Article

pubs.acs.org/IECR

Optimization and Characterization of an Amino Acid Ionic Liquid and

Polyethylene Glycol Blend Solvent for Precombustion CO2 Capture:
Experiments and Model Fitting
Muhammad Usman, Huang Huang, Jun Li, Magne Hillestad, and Liyuan Deng*,

Department of Chemical Engineering, Norwegian University of Science and Technology, Sem Slandsvei 4, 7491 Trondheim,
Norway

Shanghai Research Institute of Petrochemical Technology, 1658 Pudong Beilu, Shanghai 201208, China
S Supporting Information
*

ABSTRACT: Amino acid ionic liquids are green solvents with

low toxicities and properties suitable for precombustion CO2
capture, such as high CO2 absorption, good thermal stability,
and negligible vapor pressure. However, their high viscosities
and relatively high costs have hampered their industrial
applications. In this work, we systematically studied the
amino acid ionic liquid tetrabutylphosphonium glycinate
([P4444][Gly]) and its blends with the low-cost and less
viscous cosolvent poly(ethylene glycol) (PEG400). The
concentration of the blend solvent was optimized with respect
to CO2 solubility, regeneration eciency, and cyclic capacity.
The solubilities of CO2 in [P4444][Gly], PEG400, and their
blends of four dierent concentrations were measured experimentally in the temperature range of 60140 C and up to a
pressure of 17 bar. The results showed that the CO2 solubility increased with increasing ionic liquid concentration in the blend
and decreased with increasing temperature. The optimum CO2 absorption was determined to occur at 30 wt % of [P4444][Gly] in
the blend. The regeneration study of the 30 wt % [P4444][Gly]70 wt % PEG400 blend for three cycles veried its reusability in
the process and conrmed that the reaction between [P4444][Gly] and CO2 can be reversed at 140 C. The CO2 absorption
capacity of the blend absorbent was found to be up to a loading of 1.23 mol of CO2/mol of absorbent. The parameter tting of
the experimental data using empirical correlations was evaluated, and these correlations were developed in particular to predict
the blend solvent of an amino acid ionic liquidPEG400 system based on the ionic liquid concentration and temperature.

1. INTRODUCTION
Prolic carbon dioxide emissions due to a strong dependence
on fossil fuels for energy requirements have led to global
climate change. These CO2 emissions originate from the
combustion of fossil fuels in the petroleum industry, power
plants, and the petrochemical industry.1 Such emissions can be
substantially reduced by employing carbon dioxide capture,
which is an energy-intensive process and demands higher
operating costs.2 Researchers are striving for an energy-ecient
and cost-eective CO2 capture process. Three dierent routes
for CO2 capturing techniques are under investigation, namely,
precombustion, postcombustion, and oxy-fuel combustion
processes. These processes vary in terms of the source and
conditions of CO2 capture.
Postcombustion CO2 capture is a widespread and wellstudied capture method. However, the precombustion CO2
capture process oers the advantages of higher CO 2
concentrations and hence higher CO2 partial pressures,
resulting in a greater driving force for separation and smaller
footprints. Several technologies are being investigated for CO2
capture on the laboratory and industrial scales, including
XXXX American Chemical Society

absorption, adsorption, cryogenics, and membrane separations.311 Of these, the chemical absorption of CO2 is the most
investigated and mature technology.12,13 Aqueous alkanolamine
solutions are considered to be established chemical absorbents
in the industry for CO2 capture because of their high reactivity
and low costs. However, aqueous amine solutions face obstacles
in their application because of their low cyclic capacities,
equipment corrosion, solvent degradation, high solvent
regeneration costs, and loss of solvent by entrainment. To
overcome these challenges, a new class of solvents known as
ionic liquids is being applied for CO2 capture.
Ionic liquids have gained much attention in recent years in
various industrial sectors.1425 Ionic liquids are molten salts at
temperatures of less than 100 C. They have appealing and
diverse characteristics such as undetectable vapor pressures,
high thermal and chemical stabilities, tunable characteristics,
Received:
Revised:
Accepted:
Published:
A

June 27, 2016

October 17, 2016
October 26, 2016
October 26, 2016
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measured up to a temperature of 200 C. The densities of these

blends were measured for the temperature range of 2080 C
at ambient pressure, and their viscosities were tested for the
temperature range of 2090 C. The density, viscosity, and
solubility data were tted by concentration- and temperaturebased empirical correlations. The models were found to t the
experimental data very well. The CO2 absorption capacities in
these blends were tested at 60, 100, and 140 C and at
pressures up to 18 bar. CO2 absorption experiments were also
run in a decreasing pressure range to validate the experimental
setup and procedure. The regeneration of the absorbent is a key
consideration in the selection of an absorption process. The
regeneration of the 30 wt % [P4444][Gly]70 wt % PEG400
blend was investigated for three cycles of absorption
desorption. Absorption was maintained at 60 C, and
desorption was performed at 140 C for the measurements.
The cyclic capacities and CO2 removal eciencies of
[P4444][Gly], PEG400, and their blends were evaluated.

and strong absorption capacities. Ionic liquids can be tailored

for a particular process by adjusting their cations and anions. A
diverse range of ionic liquid cations and anions have been
reported for CO2 separation.2629 Room-temperature ionic
liquids, task-specic ionic liquids, and supported ionic liquid
membranes have been investigated for CO2 capture in the
literature.3034
Amino acid ionic liquids are green solvents with low toxicities
and properties suitable for precombustion CO2 capture, such as
high CO2 absorption, good thermal stability, and negligible
vapor pressure.35,36 Amino-acid-based ionic liquids have a N
H group similarly to amines and react with CO2 to enhance its
absorption capacity. The reaction between amino acid ionic
liquids and CO2 was reported by Zhang et al.37 to be a two-step
process. In the rst step, a proton transfers from the N atom in
glycine to the oxygen atom of the carboxyl group in glycine,
whereas the second step involves proton sharing between the
oxygen atoms of CO2 and the carboxyl group of the anion.
However, the high viscosities and relatively high costs of amino
acid ionic liquids have become major obstacles in the
development of their industrial applications. Phosphoniumbased amino acid ionic liquids have viscosities that are lower
than those of other types of ionic liquids but still higher than
those of amines.38 One way to deal with the high viscosity is to
blend the amino acid anion ionic liquids with low-molecularweight organic solvents to reduce the viscosity.
Li et al.39 investigated the amino acid (sodium glycinate)
ionic liquid ([Bmim][BF4]) system for CO2 absorption with
dierent blending ratios and came to the conclusion that a high
absorption capacity was obtained for a molar ratio of 4:1
(amino acid/IL). Sistla and Khanna35 reported the absorption
of in aminated anion ionic liquids, which resulted in a CO2
absorption capacity (mass of CO2/mass of ionic liquid) in
amino acid ionic liquids of 70% more than that in primary
aminecation ionic liquids and 600% more than that in tertiary
aminecation ionic liquids. Zhang et al.40 studied four
dicationic amino acid ionic liquids for CO2 absorption and
found the nearly equimolar absorption of CO2 in the ionic
liquids accompanied by the reversibility of the absorbent. They
also addressed the enhancement in CO2 absorption capacity
when water was added to the ionic liquids because of the
decrease in the viscosity of the liquid. Poly(ethylene glycol)s
have been investigated for CO2 solubility.40
Considering the above-mentioned characteristics and our
previous study,41 the amino-acid-based ionic liquid tetradecylphosphonium glycinate [P4444][Gly] is proposed for precombustion CO2 capture applications at high temperature and
pressure. However, because ionic liquids have high viscosities,
which make them challenging for this application, the aminoacid-based ionic liquid [P4444][Gly] was blended with the lowmolecular-weight polymer poly(ethylene glycol) (PEG400) in
this work to reduce the viscosity of the absorbent and enhance
the CO2 sorption. The PEG400 has a CO2 absorption capacity
comparable to those of ionic liquids, good thermal stability, and
negligible vapor pressure,42 and [P4444][Gly] has been reported
to react chemically with CO2;37 thus, blends of [P4444][Gly]
and PEG400 will combine both chemical absorption and
physical sorption, so a CO2 absorption capacity higher than that
obtained in either solvent is expected.
The present work investigated and optimized the CO2
absorption capacity for blends of [P4444][Gly] and PEG400
under precombustion CO2 capture conditions. The thermal
stabilities of the amino acid ionic liquidPEG400 blends were

2. EXPERIMENTAL SECTION
2.1. Materials. Carbon dioxide was purchased from Praxair
with a nominal purity of 99.99%. Poly(ethylene glycol) was
obtained from Sigma-Aldrich with a purity of 99%. The ionic
liquid [P4444][Gly] was synthesized in the laboratory. The
procedure of ionic liquid synthesis was the same as described in
refs 38 and 43. The other raw materials used for synthesis were
tetrabutylphosphonium hydroxide solution (40 wt % in water),
acetonitrile (99.8%), methanol (99.8%), and deuterium oxide
(99.9 atom %), which were purchased from Sigma-Aldrich and
used as received.
2.2. Methods. 2.2.1. Synthesis of Tetrabutylephosphonium Glycinate ([P4444][Gly]). The ionic liquid [P4444][Gly] was
synthesized in the laboratory using the same method as
reported in refs 43 and 44. A solution of tetrabutylphosphonium hydroxide [P4444][OH] (with 40% water by weight) was
mixed dropwise into a marginally excess equimolar aqueous
glycine solution. This mixture was allowed to stir for 12 h at
room temperature to become well mixed. Water evaporation of
this mixture was carried out at 45 C in a rotary evaporator for
56 h. A mixture of acetonitrile and methanol in a volume ratio
of 9:1 was poured into this water-evaporated mixture, and the
overall mixture was stirred vigorously for 9 h. The undissolved
excess amino acid salt was removed from this mixture by
ltration using lter paper. The ltrate product was further
evaporated to remove solvents and dried in a vacuum oven at
70 C for 48 h.
The purity and chemical identity of the ionic liquid was
analyzed by NMR spectrometry using a Bruker Avance DPX
400 MHz NMR spectrometer. The sample for NMR analysis
was prepared by mixing D2O with the synthesized ionic liquid.
First, D2O was dissolved in the ionic liquid sample at room
temperature in an NMR tube and subjected to ultrasonic
mixing to ensure a constant concentration of the sample. The
1
H NMR spectrum was obtained at 25 C with 16 scans, a pulse
duration of 10.5 s, and an acquisition time of 3.95 s. The 1H
NMR spectrum was analyzed using TopSpin software. The 1H
NMR spectrum was compared with the reported values of the
spectrum peaks for accuracy. The ionic liquid was stored in a
desiccator to avoid moisture uptake before use.
The 1H NMR spectrum of the synthesized ionic liquid
obtained from the NMR analysis is shown in Figure 1.
The rst chemical shift at 0.92 ppm represents four CH3
groups with 12 protons attached to the P atom, and the second
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Figure 2. Experimental setup for CO2 solubility measurements: (1)

gas cylinder, (2,3) oil bath, (4) gas storage vessel, (5) absorption
vessel, (6) magnetic stirrer, (7) pressure transmitter, (8) computer
program. Reproduced with permission from ref 46.Copyright 2012
American Chemical Society.

was observed with a mounted pressure transducer (series 33X,

Keller Co.) with an accuracy limit of 0.3 kPa. A magnetic
stirrer was used in the gas absorption vessel to stir the mixture
at a speed of 450 rpm.
The whole apparatus was rst evacuated using a vacuum
pump for about 1 h and was checked for leaks. The gas was
then stored in the vessel at a certain pressure, and the pressure
(Ps) was allowed to become stabilized in the vessel. The middle
valve between the two vessels was opened, the magnetic stirrer
was turned on, and equilibrium was allowed to be achieved.
The equilibrium pressure is denoted as Pe. The dierence in
pressure values (Ps Pe) gives the amount og CO2 absorbed in
the liquid by converting the pressure into moles using the PVT
data with the SoaveRedlichKwong (SRK) equation of state.
The amount of CO2 absorbed in the absorbent was estimated
from the dierence between the number of moles of CO2 in the
gas vessel and the number of moles of CO2 in the gas phase at
equilibrium. The same procedure was employed for all of the
data points.
Desorption experiments were performed when the system
was at the maximum observed pressure. The gas was released
into the vacuum line by closing the middle valve rst. Then, the
gas storage vessel was allowed to achieve a stable pressure
following the opening of the middle valve and achieving
equilibrium in the absorption vessel. The same steps were
followed while the gas was desorbed up to a minimum
achievable pressure. All experimental data were recorded using
the LabView computer program.
2.2.6. Error Analysis. The error analysis for density, viscosity,
and CO2 solubility measurements was performed by calculating
the ratio of the standard deviation and average value of two or
more observations. The inherent errors were mentioned for
each instrument used for measurements in section 2.2. Density
and viscosity measurements were run at least twice to
reproduce the data with an accuracy of 0.05% and 3%,
respectively. As stated in the experimental procedure, CO2 gas
at various pressures was lled into the gas vessel manually in
this study. It was challenging to replicate the exact same
pressure point for the CO2 solubility measurements for each
temperature and concentration of ionic liquid because of the
diculty in controlling the pressure. For this reason, at least
two measurements were commonly performed to produce the
data for CO2 solubility and ensure accuracy, but it was not
possible to calculate the standard deviations for variables. The
evaluated maximum uncertainties for the reported CO2 loading
value and equilibrium partial pressure of CO2 are 3% and 5%,

Figure 1. 1H NMR spectrum of the ionic liquid [P4444][Gly] from the

NMR analysis.

shift in the range of 1.341.52 ppm represents four CH2

groups with 16 protons. The third chemical shift at 2.132.23
ppm indicates CH2 attached to P with eight protons. The last
chemical shift at 3.0 ppm corresponds to the functional group
NCH2CO2 with two protons. Through a comparison of the
adjusted results and the literature, the gure clearly shows four
peaks with values on the x axis similar to those reported by
Zhang et al.45 The 1H NMR results agree with the literature
and indicate the successful synthesis of [P4444][Gly]. There
were also two small hetero peaks in the scan, but they are
insignicant. The synthesis and rening of the ionic liquid
[P4444][Gly] was thus authenticated by the 1H NMR data.
2.2.2. Density. The densities of all of the samples were
measured on an Anton Paar DMA 4500 M density meter
within the temperature range of 2080 C at atmospheric
pressure. This density meter consists of a U-tube with a Pt-100
thermocouple (accuracy of 0.01 C). The measuring volume
was approximately 9.5 mL, and the sample needs to be placed
in a test vial and covered with a cap (Usman, 2012). The
available temperature range is set in the apparatus at an
operating temperature of 2080 C.
2.2.3. Viscosity. The viscosity measurements were carried
out with a rheometer (ARG2 by TA Instruments). All of the
samples were tested within the temperature range of 2090 C
at atmospheric pressure with an accuracy of 2%.
2.2.4. Thermal Decomposition Temperature Measurements. The thermal decomposition temperatures of the ionic
liquids and their blends with PEG400 were measured with a
thermogravimetric analyzer (Q500, TA Instruments) with an
accuracy of 0.01%. A known amount of sample (1015 mg)
was placed in a platinum pan, and thermogravimetric analysis
(TGA) measurements were performed under a nitrogen
atmosphere (60 mL/min) over the temperature range of 21
400 C at a heating rate of 10 C/min.
2.2.5. CO2 Solubility. The CO2 solubility experiments were
performed with an in-house built apparatus as shown in Figure
2. Both the CO2 absorption and desorption tests were carried
out using the same apparatus, which mainly consisted of two
steel vessels, one for gas storage (80.7 0.1 cm3) and the other
for gas absorption into liquid (33.9 0.1 cm3). The
temperatures of both vessels were controlled by silicon oil
baths with an accuracy of 0.1K. The pressure of the system
C

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respectively, according to the deviation found from the
reproduction of at least two measurements.

Table 1. Model Parameters for the Density Correlation in Eq

1 as a Function of the Mole Fraction of the Ionic Liquid in
the Blend

3. RESULTS AND DISCUSSION

3.1. Density of [P4444][Gly] and Blends. The density of a
solvent is an important physical property for the evaluation of
reaction kinetics and mass transfer, as well as the estimation of
the CO2 solubility in the solvent. In this work, the pressure
drop method was employed to estimate the CO2 solubility in
the ionic liquid and blends, so the density of the solvent was
required to calculate the gas-phase volume.
The densities of [P4444][Gly], PEG400, and their blends were
measured for the temperature range of 2080 C with an
accuracy of 1% under ambient-pressure conditions (see Table
S1 in the Supporting Information). The densities of deionized
water and the [P4444][Gly]PEG400 blends were also
measured to ensure the reliability of the apparatus and validate
the experiments. The density data for deionized water agreed
well with the literature with a standard deviation of 0.2%. The
measured density data were tted as a function of the mole
fraction of the ionic liquid at dierent temperatures using the
empirical correlation47
b
b
b
2
= b1 + 2 (1 1) exp 3 + 4 1 + b5 1
T
T
T
T
(1)

parameter

value

b1
b2
b3
b4
b5
AARD (%)

0.8142
78.1176
12.8995
36.2356
2.5529
0.166

the density decreases as the concentration of PEG400 in the

blend decreases and as the temperature increases. The density
correlation given in eq 1 tted the experimental data very well
with an AARD of 0.166% for all of the concentrations and
temperatures. A comparison of the experimental and modeled
density data is presented in Figure 4, which shows that the
model predicts the densities very well.

where 1 is the weight fraction of the ionic liquid [P4444][Gly]

in the blend and b1, b2, b3, b4, and b5 are tted parameters of eq
1. The density data and tting are presented in Figure 3. The

Figure 4. Parity plot between the experimental and predicted densities

of [P4444][Gly] and blends with PEG400.

The density of PEG400 measured in this work was compared

with the literature4850 to verify the accuracy of the test
apparatus, as shown in Figure 5.4850 For example, Wu et al.48
reported the density of PEG400 as 1.1122, 1.0973, and 1.0815
g/cm3 at 40, 60, and 80 C, respectively, which are in good
agreement with the values observed in this work. Density data
for [P4444][Gly] are not available in the literature.
3.2. Viscosity. Viscosity is an important parameter in the
selection of the solvent for CO2 capture. The viscosities of the
ionic liquid [P4444][Gly], PEG400, and their blends were
measured for the temperature range of 2090 C (Table S2).
The results for these measurements are presented in Figure 6.
The experimental viscosity data were correlated by the
equation47

Figure 3. Densities of [P4444][Gly], PEG400, and blends as a function

of increasing ionic liquid concentration in the blend at (olive triangles)
20 C, (blue plusses) 30 C, (red squares) 40 C, (gray circles) 60 C,
and (green diamonds) 80 C. The uncertainty in the density is 0.05%.

objective function is dened as the absolute average relative

deviation, given by
AARD (%) =

1
n

i=1

|exp, i mod, i |
exp, i

100

k
k
kxx
k1x1
k x x 2
= 1 +
+ 2 12 2 exp1 + 3 + 42 + 5 13 2

T
T
T
T
T

(2)

where the subscripts exp and mod indicate the experimental

and modeled results, respectively. The tted parameters of eq 1
are provided in Table 1.
At a constant temperature, the density of PEG400 is greater
than that of [P4444][Gly]. The results in Figure 3 indicate that

(3)

and the tted parameters are presented in Table 2. The

criterion for the tting was to minimize the sum of square error
deviation, where the deviation is given as by (exp mod)/exp.
D

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had a maximum value of 358.4 mPas at a temperature of 20 C,

and this decreased to 22.5 mPas at a temperature of 90 C.
Under these conditions, the viscosities of the absorbents
became comparable to those of aqueous alkanol amine
solutions.
From Figure 6, it can be observed that the viscosity
decreased dramatically at temperatures lower than 70 C, and
then the reduction became less signicant at higher temperatures.
The model dened for viscosity as a function of
concentration and temperature adequately correlates the
experimental data, with square error deviations of 3.77%. A
parity plot of viscosity is shown in Figure 7, which clearly
demonstrates the accuracy of the model.

Figure 5. Densities of PEG400 in the temperature range of 2080 C

and comparison with literature data: (black squares) this work, (blue
triangles) Wu et al.,48 (red circles) Zhang et al.,50 (green triangles)
Han et al.49

Figure 7. Parity plot between the experimental and modeled

viscosities.

3.3. Thermal Decomposition Temperature. As the

precombustion process takes place under high-temperature
conditions (180200 C), the thermal stability of an absorbent
at a temperature of 200 C is a critical consideration in the
selection of the absorbent.
Conventional alkanol amine absorbents are reported to
either experience degradation or cause equipment corrosion at
elevated temperatures.5153 However, ionic liquids are
generally claimed to have high thermal stability.54,55 The
thermal stabilities of the ionic liquid [P4444][Gly], PEG400, and
their blends were determined by thermogravimetric analysis.
The results obtained are presented in Figure 8. The point of
thermal degradation is termed Tonset and was calculated using
TA Instruments Universal Analysis software.
Tonset is dened by the intercept of the baseline of the weight
loss and the tangent line derived from the weight loss versus
temperature curve. The actual thermal degradation is said to
start before Tonset.56 The Tonset values of all of the samples
tested are listed in Table 3. All of these samples showed good
thermal stability up to 200 C. The thermal stability of pure
PEG400 was the best among all of the samples. The pure ionic
liquid [P4444][Gly] exhibited the lowest value of Tonset;
however, even the highest weight loss was only 0.197%,
which is very low.
3.4. Eect of Pressure on CO2 Solubility. The eects of
pressure on the CO2 solubility in mixtures of [P4444][Gly] and

Figure 6. Viscosities of the systems as a function of temperature:

(black squares) PEG400, (red circles) 70 wt % PEG40030 wt %
[P4444][Gly], (blue triangles) 50 wt % PEG40050 wt % [P4444][Gly],
(green triangles) 30 wt % PEG40070 wt % [P4444][Gly], (lines)
tted model. The uncertainty in the viscosities is 3%.

Table 2. Fitted Model Parameters for Viscosity as a Function

of the Mole Fraction of the Ionic Liquid in the Blend
parameter

value

k1
k2
k3
k4
k5

721.184
171519.275
2290.084
996741.678
52581.902

It can be seen from Figure 6 that the viscosity of the solvent

increased as the blend became more concentrated in the ionic
liquid and decreased as the temperature rose. The viscosity of
PEG400 was the lowest among all of the solvents tested, and
that of [P4444][Gly] with the lowest amount of PEG400 was the
highest. The viscosity of the [P4444][Gly]PEG400 mixtures
E

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mole of absorbent. The CO2 solubilities in the [P4444][Gly]

ionic liquid and PEG400 were correlated by the following
empirical correlation based on concentration- and temperaturedependent terms
B
ln PCO2 = A ln + k1 +
1 + k 2 k3
(4)
In this correlation, A and B are concentration-dependent
parameters, dened by the equations
A = A 0 + A1 + A 2 2

(5)

B = B0 + B1 + B2 2 + B33

(6)

whereas k1, k2, and k3 the functions of temperature, given by the

equations
Figure 8. Thermal gravimetric analysis of [P4444][Gly], PEG400, and
blends (N2 ow = 60 mL/min): (pink line) [P4444][Gly], (black line)
PEG400, (red line) 30 wt % [P4444][Gly]70 wt % PEG400, (blue
line) 50 wt % [P4444][Gly]50 wt % PEG400, (green line) 70 wt %
[P4444][Gly]30 wt % PEG400.

Tonset (C)

0
0.3
0.5
0.7
1.0

280.97
262.70
270.70
281.14
296.30

(7)

1
k 2 = expk 2a + k 2b

(8)

k 3a
+ k 3b
(9)
T
The tted parameters derived from the experimental data for
this correlation are reported in Table 4. Figure 9 indicates that

Table 3. Tonset Values of [P4444][Gly], PEG400, and Their

Blends
a

1
k1 = k1a + k1b
T

k3 =

Table 4. Fitted Parameters for CO2 Solubility in the System

as a Function of Weight Fraction and Temperature

Weight fraction of [P4444][Gly] in the blend.

PEG400 were investigated, and the experimental results of CO2

solubility in terms of loading up to a pressure of 18 bar are
presented in Figure 9 (also see Table S3). The loading of CO2
() is represented in terms of the number of moles of CO2 per

parameter

value

parameter

value

A0
A1
A2
B0
B1
B2
B3

0.9074
1.1680
7.5970
0.4795
8.7843
69.530
36.547

k1a
k1b
k2a
k2b
k3a
k3b

1028.481
11.908
49.318
2.2616
1370.94
1.6161

increasing pressure results in an increasing trend in CO2

solubility. This incremental trend in CO2 loading with respect
to pressure is true for both the cases of physical absorption
(PEG400) and chemical absorption ([P4444][Gly] blends with
PEG400). The loadings of CO2 were observed to be within the
range of 0.0131.051 molCO2/molabs for the pressure range of
0.8717.36 bar at 60 C.
The high solubility of the ionic liquid in blends with PEG400
resulted from the chemical reaction between the ionic liquid
and CO2. As the reaction proceeded, the CO2 solubility
increased, and it showed a maximum when the concentration of
[P4444][Gly] in the blend was the highest (70%). The chemical
reaction between the ionic liquid and CO2 takes place at lower
pressures, so that a further increase in pressure could enhance
the CO2 solubility only through the physical absorption of CO2.
It was observed that the time required for the system to
attain equilibrium was longer at low pressures. This eect could
be a result of the increase in viscosity with increasing
concentration of ionic liquid in the blend and the formation
of carbamate species through the chemical reaction taking place
between the ionic liquid and CO2. A higher viscosity of the
absorbent limits the mass-transfer and reaction kinetics, thus

Figure 9. Eects of pressure on the CO2 loading (molCO2/molabs) at a

temperature of 60 C: (gray squares) PEG400, (red circles) 70 wt %
PEG40030 wt % [P4444][Gly], (blue triangles) 50 wt % PEG40050
wt % [P4444][Gly], (pink triangles) 30 wt % PEG40070 wt %
[P4444][Gly]. The uncertainties in the CO2 loading values and
equilibrium partial pressures of CO2 are 3% and 5%, respectively.
F

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resulting in a signicantly longer time required to attain
equilibrium.
3.5. Eects of Temperature and Composition of Ionic
Liquid in the Blend. The ionic liquid was blended with
PEG400 in dierent weight percentages to examine the
optimum CO2 absorption in the blends. The temperature
and the absorbent composition are key factors in carefully
studying CO2 solubility. The experimental results for the
equilibrium partial pressure of CO2 in 70 wt % PEG40030 wt
% [P4444][Gly] as a function of CO2 loading are presented in
Figure 10 for temperatures of 60, 100, and 140 C. The

Figure 10. Eects of temperature on the CO2 solubility in 70 wt %

PEG40030 wt % [P4444][Gly]: (pink triangles) 60 C, (black circles)
100 C, (blue triangles) 140 C. The uncertainties in the CO2 loading
values and equilibrium partial pressures of CO2 are 3% and 5%,
respectively.

experimental data are presented as data points, and the lines are
the tted experimental data resulting from the correlation
dened by eq 4. The CO2 absorption capacity dropped as the
temperature was increased from 60 to 140 C (Table S4). The
CO2 loading was found to have a value of 0.6 at 60 C, which
was the maximum value for all of the temperatures studied in
this work.
The CO2 solubilities for each concentration of ionic liquid in
the blend are presented in panels a and b of Figure 11 at
temperatures of 100 and 140 C, respectively (Tables S5 and
S6). The CO2 solubility was enhanced as the weight percentage
of the ionic liquid in the blend increased at all of the pressures
and temperatures studied. In Figure 11b, one can see that the
CO2 loading in PEG400 was the minimum (0.28). The
addition of the ionic liquid increased the CO2 absorption as a
result of the chemical reaction taking place between the ionic
liquid and CO2. The glycinate anion contains one primary
amine group, which reacts with CO2 and eventually boosts the
absorption capacity. As [P4444][Gly] contains a glycine anion,
the reaction between the ionic liquid and CO2 should have the
same stoichiometry as that between a primary amine and CO2
(i.e., a CO2 loading of 0.5). It can be observed from Figure 11a
that a CO2 loading of 0.5 could be achieved only for
concentrations of ionic liquid in the blend higher than 50 wt
% at all pressures and 60 C. In the case of 30 wt % of the ionic
liquid in the blend, this ratio could be attained at CO2 pressures
greater than 16 bar. The maximum CO2 loading achieved was

Figure 11. Eects of blend composition on the CO2 solubility at (a)

100 and (b) 140 C: (gray squares) PEG400, (red circles) 70 wt %
PEG40030 wt % [P4444][Gly], (blue triangles) 50 wt % PEG40050
wt % [P4444][Gly], (pink triangles) 30 wt % PEG40070 wt %
[P4444][Gly]. The uncertainties in the CO2 loading values and
equilibrium partial pressures of CO2 are 3% and 5%, respectively.

1.08 in the case of 70 wt % of the ionic liquid in the blend,

which represents about 50% higher absorption capacity than for
conventional amines. The plots for the blends with 50 and 70
wt % of the ionic liquid show larger plateaus at higher
pressures, which demonstrates the dominance of the chemical
absorption in the ionic liquid. The model used for CO2
solubility in terms of equilibrium pressure describes the
experimental data quite well at all temperatures. Temperature
also plays a key role in the CO2 solubility in the absorbent. The
CO2 capacity of the absorbent decreased as the temperature
was increased. The CO2 loading was reduced to 0.7 from 1.08
when the temperature approached 140 C.
3.6. Cyclic Capacity of the Solvent. As CO2 absorbents
are intended for use in a continuous absorptiondesorption
process, the cyclic capacity of the absorbent is an important
parameter to be addressed. The cyclic capacity must be
suciently high that the solvent can be reused in a continuous
absorptiondesorption cycle. The CO2 removal eciency
should also be taken into account along with the cyclic
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system was 0.22, which is smaller than the cyclic capacity of the
absorbent in this work.
3.7. Regeneration of the Solvent. Solvent regeneration
consumes most of the energy in an absorption process using
aqueous solvents. Aqueous alkanolamine solvents have the issue
of high energy consumption due to solvent evaporation and
degradation at high temperatures in desorbers.51 As the ionic
liquid [P4444][Gly] and PEG400 have negligible vapor
pressures, solvent evaporation is not an issue for this system,
which makes the absorption process signicantly more energyecient. The 30 wt % [P4444][Gly]70 wt % PEG400 blend
was investigated in a regeneration study.
CO2 was rst absorbed into the blend absorbent at a
temperature of 60 C and a pressure of about 16 bar and
desorbed CO2 at a temperature of 140 C and a pressure of 1
bar. The CO2-rich solvent from the rst cycle was then fed into
the second cycle and so on. Three cycles were run following the
same procedure. The results for CO2 absorption in the three
cycles are shown in Figure 13, where the CO2 loading is plotted

capacity for the optimization of the blend composition. The

cyclic capacity and CO2 removal eciency for all four
concentrations of [P4444][Gly]PEG400 were studied, as
presented in Figure 12. The cyclic capacity of an absorbent
can be determined by the dierence between the CO2 loading
under absorption conditions and that under stripping
conditions.

Figure 12. Performance analysis of solvents according to the (blue

squares) CO2 removal eciency and (black circles) cyclic absorption
capacity.

The CO2 removal eciency was calculated as

CO2 removal efficiency =
100

CO2 absorbed CO2 stripped

CO2 absorbed
(10)

The cyclic capacity experiments were carried out by testing

CO2 absorption at 60 C and stripping at 140 C, with relative
propagation errors of 3.2% and 5.2% for the cases of physical
and chemical absorption, respectively. It can be observed from
Figure 12 that the CO2 removal eciency decreased from 96%
to 12% as the concentration of the ionic liquid in the blend was
enhanced, but the cyclic capacity followed the opposite trend
up to an ionic liquid concentration of 50 wt %.
The cyclic capacity was reduced as the concentration of ionic
liquid was increased beyond 50 wt %. The reason for this
nding could be that equilibrium was not achieved completely
in the tests of the solvents with higher concentrations of ionic
liquid. The performances of the blends with 30 and 50 wt % of
the ionic liquid were found to be comparable, which indicates
that the best performance of the absorbent in terms of cyclic
capacity and CO2 removal eciency can be achieved for 3050
wt % of the ionic liquid in the blend. Given that the ionic liquid
is quite viscous compared to PEG400 and that a higher amount
of ionic liquid in the blend will lead to a higher viscosity of the
blend and, hence, low mass-transfer rates, the blend with 30 wt
% of the ionic liquid was considered to be the optimal
absorbent and was further studied in this work. Pinto et al.57
conducted experiments for the absorption and desorption of
ionic liquids that function as physical and chemical absorbents.
According to their studies, the cyclic capacity of an ionic liquid
follows the same trend as shown here. The cyclic capacity
reaches a minimum for the highest concentration of chemical
absorbent. The maximum attainable cyclic capacity in their

Figure 13. Regeneration eciency of the solvent 30 wt %

[P4444][Gly]70 wt % PEG400 in three absorptiondesorption cycles
involving CO2 absorption at 60 C and desorption at 140 C.

against the number of regeneration cycles. It can be clearly seen

from Figure 13 that there were no appreciable dierences in the
CO2 loading and absorbent among the three cycles. The
dierences in the CO2 loading between the rst and second
cycles as well as between the second and third cycles were fairly
small and within the range of the error bars (5%), most likely
resulting from the uncertainty in measuring the pressures.
Moreover, the tested blend solvent exhibits both physical and
chemical absorption, so the absorption capacity can also be
expected to vary to a small extent. These results also indicate
that chemical reaction between the ionic liquid and CO2 can be
reversed at high temperature (140 C) and that the solvent can
be reused during the absorption process. The regeneration
eciency of a combined physical- and chemical-absorbent
solvent (an amino-acid-based ionic liquid) is reported by Li et
al.,39 and according to their ndings, the absorbent lost 19% of
its CO2 absorption capacity after the rst regeneration cycle. In
contrast, the regeneration eciency of the absorbent in this
work was approximately 95% after the rst cycle and 87.9%
after three cycles.
3.8. Comparison with the Literature. The blends of
amino acid ionic liquid and PEG400 in this work showed
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on the cyclic capacity and CO2 removal eciency, but 30 wt %

[P4444][Gly] was chosen as the optimal solvent considering the
high viscosity and cost of the ionic liquid. A correlation derived
on the basis of concentration- and temperature-dependent
terms tted the experimental data well in the observed
temperature and pressure ranges. This validates the accuracy
of the experimental data. The regeneration of the absorbent was
veried by a temperature swing from 60 to 140 C and a
pressure swing from 16 to 1 bar, which demonstrated the
reversibility of the reaction and possibility for reuse of the
absorbent.59

procient CO2 solubility, indicating that they are suitable for

CO2 separations at elevated temperatures and pressures.
However, data for blended solvents have scarcely been reported
at similar conditions. A comparison is made in Figure 14 with
the few reported data on blended amineIL solvents, where the
CO2 solubility is represented by the CO2 loading (moles of
CO2 per mole of absorbent).

ASSOCIATED CONTENT

S Supporting Information
*

The Supporting Information is available free of charge on the

ACS Publications website at DOI: 10.1021/acs.iecr.6b02457.
Densities of [P4444][Gly], PEG400, and blends as a
function of increasing ionic liquid concentration in the
blend at 20, 30, 40, 60, and 80 C (Table S1), viscosities
of the systems PEG400, 70 wt % PEG40030 wt %
[P4444][Gly], 50 wt % PEG40050 wt % [P4444][Gly],
and 30 wt % PEG40070 wt % [P4444][Gly] as a
function of temperature (Table S2), eects of pressure
on the CO2 loading (molCO2/molabs) at a temperature of
60 C for PEG400, 70 wt % PEG40030 wt %
[P4444][Gly], 50 wt % PEG40050 wt % [P4444][Gly],
and 30 wt % PEG40070 wt % [P4444][Gly] (Table S3),
eects of temperature on the CO2 solubility in 70 wt %
PEG40030 wt % [P4444][Gly] (Table S4), eects of
blend composition on CO2 solubility at 100 C (Table
S5), and eects of blend composition on CO2 solubility
at 140 C (Table S6) (PDF)

Figure 14. Comparison of the CO2 solubility in the ionic liquid

PEG400 blend and the reported literature at 60 C: (black squares) 70
wt % [P4444][Gly]30 wt % PEG400, (red line) 30 wt % MEA10 wt
% [C2OHmim][DCA],58 (blue line) 4 M MDEA1 M [gua][OTf].59

Monoethanolamine (MEA) and methyldiethanolamine

(MDEA) are the most industrially used solvents for CO2
absorption. The results obtained in this work were compared
with those reported for MEAIL and MDEAIL blend
absorbents. The ionic liquidPEG400 blend tested in this
work exhibits a higher CO2 solubility than the reported 30 wt %
MEA10 wt % [C2OHmim][DCA]58 and 4 M MDEA1 M
[gua][OTf]59 blends {where [C2OHmim][DCA] is 1-(2hydroxyethyl)-3-methyl-imidazolium dicyanamide and [gua][OTf] is guanidinium triuoromethanesulfonate}. Both of the
reported ionic liquidamine absorbents also chemically react
with CO2. The 4 M MDEA1 M [gua][OTf] blend was found
to have a lower CO2 solubility than the 30 wt % MEA10 wt %
[C2OHmim][DCA] blend.

AUTHOR INFORMATION

Corresponding Author

*E-mail: deng@nt.ntnu.no.
Notes

The authors declare no competing nancial interest.

ACKNOWLEDGMENTS
This work was supported by the Research Council of Norway
through the CLIMIT program (MCIL-CO2 project, 215732).

4. CONCLUSIONS
Four dierent blending ratios of [P4444][Gly] and PEG400 in
blend solvents and the CO2 absorption behaviors of these
solvents at temperatures of 60, 100, and 140 C were reported
in this work. The density of [P4444][Gly] was found to be less
than that of water, whereas the density of PEG400 is more than
those of both deionized water and [P4444][Gly]. The viscosity
of the blend solvent decreased with increasing addition of
PEG400. The blends of [P4444][Gly] and PEG400 exhibited
high thermal stability in tests up to 200 C, making them
feasible for precombustion applications at elevated operating
temperatures. CO2 absorption could be achieved to a loading of
1.23 molCO2/molabs at a temperature of 60 C and a pressure of
17 bar when pure [P4444][Gly] was used, but the cyclic capacity
of the solvent and its CO2 removal eciency were low. The
optimum CO2 absorption was observed within the concentration range of 3050 wt % of [P4444][Gly] in the blend based

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