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Modelling solubility of CO 2 and hydrocarbon gas mixture in ionic liquid
([emim][FAP]) using ASPEN Plus

Bishwadeep Bagchi, SushmitaSati, Vidyasagar Shilapuram

PII: S0167-7322(16)32222-X
DOI: doi: 10.1016/j.molliq.2016.09.071
Reference: MOLLIQ 6348

To appear in: Journal of Molecular Liquids

Received date: 12 August 2016


Revised date: 7 September 2016
Accepted date: 22 September 2016

Please cite this article as: Bishwadeep Bagchi, SushmitaSati, Vidyasagar Shilapuram,
Modelling solubility of CO2 and hydrocarbon gas mixture in ionic liquid ([emim][FAP])
using ASPEN Plus, Journal of Molecular Liquids (2016), doi: 10.1016/j.molliq.2016.09.071

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Modelling solubility of CO2 and Hydrocarbon gas mixture in Ionic Liquid


([emim][FAP]) using ASPEN Plus

Bishwadeep Bagchi, SushmitaSati, Vidyasagar Shilapuram*

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Chemical Engineering Department, National Institute of TechnologyWarangal.

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Telangana State-506 004, India

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ABSTRACT - In the present study bubble point pressure, solubility and selectivity of CO2

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and Hydrocarbon mixture with [emim][FAP] as an ionic liquid has been studied by ASPEN

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Plus simulations. Ternary systems considered were CO2, [emim][FAP] and one of the

hydrocarbons (HC) viz., methane, ethane, propane, and butane. Peng Robinson equation of
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state with quadratic van der Waals (vdW) mixing rule model was chosen to perform the

thermodynamic calculations in FLASH3 column. Wide range of temperatures, molar ratios


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of CO2/HC, and HC/[emim][FAP] were considered for this study. Results showed that, type
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of hydrocarbon (or carbon chain length) had a dominant effect on the selectivity of CO2 over
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hydrocarbon. Selectivity of CH4 compared with other hydrocarbons is higher by more than
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one order of magnitude. Concentration of hydrocarbon in the feed stream of the ternary

system is the main deciding factor in addition to temperature in determining the solubility,
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bubble point pressure and phase transition from two phase liquid system to single liquid

phase.

Keywords: ASPEN Plus, Ionic liquids, Natural Gas, Carbon dioxide, Hydrocarbons,

Selectivity

* Corresponding Author

Email: vidyasagars@nitw.ac.in Phone: +91 83329 69463

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1. Introduction

Natural gas, which is a major source of energy, must satisfy certain specifications of

allowable concentrations of impurities while transportation. Presence of CO2 above allowable

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limit in the natural gas stream may lead to formation of dry ice during liquefaction process,

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gas hydrate formation during transportation, and reduction in the heating value [1-3].

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Conventionally, the removal of CO2 from the natural gas or flue gas from any industrial

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stream is achieved by sending it through an absorber stripper combination in which a solvent

is utilized to selectively dissolve CO2 [4]. Conventional solvents such as mono ethanol amine

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(MEA), Selexol, etc. are employed for CO2 removal [1-2, 5]. The MEA process suffers from
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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
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vapour pressure, high electroelasticity, non-flammability, high thermal and chemical stability
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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
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CO2 in ionic liquid. It has been observed that ILs with fluorous anions like [Tf2N-], [BF4-] and
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[PF6-] exhibit highest CO2 solubility [12]. A highly fluorinated IL with a large anion would
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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 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 considered where three fluorine atoms of

hexafluorophosphate has been replaced by pentafluoroethyl group. Hence, an IL named 1-

ethyl-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate, represented as

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[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 present in natural gas is required. Althuluth et. al. [16-19] experimentally

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measured the bubble point pressure for a binary system comprising of [emim][FAP] with

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CO2, methane, ethane, propane and butane individually. Estimated ideal selectivities from

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solubility data of CO2, methane, ethane, propane and butane with IL showed that CO2 was

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preferentially absorbed over hydrocarbons. However, above results showed that limited

amount of data is available covering a narrow temperature range between 300 K and 360 K.

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Typical natural gas is composed of methane with 80% mole fraction and above, along
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with other HCs namely ethane, propane, butane and pentane (below 10% mole fraction) and

impurities. Therefore, it is important to study the relative effect of the presence of


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hydrocarbons on CO2 and methane solubility and bubble point pressure. To the best of
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authors knowledge, very few experimental or theoretical works on ternary systems

comprising of IL with CO2 and CH4 are available which have estimated the bubble point
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pressures or solubility of CO2/CH4 mixtures [3,20-21]. However, reported results are

available for a limited temperature and mole fraction range. Also, to the authors knowledge,
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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 pressure 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 approach [20]. The binary

interaction parameters were obtained through regression of the experimental Vapour-Liquid-

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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, effect of temperature and

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molar ratios of CO2 to HC (x1/x2) and HC to IL (x2/x3) on bubble point pressure, solubility

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and selectivity has been studied for a wide range.

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It should be noted that pure IL was considered while performing the simulations since

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the presence of impurities in the IL gives rise to various changes in its physical and chemical

properties which can change its stability and solubility. ILs with highly fluorinated anions

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such as FAP become unstable in the presence of water at high temperatures and can
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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
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and desorption rates [16]. The presence of chlorides drastically increases the viscosity of IL
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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
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practically, care must be taken to ensure the purity of the IL.


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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

where P is the pressure, T is temperature, is the mixture molar volume, 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

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present study the quadratic van der Waals (vdW) mixing rule as presented below were

adopted.

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with

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Here, and are the binary interaction parameters, and are pure component

parameters responsible for molecular interaction and co-volume respectively.


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3. Modelling and Simulation Details


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As mentioned above, the main objective of this work is to determine the bubble point
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pressures for systems of Carbon Dioxide and Hydrocarbon (viz. Methane, Ethane, Propane
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and Butane) in an IL. Also, the vapour phase and liquid phase compositions at the calculated
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bubble point pressure for a given temperature were deduced.

Aspen Pluss model library offers the option of carrying out VLE calculations by
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choosing FLASH2 or FLASH3 block. Flash3 block is employed to perform rigorous three

phase vapour-liquid-liquid equilibrium 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 balance and equilibrium equations depending on the input provided. Within

the range of temperatures chosen and with the selected equation 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 simulations. By
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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 environment to zero, bubble point pressures were computed [27].

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ASPEN Plus (Version 8.4) was employed to perform the thermodynamic modelling of

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the CO2+HC+IL ternary system. Each simulation was carried out by considering a different

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hydrocarbon each time along with Carbon Dioxide and Ionic Liquid. CO2 and Hydrocarbon

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were specified in the component specifications of ASPEN Plus. [emim][FAP] component is

not available in the inbuilt data banks of ASPEN Plus. Molecular structure and functional

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groups of [emim][FAP] were provided as an input to specify this compound. Peng Robinson
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equation of state (EOS) with quadratic mixing rule (VLMXQUAD) was chosen.

For each binary system of CO2 + IL and HC+IL, the binary interaction parameters
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required for PR EOS modelling were obtained by regressing the binary vapour liquid
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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), with
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both single temperature dependant term and also with two temperature dependant terms. It
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was observed that using two temperature dependant terms gave a lower root mean square
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error (RMSE) value. A second binary interaction parameter lij with a single temperature

independent term was also used to correct the volume of mixing [16]. For the HC-IL system,

the binary interaction parameter kij with single temperature dependant term and lij with a

single temperature independent term was fitted to the VLE data. RMSE value of less than 5%

was obtained when both kij and lij were used. Binary interaction parameters obtained are

presented in Table 1. Standard deviation of uncertainties of temperature, pressure and mole

fraction of inlet feed components of 0.01K, 0.003MPa, and 0.005 respectively are considered

for regression of binary interaction parameters. Critical properties of the hydrocarbons were

taken from literature [28] while the critical properties for the IL were taken from the values

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estimated by Althuluth et.al using the modified group contribution method of Lydersen-

Joback-Reid [30].

The flowsheet developed for modelling the ternary system is shown in Fig. 1.

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FLASH3 column with two inlet streams and three outlet streams were chosen. One of the

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inlet streams carried the feed gas mixture of CO2 and HC while the other stream carried the

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solvent (IL). The temperatures of each stream and of the FLASH3 column were set to the

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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 stream of FLASH3 does not carry any

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material and all the feed entering into the FLASH3 i.e. CO2+HC+IL flow exists in the liquid
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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.
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Reason for choosing FLASH3 column is to explore the possibility of extending our
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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
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one liquid phase (two immiscible liquid phases) may form, Since FLASH3 has one outlet
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vapour stream and two outlet liquid streams, it can identify all the phases but not FLASH2
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column depending on the prevailing conditions in that unit.

4. Design of Experiment

In real time situation, ionic liquid is chosen to maximize the CO2 solubility and minimise 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 mole 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

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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

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individual CO2, HC and IL in the feed stream. These mole fractions obtained were multiplied

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by 100 so that to choose 100 kmol/time as the total molar flow rate as the basis which were

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then multiplied by 100(basis) to make the total input mole flow of ternary system

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(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 comprising of 13 different values resulted

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in 117 cases. The design matrix of input molar flow rates considering the above broad range
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of mole ratios chosen is shown in the Table S1 of the Supporting Information. Corresponding

design matrix is also depicted in Fig.2. Temperature range was chosen to be from 183.15 K
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to 493.15 K. A lower range of 183.15 K was chosen as neither any hydrocarbon nor carbon
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dioxide remains in vapour phase at temperatures lower than it. Upper limit temperature of

493.15 K was chosen since IL begins to decompose from this temperature onwards [16].
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The values of molar flow rates of CO2, HC and IL along with the flash temperature
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was provided as input to the FLASH3 column of ASPEN in the simulation environment. The
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bubble point pressures along with the liquid and vapour phase compositions, and selectivity

were determined by the simulation.

Real selectivity is obtained using the given relation

where and respectively denote the gas phase and liquid phase composition 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.

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5. Results and Discussions

5.1 Model validation

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The above adopted methodology was verified by implementing it to the experimental

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conditions of Ramdin et.al [20] and validating their results. In their study, bubble point

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pressure of CO2, CH4 and IL ternary system was determined for three different ionic liquids

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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 and365 K were

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considered to determine the bubble point pressures.
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Figure 3 shows the validation of the experimental results with the present 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.
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In other words, pressure and bubble point pressure is used interchangeably. It was observed

that for the system of CO2 + CH4 + [emim][dep], simulated values are in close agreement
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with the experimental values, with a deviation within 5%. Whereas for the system of CO2 +
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CH4 + [bmim][Tf2N] and for CO2 + CH4 + [thtdp][dca], the error % between experimental
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and predicted were within 15% and 10% respectively. 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 the case of [thtdp][dca]

resulted in large deviation. Otherwise, the deviation between experimental and predicted

might have been well within 5%. Thus, it may be concluded that the applied ASPEN Plus

methodology 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 (either methane or ethane or

propane or butane) with an accuracy of 15%.

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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

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the lowest bubble point pressure as compared to their ionic liquids as shown in Fig. 4. This

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establishes the superiority of [emim][FAP] over other ILs in terms of ease of solubility.

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After validating the present simulation methodology with the experimental conditions

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as discussed above, same methodology was extended to the ternary system of CO2 + HC +

[emim][FAP] for a wide range of compositions and temperatures. Each time HC considered

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was either one of methane/ethane/propane/butane. Hence, individually simulations were run
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by considering one hydrocarbon at a time for the ternary system and the respective solubility,

bubble point pressure and selectivity was calculated for a set of x1/x2 and x2/x3 at a particular
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value of temperature. At this condition of x1/x2 and x2/x3 simulations were repeated for
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different temperatures so as to cover broad temperature range from the highest melting point

of a pure species of ternary system to the degradation temperature of ionic liquid.


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5.2 CO2 + CH4+ [emim][FAP] system:


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'xi' stands for input mole fraction of component 'i' into the FLASH3 column. Subscript 1, 2,

and 3 stands for CO2, HC, and IL respectively. Individually 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 -183.15K to 473.15K with a

temperature increment of 10K.

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

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hydrocarbon, under those particular molar ratios, single liquid phase was not observed 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

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different liquid phases. With further increase in temperature, the ternary system appears in a

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single liquid phase from two different liquid phases. Table S2 shows that the temperature

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range from lowest possible to highest possible temperature in which single liquid phase

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existed was depending on the x1/x2, x2/x3, and type of hydrocarbon (or equivalently carbon

chain length). As mentioned earlier, detailed investigation of phase identification is in

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progress for the ternary systems considered in this study, hence, those results are not
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presented here. Since the objective of the present study is to find the solubility, bubble point

pressure and selectivity, the molar ratios (x1/x2 and x2/x3) and temperature range in which
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only single liquid phase exists is considered for this study. Out of the 117 cases of Table S1,
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the operable mole ratios (x1/x2 and x2/x3) and temperature ranges that were common to all the

hydrocarbons in which only one liquid phase exists is provided in Table S2 of Supporting
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Information. Hence, in the present study, results corresponding to these conditions (x1/x2,
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x2/x3, and temperature range) are presented from Fig. 5 onwards. Therefore, caution is to be
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noticed that all the results presented from Fig.5 is when the ternary system is in single liquid

phase. The respective molar flow rates corresponding to different set of x 1/x2 and x2/x3 can be

deduced from the Table S1.

Figure 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 pressure 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

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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

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system. Consecutively, the effect of mole fraction of carbon dioxide on the bubble point

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pressure is less. In other words, for a system of carbon dioxide and methane, carbon dioxide

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gets completely dissolved into the IL at a pressure much lower than that at which CH4 gets

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dissolved.

At lower values of x2/x3, it can be observed that pressure increases monotonically

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with increase in temperature. This monotonic behaviour (Type-1) is observed till a particular
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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
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value at lower temperatures followed by decrease in bubble point pressure for further
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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
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completely solubilise it increases, especially at lower temperatures. This can be explained as


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to solubilise an amount of CH4 in an almost equal quantity of IL requires a very high


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pressure. This behaviour, noticed 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 temperature range because below 440.15 K two

liquid phases were observed as discussed in discussion w.r.to Table S2. The bubble point

pressure decreased with increase in temperature beyond this temperature. Reason is, once the

single liquid phase starts, with increase in temperature the solubility of both HC and CO2

might be increasing causing to decrease in bubble point pressure. This behaviour of decrease

in bubble point pressure with temperature beyond particular value of x 2/x3 (Type-2) is not

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noticed for the methane at all other x1/x2s but only upto x1/x2 of 0.5 (Refer Figure S1 of the

supporting information).

Selectivity of the CO2/CH4 system has been calculated by using the Eq. (4). These

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were calculated at different molar ratios (x1/x2 and x2/x3) for a wide temperature range. Since

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the objective is to maximize the solubility of CO2 and minimize the solubility of HC, this

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study will give an idea of the temperature and molar flows that can maximize the selectivity.

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Higher the selectivity better is the CO2 removal over hydrocarbon with an IL.

Selectivity is plotted as a function of temperature for x 2/x3=0.04 at various values of

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x1/x2 for CO2+CH4+[emim][FAP] ternary system. As temperature is increased, it can be seen
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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
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in vapour phase decreases while the mole fraction of CO2 in vapour phase increases because
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of temperature affect on relative solubility of CH4 and CO2. This contributes to a decrease in

selectivity of CO2 over CH4. It can also be observed that effect of x1/x2 is negligible
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compared to temperature. Results show that for a particular x2/x3, the selectivity is mostly
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dependent on the temperature of the system as compared to x1/x2. Selectivity values changed
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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 conducted 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 composition, at a

particular temperature (Refer Figure S2 of the supporting information). As the ratio of x2/x3 is

gradually increased, selectivity decreases significantly. Even at higher values of x2/x3 for

temperatures above, say 280K, selectivity values do not change much by changing x1/x2.

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5.3 CO2 + C2H6+ [emim][FAP] system:

Fig. 7 shows the bubble point isopleths of the ternary system as a function of temperature at

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x1/x2=0.33 for different x2/x3 for CO2+C2H6+[emim][FAP] ternary system. A trend similar to

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the CO2+CH4+[emim][FAP] system is observed for the bubble point pressure verses

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temperature behaviour (Type-1 & 2). For a constant ratio of CO2/C2H6, pressure increases

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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

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0.3 when HC as CH4) at which this transition takes place may be different for different
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hydrocarbons.

Fig. 8 shows the selectivity of the ternary system as a function of temperature at


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x2/x3=0.04 for different x1/x2 for CO2+C2H6+[emim][FAP] ternary system. This shows that at
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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


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increase in x1/x2 at a given temperature and its effect is dominant at lower temperature. As
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the temperature increases, selectivity at different x1/x2s is almost approaching each other.
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Upon comparison of selectivity as a function of temperature at different x 2/x3, similar profiles

were observed (Refer Figure S4 of the supporting information). Maximum selectivity of

about 5.5 with a minimum of about 1.5 has been noticed for the entire temperature change

studied.

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

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behaviour. 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.

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Fig. 10 shows the selectivity of the ternary system as a function of temperature at

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x2/x3=0.5 for different x1/x2 for CO2+C3H8+[emim][FAP] ternary system. At lower

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temperatures, selectivity increases with increase in temperature and reaches a peak value and

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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 temperatures; it remains in liquid state which

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results in this opposite trend. At very low temperatures, selectivity is less than 1, implying
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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
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to the solubility. Maximum selectivity of about 1.3 with a minimum of about 0.7 has been
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noticed for the entire temperature change studied. Temperatures between 250K to 300 K. this

maximum selectivity was observed depending on the x2/x3 ratio.


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5.5 CO2 + C4H10+ [emim][FAP] system:


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Fig. 11 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+C4H10+[emim][FAP] ternary system. Two types of

behaviour similar to the other hydrocarbons is noticed in this case where pressure increases

with temperature for a constant x2/x3. As similar to C3H8 + CO2 system, for larger values of

x2/x3, starting from 0.4, pressure starts decreasing with increase in temperature.

Fig. 12 shows the selectivity of the ternary system as a function of temperature at

x2/x3=0.04 for different x1/x2s for CO2+C4H10+[emim][FAP] ternary system. Selectivity

shows an opposite behaviour compared to other hydrocarbons. Here, selectivity increases

with increase in temperature. Also, selectivity of CO2 over C4H10 is less than one, implying

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that C4H10 is preferentially more soluble in the IL compared to Carbon dioxide. As the

temperature increases, selectivity tends towards 1. Also, selectivity is improved by increasing

x2/x3 ratio (Refer supporting information). As more amount of C4H10 is sent as compared to

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carbon dioxide, the difference between the mole fractions of C4H10 and IL fades, selectivity

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gets enhanced and crosses 1 at combinations of some higher values of C4H10/IL and high

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temperatures. Crossing a value of 1 for selectivity implies that carbon dioxide is now more

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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.
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5.6 Comparison of CO2+HC+IL system
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As mentioned earlier, natural gas consists of mixture of hydrocarbons from methane to


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pentane) and impurities such as CO2, H2S, and nitrogen compounds. Hence, individually

solubility, bubble point pressure and selectivity studies have been studied for a ternary system
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considering two gases, one of which is CO2 and the other being HC in [emim][FAP].
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Comparison of these ternary systems would give an idea of the scenario when all the gases
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are present together in the natural gas for the removal of CO2.

Figure 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). Fig. 5 to 10 spans for all hydrocarbons from methane to butane as one of the

component in the ternary system. For all hydrocarbons, at lower values of x2/x3, pressure

increases monotonically with increase in temperature. This monotonic behaviour is observed

till a particular value of x2/x3. That particular value of x2/x3 may be different for different

hydrocarbons and for different x1/x2. Beyond this particular x2/x3, only for CH4 at x1/x2=0.33,

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different trend of variation of bubble point pressure with temperature is noticed. The reason

for this has been explained for fig. 5.

It can be observed from fig. 13 that decrease in bubble point pressure is noticed after a

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particular value of x2/x3. Beyond this x2/x3, it can be noticed that bubble point pressures are

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not applicable for entire region when all HCs are considered together. For example, for

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x2/x3=0.5 bubble point pressure is obtained for narrower temperature range as the HC is

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moving from methane to butane (also refer Table S2). Recall that all the results presented in

this fig. belongs to a single liquid phase, since at lower temperatures in which data is not

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reported corresponds to two liquid phase region. Results imply that the type of hydrocarbon
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plays a significant role.The reason for decrease in bubble point pressure with temperature at

higher x2/x3 is as follows. At a given x2/x3, for fixed x1/x2 (fixed composition) and type of
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hydrocarbon, just below this temperature there were two liquid phases existing. Hence, high
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pressures are required for higher x2/x3 (since x2 is HC) to let the HC solubilise in the IL. Once

the single liquid phase starts, with increase in temperature the solubility of both HC and CO2
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might be increasing causing to decrease in bubble point pressure. All these observations are
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attributed to the hydrocarbon chain length and different levels of interactions among the
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ternary system at prevailing conditions i.e., molar compositions 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/x3is noticed only up to x1/x2 of 0.75. Beyond x1/x2 of 0.75 for all hydrocarbons which

there were monotonic increase (systematic trends) in bubble point pressure with increase in

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temperature i.e., only type-1 behaviour (Refer FigureS1, S3, S5 and S7 of supporting

information).

Figure 14 shows the comparison of selectivity of the CO2+HC+[emim][FAP] ternary

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system as a function of temperature at x2/x3=0.2 for different x1/x2. Selectivity of the CO2/HC

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system has been calculated by using the Eq. (4). Since objective is to maximize the solubility

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of CO2 and minimize the solubility of HC, this study will give an idea of temperature and

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molar flows that can be chosen to maximize the selectivity. Higher the selectivity better is the

CO2 removal over hydrocarbon with an IL.

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Upon comparison of fig. 14 for all HCs, at a given x1/x2 and x2/x3 (molar composition
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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
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HC, increase followed by decrease with ethane or propane as HC and monotonic increase
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with butane as HC. In addition, at a particular molar composition and temperature, there is

drastic difference in selectivity of CO2 with methane compared to CO2 with ethane, propane
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and butane. Quite high values of selectivity are noticed with methane compared to other HC.
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These significant differences in trends and values could be attributed to the carbon chain
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length or type of hydrocarbon 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 more than 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 presented in

supporting information (Fig. S1 to S8), the best possible molar ratios and operating

temperatures for better separation can be obtained. In addition, for a particular ternary system

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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 simultaneously to dissolve

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in the IL. However, the interactions among the components of the ternary system at different

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conditions of molar composition, and system temperature play an important role. Thus the

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ideal selectivity calculated from individual binary system of CO2+IL and HC+IL may be

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different from real case scenario of ternary CO2+HC+IL system. Fig. 13 and 14 shows the

comparisons of hydrocarbons from individual subplots of each hydrocarbon as one of the two

solutes.
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Figure 15 shows the effect of hydrocarbons on bubble point pressure at constant

composition (x1/x2 and x2/x3) and constant temperature. It can be observed from the figure
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that bubble point pressure for CO2+CH4+IL system is substantially higher than the bubble
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point pressures of other CO2+HC+IL system. This difference consistently declines as the

temperature is raised with increase in selectivity (Refer Table S9 to S17). For low x2/x3, at
P

higher temperatures (more than 400 K) the bubble point pressures of all the CO2+HC+IL
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become almost equal. Higher hydrocarbons are more soluble in the IL as compared to lower
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hydrocarbons. As explained previously and from these results, bubble point pressure is

largely dependent on the concentration of HC.

Figure 16 shows that effect of hydrocarbons on selectivity at constant composition

(x1/x2 and x2/x3) and constant temperature. It can be observed from the figure that selectivity

for CO2+CH4+IL system is substantially higher than the selectivity of other CO2+HC+IL

system (Refer Table S18 to S20 of Supporting Information). This difference consistently

declines as the temperature is raised with decrease in selectivity. An order of difference in

selectivity between CH4 compared to other HC over CO2 is noticed at lower temperature but

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at higher temperatures, though the selectivity is higher for CH4 compared to other HC over

CO2 but the difference gets reduced.

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5.7 Henrys Constant and Ideal Selectivity

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Henry's constant can be defined for a binary system as

R
SC
where is the fugacity of the solute '1' in solvent '2' and is the mole fraction of solute '1'

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in solvent. can be estimated by employing a suitable equation of state with the assumption

that only pure solute is present in the vapour phase and applying the equilibrium condition of
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= .

Henry's constant provides an estimate about the solubility of a gas component in a


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liquid. Lower the value of Henry's constant, higher is its solubility. For the present analysis,
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Henry's constant was modelled by using the modified form of KrichevskyKasarnovsky


P

equation [18, 30]


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where is the fugacity of the solute in vapour phase, is the mole fraction of solute

dissolved in solvent, P is the bubble point pressure, H21 is the Henry's constant of gas in the

solvent at the liquid saturation pressure, 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

was considered as zero and can be taken as the fugacity of pure solute.

When the solubility (P-x) data at a constant temperature is plotted as versus P,

the slope of the line yields the value of , while the intercept is . During simulations,

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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.

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The values of the Henrys constant obtained for this system obtained by simulations

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are compared against the experimental values provided by Althuluth et. al [17-19] in Table

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2. It may be observed that deviations of the simulated values of Henrys constant from the

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reported values in literature are negligible.

Ideal selectivity can be calculated from the obtained values of Henry's Constants.

Ideal Selectivity is defined as


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MA

which is the ratio of Henry's constant of hydrocarbon over Henry's constant of CO 2. A


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comparison of simulated values of ideal selectivity of CO2 over hydrocarbons against


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reported values in literature at various temperatures are provided in Table 3.


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Fig 17 shows the comparison of variation in ideal selectivity of CO2 over


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hydrocarbons as a function of temperature. The trends observed in all these plots are similar

to the trends observed for variation in Real Selectivity with temperature which is shown in
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Fig 14. The range of values taken by both real selectivity and ideal selectivity for a particular

hydrocarbon are almost identical. Variations in their actual values at a particular temperature

occur since real selectivity is dependent on the composition of the system and takes into

account the interaction effects between the solutes.

6. Conclusions

Peng Robinson equation of state with quadratic van der Waals (vdW) mixing rule model

was chosen with FLASH3 block to estimate the bubble point pressure, solubility and

selectivity of various ternary systems with methane, ethane, propane, and butane as one

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of the component with CO2 in an ionic liquid [emim][FAP] using ASPEN Plus

simulations with an accuracy of less than 15% in measurement of bubble point pressure

Adopted methodology has been verified within reasonable accuracy of 15% with the

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experimental data of the reported literature pertaining to solubility of the CO2 and CH4

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gas mixture in three ILs ([bmim][Tf2N], [emim][dep], and [thtdp][dca]) which were

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different from the IL chosen for the present study

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At a given CO2 to HC ratio from 0.01 to 0.75, two types of behaviour in bubble point

pressure that is increase with increase in temperature up to particular value of CH4 to IL

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ratio followed by decrease in bubble point pressure with increase in temperature at
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higher CH4 to IL ratio is noticed for all four ternary systems considered. Whereas beyond

0.75 of CO2 to HC ratio only increase in bubble point pressure with temperature is
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observed for all CH4 to IL ratio


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Type of hydrocarbon (or carbon chain length) had a dominant effect on the selectivity of

CO2 over hydrocarbon. Different hydrocarbons showed different behaviour of selectivity


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with composition and temperature. Temperature has a significant effect compared to


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molar ratios (or molar composition) of feed on selectivity


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Selectivity of CH4 as compared to other hydrocarbons is higher in more than one order of

magnitude with [emim][FAP]

Concentration of hydrocarbon in the ternary system is the major factor deciding the

phase transition from two phase liquid system to single liquid phase, solubility and

bubble point pressure, temperature being the second major factor for the same.

Nomenclature

a Constant

ai Pure component 'i' parameter

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b Constant

bi Pure component 'i' parameter

HC Hydrocarbon (methane/ethane/propane/butane)

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IL Ionic Liquid

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kii,kij,kji,kjj Binary interaction parameters

R
lii, ljj Binary interaction parameters

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P Pressure

R Universal Gas constant

RMSE Root mean square error


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S Selectivity

T Temperature in K
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VLE Vapour-Liquid-Equilibrium
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Vm Molar volume

xi Mole fraction of a component 'i' in liquid stream


P

yi Mole fraction of a component 'i' in vapour stream


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Subscript
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i Component i (i=1 for CO2, i=2 for CH4/C2H6/C3H8/C4H10, i=3 for IL)

Superscript

R Real

References

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Houston, 2005.

[2] K. Simons, K. Nijmeijer, M. Wessling, Gasliquid membrane contactors for CO2

removal, J. Membr. Sci. 340 (2009) 214-220.

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Greenhouse Gas Control, 20 (2014) 87116.


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is CO2 so Soluble in Imidazolium-Based Ionic Liquids?, J. Am. Chem. Soc. 126 (2004)

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Technology, Elsevier Science Ltd, 2014

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[15] N. V. Ignatev, U. Welz-Biermann, A. Kucheryna, G. Bissky, H. Willner, New ionic

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Eindhoven University of Technology, The Netherlands, 2014.
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[17] M. Althuluth, M.C. Kroon, C.J. Peters, Solubility of Methane in the Ionic Liquid 1-

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D

Res., 51 (2012) 16709-16712.


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[18] M. Althuluth, M.T. Mota-Martinez, M.C. Kroon, C.J. Peters, Solubility of Carbon

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Tris(pentafluoroethyl)trifluorophosphate, J. Chem. Eng. Data 57 (2012) 3422-3425.


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[19] M. Althuluth, M.T. Mota-Martinez, A. S. Berrouk, M.C. Kroon, C.J. Peters, Removal
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of Small Hydrocarbons (Ethane, Propane, Butane) from Natural Gas Streams using the

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(2000) 2275.

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D.-Y. Peng, D.B. Robinson, A New Two-Constant Equation of State, Ind. Eng.
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Chem.Fundam., 15 (1976) 59-64.

[26] Ralph Schefflan, Teach Yourself the Basics of Aspen Plus, Wiley, 2016
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[27] Stanley I. Sandler, Using Aspen Plus in Thermodynamics Instruction: A Step by step
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guide; American Institute of Chemical Engineers and John Wiley& Sons Inc. USA,

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[28] J. M. Smith, H. Van Ness, M. M. Abbott, Introduction to Chemical Engineering


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Thermodynamics, Seventh ed., McGraw-Hill, 2005.


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[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 PengRobinson 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,

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List of Figures

Sr. No Caption
1 Aspen Plus flowchart used for the modelling and simulation of CO2 and Hydrocarbon
mixture in [emim][FAP]

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2 Experimental design of the Ternary system CO2+HC+ [emim][FAP] considered for

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simulations

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3 Validation of experimental results of Ramdin et al. [19] by present Aspen Plus simulation

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methodology for (a) CO2 +CH4+[bmim][Tf2N], (b) CO2 +CH4+[emim][dep], (c) CO2
+CH4+[thtdp][dca]
4 Comparison of bubble point pressure of CO2+CH4 gas mixture with [emim][FAP] with

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that of Ramdin et al. [19] (a) bmim][Tf2N], (b) emim][dep], (c) [thtdp][dca]
5 Bubble point isopleths of the ternary system as a function of temperature at x 1/x2=0.33
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for different x2/x3 for CO2+CH4+[emim][FAP] ternary system
6 Selectivity of CO2+CH4+[emim][FAP] ternary system as a function of temperature at
x2/x3=0.04 for different x1/x2
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7 Bubble point isopleths of the ternary system as a function of temperature at x 1/x2=0.33


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for different x2/x3 for CO2+C2H6+[emim][FAP] ternary system


8 Selectivity of CO2+C2H6+[emim][FAP] ternary system as a function of temperature at
P

x2/x3=0.1 for different x1/x2


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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
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10 Selectivity of CO2+C3H8+[emim][FAP] ternary system as a function of temperature at


x2/x3=0.5 for different x1/x2
11 Bubble point isopleths of the ternary system as a function of temperature at x 1/x2=0.33
for different x2/x3 for CO2+C4H10+[emim][FAP] ternary system
12 Selectivity of CO2+C4H10+[emim][FAP] ternary system as a function of temperature at
x2/x3=0.03 for different x1/x2
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]
14 Comparison of selectivity of the ternary system as a function of temperature at x 2/x3=0.2
for different x1/x2 for (a) CO2+CH4+[emim][FAP], (b) CO2+C2H6+[emim][FAP],(c)

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CO2+C3H8+[emim][FAP], (d) CO2+C4H10+[emim][FAP]


15 Effect of hydrocarbons on bubble point pressure at constant composition at x 1/x2=1 for
(a) T=193.15K, (b) T=493.15 K
16 Effect of hydrocarbons on the real selectivity at constant composition at x1/x2=10 for

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(a) T=183.15K, (b) T=493.15 K

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17 Comparison of ideal selectivity of CO2 over hydrocarbons as a function of temperature

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D
P TE
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Fig. 1

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R
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NU
MA
D
PTE
CE
AC

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Fig. 2

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R
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D
PTE
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Fig. 3 (a)
14

12

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+15%

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10

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-15%
Pressure Predicted (MPa)

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6

4
NU
MA
2
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Number of data points=63


0
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0 2 4 6 8 10 12 14
Pressure Experimental (MPa)
P
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Fig. 3 (b)

+5%
7

T
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-5%
6

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Predicted Bubble point Pressure (MPa)

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4

NU
MA
2

1
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Number of data point=63


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0
0 1 2 3 4 5 6 7 8
Experimental Bubble point Pressure (MPa)
P
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AC

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Fig. 3 (c)
6

+10%

T
5
-10%

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Predicted Bubble Point Pressure (MPa)

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4

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3

2 NU
MA

1
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Number of data points= 63


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0
0 1 2 3 4 5 6
Experimental Bubble Point Pressure (MPa)
P
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Fig. 4(a)
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25-75 mixture

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12

R IP
10

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8
Pressure (MPa)

6
NU x2 /x3
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0.043
4 0.129
0.201
D

2
TE

0
P

300 310 320 330 340 350 360 370


Temperature (K)
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AC

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Fig. 4 (b)

6
50-50 mixture

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5

R
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4
Pressure (MPa)

3
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MA
2
D

x2 /x3
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1 0.02

0.033
P

0.049
0
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300 310 320 330 340 350 360 370


Temperature (K)
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Fig. 4 (c)
12
75-25 mixture

T
x2 /x3

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10 0.086

0.121

R
0.174

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8
0.258
Pressure (MPa)

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6 MA
4
D

2
TE

0
P

300 310 320 330 340 350 360 370


Temperature (K)
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Fig. 5

120
x1 /x2 = 0.33
x2 /x3

T
0.01

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100 0.02
0.03

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0.04

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80 0.05
0.1
0.2

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60 0.3
Pressure (MPa)

0.4
0.5
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40 0.6
D

20
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0
P

180 230 280 330 380 430 480


Temperature (K)
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Fig. 6
180
x2 /x3 = 0.04

T
160

IP
140

R
x1 /x2

SC
120
Selectivity

0.1

100 0.33

NU
0.5
80 0.75
MA
1
60
3

5
40
7
D

10
20
TE

0
P

180 230 280 330 380 430 480


Temperature (K)
CE
AC

39
ACCEPTED MANUSCRIPT

Fig. 7

T
IP
R
SC
NU
MA
D
PTE
CE
AC

40
ACCEPTED MANUSCRIPT

Fig. 8
6
x2 /x3 = 0.1 x1 /x2

T
0.1

IP
5
0.33

0.5

R
0.75

SC
4
1
Selectivity

NU
5
3
7
MA
2
D

1
TE

0
P

180 230 280 330 380 430 480


Temperature (K)
CE
AC

41
ACCEPTED MANUSCRIPT

Fig. 9

40
x2 /x3 x1 /x2 = 0.33

T
0.01
35

IP
0.02

R
30 0.03
Pressure (MPa)

SC
0.04
25
0.05

0.1

NU
20
0.2

0.3
MA
15
0.4

10 0.5
D

0.6

5
TE

0
P

180 230 280 330 380 430 480


Temperature (K)
CE
AC

42
ACCEPTED MANUSCRIPT

Fig. 10
1.4

x2 /x3 =0.5

T
1.2

R IP
1

SC
Selectivity

0.8
x1 /x2

NU
0.1
0.6 0.33
MA
0.5
0.75
0.4
1
3
D

0.2 5
TE

7
10
0
P

180 230 280 330 380 430 480


Temperature (K)
CE
AC

43
ACCEPTED MANUSCRIPT

Fig. 11

T
IP
R
SC
NU
MA
D
PTE
CE
AC

44
ACCEPTED MANUSCRIPT

Fig. 12

1
x1 /x2 x2 /x3 = 0.03

T
0.9
0.1

IP
0.8 0.33

R
0.5
0.7
0.75

SC
0.6 1
Selectivity

3
0.5

NU
5
0.4 7
MA
0.3 10

0.2
D

0.1
TE

0
180 230 280 330 380 430 480
Temperature (K)
P
CE
AC

45
ACCEPTED MANUSCRIPT

Fig. 13 (a)

T
100
x2 /x3 x1 /x2 = 0.1

IP
0.01
90 0.02
0.03

R
80 0.04
0.05

SC
0.1
70
0.2
0.3
Pressure (MPa)

NU
60 0.4
0.5
0.6
50
0.7
MA
40

30
D

20
TE

10
P

0
CE

180 230 280 330 380 430 480


Temperature (K)
AC

46
ACCEPTED MANUSCRIPT

Fig. 13 (b)

T
45
x2 /x3 x1 /x2 = 0.1

IP
40 0.01
0.02

R
0.03
35

SC
0.04
Pressure (MPa)

0.05
30
0.1

NU
0.2
25 0.3
0.4
MA
20 0.5
0.6
15 0.7
D

10
TE

5
P

0
CE

180 230 280 330 380 430 480


Temperature (K)
AC

47
ACCEPTED MANUSCRIPT

Fig. 13 (c)

T
40
x2 /x3 x1 /x2 = 0.1

IP
0.01
35

R
0.02

SC
30 0.03
Pressure (MPa)

0.04
25

NU
0.05

0.1
20
0.2
MA
0.3
15
0.4
D

10 0.5
TE

0.6

5
P

0
CE

180 230 280 330 380 430 480


Temperature (K)
AC

48
ACCEPTED MANUSCRIPT

Fig. 13 (d)

T
14
x2 /x3 x1 /x2 = 0.1

IP
0.01
12

R
0.02

SC
0.03
10
0.04

NU
Pressure (MPa)

8 0.05

0.1
MA
6 0.2

0.3
4 0.4
D

0.5
TE

2
P

0
180 230 280 330 380 430 480
CE

Temperature (K)
AC

49
ACCEPTED MANUSCRIPT

Fig. 14 (a)
180
x2 /x3 = 0.2

T
160 x1 /x2

IP
0.1
140 0.33

R
0.5

SC
120 0.75

1
Selectivity

100
3

80
NU
MA
60

40
D

20
TE

0
P

180 230 280 330 380 430 480


Temperature (K)
CE
AC

50
ACCEPTED MANUSCRIPT

Fig. 14 (b)
6
x2 /x3 = 0.2
x1 /x2
0.1

T
5
0.33

IP
0.5
0.75

R
4 1
3

SC
Selectivity

2
NU
MA
1
D
TE

0
180 230 280 330 380 430 480
Temperature (K)
P
CE
AC

51
ACCEPTED MANUSCRIPT

Fig. 14 (c)
1.6
x2 /x3 = 0.2

1.4

T
IP
1.2

R
1
Selectivity

SC
0.8

0.6

NU x1 /x2
MA
0.1
0.4
0.33
0.5
0.2 0.75
D

1
3
TE

0
180 230 280 330 380 430 480
Temperature (K)
P
CE
AC

52
ACCEPTED MANUSCRIPT

Fig. 14 (d)

1.2
x2 /x3 = 0.2

T
IP
x1 /x2

0.8 0.1

R
0.33

SC
0.5
0.6
0.75
Selectivity

NU
1
0.4 3
MA
0.2
D

0
TE

180 230 280 330 380 430 480


Temperature (K)
P
CE
AC

53
ACCEPTED MANUSCRIPT

Fig. 15 (a)

0.7
0.045
x1/x2 = 1

T
0.04
0.035

IP
0.6
0.03
0.025

R
0.02
0.5

SC
0.015
0.01
0.005
0.4 0

NU
0 0.02 0.04 0.06 CH4
Bubble Point Pressure (Mpa)

C2H6
C3H8
0.3
MA
C4H10

0.2
D
TE

0.1
P

0
0 0.01 0.02 0.03 0.04 0.05 0.06
CE

x2/x3
AC

54
ACCEPTED MANUSCRIPT

Fig. 15 (b)

T
25

IP
x1 /x2 =1

R
20

SC
15

NU
Bubble point Pressure(Mpa)

CH4
MA
10 C2H6
C3H8
C4H10

5
D
TE

0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45
P

x2 /x3
CE
AC

55
ACCEPTED MANUSCRIPT

Fig. 16 (a)

180

T
Selectivity vs x2/x3
160

IP
140

R
CH4

SC
Selectivity

120
C2H6

6 C3H8
100

NU
C4H10
5
80
4
MA
3
60
2
40
D

1
TE

0
20
0 0.01 0.02 0.03 0.04 0.05 0.06
P

0
0 0.01 0.02 0.03 0.04 0.05 0.06
x2/x3
CE
AC

56
ACCEPTED MANUSCRIPT

Fig. 16 (b)

2.5

T
Selectivity vs x2 /x3
CH4

IP
C2H6
2

R
C3H8

C4H10

SC
1.5

NU
Selectivity

MA
1
D
TE

0.5
P
CE

0
0 0.01 0.02 x2 /x3 0.03 0.04 0.05 0.06
AC

57
ACCEPTED MANUSCRIPT

Fig. 17
180
CH4 Ideal Selectivity vs Temperature

T
160 C2H6 7
1.6

IP
C3H8
1.4
140 6
C4H10 1.2

R
1
5 0.8

SC
120
0.6
4 0.4
100 0.2

NU
0
3
Ideal Selectivity

170 270 370 470 570


80
2
MA
60
1

40
0
D

170 270 370 470 570


20
TE

0
170 270 370 470 570 670 770
P

Temperature (K)
CE
AC

58
ACCEPTED MANUSCRIPT

List of Tables

Sr. Caption

No

T
1 Binary interaction parameter obtained from ASPEN Plus

IP
2 Comparison of experimental values of Henrys constant of ref. [17-19] with the

R
simulated values for binary system

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

NU
MA
D
P TE
CE
AC

59
ACCEPTED MANUSCRIPT

T
Table 1:Binary interaction parameter obtained from ASPEN Plus

IP
Pair Interaction Parameter Source

CR
CO2-CH4 kij = 0.0919 Aspen Database

US
CO2- C2H6 kij = 0.1322 Aspen Database

N
CO2- C3H8 kij = 0.1241 Aspen Database

MA
CO2- C4H10 kij = 0.1333 Aspen Database

D
CO2-[emim][FAP] Regression of VLE Data of Ref.[18]

P TE
CE
lij = -0.114290764; lji = -0.382557421
AC
CH4-[emim][FAP] Regression of VLE Data of Ref. [17]

C2H6-[emim][FAP] Regression of VLE Data of Ref. [19]

C3H8-[emim][FAP] Regression of VLE Data of Ref. [19]

C4H10-[emim][FAP] Regression of VLE Data of Ref. [19]

60
ACCEPTED MANUSCRIPT

Table 2: Comparison of experimental values of Henrys constant of ref. [17-19] with the simulated values for binary system

Temp (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa) (MPa)

T
(K)

IP
(Ref. [17]) Simulated (Ref. [19]) Simulated (Ref. [19]) Simulated (Ref. [19]) Simulated (Ref. [18]) Simulated
283 - - - - - - - - 2.24 2.28

CR
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

US
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

N
333 41.43 41.40 14.30 14.36 7.21 7.29 3.67 3.66 5.36 5.64

MA
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

D
363 43.66 43.75 18.17 18.24 10.21 10.13 5.78 5.75 7.71 8.24

P TE
CE
AC

61
ACCEPTED MANUSCRIPT

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

T
Temp

IP
(K)
(ref. [19]) Simulated (ref. [19]) Simulated (ref. [19]) Simulated (ref. [19]) Simulated

CR
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

US
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

N
343 6.96 6.61 2.56 2.45 1.34 1.29 0.71 0.67

MA
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

D
P TE
CE
AC

62
ACCEPTED MANUSCRIPT

Highlights

ASPEN Plus simulations with FLASH3 block to study CO2-HC-IL system

T
Bubble Point Isopleths exhibited two distinct behaviors at different compositions

IP
Carbon chain length influenced the selectivity of CO2 over hydrocarbon

R
Selectivity of CO2 over CH4 compared to other hydrocarbons is higher by at least one

SC
order of magnitude

NU
MA
D
P TE
CE
AC

63