pubs.acs.

org/IECR Article

Efficient SO2 Absorption by Anion-Functionalized Deep Eutectic

Solvents
Ge Cui, Dezhong Yang,* and Hongbin Qi*
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ABSTRACT: In this work, the anion-functionalized deep eutectic

solvents (DESs) comprising solid organic salt tetraethylammonium
Downloaded via UNIV TEKNOLOGI PETRONAS on June 14, 2021 at 14:23:46 (UTC).

tetrazolate ([N2222][Tetz]) and ethylene glycol (EG) at a molar ratio

1:2 were synthesized to capture SO2. DESs [N2222][Tetz]-EG(1:2)
could capture 0.853 g of SO2/g solvent (4.31 mol SO2/mol solvent) at
1.0 atm and 20 °C. Interestingly, [N2222][Tetz]-EG(1:2) exhibited a
high SO2 absorption capacity of 0.140 g of SO2/g solvent (0.708 mol SO2/mol solvent) at 2000 ppm, which was much higher than
the absorption capacity (0.002 g of SO2/g solvent or 0.009 mol SO2/mol solvent) of non-functionalized DESs consisting of
tetraethylammonium chloride ([N2222][Cl])-EG(1:2) under the same conditions. Moreover, [N2222][Tetz]-EG(1:2) can be reused
and showed good reversibility. Nuclear magnetic resonance and Fourier transform infrared results indicated that the high SO2
absorption capacity of [N2222][Tetz]-EG(1:2) was due to the chemical reaction between SO2 and anion [Tetz]−, and the SO2
absorption enthalpy of [N2222][Tetz]-EG(1:2) was −52.7 kJ/mol which also confirmed the strong interaction between SO2 and
[N2222][Tetz]-EG(1:2).

■ INTRODUCTION
Air pollution is an ever-increasing issue which should be
addressed by humans as a result of the fast development of the
world economy. SO2 is a toxic and main air contaminant that
could cause acid rain, smog, and respiratory diseases, posing a
high risk to the environment and human health. SO2 mainly
arises from the industrial process by burning coal and oil.1 The
widely commercialized method to reduce SO2 emissions in the
industry is the wet limestone flue gas desulfurization (FGD)
technology with a high SO2 removal efficiency, which uses an
aqueous suspension of limestone to capture SO2.2 However,
the limestone-based method holds inherent problems, such as
an irreversible absorption process, large water consumption,
equipment corrosion, and high capital cost.3,4 Although the
ammonia scrubbing method is another popular FGD process,
it suffers from several drawbacks including solvent volatiliza-
tion, degradation, and intense energy cost for regeneration.5
In the past decade, ionic liquids (ILs) have received great
attention as promising SO2 absorbents because of their
inherent properties including extremely low vapor pressure
and high thermal stability.6,7 A lot of ILs have been developed
to capture SO2 since the first example was reported by Han et
al. in 2004.8 In particular, functionalized ILs containing amine
groups on cations or anions exhibit a high SO2 loading capacity
because SO2 chemically interacts with amine groups by
forming a charge-transfer complex, which can be decomposed
by heating, ensuring the reversibility of absorbents and the
recovery of SO2.9−12 However, the multiple synthesis
procedures of these amine-based ILs render their practical
applications unsuitable.
Recently, a new class of solvent called deep eutectic solvents
(DESs) has been investigated to capture acid gases, such as
CO2,13−16 NO,17 and SO2.18,19 DESs are liquid mixtures with
high purity formed by two or more components under
appropriate conditions.20 Most DESs are obtained by mixing
hydrogen bond donors (HBDs) with hydrogen bond acceptors
(HBAs), in which the intermolecular hydrogen bonds are
formed between HBDs and HBAs that result in the lower
melting point of the mixture than those of the starting
components.21 DESs have many similar properties of ILs such
as low vapor pressure, the ability to dissolve many compounds,
and tunable structures.22 Till now, DESs have been studied for
many applications including material synthesis, organic
reactions, electrochemistry, and nanotechnology.23−25 More-
over, DESs are also used in the field of SO2 absorption. Among
them, the choline chloride-based26,27 and azole-based28−30
DESs exhibit a high SO2 absorption capacity. In our previous
work, we found that the DESs formed by 1-ethyl-3-
methylimidazolium chloride ([Emim][Cl]) with ethylene
glycol (EG),31 triethylene glycol (TEG),32 or succinonitrile33
can also efficiently capture SO2 with a high gravimetric
capacity.
Received: October 12, 2020
Revised: March 3, 2021
Accepted: March 10, 2021
Published: March 22, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.iecr.0c04981

4536 Ind. Eng. Chem. Res. 2021, 60, 4536−4541
Industrial & Engineering Chemistry Research
As we know, the SO2 concentration in flue gas is extremely
low (∼0.20 vol %), thus designing new DESs with a high
absorption capacity for low concentration SO2 is still needed.
At present, the anion in DESs used for SO2 absorption is
chloride or bromide, and its ability to capture SO2 at low SO2
partial pressure is reduced because of the strong hydrogen
bonding existed between anions and HBDs, which weakens the
interaction between anions and SO2. Therefore, if chloride or
bromide used in DESs is replaced by other anions which can
chemically capture SO2, the DESs’ absorption capacity for low
concentration SO2 will be increased.
On the basis of above analysis, we synthesized anion-
functionalized DESs consisting of tetraethylammonium
tetrazolate ([N2222][Tetz]) and EG for SO2 absorption.
Interestingly, the results indicated that DESs [N2222][Tetz]-
EG (1:2, molar ratio) could capture 0.140 g of SO2 per g of
solvent at 2000 ppm and 20 °C, which was much higher than
the absorption capacity (0.002 g of SO2/g solvent) of non-
functionalized DESs consisting of tetraethylammonium
chloride ([N2222][Cl]) and EG at a 1:2 molar ratio under
the same conditions. The structures of [N2222][Tetz] and
[N2222][Cl] used in this work are shown in Scheme 1.
Scheme 1. Structures of [N2222][Tetz] and [N2222][Cl]
■ EXPERIMENTAL SECTION
Materials and Characterization. Tetraethylammonium
hydroxide (35% w/w) and tetraethylammonium chloride
(98%) were purchased from Alfa Aesar. Tetrazole (98%) was
obtained from Beijing Ouhe Sci. and Tech. Co. Ltd. EG
(99.5%) was provided by J&K Scientific Ltd. SO2 (99.9%) and
SO2 of 2000 ppm in the mixture of N2−SO2 were provided by
Beijing ZG Special Gases Sci. and Tech. Co. Ltd. The infrared
spectra were recorded on a PerkinElmer Frontier FTIR
spectrometer on KBr disks. The 1H NMR spectra were taken
on a Bruker spectrometer (400 MHz), and the 13C NMR
spectra were recorded at 100.6 MHz using the DMSO-d6 as
the internal reference. Differential scanning calorimetry (DSC)
curves were determined on a TA-Q200 equipment. Samples
were cooled to −70 °C under a N2 atmosphere and then
heated with a rate of 10 °C/min. The DSC data used in this
work were obtained from the second heating cycle.
Synthesis of [N2222][Tetz]. The IL [N2222][Tetz] was
prepared based on the reported procedure.11 The concen-
tration of [N2222][OH] in water was titrated with potassium
hydrogen phthalate. Equimolar tetrazole was added to the
water solution of [N2222][OH]. After the mixture was stirred
for 4 h at room temperature, the water in the solution was
removed by using rotary evaporation at 70 °C, and the
obtained product was dried under vacuum at 80 °C.
Synthesis of DESs. The organic salt and EG were simply
mixed at the molar ratio of 1:2, and then, the mixture was
stirred at 80 °C until a homogeneous liquid was obtained,
which was cooled to room temperature prior to use.
4537
pubs.acs.org/IECR Article
Absorption and Desorption of SO2. The experimental
details of absorption and desorption of SO2 can be found in
our previous report.33
The SO2 capacity was determined using a glass tube with an
inner diameter of 10 mm. At first, DES (∼1.0 g) was added
into the tube, and a rubber lid with two needles was used to
seal the tube. One needle was for the SO2 inlet, and the other
one was for the SO2 outlet. Then, the tube was partially
immersed into a water bath at desired temperature. Pure SO2
(50 mL/min) was bubbled into the DESs through the needle.
The weight of the tube was determined by a balance (±0.1
mg) at regular time. SO2 absorption capacity of the DESs can
be calculated from the weight change of the tube before and
after SO2 absorption.
For the absorption of 2000 ppm SO2, the flow rate of SO2 of
2000 ppm was 100 mL/min.
After SO2 absorption, the glass tube was partially immersed
in an oil bath at 80 °C. N2 was bubbled into the solution in the
tube at a rate of 50 mL/min. The weight of the tube was also
determined by the balance (±0.1 mg) at regular time during
the desorption process.
■ RESULTS AND DISCUSSION
[N2222][Tetz] can be easily obtained by the neutralization
reaction between the traditional aqueous solution of
[N2222][OH] and tetrazole. [N2222][Tetz] is solid at room
temperature, and it can form a liquid mixture with EG at a 1:2
molar ratio. The DSC curve of [N2222][Tetz]-EG(1:2) is
shown in Figure S1. As can be seen in Figure S1, no melting
point can be found even down to −70 °C, suggesting the
formation of DESs. The amount of SO2 captured by
[N2222][Tetz]-EG(1:2) and [N2222][Cl]-EG(1:2) at 20 °C
and 1.0 atm is presented in Figure 1. It can be found that
Figure 1. Absorption of SO2 by DESs at 20 °C and 1.0 atm.
[N2222][Tetz]-EG(1:2) could capture 0.853 g of SO2/g solvent
(4.31 mol SO2/mol solvent), which is higher than the
absorption capacity (0.791 g of SO2/g solvent or 3.58 mol
SO2/mol solvent) of [N2222][Cl]-EG(1:2), indicating the
important role of anion in improving the absorption capacity
of DESs.
The reversibility of [N2222][Tetz]-EG(1:2) has been
investigated because of its high absorption capacity. Most
SO2 (>99%) absorbed by [N2222][Tetz]-EG(1:2) can be
released by bubbling N2 at 80 °C. As shown in Figure 2, no
notable loss of capacity can be found in the five consecutive
absorption−desorption processes, suggesting the good rever-
sibility of [N2222][Tetz]-EG(1:2) DESs. [N2222][Tetz]-EG-
(1:2) also showed good thermal stability (Figure S2).
The SO2 absorption capacity of the solvent used in this work
at 2000 ppm of SO 2 was also studied because the
https://doi.org/10.1021/acs.iecr.0c04981
Ind. Eng. Chem. Res. 2021, 60, 4536−4541
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

that the absorption capacity of [N2222][Tetz]-EG(1:2) at 2000

Figure 2. Five consecutive absorption−desorption cycles of [N2222]-
[Tetz]-EG(1:2). Absorption: 20 °C; and desorption: 80 °C.
ppm decreased contentiously with increasing temperature. As
the temperature increased from 20 to 50 °C, SO2 absorption
capacity of [N2222][Tetz]-EG(1:2) decreased from 0.140 to
0.050 g of SO2/g solvent, indicating that low temperature is
favorable for SO2 absorption.
The interactions between SO2 and DESs have been
investigated by using FTIR and NMR characterization
methods. The FTIR spectra of [N2222][Cl]-EG(1:2) and
[N2222][Tetz]-EG(1:2) before and after SO2 absorption are
shown in Figures 4 and 5, respectively. Compared with the

concentration of SO2 in flue gases is very low (∼0.20 vol %).

[N2222][Tetz]-EG(1:2) could capture 0.140 g of SO2/g solvent
(0.708 mol SO2/mol solvent) at 20 °C and 2000 ppm.
However, [N2222][Cl]-EG(1:2) only captured 0.002 g of SO2/
g solvent, which was much lower than the capacity of
[N2222][Tetz]-EG(1:2) under the same conditions. The SO2
capacity of [N2222][Tetz]-EG(1:2) was compared with those of
other DESs (Table 1). Moreover, the gravimetric absorption
Figure 4. FTIR spectra of [N2222][Cl]-EG(1:2) before and after SO2
Table 1. SO2 Absorption Capacities of Different DESs under absorption.
Low SO2 Concentration
absorbent T/°C SO2/ppm capacitya reference
[N2222][Tetz]-EG(1:2) 20 2000 0.140 this work
[Emim][Cl]-NMF(1:1) 20 2000 0.135 37
[Emim][Cl]-SN(1:1) 20 2000 0.120 33
[Emim][Cl]:2-Pyr(1:1) 20 2000 0.115 38
[Emim][Cl]:2-Pyr(1:2) 20 2000 0.088 38
[Emim][Cl]-EG(1:1) 20 2000 0.047 33
Im-Gly(1:2) 40 2000 0.161b 29
L-car:EG(1:3) 40 3700 0.119 39
ACC-Im(1:2) 40 3300 0.116b 28 Figure 5. FTIR spectra of [N2222][Tetz]-EG(1:2) before and after
Bet-EG(1:3) 40 3700 0.0342 39 SO2 absorption.
PPZBr-Gly(1:4) 20 10,000 0.103 40
[Bmim][Cl]-Im(2:1) 20 20,000 0.225 30
a
g SO2/g solvent. bAvailable capacity. FTIR spectrum of fresh solvent, two new peaks at 1310 and
1141 cm−1 could be found in the spectrum of [N2222][Cl]-
capacity of [N2222][Tetz]-EG(1:2) is also higher than that of EG(1:2) after SO2 absorption (Figure 4), which were assigned
IL [P66614][Tetz] (0.101 g of SO2/g solvent) at 2000 ppm. The to asymmetrical and symmetrical stretching vibrations of SO2,
higher SO2 absorption capacity of [N2222][Tetz]-EG(1:2) at respectively.34,35 The asymmetrical stretching band of SO2 in
2000 ppm is mainly due to the strong interaction between SO2 the [N2222][Tetz]-EG(1:2) system centered at 1230 cm−1
and anion [Tetz]−,9,11 which is investigated using FTIR and (Figure 5), which was lower than that in the [N2222][Cl]-
nuclear magnetic resonance (NMR) spectra in the following EG(1:2) (1310 cm−1) system, indicating that the interaction
section. between [Tetz]− and SO2 was stronger than that between
The effect of temperature on SO2 absorption was also [Cl]− and SO2. Moreover, another new absorption peak at 968
studied, and the results are shown in Figure 3. It can be seen cm−1 attributable to the S−O stretch band can be seen in the
spectrum of [N2222][Tetz]-EG(1:2) after SO2 absorption,11
suggesting the chemical interaction between SO2 and anion
[Tetz]−.
The chemical reaction between SO2 and [Tetz]− was further
confirmed by analyzing the NMR results of [N2222][Tetz]-
EG(1:2) before and after SO2 absorption (Figure 6). After SO2
absorption, the typical signal of anion [Tetz]− shifted
downfield from 8.14 to 9.28 ppm in 1H NMR spectra and
shifted upfield from 149.6 to 144.2 ppm in 13C NMR spectra.9
On the basis of above findings, the proposed chemical
absorption mechanism of SO2 by [N2222][Tetz]-EG(1:2) is
presented in Scheme 2.
Figure 3. Effect of temperature on SO2 absorption by [N2222][Tetz]- Based on the above results, it can be concluded that there
EG(1:2) at 2000 ppm. are two kinds of SO2 absorption in [N2222][Tetz]-EG(1:2)
4538 https://doi.org/10.1021/acs.iecr.0c04981
Ind. Eng. Chem. Res. 2021, 60, 4536−4541
Industrial & Engineering Chemistry Research pubs.acs.org/IECR Article

Figure 6. NMR spectra of [N2222][Tetz]-EG(1:2) before and after SO2 absorption: (a) 1H NMR and (b) 13C NMR.

Scheme 2. Proposed Reaction Mechanism between SO2 and

[N2222][Tetz]-EG(1:2)

DESs: physical absorption and chemical absorption, which can

be directly expressed as eqs 1 and 2, respectively.
Figure 7. Linear relationship between ln Kx and 1/T for [N2222]-
H [Tetz]-EG(1:2).
SO2 (g) → SO2 (l) (1)
K1
SO2 (l) + IL(l) ⎯→
⎯ IL‐SO2 (l) (2)
(−53.2 kJ/mol),36 indicating the strong interaction between
where H is Henry’s law constant and K1 is the equilibrium SO2 and [Tetz]−.
constant. Therefore, the overall reaction can be expressed as eq
3
K
■ CONCLUSIONS
The DESs consisting of [N2222][Tetz] and EG exhibited a high
SO2 (g) + IL(l) → IL‐SO2 (l) (3) SO2 absorption capacity, especially at low SO2 partial pressure.
where K, expressed as eq 4, is the equilibrium constant of the [N2222][Tetz]-EG(1:2) showed a SO2 absorption capacity of
overall reaction. 0.140 g of SO2/g solvent (0.708 mol SO2/mol solvent) at 20
γIL ‐ SO x IL ‐ SO2 °C and 2000 ppm, which was much higher than that of
x IL ‐ SO2 γIL ‐ SO2 γIL ‐ SO
K= 2
= P • = K x• 2 [N2222][Cl]-EG(1:2) (0.002 g of SO2/g solvent) under the
PSO2
γSO θ γILx IL
SO2
x γ γ
SO2 IL
γ γ
SO2 IL same conditions. The high capacity of [N2222][Tetz]-EG(1:2)
2 P P θ IL (4)
was due to the chemical reaction between SO2 and anion
∂ ln K ∂ ln Kx ΔH [Tetz]−, which was confirmed by NMR and FTIR results as
= = r 2 well as the absorption enthalpy of [N2222][Tetz]-EG(1:2)
∂T ∂T RT (5)
(−52.7 kJ/mol). We believed that this work will promote the
In eq 4, γSO2 is the fugacity coefficient of SO2 in the gas phase. development of DESs and open new pathways for DES design
γIL and γIL‑SO2 are activity coefficients of IL and IL-SO2 with the aim of improving the absorption capacity for low
concentration SO2.

■
complex in the liquid phase, respectively. PSO2 is the pressure
of SO2 in kPa, andPθ refers to the standard pressure of 100 kPa. ASSOCIATED CONTENT
xIL andxIL‑SO2 are molar fractions of IL and IL-SO2 complex, * Supporting Information
sı
respectively. Since SO2 concentration is extremely low (2000 The Supporting Information is available free of charge at
ppm), γSO2 can be regarded as 1. The activity coefficients γIL https://pubs.acs.org/doi/10.1021/acs.iecr.0c04981.
and γIL‑SO2 can be assumed as constant when the temperature DSC curves of [N2222][Tetz]-EG(1:2) and thermal
increased from 20 to 50 °C because the change of temperature stability of [N2222][Tetz]-EG (1:2) at 80 °C under the
was little and the effect of temperature on the activity N2 sweeping process (PDF)
coefficient can be neglected. After above deduction, eq 5 can
be obtained according to the van’t Hoff equation. The
absorption enthalpy (ΔrH) of [N2222][Tetz]-EG(1:2) can be
■ AUTHOR INFORMATION
Corresponding Authors
calculated using eq 5 by drawing a linear fit of ln Kx to 1/T Dezhong Yang − School of Science, China University of
(Figure 7). The value of absorption enthalpy was found to be Geosciences, Beijing 100083, China; orcid.org/0000-
−52.7 kJ/mol, which was close to that of [P66614][Tetz] 0003-4490-3423; Email: yangdz@cugb.edu.cn
4539 https://doi.org/10.1021/acs.iecr.0c04981
Ind. Eng. Chem. Res. 2021, 60, 4536−4541
Industrial & Engineering Chemistry Research
Hongbin Qi − School of Science, China University of
Geosciences, Beijing 100083, China; Email: qihb@
cugb.edu.cn
Author
Ge Cui − School of Science, China University of Geosciences,
Beijing 100083, China
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.iecr.0c04981
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors are grateful to the Fundamental Research Funds
for the Central Universities (no. 2652019111) and the
National Natural Science Foundation of China
(no.21503196) for financial support.
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