydrocarbons such as benzene, toluene and xylene from
aromatic streams. Thus, having a model for predicting thermody-
namic properties and phase equilibrium of systems containing
morpholine and its derivatives and hydrocarbons is necessary. The
high solubility of NFM in self-association uids e.g. ethylene glycol,
methanol and water, suggests increased association, which can be
explained by strong specic interactions between NFM and self-
associating molecules. Also, NFM is a morpholine-type molecule
and thus, CHO hydrogen bonds can form between the layers of
this molecule. For these reasons in this study N-formylmorpholine
was considered as an associating compound.
In this study, the CPA EoS parameters are rst obtained for
NFM. Using these parameters, liquidliquid equilibrium of binary
mixtures including NFM and heptane, hexane, octane, nonane,
2,2,4-trimethylpentane and 3-methylpentane and vaporliquid
equilibrium for binary mixtures containing NFM and benzene,
toluene, o-xylene and m-xylene are studied. Finally, appropriate
association scheme for predicting the thermodynamic properties
of mixtures containing NFM is investiagted.
2. Cubic-Plus-Association (CPA) equation of state
The CPA EoS which combines the SRK equation of state term
and the contribution of the association term is given by the
following expressions in term of pressure as presented by
Michelsen and Hendriks (2001)
P
RT
b

a
b

1
2
RT

1
ln g

_ _

i
x
i

A
i
1X
A
i

a a
0
1 c
1
1

T
r
_

2
; T
r

T
T
C
1
In this equation, R is the gas constant, T
r
is reduced tempera-
ture, T is the temperature of system, x
i
is the mole fraction of
component i in the liquid and vapor phases, is molar volume, P is
the pressure of system, T
c
is the critical temperature, a
0
, and c
1
are
parameters in the energy term, a is the energy term in the SRK
part, b is the co-volume parameter, g is the radial distribution
Nomenclature
a energy term in the SRK part
a
0
parameter in the energy term
b co-volume parameter
c
1
parameter in the energy term
C
1
C
7
constants of Eqs. (13) and (14).
g radial distribution function
k
ij
binary interaction parameter
N number of experimental data point
P pressure
R gas constant
T absolute temperature
molar volume
x
i
mole fraction of component i in the liquid or vapor
phases
X
Ai
fraction of molecule i not bonded at site A
y
i
mole fraction of component i in the vapor phase
A
i
site A on molecule i
B
j
site B on molecule j
Z compressibility factor
II hydrocarbon rich phase
Greek Letters
association volume parameter
association strength
association energy parameter
fugacity coefcient
reduced density
molar density
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 153
function, X
A
i
is the fraction of molecule i not bonded at site A and
depends on the association strength (
A
i
B
j
) between site A on
molecule i and site B on molecule j. X
A
i
is calculated by solving the
following set of equations:
X
A
i

1
1
1

j
x
j

B
j
X
B
j

A
i
B
j
2
where X
B
i
is any kind of association sites other than A. The key
quantity in the CPA EoS is the association strength. In the CPA EoS,
this quantity is dened by the following equation:

A
i
B
j
g
1

_ _
ref
exp

A
i
B
j
RT
_ _
1
_ _
b
ij

A
i
B
j
3
where and are the association energy and volume parameters
respectively. Hard sphere radial distribution function is expressed
by the following equation:
g
1

_ _
ref

1
11:9
4

b
4
_ _
5
where is the reduced density.
The extension of the CPA EoS to mixtures requires mixing rules
for obtaining the parameters of the SRK equation. One of these
mixing rules is the van der Waals mixing rules which is applied for
obtaining a
mix
and b
mix
in the SRK equation:
a
mix

c
i 1

c
i 1
x
i
x
j
a
ij
6
b
mix

c
i 1

c
i 1
x
i
x
j
b
ij
7
where the usual combining rules are used as follows:
a
ij
a
i
a
j

1=2
1k
ij
8
b
ij

b
i
b
j
2
9
k
ij
is the binary interaction parameter.
The association term in the CPA EoS depends on the selection of
the association scheme and the number of association sites of the
components. Huang and Radosz (1990) classied 8 association
schemes that can be applied for different molecules noting the
type and number of association sites. The extension of association
term in the CPA EoS to mixtures requires only combining rules for
the parameters
A
i
B
j
and
A
i
B
j
. In this work, the combining rule 1
(CR1) (Kaarsholm et al., 2005) has been used as follows:

A
i
B
j

A
i
B
i

A
j
B
j
2
;
A
i
B
j

A
i
B
i

A
j
B
j
_
10
This combining rule was rst proposed by Wolbach and Sandler
(1998) based on quantum calculations in the 1998.
Because aromatics and alkanes are not self-associated, the
association energy and volume parameter are considered zero
for them in the CPA EoS, thus the CR1 combining rule in this state
is transformed to Eq. (11), that is the association energy parameter
(
A
i
B
j
) for the mixtures of associating compound and aromatics and
alkanes is equal to the value of the associating compound divided
by two and the association volume parameter (
A
i
B
j
) must be tted
with experimental data (Folas et al., 2006). Thus

A
i
B
j

A
i
B
i
2
and
A
i
B
j
f itted 11
Considering the applied mixing rules (Eqs. (6)(9)) and the
relationship obtained by Michelsen and Hendriks (2001) for the
chemical potential resulting from the association term, fugacity
cofcient of component i (f
i
) in the mixture using the CPA EoS is
obtained by following equation:
ln
i
^
ln
b

_ _

b
i
b

a
bRT
2

i
x
j
a
ij
a

b
i
b
_
_
_
_
ln
b

a
bRT
b
i
b
_ _

NS
i
A
lnX
A
i

1
2
1:9b
i

41:9b
_ _

C
j 1
x
j

NS
j
A
1X
A
j
ln Z 12
where Z is the compressibility factor of the mixture.
3. Results and discussion
3.1. The CPA parameters
The CPA EoS has ve parameters that three of them are related
to the physical part (a
0
, b, c) and two of them are related to the
association part
A
i
B
j
;
A
i
B
j
. For studying the accurancy of the CPA
EoS in determining the phase behavior of NFM, rst it is necessary
that the CPA parameters be determined for NFM. These para-
meters are obtained by tting the vapor pressure and saturated
liquid volume data in the reduced temperature range
0.398oT
r
o0.968. Also, experimental data for vapor pressure of
NFM for a limited range of T
r
are available in the literature
(VonNiederhausern et al., 2006), but there were no experimental
data for saturated liquid density and vapor pressure of NFM in the
wide range of T
r
, so the CPA parameters were tted to the DIPPR
correlations results. The DIPPR correlation was compared to this
3
4
5
6
7
8
9
l
n

P

(
k
P
a
)
Exp
DIPPR correlation
%AAD = 0.39
-1
1
3
5
7
l
n

P

(
k
P
a
)
DIPPR correlation
1A
1
0.0012 0.0014 0.0016 0.0018 0.002 0.0022 0.0024 0.0026
2
3
4
5
6
7
8
9
l
n

P

(
k
P
a
)
1/ T (1/K)
Exp
DIPPR correlation
%AAD = 0.39
-5
-3
0.0018 0.0013 0.0023 0.0028 0.0033
-1
1
3
5
7
l
n

P

(
k
P
a
)
1/T (1/ K)
DIPPR correlation
1A
2B
3B
4B
4C
Fig. 1. Vapor pressure curve of NFM. (a) Experimental (VonNiederhausern et al.,
2006) (symbols) and DIPPR correlation (curve), (b) DIPPR correlation (symbols) and
CPA results (curve) with different association schemes.
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 154
experimental vapor pressure data and the results are shown in
Fig. 1a within 0.39 of %AAD.
The DIPPR correlations for saturated liquid density and vapor
pressure of NFM are as follows:

liq

C
1
C
2
11T=C
3

C
4
13
lnP
sat
C
1
C
2
T C
3
C
4
T C
5
ln T C
6
T
C7
14
In the above equations,
liq
is the saturated liquid density, P
sat
stands for the vapor pressure and T represents absolute temperature.
The constants of DIPPR equations for NFM are reported in Table 1.
The association term of CPA EoS depends upon the choice and
nature of the association scheme. It includes the number and the
type of association sites. Huang and Radosz (1990) provided a
framework for determination of association monomer fraction by
identifying different association schemes. The rigorous schemes
are shown in Table 2 for NFM molecule. The presence of aromatic
group and electronegative heteroatoms (N, O) makes this molecule
highly polarizable that may affect the reactivity and solvation of
the molecule.
According to the nomenclature of Huang and Radosz (1990),
when the one-site (1A) scheme is used for NFM, assuming that this
site behaves as a glue spot, able to bond with a lone pair electron
(an electron donor site) or a H atom (an electron acceptor site).
Use of the 2B scheme for NFM, which proposes that association
occurs between all hydrogen atoms and one of the lone pairs of
electrons from the oxygen atom. In 3B scheme, lone pair electrons
on oxygen molecules are considered as two electron donor site
and all hydrogen atoms are considered as one electron acceptor
site. In the 4B formalism, lone pair electrons on oxygen atoms are
considered as 3 electron donor sites and all hydrogen atoms are
considered as one electron acceptor site. A four-site (4C) associa-
tion scheme does consider that association occurs between the
two hydrogen atoms and the two lone pairs of electrons in the
oxygen of the NFM molecule.
It should be noted that the contribution of the nitrogen in
association did not consider because there was not any NH bond
and the steric effect of nitrogen.
Best association scheme for NFM should be chosen based on
spectroscopic data on monomer fraction and molecular simulation
calculations. To the best of our knowledge, these types of data are
not reported in literatures, thus we had to examine all 5 association
schemes and suggest the proper scheme and the best set of
parameters were considered to the VLE and LLE modeling results.
The following objective function was used to obtain the CPA
parameter for NFM:
OF
1
N

N
i 1
jP
i
exp
P
i
cal
j
P
i
exp
_ _

j
exp
l
i

cal
l
i
j

exp
l
i
_ _ _ _
15
where P is vapor pressure,
l
is saturated liquid volume, N is
number of data points, exp and cal represent experimental data
and computational results with the CPA EoS, respectively. The
parameters of the CPA EoS for NFM that have been obtained using
different association schemes in this work are reported in Table 3.
For each association schemes, multiple parameters set were
obtained and examined for LLE and VLE calculations and the best
set of parameters are reported. According to Table 3, it appears
that the 1A, 2B and 4C association schemes yield better results for
predicting the vapor pressure and saturated liquid volume of pure
NFM. Figs. 1b and 2 present the results of all association schemes
for vapor pressure and saturated liquid volume data, respectively.
3.2. Liquidliquid phase equilibrium for mixtures containing NFM
In order to obtain the proper association scheme for the NFM
molecule, in addition to obtain the CPA EoS parameters for NFM
using the vapor pressure and saturated liquid volume data, there is
a need to evaluate the liquidliquid equilibrium of this substance
with the compound that do not associate like alkanes. For
this purpose, the following mixtures have been examined:
NFMheptane, NFMhexane, NFMoctane, NFMnonane, NFM
2,2,4-trimethylpentane and NFM3-methylpentane. By using the
parameters presented in Table 3 for NFM and also the values of the
CPA EoS parameters available in the literature (Voutsas et al., 1997;
Yakoumis et al., 1998; Folas et al., 2006; Garrido et al., 2008) for
alkanes, liquidliquid equilibrium calculations for the systems
containing NFMhydrocarbon have been performed. For the better
prediction of equilibrium data for binary systems of NFMhydro-
carbon, temperature independent interaction parameter is
required. For prediction of this parameter, the following objective
function has been used:
OF
1
N

N
i 1
jT
i
exp
T
i
cal
j
T
i
exp
_ _

jx
IIexp
i
x
IIcal
i
j
x
IIexp
i
_ _ _ _
16
where T is temperature and x is mole fraction of NFM in hydro-
carbon phase. The NFM solubility in hydrocarbon (HC) and the
solubility of HC in NFM are modeled using CPA EoS with single
temperature-independent binary interaction parameter. The
importance of solvation of hydrocarbons in NFM is examined for
all systems. In this manner calculations were performed assuming
that hydrocarbons are non-self-associating uids but they have an
electron donor or acceptor site which can associate with NFM.
Eq. (11) was used in order to estimate the cross-association
parameters.
Table 4 summarizes the LLE results, while Figs. 38 present
mutual solubility of NFM and HC. Because 2B and 4C association
schemes for NFM show better results (Mahmoudjanlou, 2012), in
this table and gures only 2B and 4C association schemes were
represented for NFM.
For each of binary systems NFMalkanes, the results were
obtained as follows:
1. HexaneNFM system: the modeling results are presented in
Fig. 3 and Table 4. For this system, both association schemes
give reasonable results (especially 4C & CR-1). %AAD in solubi-
lity of NFM in HC is approximately high for both schemes
without solvation.
2. OctaneNFM system: with respect to Table 4 and Fig. 4, the best
results are obtained for NFMoctane mixture with the para-
meter sets 2B & CR-1 and 4C & CR-1. Although, the NFM
solubility is over estimated in all cases, both schemes provide
good LLE predictions using a small value of k
ij
.
3. NonaneNFM system: CPA (with considering solvation effects)
can satisfactorily describe solubility of NFM and nonane
Table 1
DIPPR equation constants for calculating vapor pressure and saturated liquid
volume for NFM.
Parameter Values
For saturated liquid density
calculation
kmol
m
3
_ _
; TK
_
For vapor pressure
calculation [P(kPa), T(K)]
C
1
0.74281 83.04024472
C
2
0.24884 10567
C
3
762 0
C
4
0.2891 0
C
5
9.273
C
6
3.33E18
C
7
6
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 155
Table 2
Association schemes based on the terminology of Huang and Radosz (1990) for NFM molecule.
Association scheme Bonding type Structure
1A Both electron donor and electron acceptor site
2B An electron donor site and an electron acceptor site
3B Two electron donor sites and an electron acceptor site
4B Three electron donor sites and an electron acceptor site
4C Two electron donor sites and two electron acceptor sites
Table 3
The values of CPA EoS parameters and average absolute deviation for NFM.
Association scheme Parameters values
*
%AAD
a
0
Lit
2
:bar
mol
_ _
b
Lit
mol
_ _
c
1
Lit:bar
mol
_ _
P
sat

l
1A 34.2101 0.0974 0.8009 221.8560 0.0015 1.08 2.83
2B 34.2712 0.0981 0.8349 161.6425 0.0022 1.21 2.74
3B 12.8085 0.0914 2.0356 119.6179 0.6267 3.36 1.37
4B 13.3640 0.0921 1.9698 117.0563 0.3663 3.338 0.86
4C 33.7734 0.0985 0.8055 123.0235 0.0035 1.24 2.96
Ave: 2.04 Ave: 2.16
NFM critical temperature (T
c
) is 762 K.
n
For all sets of parameters,0.398oT
r
o0.968.
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 156
especially in temperature range of 300420 K as shown in
Fig. 5. Without the solvation effects, the solubility of nonane in
NFM is under estimated at lower temperatures and over
estimated at upper temperatures. As can be seen in this table,
the 4C association scheme yields better results compared to 2B
association scheme.
4. HeptaneNFM system: the results are slightly dependent on the
choice of the NFM association scheme as is seen in Fig. 6 and
Table 4. The 2B scheme for NFM has been found to give larger
value of %AAD in temperature as well as in NFM solubility. The
immiscibility between NFM and heptane in both phases are
adequately predicted with 4C association scheme.
The results for these 4 binary system show that binary inter-
action parameters between NFM and linear hydrocarbon stu-
died are almost constant in the 4C & CR1 association scheme
while variations of binary interaction parameters in 2B & CR1
association scheme are greater than 4C & CR1.
5. 2,2,4-trimethylpentaneNFM system: the CPA correlation for
solubility of NFM and 2,2,4-trimethylpentane along with the
experimental data is given in Fig. 7. The solubility of 2,2,4-
trimethylpentane in NFM is estimated very satisfactorily with
low interaction parameters reported in Table 4 and considering
cross-associating (as can be seen in Fig. 7.) More deviation from
the experimental data is seen at higher temperatures for NFM
solubility in 2,2,4-trimethylpentane. A qualitative correlation
for temperature has been possible only when the cross
association was assumed. Using the 2B association scheme for
NFM, the binary interaction parameters and %AAD in tempera-
ture are higher. However, the average absolute deviation in
NFM solubility in HC for 4C association scheme (12.62%) is a
little more than 2B association scheme (10.1%).
6. 3-methylpentaneNFM system: although the temperature and
the solubility of HC in NFM in the entire temperature range is
0 18
0.19
0.2
DIPPR correlation
1A
2B
3B
0.16
0.17
DIPPR correlation
1A
2B
3B
4B
4C
0.13
0.14
0.15
V
l

(
l
i
t
)
DIPPR correlation
1A
2B
3B
4B
4C
0.11
0.12
DIPPR correlation
1A
2B
3B
4B
4C
0.1
300 350 400 450 500 550 600 650 700 750
T (K)
DIPPR correlation
1A
2B
3B
4B
4C
Fig. 2. Saturated liquid volume of NFM. DIPPR correlation (symbols) and CPA
results (curve) with different association schemes.
Table 4
The values of association volume and the interaction parameters for liquidliquid systems containing NFM with 2B and 4C association schemes and average absolute
deviation in temperature and NFM mole fraction in hydrocarbon rich phase.
System Association scheme
2B 2B & CR1 4C 4C & CR1
k
ij
%AAD k
ij

2
%AAD k
ij
%AAD k
ij

2
%AAD
T x
II
T x
II
T x
II
T x
II
NFMhexane 0.065 2.55 97.9 0.0716 0.0001 3.10 28.39 0.055 2.53 77.7 0.040 0.0001 2.46 31.35
NFMhexane 0.065 2.55 97.9 0.0716 0.0001 3.10 28.39 0.055 2.53 77.7 0.040 0.0001 2.46 31.35
NFMheptane 0.048 1.55 57.0 0.0460 0.0001 1.78 52.1 0.039 1.52 37.3 0.047 0.0001 1.46 26.60
NFMoctane 0.044 1.41 127.0 0.0509 0.0001 3.75 27.45 0.035 1.37 105.2 0.0393 0.0001 3.46 31.47
NFMnonane 0.044 4.96 62.0 0.0585 0.0001 2.00 26.5 0.035 4.95 49.65 0.047 0.0001 1.77 24.58
NFM2,2,4-trimethylpentane 0.030 4.20 53.0 0.0291 0.0001 1.26 10.1 0.021 4.18 45.7 0.017 0.0001 1.04 12.62
NFM3-methylpentane 0.032 1.05 153.0 0.0314 0.0001 0.99 140 0.029 1.05 115.0 0.027 0.0001 1.03 105.00
Fig. 3. Solubility (mole fraction) of NFM in HC (hexane) and HC in NFM at 100 kPa
(, experimental data (Ko et al., 2002)), NFM with 2B and 4C association schemes
and using CR1 combining rules.
Fig. 4. Solubility (mole fraction) of NFM in HC (octane) and HC in NFM at 100 kPa
(, experimental data (Ko et al., 2002)), NFM with 2B and 4C association schemes
and using CR1 combining rules.
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 157
well described, the CPA EoS is not able to describe the solubility
of NFM in HC as is seen from Fig. 8. It can be due to the lower
temperature and NFM concentration in HC of this mixture
compared to other LLE systems, because the importance of the
solvation is expected to be pronounced at lower temperatures
and in dilute solution. As Table 4 indicates, positive and small
binary interaction parameters are required to obtain a descrip-
tion of the liquidliquid phase behavior with global average
deviations inferior to approximately 1.1% in temperature.
3.3. Vaporliquid phase equilibrium for mixtures containing NFM
Considering the 2B and 4C association schemes that yield
acceptable results for NFM, in this section we investigate the
vaporliquid equilibrium of binary mixtures including NFM and
aromatics. The binary mixtures used in this study include NFM and
benzene, toluene, m-xylene and o-xylene. The CPA EoS parameters
for these aromatics obtained from literatures (Folas et al., 2006;
Oliveira et al., 2007). For prediction of temperature independent
interaction parameter, the following objective function is used:
OF
1
N

N
i 1
jT
i
exp
T
cal
i
j
T
i
exp
_ _

jy
exp
i
y
cal
i
j
y
exp
i
i
_ _ _ _
17
where T is temperature and y is mole fraction of NFM in vapor phase.
The optimized interaction parameter between two components with-
out solvation effects, optimized interaction parameter and association
volume parameter with solvation effect and average absolute devia-
tion in bubble point temperature and in NFM mole fraction in the
vapor phase have been reported in Table 5. In general, for modeling
the vaporliquid equilibrium of aromaticsNFM systems, the CPA EoS
with 2B and 4C association schemes yields satisfactory results using a
small value of the interaction parameter and for most cases 4C
association scheme yields better results compared to other association
schemes. Best results are obtained for NFMo and m-xylene. The
results of vaporliquid equilibrium also show that when cross associa-
tion was considered between NFM and aromatics the results were
better than that when only NFM was considered as associating
compound. This veried that the aromatic ring can act as an electron
donor site on aromatic molecules.
3.4. Comparison between the CPA EoS, NRTL and UNIQUAC models:
Comparisons to other thermodynamic models are always use-
ful for evaluation of the performance of a model, especially when
compared to more conventional engineering models for handling
polar mixtures. In this section, a comparison between CPA EoS and
NRTL and UNIQUAC models(Ko et al., 2002; Wang et al., 2011; Park
Fig. 5. Solubility (mole fraction) of NFM in HC (nonane) and HC in NFM at 101.8 kPa
(, experimental data (Wang et al., 2011)), NFM with 2B and 4C association
schemes and using CR1 combining rules.
Fig. 6. Solubility (mole fraction) of NFM in HC (heptane) and HC in NFM 101.8 kPa
(, experimental data (Wang et al., 2011)), NFM with 2B and 4C association and
using CR1 combining rules.
Fig. 7. Solubility (mole fraction) of NFM in HC (2,2,4-trimethylpentane) and HC in
NFM at 101.8 kPa (, experimental data (Wang et al., 2011)), NFM with 2B and 4C
association schemes and using CR1 combining rules.
Fig. 8. Solubility (mole fraction) of NFM in HC (3-methylpentane) and HC in NFM at
101.8 kPa (, experimental data (Wang et al., 2011)), NFM with 2B and 4C
association schemes and using CR1 combining rules.
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 158
and Gmehllng, 1989; Yin et al., 2010; Huang et al., 2008; Cincotti
et al., 1999) that was employed for NFM containing mixture is
discussed. For liquidliquid equilibrium systems, the performance
of the NRTL and UNIQUAC models is better than CPA EoS. It can be
due to use of more adjustable parameters in NRTL and UNIQUAC
models. In the NRTL model 4 and 7 adjustable parameters were
used(Ko et al., 2002; Wang et al., 2011) and in the UNIQUAC model
between 2 and 6 adjustable parameters were used(Ko et al., 2002;
Wang et al., 2011; Cincotti et al., 1999). While in the CPA EoS only
two or one adjustable parameters were used. In the vaporliquid
equilibrium system, the results of NRTL and UNIQUAC are slightly
better than CPA EoS while in the NRTL and UNIQUAC model 3 and
2 adjustable parameters were used(Park and Gmehllng 1989; Yin
et al., 2010; Huang et al., 2008), respectively.
4. Conclusion
In this study, the CPA EoS has been applied to predict thermo-
dynamic properties of systems containing N-formylmorpholine.
Using vapor pressure, saturated liquid density and liquidliquid
equilibrium data, the CPA EoS parameters were obtained for NFM.
Then, for determining the best association scheme and proper para-
meters for predicting the themodynamic properties of NFM, the
liquidliquid phase equilibrium was studied for binary mixtures
including NFM. It was found out that 2B and 4C association schemes
give better results than other association schemes for NFM.
Taking into account the latter two association schemes, the
vaporliquid equilibrium for binary systems containing NFM was
modeled. Satisfactory results were achieved for modeling of the
vaporliquid equilibrium of binary mixtures containing aromatics.
Comparison between CPA EoS and NRTL or UNIQUAC models
shows that in the modeling liquidliquid equilibrium with CPA
EoS, more than two adjustable parameters were required. Prob-
ably association energy or binary interaction parameter must be
considered as temperature dependent.
Considering the results, we have chosen the 4C association
scheme for NFM as an assigned type for modeling its thermo-
dynamic properties using the CPA EoS.
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Table 5
The values of association volume and the interaction parameters for vapor -liquid systems containing NFM with 2B and 4C association schemes and average absolute
deviation in temperature and NFM mole fraction in vapor phase. Experimental data from literatures.Park and Gmehllng (1989; Yin et al., 2010; Huang et al., 2008).
System Association scheme
2B 2B & CR1 4C 4C & CR1
%AAD %AAD %AAD %AAD
k
ij
T y k
ij

2
T y k
ij
T y k
ij

2
T y
m-XyleneNFM 0.0146 0.23 15 0.0165 0.001 0.13 14.5 0.0041 0.2 13.36 0.005 0.001 0.10 13.0
o-XyleneNFM 0.0066 0.16 21.8 0.0151 0.001 0.12 18.71 0.002 0.2 19.5 0.001 0.0002 0.12 19.17
BenzeneNFM 0.006 0.4 17 0.0038 0.001 0.26 16.6 0.022 0.23 17 0.014 0.001 0.13 17.37
TolueneNFM 0.063 0.56 23.12 0.0613 0.001 0.52 21.4 0.047 0.54 21.3 0.051 0.0001 0.28 20.0
H. Mahmoudjanloo et al. / Chemical Engineering Science 98 (2013) 152159 159