Journal of Molecular Liquids 224 (2016) 30–42

Contents lists available at ScienceDirect

Journal of Molecular Liquids

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

Modelling solubility of CO2 and hydrocarbon gas mixture in ionic liquid

([emim][FAP]) using ASPEN Plus
Bishwadeep Bagchi, Sushmita Sati, Vidyasagar Shilapuram ⁎
Chemical Engineering Department, National Institute of Technology, Warangal, Telangana State 506 004, India

a r t i c l e i n f o a b s t r a c t

Article history: In the present study bubble point pressure, solubility and selectivity of CO2 and Hydrocarbon mixture with
Received 12 August 2016 [emim][FAP] as an ionic liquid has been studied by ASPEN Plus simulations. Ternary systems considered were
Received in revised form 7 September 2016 CO2, [emim][FAP] and one of the hydrocarbons (HC) viz., methane, ethane, propane, and butane. Peng Robinson
Accepted 22 September 2016
equation of state with quadratic van der Waals (vdW) mixing rule model was chosen to perform the thermody-
Available online 23 September 2016
namic calculations in FLASH3 column. Wide range of temperatures, molar ratios of CO2/HC, and HC/[emim][FAP]
Keywords:
were considered for this study. Results showed that, type of hydrocarbon (or carbon chain length) had a domi-
ASPEN Plus nant effect on the selectivity of CO2 over hydrocarbon. Selectivity of CH4 compared with other hydrocarbons is
Ionic liquids higher by more than one order of magnitude. Concentration of hydrocarbon in the feed stream of the ternary sys-
Natural gas tem is the main deciding factor in addition to temperature in determining the solubility, bubble point pressure
Carbon dioxide and phase transition from two phase liquid system to single liquid phase.
Hydrocarbons © 2016 Elsevier B.V. All rights reserved.
Selectivity

1. Introduction
Natural gas, which is a major source of energy, must satisfy certain
specifications of allowable concentrations of impurities while transpor-
tation. Presence of CO2 above allowable limit in the natural gas stream
may lead to formation of dry ice during liquefaction process, gas hydrate
formation during transportation, and reduction in the heating value [1–
3]. Conventionally, the removal of CO2 from the natural gas or flue gas
from any industrial stream is achieved by sending it through an absorb-
er stripper combination in which a solvent is utilized to selectively dis-
solve CO2 [4]. Conventional solvents such as monoethanolamine (MEA)
and Selexol are employed for CO2 removal [1–2,5]. The MEA process
suffers from various drawbacks, hence, the use of ionic liquids (IL) as
an alternative solvent is gaining prominence [5–8]. Unique properties
of ILs such as non-toxicity, high heat capacity, low vapour pressure,
high electroelasticity, non-flammability, high thermal and chemical sta-
bility has made it as an attractive alternative for the CO2 capture process
[9–11].
The anionic part of the IL is primarily responsible for determining the
solubility of CO2 in ionic liquid. It has been observed that ILs with
fluorous anions like [Tf2N−], [BF− −
4 ] and [PF6 ] exhibit highest CO2 solu-
bility [12]. A highly fluorinated IL with a large anion would be stable
in presence of moisture and air [13]. A disadvantage of using ionic
liquids with hexafluorophosphate anion is that it is unstable during
hydrolysis, especially at higher temperatures it releases hydrofluoric
⁎ Corresponding author.
E-mail address: vidyasagars@nitw.ac.in (V. Shilapuram).
acid (HF) which is a toxic and corrosive substance, leading to a negative
environmental impact [14]. In order to overcome this disadvantage,
some of the fluorine atoms are replaced by the perflouroalkyl groups
which help in increasing the stability of fluorophosphates [15]. An IL
bearing the anion tris(pentafluoroethyl)trifluorophosphate was consid-
ered where three fluorine atoms of hexafluorophosphate have been
replaced by pentafluoroethyl group. Hence, an IL named 1-ethyl-3-
methylimidazolium tris(pentafluoroethyl)trifluorophosphate, repre-
sented as [emim][FAP] was chosen for this particular study. Since only
carbon dioxide is to be dissolved into the solvent, a high CO2 solubility
coupled with a low affinity towards CH4 and other hydrocarbons pres-
ent in natural gas is required. Althuluth et al. [16–19] experimentally
measured the bubble point pressure for a binary system comprising of
[emim][FAP] with CO2, methane, ethane, propane and butane individu-
ally. Estimated ideal selectivities from solubility data of CO2, methane,
ethane, propane and butane with IL showed that CO2 was preferentially
absorbed over hydrocarbons. However, above results showed that lim-
ited amount of data is available covering a narrow temperature range
between 300 K and 360 K.
Typical natural gas is composed of methane with 80% mole fraction
and above, along with other HCs namely ethane, propane, butane and
pentane (below 10% mole fraction) and impurities. Therefore, it is im-
portant to study the relative effect of the presence of hydrocarbons on
CO2 and methane solubility and bubble point pressure. To the best of
authors' knowledge, very few experimental or theoretical works on ter-
nary systems comprising of IL with CO2 and CH4 are available which
have estimated the bubble point pressures or solubility of CO2/CH4 mix-
tures [3,20–21]. However, reported results are available for a limited

http://dx.doi.org/10.1016/j.molliq.2016.09.071
0167-7322/© 2016 Elsevier B.V. All rights reserved.
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
temperature and mole fraction range. Also, to the authors' knowledge,
no experimental or theoretical data is available for ternary systems
comprising of IL with CO2 and C2H6 or CO2 with C3H8 or CO2 with
C4H10. In addition, it is practically impossible to study the solubilities
of these hydrocarbons along with CO2 in ionic liquids experimentally
for a wide range. Hence, the motivation behind this work is to develop
a model in Aspen Plus that can provide the solubility, bubble point pres-
sure data and selectivity of CO2 over hydrocarbons (methane, ethane,
propane and butane) in an IL for a wide range of temperatures, and
feed gas compositions. As a first step, the reported experimental data
available in the literature has been used to validate the adopted ap-
proach [20]. The binary interaction parameters were obtained through
regression of the experimental vapour-liquid-equilibrium (VLE) data
available. These binary interaction parameters were used in simulations
to cover a wide range of temperature and composition. Since both CO2
and hydrocarbon are competing for its solubility in the ionic liquid, ef-
fect of temperature and molar ratios of CO2 to HC (x1/x2) and HC to IL
(x2/x3) on bubble point pressure, solubility and selectivity has been
studied for a wide range.
It should be noted that pure IL was considered while performing the
simulations since the presence of impurities in the IL gives rise to vari-
ous changes in its physical and chemical properties which can change
its stability and solubility. ILs with highly fluorinated anions such as
FAP become unstable in the presence of water at high temperatures
and can hydrolyze to form hydrogen fluoride [22]. The presence of
moisture and halide content in IL affects its viscosity [23]. An IL with
higher viscosity exhibits comparatively lower absorption and desorp-
tion rates [16]. The presence of chlorides drastically increases the viscos-
ity of IL while the presence of water reduces it. The halides present in
the ILs may also increase its corrosive ability [24]. Hence, while
attempting to reproduce these simulation results practically, care
must be taken to ensure the purity of the IL.
2. Thermodynamic modelling
Peng Robinson Equation of State (PR EOS) has been applied to model
the thermodynamic data [25]. PR EOS can be expressed as
RT a with both single temperature dependant term and also with two tem-
P¼ − ð1Þ
V m −b V m ðV m þ bÞ þ bðV m −bÞ
where P is the pressure, T is temperature, Vm is the mixture molar vol-
ume, a and b are constants contributing for molecular interaction and
co-volume, and R is the universal gas constant. This equation of state
can be applied to a single species or a mixture. However, in the case of
a mixture, different mixing rules may be adopted in estimation of ‘a’
and ‘b’. In present study the quadratic van der Waals (vdW) mixing
rule as presented below were adopted.
a ¼ ∑∑xi x j aij ð2Þ
b ¼ ∑∑xi x j bij ð3Þ
with
pffiffiffiffiffiffiffiffiffi 
aij ¼ ai a j 1−kij kii ¼ kjj ¼ 0
bi þ b j  
bij ¼ 1−lij lii ¼ ljj ¼ 0
2 stream of FLASH3 does not carry any material and all the feed entering
Here, kij and lij are the binary interaction parameters, aiand bi are
pure component parameters responsible for molecular interaction and
co-volume respectively.
31
3. Modelling and simulation details
As mentioned above, the main objective of this work is to determine
the bubble point pressures for systems of carbon dioxide and hydrocar-
bon (viz. methane, ethane, propane and butane) in an IL. Also, the va-
pour phase and liquid phase compositions at the calculated bubble
point pressure for a given temperature were deduced.
Aspen Plus's model library offers the option of carrying out VLE cal-
culations by choosing FLASH2 or FLASH3 block. FLASH3 block is
employed to perform rigorous three phase vapour-liquid-liquid equilib-
rium calculations. Liquid-liquid equilibrium can also be solved using
this column [26]. As an input to the block (FLASH3), two out of the
four given specifications need to be provided: flash temperature, flash
pressure, heat duty, and the fraction of the feed vaporized to perform
equilibrium calculations. It solves the appropriate material, energy bal-
ance and equilibrium equations depending on the input provided.
Within the range of temperatures chosen and with the selected equa-
tion of state, for the ternary system considered, it was observed to
have a maximum of three phases (a vapour phase and two liquid
phases). Hence, FLASH3 block was chosen for performing the simula-
tions. By providing the initial flow rates of CO2, CH4 and IL to the flash
column at the chosen temperature and setting the vapour fraction of
the FLASH3 unit available in separators of model pallet in simulation en-
vironment to zero, bubble point pressures were computed [27].
ASPEN Plus (Version 8.4) was employed to perform the thermody-
namic modelling of the CO2 + HC + IL ternary system. Each simulation
was carried out by considering a different hydrocarbon each time along
with carbon dioxide and ionic liquid. CO2 and hydrocarbon were speci-
fied in the component specifications of ASPEN Plus. [emim][FAP] com-
ponent is not available in the inbuilt data banks of ASPEN Plus.
Molecular structure and functional groups of [emim][FAP] were provid-
ed as an input to specify this compound. Peng Robinson equation of
state (EOS) with quadratic mixing rule (VLMXQUAD) was chosen.
For each binary system of CO2 + IL and HC + IL, the binary interac-
tion parameters required for PR EOS modelling were obtained by
regressing the binary vapour liquid equilibrium (VLE) data extracted
from Althuluth et al. [16–19]. The VLE data for the CO2-IL system was
regressed to obtain the first binary interaction parameter, kij(kij = kji),
perature dependant terms. It was observed that using two temperature
dependant terms gave a lower root mean square error (RMSE) value. A
second binary interaction parameter lij with a single temperature inde-
pendent term was also used to correct the volume of mixing [16]. For
the HC-IL system, the binary interaction parameter kij with single tem-
perature dependant term and lij with a single temperature independent
term was fitted to the VLE data. RMSE value of b5% was obtained when
both kij and lij were used. Binary interaction parameters obtained are
presented in Table 1. Standard deviation of uncertainties of tempera-
ture, pressure and mole fraction of inlet feed components of 0.01 K,
0.003 MPa, and 0.005 respectively are considered for regression of bina-
ry interaction parameters. Critical properties of the hydrocarbons were
taken from literature [28] while the critical properties for the IL were
taken from the values estimated by Althuluth et al. [29] using the mod-
ified group contribution method of Lydersen-Joback-Reid [30].
The flowsheet developed for modelling the ternary system is shown
in Fig. 1. FLASH3 column with two inlet streams and three outlet
streams were chosen. One of the inlet streams carried the feed gas mix-
ture of CO2 and HC while the other stream carried the solvent (IL). The
temperatures of each stream and of the FLASH3 column were set to the
same value. Vapour fraction in the FLASH3 block was set to 0 to calculate
the bubble point pressure [27]. This means that the out let vapour
into the FLASH3 i.e. CO2 + HC + IL flow exists in the liquid phase. The
block pressure and the compositions of all components in the streams
leaving the block were tabulated. A calculator block was employed to
calculate the selectivity.
32 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
Table 1
Binary interaction parameter obtained from ASPEN Plus.
Pair Interaction parameter
CO2\
\CH4 kij = 0.0919
CO2\
\C2H6 kij = 0.1322
CO2\
\C3H8 kij = 0.1241
CO2\
\C4H10 kij = 0.1333
CO2-[emim][FAP] kij ¼ −1:02193214 þ 1:93992822  10−3  ðTÞ þ 101:717029
lij = −0.114290764; lji = −0.382557421
−2
CH4-[emim][FAP] kij = 2.68307642 × 10 + 1.02986266 × 10 × (T)
C2H6-[emim][FAP] kij = − 3.46609217 × 10−2 + 9.56585708 × 10−4 × (T)
C3H8-[emim][FAP] kij = − 3.4635247 × 10−3 + 7.95510542 × 10−4 × (T)
C4H10-[emim][FAP] kij = − 6.257 × 10−3 +7.67 × 10−4 × (T)
Reason for choosing FLASH3 column is to explore the possibility of
extending our simulations to identify the phases by varying wide
range of temperatures/pressures in our future work. For this ternary
system there is a possibility that at some conditions more than one liq-
uid phase (two immiscible liquid phases) may form, Since FLASH3 has
one outlet vapour stream and two outlet liquid streams, it can identify
all the phases but not FLASH2 column depending on the prevailing con-
ditions in that unit.
4. Design of experiment
In real time situation, ionic liquid is chosen to maximize the CO2 sol-
ubility and minimize the HC solubility. Hence, molar feed ratio of input
streams decides the extent of solubility/bubble point pressure/phase
behaviour. A maximum solubility of 0.8 mol fraction of CH4 in
[emim][FAP] was observed. The lowest solubility observed was around
0.01. Hence, HC/IL ratio (x2/x3) was varied from 0.01 to 0.8 to cover
the entire spectrum. In order to investigate the relative effect of mole
flows of HC on CO2 solubility, the carbon dioxide to hydrocarbon ratio
(x1/x2) was varied from 0.1 to 10. This was done so that both the
cases where the molar flow rate of hydrocarbon is more than the
molar flow rate of carbon dioxide and vice versa can be observed.
These values of x1/x2 and x2/x3 were solved to yield the mole fractions
of individual CO2, HC and IL in the feed stream. These mole fractions ob-
tained were multiplied by 100 so that to choose 100 kmol/time as the
total molar flow rate as the basis which were then multiplied by 100
(basis) to make the total input mole flow of ternary system (CO2 +
HC + IL) to 100 kmol/time as the basis. ‘x1/x2’ ranging from 0.1 to 10
comprising of 9 different values and x2/x3 ranging from 0.01 to 0.8 com-
prising of 13 different values resulted in 117 cases. The design matrix of
input molar flow rates considering the above broad range of mole ratios
chosen is shown in the Table S1 of the Supporting Information. Corre-
sponding design matrix is also depicted in Fig. 2. Temperature range
was chosen to be from 183.15 K to 493.15 K. A lower range of
183.15 K was chosen as neither any hydrocarbon nor carbon dioxide re-
mains in vapour phase at temperatures lower than it. Upper limit tem-
perature of 493.15 K was chosen since IL begins to decompose from this
temperature onwards [16].
The values of molar flow rates of CO2, HC and IL along with the flash
temperature was provided as input to the FLASH3 column of ASPEN in
Fig. 1. Aspen Plus flowchart used for the modelling and simulation of CO2 and hydrocarbon mixture in [emim][FAP].
Source
Aspen database
Aspen database
Aspen database
Aspen database
T
Regression of VLE data of Ref. [18]
−3
Regression of VLE data of Ref. [17]
Regression of VLE data of Ref. [19]
Regression of VLE data of Ref. [19]
Regression of VLE data of Ref. [19]
the simulation environment. The bubble point pressures along with
the liquid and vapour phase compositions, and selectivity were deter-
mined by the simulation.
Real selectivity is obtained using the given relation
!
yHC =xHC
SRCO2 =HC ¼ ð4Þ
yCO2 =xCO2
p;T
where yi and xi respectively denote the gas phase and liquid phase com-
position of the respective component ‘i’. Both of these compositions are
computed using the PR EOS. This relation takes into consideration the
non idealities present in the system. Please read “Selectivity” as “Real
Selectivity” throughout the text unless otherwise mentioned.
5. Results and discussions
5.1. Model validation
The above adopted methodology was verified by implementing it to
the experimental conditions of Ramdin et al. [20] and validating their
results. In their study, bubble point pressure of CO2, CH4 and IL ternary
system was determined for three different ionic liquids viz.,
[bmim][Tf2N], [emim][dep], and [thtdp][dca]. Three different CO2/CH4
ratios (x1/x2) with variations in CH4/IL ratio (x2/x3) for temperatures
between 300 K and 365 K were considered to determine the bubble
point pressures.
Fig. 3 shows the validation of the experimental results with the pres-
ent simulation methodology for all the ionic liquids chosen by Ramadin
et al. [20] in terms of parity plots. Please read “pressure” as “bubble
point pressure” throughout including in tables and figures. In other
words, pressure and bubble point pressure is used interchangeably. It
was observed that for the system of CO2 + CH4 + [emim][dep], simulat-
ed values are in close agreement with the experimental values, with a
deviation within ± 5%. Whereas for the system of CO2 +
CH4 + [bmim][Tf2N] and for CO2 + CH4 + [thtdp][dca], the error % be-
tween experimental and predicted were within ±15% and ±10% re-
spectively. Upon observation of all these parity plots, it can be seen
that for only the experimental data points corresponding to the higher
values of x2/x3 i.e. 0.201 in the case of [bmim][Tf2N] and of 0.174 in
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
Fig. 2. Experimental design of the ternary system CO2 + HC + [emim][FAP] considered for simulations.
the case of [thtdp][dca] resulted in large deviation. Otherwise, the devi-
ation between experimental and predicted might have been well within
±5%. Thus, it may be concluded that the applied ASPEN Plus methodol-
ogy with FLASH3 block can be adopted in our present study with the
chosen IL of [emim][FAP] with different gas mixture of CO2 with HC (ei-
ther methane or ethane or propane or butane) with an accuracy of ±
15%.
As the next step, comparison was made between the ILs chosen by
Ramdin et al. [20] with [emim][FAP] in terms of bubble point pressures
at same conditions of temperature and compositions for the CO2, CH4
and IL ternary system. It was observed that [emim][FAP] has the lowest
bubble point pressure as compared to their ionic liquids as shown in
Fig. 4. This establishes the superiority of [emim][FAP] over other ILs in
terms of ease of solubility.
After validating the present simulation methodology with the exper-
imental conditions as discussed above, same methodology was extend-
ed to the ternary system of CO2 + HC + [emim][FAP] for a wide range of
compositions and temperatures. Each time HC considered was either
one of methane/ethane/propane/butane. Hence, individually simula-
tions were run by considering one hydrocarbon at a time for the ternary
system and the respective solubility, bubble point pressure and selectiv-
ity was calculated for a set of x1/x2 and x2/x3 at a particular value of tem-
perature. At this condition of x1/x2 and x2/x3 simulations were repeated
for different temperatures so as to cover broad temperature range from
33
the highest melting point of a pure species of ternary system to the deg-
radation temperature of ionic liquid.
5.2. CO2 + CH4 + [emim][FAP] system
‘xi’ stands for input mole fraction of component ‘i’ into the FLASH3
column. Subscripts 1, 2, and 3 stand for CO2, HC, and IL respectively. In-
dividually each simulation was performed for a given CO2 + HC + IL
ternary system for all 117 cases of Table S1 of supporting information
for all hydrocarbons. Each simulation at a given composition (fixed
value of x1/x2 and x2/x3) was run from the lowest possible temperature
of −183.15 K to 473.15 K with a temperature increment of 10 K.
Table S2 of the supporting information shows the temperature range
in which CO2 + HC + IL ternary system exists in single liquid phase for
all the molar ratios considered in this study for all hydrocarbons. Data
highlighted in red colour shows that for that particular hydrocarbon,
under those particular molar ratios, single liquid phase was not ob-
served in the chosen temperature range (183.15 to 493.15 K). It has
been noticed that depending on the composition (x1/x2 and x2/x3), at
lower temperatures, simulations showed that there were two different
liquid phases. With further increase in temperature, the ternary system
appears in a single liquid phase from two different liquid phases. Table
S2 shows that the temperature range from lowest possible to highest
possible temperature in which single liquid phase existed was
34 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42

Fig. 3. Validation of experimental results of Ramdin et al. [19] by present Aspen Plus
simulation methodology for (a) CO2 + CH4 + [bmim][Tf2N], (b) CO2 +
CH4 + [emim][dep], (c) CO2 + CH4 + [thtdp][dca].
Fig. 4. Comparison of bubble point pressure of CO2 + CH4 gas mixture with [emim][FAP]
with that of Ramdin et al. [19] (a) [bmim][Tf2N], (b) [emim][dep], (c) [thtdp][dca].
depending on the x1/x2, x2/x3, and type of hydrocarbon (or equivalently
carbon chain length). As mentioned earlier, detailed investigation of objective of the present study is to find the solubility, bubble point pres-
phase identification is in progress for the ternary systems considered sure and selectivity, the molar ratios (x1/x2 and x2/x3) and temperature
in this study, hence, those results are not presented here. Since the range in which only single liquid phase exists is considered for this
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
study. Out of the 117 cases of Table S1, the operable mole ratios (x1/x2
and x2/x3) and temperature ranges that were common to all the hydro-
carbons in which only one liquid phase exists is provided in Table S2 of
Supporting Information. Hence, in the present study, results corre-
sponding to these conditions (x1/x2, x2/x3, and temperature range) are
presented from Fig. 5 onwards. Therefore, caution is to be noticed that
all the results presented from Fig. 5 is when the ternary system is in sin-
gle liquid phase. The respective molar flow rates corresponding to dif-
ferent set of x1/x2 and x2/x3 can be deduced from the Table S1.
Fig. 5 shows the bubble point pressure estimation as a function of
temperature for a particular composition (i.e. at fixed value of x1/x2
for various x2/x3). Each curve in Fig. 5 is for a definite value of x2/x3 at
x1/x2 = 0.33.
At a particular temperature, upon comparison, bubble point pres-
sure increased with increase in x2/x3. As the ratio of x2/x3 increases,
the difference between the mole fractions of CH4 and IL decreases.
Therefore, for a particular x1/x2, the effect of change of x2/x3 is much
less pronounced on the mole fraction of carbon dioxide as compared
to the mole fractions of HC and IL. This can be noticed from the Table
S1. Therefore, mole fractions of HC and IL become dominant factors in
deciding the bubble point pressure of the system. Consecutively, the ef-
fect of mole fraction of carbon dioxide on the bubble point pressure is
less. In other words, for a system of carbon dioxide and methane, carbon
dioxide gets completely dissolved into the IL at a pressure much lower
than that at which CH4 gets dissolved.
At lower values of x2/x3, it can be observed that pressure increases
monotonically with increase in temperature. This monotonic behaviour
(Type-1) is observed till a particular value of x2/x3 (up to 0.3). Beyond
this particular x2/x3 of 0.3, different trends of variation of bubble point
pressure with temperature is noticed. Increase in bubble point pressure
to a peak value at lower temperatures followed by decrease in bubble
point pressure for further increase in temperature was observed (for
the case of x2/x3 of 0.4 and 0.5). As the relative difference between the
mole fractions of x2 and x3 diminishes, the pressures required to
completely solubilise it increases, especially at lower temperatures.
This can be explained as to solubilise an amount of CH4 in an almost
equal quantity of IL requires a very high pressure. This behaviour, no-
ticed for the cases of x2/x3 at 0.4 and 0.5 was not at all observed for all
other x1/x2 ranging from 0.1 to 10 except for x1/x2 = 0.33. For x2/
x3 = 0.6, bubble point pressure was not calculated in the complete tem-
perature range because below 440.15 K two liquid phases were ob-
served as discussed in discussion w.r.to Table S2. The bubble point
Fig. 5. Bubble point isopleths of the ternary system as a function of temperature at x1/x2 =
0.33 for different x2/x3 for CO2 + CH4 + [emim][FAP] ternary system.
35
pressure decreased with increase in temperature beyond this tempera-
ture. Reason is, once the single liquid phase starts, with increase in tem-
perature the solubility of both HC and CO2 might be increasing causing
to decrease in bubble point pressure. This behaviour of decrease in bub-
ble point pressure with temperature beyond particular value of x2/x3
(Type-2) is not noticed for the methane at all other x1/x2s but only up
to x1/x2 of 0.5 (Refer Fig. S1 of the supporting information).
Selectivity of the CO2/CH4 system has been calculated by using
the Eq. (4). These were calculated at different molar ratios (x1/x2 and
x2/x3) for a wide temperature range. Since the objective is to maximize
the solubility of CO2 and minimize the solubility of HC, this study will
give an idea of the temperature and molar flows that can maximize
the selectivity. Higher the selectivity better is the CO2 removal over
hydrocarbon with an IL.
Selectivity is plotted as a function of temperature for x2/3 = 0.04
at various values of x 1 /x 2 for CO 2 + CH4 + [emim][FAP] ternary
system. As temperature is increased, it can be seen that selectivity
of CO2 over CH4 decreases. This is expected as bubble point pressures
increased with increase in temperature. As temperature is increased,
the mole fraction of CH4 in vapour phase decreases while the mole
fraction of CO 2 in vapour phase increases because of temperature
affect on relative solubility of CH 4 and CO 2 . This contributes to a
decrease in selectivity of CO2 over CH4. It can also be observed that
effect of x1/x2 is negligible compared to temperature. Results show
that for a particular x 2 /x 3 , the selectivity is mostly dependent on
the temperature of the system as compared to x1 /x2 . Selectivity
values changed by almost two order of magnitudes when the
temperature is changed from 183.15 to 493.15 K.
For lower temperatures, higher values of selectivity are observed.
Hence, the natural gas separation process from CO2 should be conduct-
ed at lowest temperatures for maximum separation. Comparison of all
the results at different x2/x3 showed that for smaller values of x2/x3
(from 0.01 to 0.05), selectivity values do not differ with change in com-
position, at a particular temperature (Refer Fig. S2 of the supporting in-
formation). As the ratio of x2/x3 is gradually increased, selectivity
decreases significantly. Even at higher values of x2/x3 for temperatures
above, say 280 K, selectivity values do not change much by changing
x1/x2.
5.3. CO2 + C2H6 + [emim][FAP] system
Fig. 7 shows the bubble point isopleths of the ternary system as a
function of temperature at x1/x2 = 0.33 for different x2/x3 for CO2 +
C2H6 + [emim][FAP] ternary system. A trend similar to the CO2 +
CH4 + [emim][FAP] system is observed for the bubble point pressure
verses temperature behaviour (Type-1 & 2). For a constant ratio of
CO2/C2H6, pressure increases with increase in temperature till a certain
ratio of C2H6/IL, after which pressure starts decreasing with increase in
temperature. However, the value of x2/x3 (in this case 0.4 whereas 0.3
when HC as CH4) at which this transition takes place may be different
for different hydrocarbons.
Fig. 8 shows the selectivity of the ternary system as a function
of temperature at x2/3 = 0.04 for different x1/x2 for CO2 +
C2H6 + [emim][FAP] ternary system. This shows that at a given x1/x2
selectivity increases with increase in temperature to a particular value
followed by decrease in selectivity with further increase in temperature.
Selectivity increases with increase in x1/x2 at a given temperature and
its effect is dominant at lower temperature. As the temperature
increases, selectivity at different x1/x2s is almost approaching each
other.
Upon comparison of selectivity as a function of temperature at dif-
ferent x2/x3, similar profiles were observed (Refer Fig. S4 of the
supporting information). Maximum selectivity of about 5.5 with a min-
imum of about 1.5 has been noticed for the entire temperature change
studied.
36 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42

5.4. CO2 + C3H8 + [emim][FAP] system

Fig. 9 shows the bubble point isopleths of the ternary system as a

function of temperature at x1/x2 = 0.33 for different x2/x3 for CO2 +
C3H8 + [emim][FAP] ternary system. CO2 + C3H8 system follows a
trend similar to the previous hydrocarbon (C2H6) i.e. two types of be-
haviour. Bubble point pressure increases monotonically with increase
in temperature. As the mole fractions of C3H8 and IL become close to
each other, pressure starts decreasing with increase in temperature.
Fig. 10 shows the selectivity of the ternary system as a function of
temperature at x2/3 = 0.5 for different x1/x2 for CO2 +
C3H8 + [emim][FAP] ternary system. At lower temperatures, selectivity
increases with increase in temperature and reaches a peak value and
then starts decreasing with increase in temperature. This could be due
to the fact that C3H8 has a boiling point of 231.15 K and at such low tem-
peratures; it remains in liquid state which results in this opposite trend.
At very low temperatures, selectivity is b1, implying that C3H8 is more
soluble as compared to CO2 in IL. Temperature is not the only factor
that affects solubility for this system but mole fractions of HC and IL
are also contributing factors to the solubility. Maximum selectivity of
Fig. 6. Selectivity of CO2 + CH4 + [emim][FAP] ternary system as a function of
about 1.3 with a minimum of about 0.7 has been noticed for the entire temperature at x2/x3 = 0.04 for different x1/x2
temperature change studied. Temperatures between 250 K to 300 K.
this maximum selectivity was observed depending on the x2/x3 ratio.
This monotonic behaviour is observed till a particular value of x2/x3.
5.5. CO2 + C4H10 + [emim][FAP] system That particular value of x2/x3 may be different for different hydrocar-
bons and for different x1/x2. Beyond this particular x2/x3, only for CH4
Fig. 11 shows the bubble point isopleths of the ternary system as a at x1/x2 = 0.33, different trend of variation of bubble point pressure
function of temperature at x1/x2 = 0.33 for different x2/x3 for CO2 + with temperature is noticed. The reason for this has been explained
C4H10 + [emim][FAP] ternary system. Two types of behaviour similar for Fig. 5.
to the other hydrocarbons is noticed in this case where pressure in- It can be observed from Fig. 13 that decrease in bubble point pres-
creases with temperature for a constant x2/x3. As similar to C3H8 + sure is noticed after a particular value of x2/x3. Beyond this x2/x3, it
CO2 system, for larger values of x2/x3, starting from 0.4, pressure starts can be noticed that bubble point pressures are not applicable for entire
decreasing with increase in temperature. region when all HCs are considered together. For example, for x2/x3 =
Fig. 12 shows the selectivity of the ternary system as a function of 0.5 bubble point pressure is obtained for narrower temperature range
temperature at x2/3 = 0.04 for different x1/x2s for CO2 + as the HC is moving from methane to butane (also refer Table S2). Recall
C4H10 + [emim][FAP] ternary system. Selectivity shows an opposite be- that all the results presented in this fig. belongs to a single liquid phase,
haviour compared to other hydrocarbons. Here, selectivity increases since at lower temperatures in which data is not reported corresponds
with increase in temperature. Also, selectivity of CO2 over C4H10 is less to two liquid phase region. Results imply that the type of hydrocarbon
than one, implying that C4H10 is preferentially more soluble in the IL plays a significant role. The reason for decrease in bubble point pressure
compared to Carbon dioxide. As the temperature increases, selectivity with temperature at higher x2/x3 is as follows. At a given x2/x3, for fixed
tends towards 1. Also, selectivity is improved by increasing x2/x3 ratio x1/x2 (fixed composition) and type of hydrocarbon, just below this tem-
(Refer supporting information). As more amount of C4H10 is sent as perature there were two liquid phases existing. Hence, high pressures
compared to carbon dioxide, the difference between the mole fractions are required for higher x2/x3 (since x2 is HC) to let the HC solubilise in
of C4H10 and IL fades, selectivity gets enhanced and crosses 1 at combi-
nations of some higher values of C4H10/IL and high temperatures. Cross-
ing a value of 1 for selectivity implies that carbon dioxide is now more
soluble in the ionic liquid as compared to butane which is desired in
most scenarios. Hence to achieve such a condition, temperatures higher
than 400 K and x2/x3 ratio of 0.2 or more is required.

5.6. Comparison of CO2 + HC + IL system

As mentioned earlier, natural gas consists of mixture of hydrocar-

bons (from methane to pentane) and impurities such as CO2, H2S, and
nitrogen compounds. Hence, individually solubility, bubble point pres-
sure and selectivity studies have been studied for a ternary system con-
sidering two gases, one of which is CO2 and the other being HC in
[emim][FAP]. Comparison of these ternary systems would give an idea
of the scenario when all the gases are present together in the natural
gas for the removal of CO2.
Fig. 13 shows the Bubble point isopleths of the CO2 + HC +
[emim][FAP] ternary system as a function of temperature at x1/x2 =
0.1 for different x2/x3 (for a particular inlet feed composition). Figs. 5
to 10 span for all hydrocarbons from methane to butane as one of the
component in the ternary system. For all hydrocarbons, at lower values Fig. 7. Bubble point isopleths of the ternary system as a function of temperature at x1/x2 =
of x2/x3, pressure increases monotonically with increase in temperature. 0.33 for different x2/x3 for CO2 + C2H6 + [emim][FAP] ternary system.
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
Fig. 8. Selectivity of CO2 + C2H6 + [emim][FAP] ternary system as a function of
temperature at x2/x3 = 0.1 for different x1/x2
the IL. Once the single liquid phase starts, with increase in temperature
the solubility of both HC and CO2 might be increasing causing to de-
crease in bubble point pressure. All these observations are attributed
to the hydrocarbon chain length and different levels of interactions
among the ternary system at prevailing conditions i.e., molar composi-
tions and temperature. This particular value of x2/x3 beyond which
this behaviour noticed is different for different hydrocarbons.
However, immaterial which type of hydrocarbon it is, this behaviour
of two different trends (Type-1 & 2) of one trend of increase in bubble
point pressure with temperature at lower x2/x3 followed by decrease
in bubble point pressure with temperature at higher values of x2/x3 is
noticed only up to x1/x2 of 0.75. Beyond x1/x2 of 0.75 for all hydrocar-
bons which there were monotonic increase (systematic trends) in bub-
ble point pressure with increase in temperature i.e., only type-1
behaviour (Refer Figs. S1, S3, S5 and S7 of supporting information).
Fig. 14 shows the comparison of selectivity of the CO2 + HC +
[emim][FAP] ternary system as a function of temperature at x2/x3 =
0.2 for different x1/x2. Selectivity of the CO2/HC system has been
Fig. 9. Bubble point isopleths of the ternary system as a function of temperature at x1/x2 =
0.1 for different x2/x3 for CO2 + C3H8 + [emim][FAP] ternary system.
37
Fig. 10. Selectivity of CO2 + C3H8 + [emim][FAP] ternary system as a function of
temperature at x2/x3 = 0.5 for different x1/x2
calculated by using the Eq. (4). Since objective is to maximize the solu-
bility of CO2 and minimize the solubility of HC, this study will give an
idea of temperature and molar flows that can be chosen to maximize
the selectivity. Higher the selectivity better is the CO2 removal over hy-
drocarbon with an IL.
Upon comparison of Fig. 14 for all HCs, at a given x1/x2 and x2/x3
(molar composition of the feed stream is fixed), it can be observed
that different profiles of selectivity variations have been noticed with
change in temperature. That is, monotonic decrease with methane as
HC, increase followed by decrease with ethane or propane as HC and
monotonic increase with butane as HC. In addition, at a particular
molar composition and temperature, there is drastic difference in selec-
tivity of CO2 with methane compared to CO2 with ethane, propane and
butane. Quite high values of selectivity are noticed with methane com-
pared to other HC. These significant differences in trends and values
could be attributed to the carbon chain length or type of hydrocarbon
Fig. 11. Bubble point isopleths of the ternary system as a function of temperature at x1/
x2 = 0.33 for different x2/x3 for CO2 + C4H10 + [emim][FAP] ternary system.
38
Fig. 12. Selectivity of CO2 + C4H10 + [emim][FAP] ternary system as a function of
temperature at x2/x3 = 0.03 for different x1/x2
Fig. 13. Bubble point isopleths of the ternary system as a function of temperature at x1/x2 = 0.1 for different x2/x3 for (a) CO2 + CH4 + [emim][FAP], (b) CO2 + C2H6 + [emim][FAP], (c)
CO2 + C3H8 + [emim][FAP], (d) CO2 + C4H10 + [emim][FAP].
B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
and prevailing conditions such as molar composition and temperature.
The Fig. 14 also confirms that this IL can solubilise more CO2 compared
to CH4 (2 to 3 order of magnitude difference) but almost equal amount
of ethane/propane/butane as that of CO2. In natural gas CH4 is N 80%
mole fraction and relatively lesser amounts of other hydrocarbons are
present, therefore, results show that this IL can be justified for selection
as an absorbent. Furthermore, from comparison of all the results pre-
sented in supporting information (Figs. S1 to S8), the best possible
molar ratios and operating temperatures for better separation can be
obtained. In addition, for a particular ternary system it can be noticed
that temperature has a dominant effect on the selectivity in addition
to nature of hydrocarbon (or hydrocarbon chain length) compared to
the molar composition.
In the ternary system, both HC and CO2 will be competing simulta-
neously to dissolve in the IL. However, the interactions among the com-
ponents of the ternary system at different conditions of molar
composition, and system temperature play an important role. Thus
the ideal selectivity calculated from individual binary system of
CO2 + IL and HC + IL may be different from real case scenario of ternary
CO2 + HC + IL system. Figs. 13 and 14 shows the comparisons of
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42 39

Fig. 14. Comparison of selectivity of the ternary system as a function of temperature at x2/x3 = 0.2 for different x1/x2 for (a) CO2 + CH4 + [emim][FAP], (b) CO2 + C2H6 + [emim][FAP], (c)
CO2 + C3H8 + [emim][FAP], (d) CO2 + C4H10 + [emim][FAP].

hydrocarbons from individual subplots of each hydrocarbon as one of 5.7. Henry's constant and ideal selectivity
the two solutes.
Fig. 15 shows the effect of hydrocarbons on bubble point pressure at Henry's constant can be defined for a binary system as.
constant composition (x1/x2 and x2/x3) and constant temperature. It
L
can be observed from the figure that bubble point pressure for CO2 + f1
H 12 ¼ lim ð5Þ
CH4 + IL system is substantially higher than the bubble point pressures x1→o x1:
of other CO2 + HC + IL system. This difference consistently declines as
the temperature is raised with increase in selectivity (Refer Tables S9 to where f1L is the fugacity of the solute ‘1’ in solvent ‘2’ and x1 is the mole
S17). For low x2/x3, at higher temperatures (N 400 K) the bubble point fraction of solute ‘1’ in solvent. f1L can be estimated by employing a
pressures of all the CO2 + HC + IL become almost equal. Higher hydro- suitable equation of state with the assumption that only pure solute is
carbons are more soluble in the IL as compared to lower hydrocarbons. present in the vapour phase and applying the equilibrium condition of
As explained previously and from these results, bubble point pressure is f1L =f1V.
largely dependent on the concentration of HC. Henry's constant provides an estimate about the solubility of a gas
Fig. 16 shows that effect of hydrocarbons on selectivity at constant component in a liquid. Lower the value of Henry's constant, higher is
composition (x1/x2 and x2/x3) and constant temperature. It can be ob- its solubility. For the present analysis, Henry's constant was modelled
served from the figure that selectivity for CO2 + CH4 + IL system is sub- by using the modified form of Krichevsky–Kasarnovsky equation [18,
stantially higher than the selectivity of other CO2 + HC + IL system 30]
(Refer Tables S18 to S20 of Supporting Information). This difference
∞
consistently declines as the temperature is raised with decrease in se- f2 V ðP Þ
ln ¼ ln H 21 þ 2 ð6Þ
lectivity. An order of difference in selectivity between CH4 compared x2 RT
to other HC over CO2 is noticed at lower temperature but at higher tem-
peratures, though the selectivity is higher for CH4 compared to other HC where f2 is the fugacity of the solute in vapour phase, x2 is the mole frac-
over CO2 but the difference gets reduced. tion of solute dissolved in solvent, P is the bubble point pressure, H21 is
40 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42

Fig. 15. Effect of hydrocarbons on bubble point pressure at constant composition at x1/
x2 = 1 for (a) T = 193.15 K, (b) T = 493.15 K.

Fig. 16. Effect of hydrocarbons on the real selectivity at constant composition at x1/x2 = 10
for (a) T = 183.15 K, (b) T = 493.15 K.
the Henry's constant of gas in the solvent at the liquid saturation pres-
∞
sure, V 2 is the partial molar volume of the gas at infinite dilution, R is
the universal gas constant, and T is the absolute temperature. Here,
the solvent [emim][FAP] has a negligible vapour pressure [31]. Hence,
the saturated vapour pressure Ps1 was considered as zero and f2 can be
taken as the fugacity of pure solute.
When the solubility (P − x) data at a constant temperature is plotted
f2 ∞
as ln x2 versus P, the slope of the line yields the value of V 2 , while the
intercept is lnH21. During simulations, the value of fugacity was directly
obtained for each of the cases by defining a suitable property set and
adding it in sensitivity analysis in order to obtain its value for each of
the cases.
The values of the Henry's constant obtained for this system obtained
by simulations are compared against the experimental values provided
by Althuluth et al. [17–19] in Table 2. It may be observed that deviations
of the simulated values of Henry's constant from the reported values in
literature are negligible.
Ideal selectivity can be calculated from the obtained values of
Henry's Constants. Ideal Selectivity is defined as

 
H HC
SICO2 =HC ¼ ð7Þ Fig. 17. Comparison of ideal selectivity of CO2 over hydrocarbons as a function of
HCO2 temperature.
 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42 41

Table 2
Comparison of experimental values of Henry's constant of Ref. [17–19] with the simulated values for binary system.

Temp (K) HCH4 (MPa) HCH4 (MPa) HC2H6 (MPa) HC2H6 (MPa) HC3H8 (MPa) HC3H8 (MPa) HC4H10 (MPa) HC4H10 (MPa) HCO2 (MPa) HCO2 (MPa)
(Ref. [17]) simulated (Ref. [19]) simulated (Ref. [19]) simulated (Ref. [19]) simulated (Ref. [18]) simulated

283 – – – – – – – – 2.24 2.28

293 – – – – – – – – 2.76 2.82
303 38.45 36.98 10.54 10.66 4.60 4.66 2.04 2.01 3.32 3.44
313 39.36 39.49 11.76 11.59 5.40 5.49 2.51 2.51 4.06 4.14
323 40.39 40.39 13.02 12.99 6.29 6.37 3.06 3.06 4.68 4.83
333 41.43 41.40 14.30 14.36 7.21 7.29 3.67 3.66 5.36 5.64
343 42.39 42.31 15.60 15.70 8.14 8.24 4.33 4.31 6.09 6.40
353 43.17 43.10 16.89 17.00 9.09 9.21 5.03 5.01 6.86 7.30
363 43.66 43.75 18.17 18.24 10.21 10.13 5.78 5.75 7.71 8.24

Table 3
Comparison of experimental values of ideal selectivity of CO2 over hydrocarbons of ref. [19] with the simulated values at various temperatures.

Temp (K) SCO2/CH4 SCO2/CH4 SCO2/C2H6 SCO2/C2H6 SCO2/C3H8 SCO2/C3H8 SCO2/C4H10 SCO2/C4H10
(Ref. [19]) simulated (Ref. [19]) simulated (ref. [19]) simulated (Ref. [19]) simulated

303 11.58 10.75 3.17 3.10 1.39 1.35 0.61 0.59

313 9.69 9.54 2.90 2.80 1.33 1.33 0.62 0.61
323 8.63 8.37 2.78 2.69 1.34 1.32 0.65 0.63
333 7.73 7.34 2.67 2.55 1.35 1.30 0.69 0.65
343 6.96 6.61 2.56 2.45 1.34 1.29 0.71 0.67
353 6.29 5.90 2.46 2.33 1.33 1.26 0.73 0.69
363 5.66 5.31 2.36 2.22 1.32 1.23 0.75 0.70

which is the ratio of Henry's constant of hydrocarbon over Henry's con- • Selectivity of CH4 as compared to other hydrocarbons is higher in
stant of CO2. A comparison of simulated values of ideal selectivity of CO2 more than one order of magnitude with [emim][FAP].
over hydrocarbons against reported values in literature at various tem- • Concentration of hydrocarbon in the ternary system is the major fac-
peratures are provided in Table 3. tor deciding the phase transition from two phase liquid system to sin-
Fig. 17 shows the comparison of variation in ideal selectivity of CO2 gle liquid phase, solubility and bubble point pressure, temperature
over hydrocarbons as a function of temperature. The trends observed being the second major factor for the same.
in all these plots are similar to the trends observed for variation in
Real Selectivity with temperature which is shown in Fig. 14. The range
of values taken by both real selectivity and ideal selectivity for a partic- Nomenclature
ular hydrocarbon are almost identical. Variations in their actual values a constant
at a particular temperature occur since real selectivity is dependent on ai pure component ‘i’ parameter
the composition of the system and takes into account the interaction ef- b constant
fects between the solutes. bi pure component ‘i’ parameter
HC hydrocarbon (methane/ethane/propane/butane)
6. Conclusions IL ionic liquid
kii,kij,kji,kjj binary interaction parameters
lii, ljj binary interaction parameters
• Peng Robinson equation of state with quadratic van der Waals (vdW)
P pressure
mixing rule model was chosen with FLASH3 block to estimate the
R universal gas constant
bubble point pressure, solubility and selectivity of various ternary sys-
RMSE root mean square error
tems with methane, ethane, propane, and butane as one of the com-
S selectivity
ponent with CO2 in an ionic liquid [emim][FAP] using ASPEN Plus
T temperature in K
simulations with an accuracy of b 15% in measurement of bubble
VLE vapour-liquid-equilibrium
point pressure.
Vm molar volume
• Adopted methodology has been verified within reasonable accuracy
xi mole fraction of a component ‘i’ in liquid stream
of ± 15% with the experimental data of the reported literature
yi mole fraction of a component ‘i’ in vapour stream
pertaining to solubility of the CO2 and CH4 gas mixture in three ILs
([bmim][Tf2N], [emim][dep], and [thtdp][dca]) which were different
from the IL chosen for the present study. Subscript
• At a given CO2 to HC ratio from 0.01 to 0.75, two types of behaviour in i component i (i = 1 for CO2, i = 2 for CH4/C2H6/C3H8/C4H10,
bubble point pressure that is increase with increase in temperature up i = 3 for IL)
to particular value of CH4 to IL ratio followed by decrease in bubble
point pressure with increase in temperature at higher CH4 to IL ratio
is noticed for all four ternary systems considered. Whereas beyond Superscript
0.75 of CO2 to HC ratio only increase in bubble point pressure with R real
temperature is observed for all CH4 to IL ratio.
• Type of hydrocarbon (or carbon chain length) had a dominant effect
on the selectivity of CO2 over hydrocarbon. Different hydrocarbons Appendix A. Supplementary data
showed different behaviour of selectivity with composition and tem-
perature. Temperature has a significant effect compared to molar ra- Supplementary data to this article can be found online at http://dx.
tios (or molar composition) of feed on selectivity. doi.org/10.1016/j.molliq.2016.09.071.
42 B. Bagchi et al. / Journal of Molecular Liquids 224 (2016) 30–42
References
[1] B. Guo, A. Ghalambor, Natural Gas Engineering Handbook, Gulf Publishing Company,
Houston, 2005.
[2] K. Simons, K. Nijmeijer, M. Wessling, Gas–liquid membrane contactors for CO2 re-
moval, J. Membr. Sci. 340 (2009) 214–220.
[3] M. Ramdin, A. Amplianitis, S. Bazhenov, A. Volkov, V. Volkov, T.J.H. Vlugt, T.W. de
Loos, Solubility of CO2 and CH4 in ionic liquids: ideal CO2/CH4 selectivity, Ind. Eng.
Chem. Res. 53 (2014) 15427–15435.
[4] R.N. Tennyson, R.P. Schaaf, Guidelines can help choose proper process for gas-
treating plants, Oil Gas J. 75 (1977) 78–86.
[5] M. Ramdin, T.W. de Loos, T.J.H. Vlugt, State-of-the-art of CO2 capture with ionic liq-
uids, Ind. Eng. Chem. Res. 51 (2012) 8149–8177.
[6] D.M. D'Alessandro, B. Smit, J.R. Long Angew, Carbon dioxide capture: prospects for
new materials, Angew Chem. Int. Ed. 49 (2010) 6058–6082.
[7] F. Karadas, M. Atilhan, S. Aparicio, Review on the use of ionic liquids (ILs) as alterna-
tive fluids for CO2 capture and natural gas sweetening, Energy Fuel 24 (2010)
5817–5828.
[8] S. Kumar, J.H. Cho, I. Moon, Ionic liquid-amine blends and CO2 BOLs: prospective sol-
vents for natural gas sweetening and CO2 capture technology—a review, Int. J.
Greenhouse Gas Control 20 (2014) 87–116.
[9] L.A. Blanchard, J.F. Brennecke, High-pressure phase behaviour of ionic liquid/CO2
systems, J. Phys. Chem. 105 (2001) 2437–2444.
[10] Z. Lei, C. Dai, X. Liu, L. Xiao, B. Chen, Extension of the UNIFAC model for ionic liquids,
Ind. Eng. Chem. Res. 51 (2012) 12135–12144.
[11] M. Wlazło, E.I. Alevizou, E.C. Voutsas, U. Domanska, Prediction of ionic liquids phase
equilibrium with the COSMO-RS model, Fluid Phase Equilib. (2015), http://dx.doi.
org/10.1016/j.fluid.2015.08.032.
[12] C. Cadena, J.L. Anthony, J.K. Shah, T.I. Morrow, J.F. Brennecke, E.J. Maginn, Why is CO2
so soluble in imidazolium-based ionic liquids? J. Am. Chem. Soc. 126 (2004)
5300–5308.
[13] M.J. Muldoon, S.N.V.K. Aki, J.L. Anderson, J.K. Dixon, J.F. Brennecke, Improving carbon
dioxide solubility in ionic liquids, J. Phys. Chem. B 111 (2007) 9001–9009.
[14] A.P. de los Rios, F.J.H. Fernandez, Ionic Liquids in Separation Technology, Elsevier Sci-
ence Ltd, 2014.
[15] N.V. Ignat'ev, U. Welz-Biermann, A. Kucheryna, G. Bissky, H. Willner, New ionic liq-
uids with tris(perfluoroalkyl)trifluorophosphate (FAP) anions, J. Fluor. Chem. 126
(2005) 1150–1159.
[16] M.A.M. Althuluth, Natural Gas Sweetening Using Ionic LiquidsPhD Thesis Eindhoven
University of Technology, The Netherlands, 2014.
[17] M. Althuluth, M.C. Kroon, C.J. Peters, Solubility of methane in the ionic liquid 1-
ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, Ind. Eng.
Chem. Res. 51 (2012) 16709–16712.
[18] M. Althuluth, M.T. Mota-Martinez, M.C. Kroon, C.J. Peters, Solubility of carbon diox-
ide in the ionic liquid 1-ethyl-3-methylimidazolium
tris(pentafluoroethyl)trifluorophosphate, J. Chem. Eng. Data 57 (2012) 3422–3425.
[19] M. Althuluth, M.T. Mota-Martinez, A.S. Berrouk, M.C. Kroon, C.J. Peters, Removal of
small hydrocarbons (ethane, propane, butane) from natural gas streams using the
ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate,
J. Supercrit. Fluids 90 (2014) 65–72.
[20] M. Ramdin, A. Amplianitris, T.W. DeLoos, T.J.H. Vlugt, Solubility of CO2/CH4 gas mix-
tures in ionic liquids, Fluid Phase Equilib. 375 (2014) 134–142.
[21] M. Ramdin, S.P. Balaji, J.M. V-Luna, A. T-Knoop, Q. Chen, D. Dubbeldam, S. Calero,
T.W. deLoos, T.J.H. Vlugt, Computing bubble-points of CO2/CH4 gas mixtures in
ionic liquids from Monte Carlo simulations, Fluid Phase Equilib. 418 (2016)
100–107.
[22] R. Quinn, J.B. Appleby, G.P. Pez, Hydrogen sulfide separation from gas streams using
salt hydrate chemical absorbents and immobilized liquid membranes, Sep. Sci.
Technol. 37 (2002) 627–638.
[23] R. Seddon Kenneth, A. Stark, M.-J. Torres, Influence of chloride, water, and organic
solvents on the physical properties of ionic liquids, Pure and Applied Chemistry
2000, p. 2275.
[24] M. Uerdingen, C. Treber, M. Balser, G. Schmitt, C. Werner, Corrosion behaviour of
ionic liquids, Green Chem. 7 (2005) 321–325.
[25] D.-Y. Peng, D.B. Robinson, A new two-constant equation of state, Ind. Eng. Chem.
Fundam. 15 (1976) 59–64.
[26] R. Schefflan, Teach Yourself the Basics of Aspen Plus, Wiley, 2016.
[27] S.I. Sandler, Using Aspen Plus in Thermodynamics Instruction: A Step by Step Guide,
American Institute of Chemical Engineers and John Wiley& Sons Inc., USA, 2015.
[28] J.M. Smith, H. Van Ness, M.M. Abbott, Introduction to Chemical Engineering Ther-
modynamics, seventh ed. McGraw-Hill, 2005.
[29] M. Althuluth, A. Berrouk, M.C. Kroon, C.J. Peters, Modeling solubilities of gases in the
ionic liquid 1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate
using the Peng–Robinson equation of state, Ind. Eng. Chem. Res. 53 (2014)
11818–11821.
[30] M. Rahmati-Rostami, C. Ghotbi, M. Hosseini-Jenab, A.N. Ahmadi, A.H. Jalili, Solubility
of H2S in ionic liquids [hmim][PF6], [hmim][BF4], and [hmim][Tf2N], J. Chem.
Thermodyn. 41 (2009) 1052–1055.
[31] S. Raeissi, C.J. Peters, A potential ionic liquid for CO2-separating gas membranes: se-
lection and gas solubility studies, Green Chem. 11 (2009) 185–192.