Fluid Phase Equilibria 365 (2014) 80–87

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Fluid Phase Equilibria

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Solubility of CO2 in aqueous mixtures of monoethanolamine and

dicyanamide-based ionic liquids
Fan Xu a,b,c , Hongshuai Gao a , Haifeng Dong a , Zhanli Wang a,b ,
Xiangping Zhang a , Baozeng Ren b,∗ , Suojiang Zhang a,∗
a
Beijing Key Laboratory of Ionic Liquids Clean Process, Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy
of Sciences, Beijing 100190, PR China
b
School of Chemical Engineering and Energy, Zhengzhou University, 450001, PR China
c
Henan Chemical Design Institute Branch of Wison Engineering Ltd., Zhengzhou 450018, PR China

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

Article history: Two low viscous ionic liquids (ILs), 1-(2-hydroxyethyl)-3-methyl-imidazolium dicyanamide
Received 16 April 2013 ([C2 OHmim][DCA]) and 1-butyl-3-methylimidazolium ([Bmim][DCA]) were selected to mixed with
Received in revised form aqueous 30 wt% monoethanolamine (MEA) for CO2 absorption. The solubility of CO2 in the aqueous
19 December 2013
mixtures of MEA + ILs was measured over a range of CO2 partial pressure of 10–800 kPa and ILs
Accepted 23 December 2013
concentrations from 10 to 50 wt% at 313.15 K and 333.15 K. Correlations of solubility as a function of
Available online 31 December 2013
CO2 partial pressure have been conducted with deviation of ±1.5%. Moreover, the density and viscosity
of pure ILs and MEA + ILs + H2 O systems with different IL mass fractions were measured at temperature
Keywords:
Ionic liquids
varying from 293.15 to 333.15 K.
Monoethanolamine © 2014 Elsevier B.V. All rights reserved.
CO2 absorption
Viscosity

1. Introduction Recently, ionic liquids (ILs) were proposed as potential sol-

Since CO2 is widely regarded as a major greenhouse gas that
leads to global climate change, there is significant interest in
CO2 capture and sequestration technologies [1]. Some technolo-
gies have been developed to separate CO2 from gas streams, such
as cryogenic distillation, gas separation membranes, adsorption
with solids and absorption with chemical and physical solvents
[2]. Among these technologies, aqueous solution of alkanolamines,
as one typical chemical solvent, has been effectively used for gas
absorption [3].
Monoethanolamine (MEA) as one kind of alkanolamine is widely
used for the removal of CO2 from flue gas [4]. It has high reactiv-
ity, low solvent cost, ease of reclamation, and low absorption of
hydrocarbons [5]. However, its aqueous solution has some intrin-
sic drawbacks, for example, the high energy consumption caused by
large amounts of water being vaporized during the thermal regen-
eration. Thus the shortcoming of MEA drives researchers to find
superior technologies.
∗ Corresponding authors. Tel.: +86 010 82544875; fax: +86 010 82544875.
E-mail addresses: xu.19880318@163.com (F. Xu), renbz@zzu.edu.cn (B. Ren),
sjzhang@home.ipe.ac.cn (S. Zhang).
vents for the absorption of CO2 due to their significant advantages
over other molecular solvents. The unique characteristics of ILs
are wide liquid range, tunable physicochemical properties, espe-
cially negligible vapor pressure and less than one-third the heat
capacity of water in a wide range of temperature (1.30 J g−1 K−1
vs 4.18 J g−1 K−1 or 1.88 J g−1 K−1 vs 4.18 J g−1 K−1 ) [6], which can
reduce greatly the loss of absorbents and save energy during the
regeneration process. However, most ILs show very low CO2 load-
ing capacity and preparing these ILs often involves several synthesis
and purification steps, thus they are not always cost effective can-
didates compared to commercial amines.
In 2008, Noble et al. put forward the idea of mixing ILs and
alkanolamines for CO2 capture, they also stated that the mixture
of ILs and alkanolamines was capable of capturing 1 mol of CO2
per 2 mol of dissolved alkanolamine. This method has two advan-
tages: (1) the desirable properties of ILs and alkanolamines may be
incorporated and (2) energy can be saved during the regeneration
process without affecting the absorption performance. However,
based on this idea, the alkanolamines used in the literature [7–13]
have mainly focused on tertiary alkanolamines such as MDEA, with
very few reports about primary alkanolamines such as MEA. More-
over, the ILs studied in these reports were usually [Bmim][BF4 ]
or [Bmim][OAc], which show poor thermal stability and high vis-
cosity. [Bmim][BF4 ] and [Bmim][OAc] easily generate hydrofluoric

0378-3812/$ – see front matter © 2014 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.fluid.2013.12.020
 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87 81

Table 1
Sample table of compounds used in this study.

Compound Source Purification method Final purity Measuring method

MEA Purchased from Beijing – 99 wt% FTIR, GC–MS

Chemical Company
Carbon dioxide Purchased from Beijing Beiwen – 99.95 mol% GC–MS
Gas Factory
1
[C2 OHmim][DCA] Synthesized in our laboratory Vacuum distillation, extraction, 97 wt% H NMR, FTIR, ESI-MS,
vacuum treatment elemental analysis, ion
chromatography, Karl–Fischer
titration
1
[Bmim][DCA] Synthesized in our laboratory Vacuum distillation, extraction, 97 wt% H NMR, FTIR, ESI-MS,
vacuum treatment elemental analysis, ion
chromatography, Karl–Fischer
titration

acid and acetic acid, respectively, when heated for a long time [14], Table 2
Comparison of the measured CO2 loading in 30 wt% MEA with the literature values.
while high viscosity not only leads to processing difficulties but also
results in the lower reaction rates [15]. The purpose of the present PCO2 (kPa) RAD from the literature × 100% Reference
study is to screen out ILs which both have better thermal stabilities 101 3.3 Jou et al. [4]
and low viscosities. 103 5.2 Shen and Li [17]
In this work, two dicyanamide-based ILs with low viscosity 135 0.1 Lee et al. [18]
have been studied and the solubility of CO2 in aqueous mixtures (1) The standard uncertainty in the temperature measurement being ±0.10 K; (2) the
of MEA + 1-(2-hydroxyethyl)-3-methyl-imidazolium dicyanamide standard uncertainty in the mass measurement being ±0.0001 g and the standard
([C2 OHmim][DCA]) and MEA + 1-butyl-3-methylimidazolium uncertainty in the mass fraction being ±0.1 wt%; (3) the standard uncertainty in the
pressure measurement being ±0.075%; and (4) the standard uncertainty in the CO2
([Bmim][DCA]) was investigated at different temperatures, ILs
solubility being ±0.002 mol CO2 /mol MEA.
concentrations and CO2 partial pressures. Dicyanamide-based ILs
was chosen as they have been shown to exhibit lower viscosity
compared with other ILs studied to date [15]. The solubility solubility in mixtures of aqueous MEA + [C2 OHmim][DCA] and
data determined has been correlated as a function of CO2 partial MEA + [Bmim][DCA] at temperature 313.15 K and 333.15 K over CO2
pressure by a second-order polynomial. Moreover, the density partial pressure ranging from 10 to 800 kPa. The capacity of the gas
and viscosity of the ternary mixtures have been measured at reservoir and equilibrium cell was measured by filling them with
temperatures from 293.15 to 333.15 K and ILs concentrations water and then measuring volume of the water using a graduated
varied from 10 to 50 wt%. cylinder. The volume of the equilibrium cell was also checked by
vernier calipers. The volume of the equilibrium cell (35.5 ml) and
2. Materials and methods the gas reservoir (499.9 ml) was measured within 0.1 ml. The exper-
iment procedure is as follows: prior to solubility measurements,
2.1. Materials the solution was heated up to predetermined temperature in glass
vessel and the pressure reduced using a vacuum pump in order
[Bmim][Cl] was obtained from Linzhou Keneng Materials Tech- to remove any dissolved gas. 15 ml of absorbent was firstly trans-
nology Co. Ltd., China. All the other reagents, including MEA, ferred to the equilibrium cell. Then evacuate using vacuum pump,
sodium dicyanamide were purchased from Beijing Chemical Com-
pany and were of analytical grade. The carbon dioxide used was Table 3
from Beijing Beiwen Gas Factory, the mass purity of the gas was CO2 loading in aqueous 30 wt% MEA mixed with various concentration of
[C2 OHmim][DCA] at 313.15 K (ω, mass fraction).
99.95. Distilled water was used as diluter solvent for all the exper-
iments. The [C2 OHmim][DCA] and [Bmim][DCA] were synthesized PCO2 (kPa) ˛ (mol CO2 /mol MEA) PCO2 (kPa) ˛ (mol CO2 /mol MEA)
according to the published procedure [16]. All the compounds used ωIL = 0.1 ωIL = 0.2
in this study were listed in Table 1. 9.15 0.506 11.31 0.492
18.21 0.528 19.49 0.513
45.70 0.562 46.23 0.546
2.2. Absorbents preparation
107.62 0.605 100.66 0.583
185.38 0.638 205.23 0.626
All absorbents were weighted by an electronic analyt- 384.13 0.695 403.98 0.676
ical balance (BS124S, Sartorius Scientific Instrument Co. 592.72 0.735 614.44 0.714
Ltd., China), and the precision was ±0.0001 g. Absorbents of 817.29 0.769 852.75 0.752

MEA + [C2 OHmim][DCA] + H2 O with different [C2 OHmim][DCA] ωIL = 0.3 ωIL = 0.5
mass fractions, 0.1000, 0.2007, 0.2999 and 0.5002, respectively, 9.47 0.486 11.89 0.479
18.39 0.506 20.25 0.495
and MEA + [Bmim][DCA] + H2 O with different [Bmim][DCA] mass
47.37 0.536 46.07 0.519
fractions, 0.1008, 0.2001, 0.2998 and 0.4996, respectively, were 93.80 0.564 88.05 0.541
prepared before experiments. The mass fraction of MEA in all the 189.83 0.602 213.61 0.582
absorbents was 0.3000 which was close to the concentration used 400.84 0.653 409.02 0.621
in the industrial application. 594.39 0.688 603.87 0.654
860.57 0.726 827.51 0.684

2.3. Solubility measurement of CO2
One gas absorption apparatus was designed and assembled
to have high accuracy of solubility measurement with low con-
sumption of solvents [16]. This setup was used to measure CO2
(1) The standard uncertainty in the temperature measurement being ±0.10 K;
(2) the standard uncertainty in the mass measurement being ±0.0001 g and the
standard uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental
pressure is 10–800 kPa and the standard uncertainty in the pressure measure-
ment being ±0.075%; and (4) the standard uncertainty in the CO2 solubility being
±0.002 mol CO2 /mol MEA.
82 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87

Table 4
CO2 loading in aqueous 30 wt% MEA mixed with various concentration of [C2 OHmim][DCA] at 333.15 K (ω, mass fraction).

PCO2 (kPa) ˛ (mol CO2 /mol MEA) PCO2 (kPa) ˛ (mol CO2 /mol MEA) PCO2 (kPa) ˛ (mol CO2 /mol MEA)

ωIL = 0.1 ωIL = 0.2 ωIL = 0.3

8.46 0.483 11.89 0.482 10.40 0.467
26.19 0.509 26.19 0.501 27.49 0.492
44.02 0.524 48.46 0.519 47.37 0.508
91.75 0.550 104.02 0.546 111.45 0.539
215.06 0.592 203.56 0.578 199.12 0.565
419.04 0.633 417.19 0.620 426.10 0.609
613.33 0.662 620.03 0.651 612.97 0.637
814.87 0.688 821.75 0.678 810.60 0.664

(1) The standard uncertainty in the temperature measurement being ±0.10 K; (2) the standard uncertainty in the mass measurement being ±0.0001 g and the standard
uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 10–800 kPa and the standard uncertainty in the pressure measurement being ±0.075%; and
(4) the standard uncertainty in the CO2 solubility being ±0.002 mol CO2 /mol MEA.

so that the liquid existed under its own vapor pressure and was Thus the moles of CO2 in the liquid phase of equilibrium cell
allowed to reach desired temperature. After that, pump a certain were obtained from
amount of CO2 to equilibrium cell. The experiment was stopped g
when the pressure in the cell remained constant for 30 min. The nlCO = nCO2 − nCO (3)
2 2
initial and final pressures of CO2 in reservoir and equilibrium cell
The solubility was expressed as per mole CO2 of mol MEA, and
were used to measure the amount of absorbed CO2 in the aqueous
the expression was
MEA + [C2 OHmim][DCA] and MEA + [Bmim][DCA] solutions.
In each experiment, the equilibrium cell containing absorbent nlCO
along with a stir bar was kept in a temperature-controlled water ˛= 2
(4)
nMEA
bath that was regulated at set temperature with an accuracy of
±0.1 K. The absorbent used for solubility measurements was con- In Eq. (1), VGR is the volume of gas reservoir, P1i is the pressure
stantly stirred throughout the experiment. of gas reservoir before pumping gas into equilibrium cell, P1f is the
In the process, the parameters of volume, temperature and qual- pressure of gas reservoir after pumping gas into equilibrium cell.
ity of the absorbent were constant and pressure was variable which In Eq. (2), VEC is the volume of equilibrium cell, VECl is the volume
needed to be recorded during every experiment. The total moles of of liquid in equilibrium cell, P0 is the initial pressure of equilibrium
CO2 in equilibrium cell were calculated by: cell, P2 is equilibrium pressure of CO2 .

VGR
nCO2 = (P1i − P1f ) (1) 2.4. Density measurement
zRT

The moles of CO2 in the gas phase of equilibrium cell were cal- The density of all the ternary mixtures, pure MEA and IL were
culated using: measured using a density meter (Anton Paar DMA 5000, Anton
Paar Co., Austria) with a precision of ±0.0001 g cm−3 , which was
g (VEC − VECl) calibrated with ultrapure water and dry air. All measurements of
nCO = (P2 − P0 ) (2)
2 zRT the density were performed between temperature 293.15 K and
333.15 K with an uncertainty of ±0.01 K, and the absolute room
pressure was about 101 kPa. Each measurement point was the aver-
Table 5
CO2 loading in aqueous 30 wt% MEA mixed with various concentration of age of the repeated experiments for three times with the same
[Bmim][DCA] at 313.15 K (ω, mass fraction). injection.
PCO2 (kPa) ˛ (mol CO2 /mol MEA) PCO2 (kPa) ˛ (mol CO2 /mol MEA)
2.5. Viscosity measurement
ωIL = 0.1 ωIL = 0.2
9.65 0.497 9.10 0.492
18.76 0.522 19.69 0.516 The viscosity of all the ternary mixtures, pure MEA and pure IL
41.97 0.554 44.58 0.546 were measured using a viscosity meter (Anton PaarAMVn, Anton
123.7 0.609 109.22 0.588 Paar Co., Austria) with an uncertainty of ±2%, which was calibrated
233.67 0.652 210.08 0.628
391.18 0.693 398.24 0.676
using ultrapure water or viscosity standard oils (No. H117, Anton
602.00 0.733 589.00 0.710 Paar Co., Austria). The temperature range of this study was from
829.17 0.767 812.08 0.746 293.15 to 333.15 K with an uncertainty of ±0.05 K which was con-
ωIL = 0.3 ωIL = 0.5 trolled by a built-in precise Peltier thermostat, and the absolute
9.10 0.486 11.51 0.475 room pressure was approximate 101 kPa at that time.
21.55 0.510 18.57 0.486
42.24 0.531 40.86 0.509
94.55 0.563 91.38 0.537 3. Results and discussion
215.92 0.609 192.99 0.571
397.69 0.653 408.42 0.620 3.1. Solubility of CO2
597.51 0.689 588.26 0.652
810.42 0.721 807.31 0.687
In this work, the solubility of CO2 in MEA + ILs + H2 O was
(1) the standard uncertainty in the temperature measurement being ± 0.10 K; investigated at different temperatures, CO2 partial pressures and
(2) the standard uncertainty in the mass measurement being ± 0.0001 g and the
ILs concentrations. The MEA concentration was kept constant at
standard uncertainty in the mass fraction being ± 0.1 wt%; (3) the experimental pres-
sure is 10 to 800 kPa and the standard uncertainty in the pressure measurement 30 wt%, which was close to the typical concentration used in indus-
being ± 0.075%; (4) the standard uncertainty in the CO2 solubility being ± 0.002 mol try. The ILs, [C2 OHmim][DCA] and [Bmim][DCA], were selected
CO2 /mol MEA. according to the following principles: low viscosity, miscibility with
 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87 83

N(CN)2 N(CN)2
N N N N
OH

Fig. 1. Structure of [C2 OHmim][DCA] and [Bmim][DCA].

1000
1000
PCO2 / kPa

100 100

PCO2/ kPa
10
10

0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.85

0.45 0.50 0.55 0.60 0.65 0.70 0.75
α (mol CO2 /mol MEA)
α (mol CO2 / mol MEA)
Fig. 2. CO2 loading in 30 wt% aqueous MEA solution at 313.15 K. , Jou et al.; ,
Shen and Li et al.; 夽, Lee et al.; , , , this work. Fig. 4. CO2 loading in 30 wt% aqueous MEA solution with different [C2 OHmim][DCA]
concentration at 333.15 K. , 30%MEA + 70%H2 O; 䊉, 30%MEA + 10%IL + 60%H2 O; ,
30%MEA + 20%IL + 50%H2 O; , 30%MEA + 30%IL + 40%H2 O.

water and MEA, and good potential of imidazolium-based ionic
liquids to absorb CO2 (see Fig. 1).
The validation experiment using the 30 wt% aqueous MEA at
313.15 K was carried out at partial pressure of CO2 varied from 10
to 800 kPa to ensure the accuracy of measurement obtained from
the apparatus, and the results were compared with those reported
by Jou et al. [4], Shen and Li [17] and Lee et al. [18], as shown in Fig. 2.
It can be seen that the results showed good consistency with the
literature results which proved the setup and the procedure used in
this work were precise enough for performing CO2 solubility mea-
surements. The absolute relative deviation (RAD) for experimental
value of this work and the literature value was also calculated by
Eq. (5) and reported in Table 2 at the same conditions.
 
 ˛ − ˛lit 
RAD =   (5)
˛ lit
In Eq. (5), ˛ is CO2 loading obtained from this work and ˛lit is
from the literature at the same conditions.
The solubility of CO2 was measured in 30 wt% MEA + ILs
solutions at temperature 313.15 K and 333.15 K and CO2 partial
pressures varied from 10 to 800 kPa with [C2 OHmim][DCA]
and [Bmim][DCA] concentration ranged from 0.1 to
0.5 mol CO2 /mol MEA. The results were listed in Tables 3–5
and shown in Figs. 3–5.

1000 1000
PCO2/ kPa

100 100
PCO2/ kPa

10 10

0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80
αCΟ2 (mol CO2/ mol MEA) α (mol CO2 / mol MEA)

Fig. 3. CO2 loading in 30 wt% aqueous MEA solution with different [C2 OHmim][DCA] Fig. 5. CO2 loading in 30 wt% aqueous MEA solution with different [Bmim][DCA]
concentration at 313.15 K. , 30%MEA + 70%H2 O; 䊉, 30%MEA + 10%IL + 60%H2 O; concentration at 313.15 K. , 30%MEA + 70%H2 O; , 30%MEA + 10%IL + 60%H2 O;
, 30%MEA + 20%IL + 50%H2 O; , 30%MEA + 30%IL + 40%H2 O; , 䊉, 30%MEA + 20%IL + 50%H2 O; , 30% MEA + 30%IL + 40%H2 O; , 30%
30%MEA + 50%IL + 20%H2 O. MEA + 50%IL + 20%H2 O.
84 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87

Table 6
Coefficients of Eq. (6), the solubility as a function of pressure (ω, mass fraction).

Solvent T (K) ωIL A B C P (kPa)

MEA + [C2 OHmim][DCA] + H2 O 313.15 0.1 −12.466 −1.2061 7.2106 10–800

313.15 0.2 −10.428 −0.1456 7.5519 10–800
313.15 0.3 −15.614 −5.1584 6.6688 10–800
313.15 0.5 −18.794 −9.0645 5.9675 10–800

MEA + [C2 OHmim][DCA] + H2 O 333.15 0.1 −21.932 −11.623 5.3686 10–800

333.15 0.2 −21.209 −11.534 5.4000 10–800
333.15 0.3 −19.667 −10.744 5.5802 10–800

MEA + [Bmim][DCA] + H2 O 313.15 0.1 −9.6255 0.9396 7.6291 10–800

313.15 0.2 −12.669 −2.0362 7.1673 10–800
313.15 0.3 −16.822 −6.4789 6.3324 10–800
313.15 0.5 −20.378 −11.509 5.2088 10–800

(1) The standard uncertainty in the temperature measurement being ±0.10 K; (2) the standard uncertainty in the mass measurement being ±0.0001 g and the standard
uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 10–800 kPa and the standard uncertainty in the pressure measurement being ±0.075%; (4)
the standard uncertainty in the CO2 solubility being ±0.002 mol CO2 /mol MEA.

Table 7
Density () and viscosity () of pure MEA from T = (293.15–333.15) K.

T (K)  (g cm−3 )  (mPa s)

This work Lit. This work Lit.

293.15 1.01596 – 23.76 –

303.15 1.00805 1.0081 [20] 14.85 15.1088
1.00817 [21] [22]
313.15 1.00009 1.0004 [20] 9.94 10.0209
1.00021 [21] [22]
323.15 0.99207 0.9927 [20] 6.98 6.9715
0.99219 [21] [22]
333.15 0.98398 0.9850 [20] 5.11 5.0473
0.98410 [21] [22]

(1) The standard uncertainty in the temperature measurement of density and viscosity being ±0.01 K and ±0.05 K, respectively; (2) the standard uncertainty in the mass
measurement being ±0.0001 g and the standard uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 101 kPa and the standard uncertainty in
the pressure measurement being ±1 kPa; and (4) the standard uncertainty in the density and viscosity measurement being ±0.0001 g cm−3 and ±2%, respectively.

3.1.1. Effect of addition ionic liquid
Figs. 3 and 5 show the effect of addition of IL to 30 wt% MEA
solutions on the CO2 equilibrium loading over a range of CO2 par-
tial pressure of 10–800 kPa at 313.15 K. The results indicated that
both [C2 OHmim][DCA] and [Bmim][DCA] give a slight decreased on
the solubility at low concentration such as below 0.1, but the effect
becomes obvious when the IL concentration increases to 0.2 and
decreases dramatically at higher concentrations. This was probably
interpreted as the salting out effect. In fact, during the absorp-
tion of CO2 , MEA in water can absorb CO2 to form carbamate, but
adding salt into the absorbents might reduce the solubility of carba-
mate in solution and inhibit CO2 absorption. Moreover, the addition
of [C2 OHmim][DCA] and [Bmim][DCA] have similar effect on the
30 wt% MEA solutions when used for CO2 capture at the same con-
dition. It can be explained that the absorption of CO2 mainly relies
on MEA but very little on ILs.
3.1.2. Effect of temperature and pressure
With the purpose of studying and comparing the effect of tem-
perature, CO2 solubilities were measured at 313.15 K and 333.15 K.
Figs. 3 and 4 show the effect of temperature on the aqueous solu-
tions of MEA + ILs. The solubility of CO2 decreases with the increase
of temperature. Specifically speaking, compared with Fig. 3, for
the same IL concentration, the curves in Fig. 4 show a moving
trend to the left side as the temperature increases from 313.15
to 333.15 K. This suggests that low temperature facilitates the

Table 8
Density () and viscosity () of pure [C2 OHmim][DCA] and [Bmim][DCA] from T = (293.15–333.15) K.

IL [C2 OHmim][DCA] [Bmim][DCA]

−3
T (K)  (g cm )  (mPa s)  (g cm−3 )  (mPa s)

This work Lit. This work Lit. This work Lit. This work Lit.

293.15 1.19285 1.12[26] 121.50 – 1.06540 1.06373 [24] 48.53 –

1.066[27] 1.0662 [25]
303.15 1.18637 – 68.67 – 1.05909 1.05735 [24] 31.73 26.286
1.0599 [25] [25]
313.15 1.17992 – 42.93 – 1.05283 1.05105 [24] 22.09 18.495
1.0537 [25] [25]
323.15 1.17352 – 28.96 – 1.04662 1.04484 [24] 16.17 13.777
1.0475 [25] [25]
333.15 1.16718 – 20.67 – 1.04048 1.03869 [24] 12.35 10.653
1.0413 [25] [25]

(1) The standard uncertainty in the temperature measurement of density and viscosity being ±0.01 K and ±0.05 K, respectively; (2) the standard uncertainty in the mass
measurement being ±0.0001 g and the standard uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 101 kPa and the standard uncertainty in
the pressure measurement being ±1 kPa; (4) the standard uncertainty in the density and viscosity measurement being ±0.0001 g cm−3 and ±2%, respectively.
 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87 85

Table 9
Density () and Viscosity () of MEA (1) + [C2 OHmim][N(CN)2 ] (2) + H2 O from T = (293.15 to 333.15) K (␻, mass fraction).

T (K) ω1 = 0.2999 ω1 = 0.2994 ω1 = 0.2999 ω1 = 0.3006 ω1 = 0.3006

ω2 = 0.1000 ω2 = 0.2007 ω2 = 0.2999 ω2 = 0.4001 ω2 = 0.5002

 (g cm−3 )
293.15 1.03010 1.04757 1.06562 1.08241 1.09992
303.15 1.02501 1.04188 1.05944 1.07588 1.09315
313.15 1.01955 1.03595 1.05311 1.069278 1.08636
323.15 1.01379 1.02980 1.04667 1.06259 1.07953
333.15 1.00776 1.02341 1.04006 1.05584 1.07268

 (mPa s)
293.15 3.53 4.49 6.02 8.52 13.55
303.15 2.61 3.28 4.34 6.03 9.44
313.15 2.00 2.50 3.27 4.46 6.88
323.15 1.59 1.96 2.54 3.41 5.18
333.15 1.29 1.58 2.03 2.68 3.98

(1) The standard uncertainty in the temperature measurement of density and viscosity being ±0.01 K and ±0.05 K, respectively; (2) the standard uncertainty in the mass
measurement being ±0.0001 g and the standard uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 101 kPa and the standard uncertainty in
the pressure measurement being ±1 kPa; (4) the standard uncertainty in the density and viscosity measurement being ±0.0001 g cm−3 and ±2%, respectively.

Table 10
Parameters of Eq. (7) and AADs for Density Correlation of MEA (1) + [C2 OHmim][DCA] (2) + H2 O (ω, mass fraction).

ω1 ω2 A0 104 A1 106 A2 100AAD

0.2999 0.1000 1.0401 4.2783 −1.5758 0.0010

0.2994 0.2007 1.1131 1.1109 −1.1417 0.0003
0.2999 0.2999 1.1850 −2.0345 −0.6954 0.0003
0.3006 0.4001 1.2413 −4.3448 −0.3670 0.0002
0.3006 0.5002 1.2861 −5.9500 −0.1371 0.0003

Table 11
Parameters of Eq. (8) and ADDs for viscosity correlation of MEA (1) + [C2 OHmim][DCA] (2) + H2 O (ω, mass fraction).

ω1 ω2 A0 A1 A2 100AAD

0.2999 0.1000 −3.2260 620.4616 −154.8770 0.0718

0.2994 0.2007 −3.2080 661.2899 −152.7160 0.0577
0.2999 0.2999 −3.0376 666.4164 −155.2640 0.1045
0.3006 0.4001 −3.2179 780.1228 −147.5960 0.1115
0.3006 0.5002 −3.3879 940.9011 −136.1470 1.5993

Table 12
Density () and viscosity () of MEA (1) + [Bmim][N(CN)2 ] (2) + H2 O from T = (293.15–333.15) K (ω, mass fraction).

T (K) ω1 = 0.3003 ω1 = 0.3005 ω1 = 0.2998 ω1 = 0.2998 ω1 = 0.3009

ω2 = 0.0499 ω2 = 0.1008 ω2 = 0.2001 ω2 = 0.3002 ω2 = 0.4996

 (g cm−3 )
293.15 1.01645 1.02039 1.02633 1.03234 1.04204
303.15 1.01160 1.01512 1.02040 1.02591 1.03511
313.15 1.00633 1.00950 1.01422 1.01930 1.02812
323.15 1.00064 1.00352 1.00779 1.01253 1.02106
333.15 0.99457 0.99721 1.00111 1.00558 1.01395

 (mPa s)
293.15 3.25 3.67 4.75 6.35 11.98
303.15 2.38 2.66 3.40 4.48 8.27
313.15 1.82 2.02 2.54 3.30 5.99
323.15 1.43 1.58 1.97 2.52 4.51
333.15 1.16 1.27 1.57 1.99 3.52

(1) The standard uncertainty in the temperature measurement of density and viscosity being ±0.01 K and ±0.05 K, respectively; (2) the standard uncertainty in the mass
measurement being ±0.0001 g and the standard uncertainty in the mass fraction being ±0.1 wt%; (3) the experimental pressure is 101 kPa and the standard uncertainty in
the pressure measurement being ±1 kPa; (4) the standard uncertainty in the density and viscosity measurement being ±0.0001 g cm−3 and ±2%, respectively.

Table 13
Parameters of Eq. (7) and AADs for density correlation of MEA (1) + [Bmim][DCA] (2) + H2 O (ω, mass fraction).

ω1 ω2 A0 104 A1 106 A2 100AAD

0.3003 0.0499 0.9771 7.3359 −2.0450 0.0005

0.3005 0.1008 1.0211 5.0573 −1.7329 0.0004
0.2998 0.2001 1.0881 1.5874 −1.2600 0.0001
0.2998 0.3002 1.1445 −1.3060 −0.8593 0.0002
0.3009 0.4996 1.2195 −5.2018 −0.2907 0.0001
86 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87

Table 14
Parameters of Eq. (8) and ADDs for viscosity correlation of MEA (1) + [Bmim][DCA] (2) + H2 O (ω, mass fraction).

ω1 ω2 A0 A1 A2 100AAD

0.3003 0.0499 −3.4174 635.8859 −154.7727 0.0111

0.3005 0.1008 −3.2726 608.2301 −160.1058 0.1438
0.2998 0.2001 −3.3738 680.3491 −155.1882 0.0711
0.2998 0.3002 −3.3181 712.3768 −155.2802 0.0554
0.3009 0.4996 −2.8266 706.9042 −160.0163 0.3603

1.12 16
(a) (b)
1.10 14

12
1.08
10
1.06
-3

η/mp·s
8
ρ/g·cm

1.04
6
1.02 4

1.00 2

0.98 0
290 300 310 320 330 340 290 30 0 31 0 320 33 0 34 0

T/K T/K

Fig. 6. Density (a) and viscosity (b) of MEA (1) + [C2 OHmim][DCA] (2) + H2 O as a function of temperature at different IL and H2 O mass fractions: 䊉, ω1 = 0.2999, ω2 = 0.1000;
, ω1 = 0.2994, ω2 = 0.2007; , ω1 = 0.2999, ω2 = 0.2999; , ω1 = 0.3006, ω2 = 0.4001; , ω1 = 0.3006, ω2 = 0.5002; The symbols represent experimental values, and the solid
curves represent the values calculated from Eqs. (5) and (6), respectively.

absorption of CO2 . We measured the solubility of CO2 in 30 wt%
MEA solutions with [C2 OHmim][DCA] concentration ranged from
0.1 to 0.3 mol CO2 /mol MEA at 333.15 K as representative which
could fully show the effect of temperature on the performance
of CO2 capture. In analogy to the reason that vapour pressure
increases with temperature, the reason for the negative impact of
temperature can be given a similar explanation [10].
The solubility of CO2 (Figs. 3–5) in aqueous solutions of MEA + ILs
increases with the increase of CO2 partial pressure. There is a
positive impact on the solubility which indicates high pressure
facilitates the absorption of CO2 . Moreover, the aqueous solutions
of MEA + ILs do not show direct proportion between the solubil-
ity and pressure also indicating that the absorption of CO2 depend
mainly on MEA but very little on ILs.
3.1.3. Correlation of solubility as function of pressure
The solubility data shown in Figs. 3–5 could be fitted as a func-
tion of CO2 partial pressure according to Eq. (6) by a second-order
polynomials follows [19]:
ln PCO2 = A(ln ˛)2 + B(ln ˛) + C
where PCO2 is CO2 partial pressure, ˛ is CO2 loading, A, B, and C are
the quadratic fitting regression parameters. The coefficients of Eq.
(6) for all studied systems are presented in Table 6. The correlation
of solubility has the percentage difference of ±1.5% when pressure
range from 10 to 800 kPa.
3.2. Density and viscosity
We compared the density and viscosity of pure MEA obtained
from this work with the data from the literature to ensure the
accuracy of the measured density and viscosity, and the results
were listed in Table 7. As seen in Table 7, the density and vis-
cosity of pure MEA in this work are all in good agreement with
those reported by Taib et al. [20], Valtz et al. [21], Li et al. [22]
respectively, which suggested that the density and viscosity data
measured in this work were dependable. The density and viscos-
ity of pure ILs and absorbents were listed in Tables 8, 9 and 12.
As shown in Tables 8, 9 and 12, the viscosity of the two ILs and
absorbents were less than 50 mPa s and 7 mPa s at 313.15 K, respec-
tively. The results indicated that the ILs and absorbents used in this
(6) work were low viscosity which could facilitate the mass transfer

1.05 14
(a) (b)
12
1.04
10
1.03
8
η/mpa·s
-3

1.02
ρ/g·cm

6
1.01
4

1.00 2

0.99 0
290 300 310 320 330 340 290 300 310 320 330 340
T/K T/K

Fig. 7. Density (a) and viscosity (b) of MEA (1) + [Bmim][DCA] (2) + H2 O as a function of temperature at different IL and H2 O mass fractions: , ω1 = 0.3003, ω2 = 0.0499; 䊉,
ω1 = 0.3005, ω2 = 0.1008; , ω1 = 0.2998, ω2 = 0.2001; , ω1 = 0.2998, ω2 = 0.3002; , ω1 = 0.3009, ω2 = 0.4996; The symbols represent experimental values, and the solid curves
represent the values calculated from Eqs. (5) and (6), respectively.
 F. Xu et al. / Fluid Phase Equilibria 365 (2014) 80–87
during the absorption of CO2 . The density and viscosity data shown
in Tables 9 and 12 could be fitted and regressed by the equations
as follows [23]:
/g cm−3 = A0 + A1 (T/K) + A2 (T/K)
2
 A1

/mPa s = exp A0 +
T/K + A2
1
n
ADD = |i,exp − i,cal |
n RAD
i=1
where  and  are the density and the viscosity, A0 , A1 , and A2 are
the quadratic fitting regression parameters which were obtained
using the method of least squares, and ADD is the average abso-
lute deviation between the experimental results and the calculated
values by Eqs. (7) and (8). For instance, the density and viscosity
of MEA + [C2 OHmim][DCA] + H2 O, MEA + [Bmim][DCA] + H2 O were
fitted by Eqs. (7) and (8), and the values of A0 , A1 , A2 , and ADD were
listed in Tables 10, 11, 13 and 14, respectively. The tendency of
the density and viscosity varied with temperature and IL concen-
tration was shown in Figs. 6 and 7. Density and viscosity changed
with temperature for other absorbents could also be fitted with a
similar tendency.
4. Conclusions
In this work, solubility of CO2 in mixtures of 30 wt% aque-
ous MEA and two types of low viscosity ILs [C2 OHmim][DCA] and
[Bmim][DCA] were measured. Moreover, the density and viscos-
ity of pure ILs and MEA + ILs + H2 O systems with different IL mass
fractions were investigated. Correlations of solubility as a function
of CO2 partial pressure have been conducted with difference of
±1.5% when pressure range from 10 to 800 kPa. The results indicate
that the solubility of CO2 in all MEA + ILs + H2 O mixtures increases
with increasing CO2 partial pressure and decreases with increas-
ing temperature and IL concentration. Since the primary results
of the experimental and modeling work of whole absorption and
desorption process show that when the concentration of ILs is
30 wt% the energy consumption decreased by 27% compared to
the conventional MEA process, when the concentration of ILs is
less than 10 wt%, the presence of ILs in aqueous 30 wt% MEA may
reduce the energy during regeneration process without affecting
their absorption performance obviously. Therefore, the absorbents
studied in this work may be potential solvents for the absorption
of CO2 in industry. This work mainly focus on absorption pro-
cess and the deeply study of experimental and modeling of whole
absorption and desorption process will be the emphasis in the
future.
List of symbols
Notation
nCO2 the total moles of CO2 in equilibrium cell
nMEA the total moles of MEA in equilibrium cell
g
nCO the moles of CO2 in the gas phase of equilibrium cell
2
nlCO the moles of CO2 in the liquid phase of equilibrium cell
2
˛, ˛lit the CO2 loading in the solvent, the CO2 loading in the
solvent from the literature
VGR the volume of gas reservoir
VEC the volume of equilibrium cell
VECl the volume of liquid in equilibrium cell
87
P1i the pressure of gas reservoir before pumping gas into
equilibrium cell
P1f the pressure of gas reservoir after pumping gas into equi-
librium cell
(7)
P0 the initial pressure of equilibrium cell
P2 equilibrium pressure of CO2
(8)
R gas constant (J mol−1 K−1 )
z compressibility factor
T absolutely temperature (K)
(9)
the absolute relative deviation
PCO2 the CO2 partial pressure in equilibrium cell
 the density
i,exp experimental density of the solvent
i,cal calculated density of the solvent
 the viscosity
A0 , A1 , A2 the quadratic fitting regression parameters
ADD the average absolute deviation
n number of experimental points
ω IL mass fraction in the solvent
Acknowledgments
We are grateful to the National Basic Research Program of China
(973 Program) (No. 2013CB733506), the Key Technologies R&D
Program of China (No. 2013BAC11B02), and the National Natural
Science Foundation of China (Nos. 21036007, 51274183) for their
partial financial support of this research.
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