International Journal of Greenhouse Gas Control 74 (2018) 119–129

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International Journal of Greenhouse Gas Control

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

An interactive chemical enhancement of CO2 capture in the MEA/PZ/AMP/ T

DEA binary solutions
⁎
Tingting Zhang, Yunsong Yu, Zaoxiao Zhang
State Key Laboratory of Multiphase Flow in Power Engineering, School of Chemical Engineering and Technology, Xi’an Jiaotong University, No. 28 Xianning West Road,
Xi’an 710049, PR China

A R T I C LE I N FO A B S T R A C T

Keywords: Chemical absorption is an effective method for CO2 capture. Due to their high absorption/desorption efficiency,
CO2 capture amines have been used in single or blended form. Compared with the single ones, blended solvents usually show
Interactive reaction better absorption/desorption performance because of their interactive enhancement effect, however the me-
Blended solvents chanism is still unclear. In this study, the chemical interactive reaction is assumed to be one of the key factors for
Chemical enhancement
the enhancement. Based on this, the reactions of CO2 absorption in binary amine solvents (the binary mixtures of
DFT
monoethanolamine (MEA)/piperazine (PZ)/2-amino-2-methyl-1-propanol (AMP)/diethanolamine (DEA)) have
been investigated. The ab initio method with Density Functional Theory (DFT) is adopted in the simulations.
Compared with other amines, numerical results showed that PZ presents the lowest forward energy barrier and
the second lowest backward energy barrier in zwitterion formation. During the intermolecular hydrogen transfer
processes, PZ shows a significant enhancement effect on MEA/DEA/AMP in the interactive reactions. For MEA, it
shows an enhancing effect on AMP but hindering effect on PZ and DEA. Moreover, it was found that the
MEA+COO− based reactions have good absorption property while the AMP+COO− based ones have good
desorption performance. These findings reveal the interactive effect between different amines during the in-
teractive reactions, which may provide theoretical instructions for solvent screening of blended solutions.

1. Introduction include secondary amines (e.g., diethanolamine (DEA)), tertiary amines

CO2 capture, utilization and storage (CCUS) from coal-fired flue
gases is considered as a useful way to reduce the large amount CO2
emission and alleviate the global climate change (IEA, 2015). One
commonly used CO2 capture method is the well-established chemical
absorption and desorption by aqueous amine solutions (Rochelle,
2009), which selectively react with CO2 from flue gases at appropriate
temperature and pressure. A large number of studies on solvent
screening have been conducted, including experiments and simulations.
Usually the absorption capacity, reaction kinetics, and regenerative
potential of the amine solutions are shed light on (Mumford et al., 2015;
Wang et al., 2011). It has been found that aqueous amine solutions with
single solvent perform well in some desired CO2 capture characteristics,
but some disadvantages were also reported (El Hadri et al., 2017; Zhu
et al., 2012). Monoethanolamine (MEA) is an alkanolamine frequently
used in CO2 absorption due to its fast reaction rate and good reaction
kinetics (Rochelle, 2009; Wang et al., 2011; Yildirim et al., 2012). The
main disadvantages are the limited CO2 absorption capacity and high
regeneration energy consumption. Other commonly discussed amines
(e.g., methyldiethanolamine (MDEA)), sterically hindered amines (e.g.,
2-amino-2-methyl-1-propanol (AMP)) and cyclic amines (e.g., Piper-
azine (PZ)) (Hüser et al., 2017; Mumford et al., 2015). AMP and MDEA
have been found to have a lower regeneration energy duty but with a
much slower reaction rate as compared with that of MEA (Hüser et al.,
2017; Liu et al., 2016; von Harbou et al., 2013). PZ has a superior
absorption rate as compared to primary amines but the viscosity is too
high (Bishnoi and Rochelle, 2000; Rochelle et al., 2011). The research
results show that single amine solvents always have some dis-
advantages, hence it is not easy to develop a perfect single amine so-
lution.
To improve CO2 capture performance, mixed solvents are proposed
and supposed to take advantage of every single component (El Hadri
et al., 2017). Binary amine solvents, as the simplest type of mixed so-
lution, emerged first. For instance, the blends of primary and tertiary
amines (e.g., mixtures of MEA and MDEA) or secondary and tertiary
amines (e.g., mixtures of DEA and MDEA) could combine the high re-
action rate of the primary/secondary amine and high equilibrium ca-
pacity of the tertiary amine (Edali et al., 2009). Other than MDEA, AMP

⁎
Corresponding author.
E-mail address: zhangzx@mail.xjtu.edu.cn (Z. Zhang).

https://doi.org/10.1016/j.ijggc.2018.04.023
Received 20 October 2017; Received in revised form 25 March 2018; Accepted 26 April 2018
Available online 04 May 2018
1750-5836/ © 2018 Elsevier Ltd. All rights reserved.
T. Zhang et al. International Journal of Greenhouse Gas Control 74 (2018) 119–129

and PZ are also often used in mixed solvent solutions. The AMP solu- this work, zwitterion formation is used as the reaction mechanism of
tions blended with MEA or DEA improve the absorption capacity and CO2 absorption in blended amine solutions to discuss the interactive
reaction kinetics (Mandal and Bandyopadhyay, 2006; Mandal et al., effect.
2003; von Harbou et al., 2013). PZ activates aqueous MDEA and DEA In the following sections, the reaction system would be described
solutions and the mixtures have been successfully applied in CO2 re- first. The amines are chosen as MEA, DEA, AMP and PZ, because MEA
moval for ammonia plants (Max Appl et al., 1982; Samanta and and DEA are typical primary and secondary alkanoamines, AMP is a
Bandyopadhyay, 2011). PZ is also used to activate other aqueous so- classical sterically hindered amine, and PZ is a commonly used cyclic
lutions such as MEA and AMP (Dang and Rochelle, 2003; Lin et al., amine. Then the main chemical processes are presented followed by
2010; Tan and Chen, 2006). PZ solutions blended with tertiary or computational method (the density functional theory is used for cal-
hindered amines usually have faster absorption rate and better CO2 culation). After that, possible reactions in the blended solutions are
cyclic capacity than MEA. Moreover, they also have a high thermal systematically studied. In each reaction process, the reaction energies
stability and low amine volatility (Du et al., 2016; Sun et al., 2005; are calculated and energy barriers are analyzed, also the structure
Yeon et al., 2004). Apart from binary amine solutions, ternary, qua- changes for each reaction configuration are presented. A comprehen-
ternary and quintuple amine systems have also been investigated sive comparison of energy barrier is made to predict the performance of
(Nwaoha et al., 2016; Yu et al., 2013). A tri-solvent solution containing different amines with respect to chemical enhancement effect caused by
AMP, PZ and MEA was found to largely reduce the heat duty in CO2 the interactive reactions. At the end, some major conclusions are drawn
absorption and shows promising potential in industrial application from the simulation results.
(Nwaoha et al., 2016). Extensive researches about blended solvents
were conducted on the overall absorption/desorption performance and 2. Theory and computational details
the results show that the mixed solutions usually have better char-
acteristics than single amine solutions (Mumford et al., 2015; Wang In this paper, six binary amine solutions, MEA + PZ, MEA + AMP,
et al., 2011). Still, screening effective solvent is a research focus for CO2 MEA + DEA, PZ + AMP, PZ + DEA and AMP + DEA are studied. The
capture. However, most of the aforementioned studies are based on main reactions of amines absorbing CO2 include two steps, zwitterion
experimental work and present specific results. Limited works have formation and the subsequently intermolecular hydrogen transfer pro-
been found on the working principle of interactive effect in blended cess (Han et al., 2011; Shim et al., 2009). In the zwitterion formation,
solvents in CO2 absorption and desorption process. As each amine has one amine molecule reacts with one CO2 molecule. The intermolecular
different nucleophilicity and basicity, the interactive reactions between hydrogen transfer process involves two amine molecules and one CO2
different amines would have different reaction properties, such as re- molecule, where these two amine molecules could be the same or dif-
action energies, energy barriers, and structural changes, which may ferent in binary amine solutions. Thus, there are two types of reactions
show enhancement or hindrance effect between the amines. Therefore, in the intermolecular hydrogen transfer process, i.e., purebred reactions
the reactions of CO2 absorption in binary amine systems are discussed (two same amine molecules) and hybrid reactions (two different amine
in this paper to explore the interactive effect (enhancement or hin- molecules).
drance) between different amines, from which the theoretical instruc- For the six binary amine solutions as aforementioned, numerous
tions are supposed to be achieved for solvent screening in blended reactions occur during the CO2 capture. The present model contains 20
combinations. reaction processes, including 4 zwitterion formation processes and 16
Extensive studies have been conducted on CO2 absorption reactions intermolecular hydrogen transfer processes. The 16 intermolecular re-
with amines (especially for the primary and secondary amines, RNH), action processes contain 4 purebred processes MEA+COO− + MEA,
however, the reaction mechanism is disputing, and three different re- PZ+COO− + PZ, AMP+COO− + AMP and DEA+COO− + DEA, and
action types were proposed (Yang et al., 2017). One is the zwitterion 12 hybrid processes MEA+COO− + PZ, PZ+COO− + MEA,
mechanism which was proposed by Caplow (Caplow, 1968) and re- MEA+COO− + AMP, AMP+COO− + MEA, MEA+COO− + DEA,
introduced by Danckwerts (Danckwerts, 1979), and was supported by DEA+COO− + MEA, PZ+COO− + AMP, AMP+COO− + PZ,
early experimental works. It is thought that the amine molecule (RNH) PZ+COO− + DEA, DEA+COO− + PZ, AMP+COO− + DEA and
first reacts with CO2 to form a short-lived zwitterion (RNH+COO−, the DEA+COO− + AMP. To simplify the discussion, the reactions are ca-
process is also termed as zwitterion formation), then the zwitterion tegorized into four groups, MEA+COO− + B (B represents amine mo-
reacts with a proton base and finally forms a carbamate anion and a lecule), PZ+COO− + B, AMP+COO− + B and DEA+COO− + B. The
protonated amine (also referred as hydrogen transfer). The second one detailed reactions are listed as below,
is the carbamic acid reaction mechanism, in which CO2 is supposed to Zwitterion formation,
react with amine molecule to form carbamic acid first (RNCOOH) and
MEA + CO2 → MEA+ COO− (1)
then the carbamic acid reacts with another amine molecule and finally
produce the product (Arstad et al., 2007; Versteeg et al., 1996). The PZ + CO2 → PZ+COO− (2)
third one is the single-step termolecular reaction, in which one CO2
molecule is thought to react with two amine molecules simultaneously AMP + CO2 → AMP+COO− (3)
and finally formed the carbamate (Crooks and Donnellan, 1989).
DEA + CO2 → DEA+COO− (4)
For primary and secondary alkanoamines, ab initio calculations and
studies show that the amine reacting with CO2 to form carbamate Intermolecular hydrogen transfer,
through a zwitterion intermediate (zwitterion formation) is considered
MEA+ COO− + MEA → MEACOO− + MEAH+ (5)
to be the most favorable reaction path (Han et al., 2011; Hwang et al.,
2015; Iida et al., 2009; Lv et al., 2015; Shim et al., 2009; Xie et al., MEA+ COO− + PZ → MEACOO− + PZH+ (6)
2010). Also the zwitterion mechanism could explain the effective re-
MEA+COO-+AMP → MEACOO-+AMPH+ (7)
action order and activation energies (Arstad et al., 2007; Xie et al.,
2010), and thus is suitable to describe the reaction processes of amine MEA+COO-+DEA → MEACOO-+DEAH+ (8)
absorbing CO2. For AMP and other sterically hindered amines, the
formation of zwitterion and bicarbonate are two possible reaction PZ+COO-+PZ → PZCOO-+PZH+ (9)
channels (Ismael et al., 2009; Xie et al., 2014; Yamada et al., 2011). For PZ+COO-+MEA → PZCOO-+MEAH+ (10)
the blended solutions with AMP, zwitterion formation is involved in the
interactive reactions while the bicarbonate formation is not. Thus, in PZ+COO-+AMP → PZCOO-+AMPH+ (11)

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PZ+COO− + DEA → PZCOO− + DEAH+
AMP+COO− + AMP → AMPCOO− + AMPH+
AMP+COO-+MEA → AMPCOO-+MEAH+
AMP+COO− + PZ → AMPCOO− + PZH+
AMP+COO− + DEA → AMPCOO− + DEAH+
DEA+COO-+DEA → DEACOO-+DEAH+
DEA+COO-+MEA → DEACOO-+MEAH+
DEA+COO− + PZ → DEACOO− + PZH+
DEA+COO− + AMP → DEACOO− + AMPH+
The ab initio calculations of the reaction processes are conducted
with Density Functional Theory (DFT). During the simulation, implicit
solvation effect with polar continuum method (PCM) and Pauling
atomic radii are used (Shim et al., 2009; Xie et al., 2010). The base set
of B3LYP/6-311G++(d, p)//B3LYP/6-31G is used in the whole reac-
tion process with high precision (da Silva and Svendsen, 2007; Lu et al.,
2016; Shim et al., 2009). The transition-state optimizations and in-
trinsic reaction coordinate (IRC) calculations are performed, and then
the geometries of the resulting reactants and products are optimized by
the IRC. Also, the vibrational frequencies are conducted for the opti-
mized reactant and product to check the local minima (no imaginary
frequency) and saddle point (one imaginary frequency). The optimi-
zation and energetic calculations are simulated by Gaussian 09 program
package (Frisch et al., 2009). The reaction energies can be calculated
as:
ΔEreaction = Eproduct − Ereactant
ΔEforwardbarrier = Ets − Ereactant
ΔEbackwardbarrier = Ets − Eproduct
where ΔEreaction is the energy difference between the reaction products
and reactants, Eproduct, Ets and Ereactant are the energy of the product,
transition state and reactant, respectively. The intrinsic reaction energy
(IRE) and Gibbs free energy with frequency analysis are investigated. A
clear comparison of the intrinsic reaction energies (IRE) would be va-
luable to show the difference of reaction energies for different reaction
processes, and the Gibbs free energies could quantitatively characterize
the quasi reaction process in the solutions.
3. Results and discussions
3.1. Zwitterion formation
Zwitterion formation is the first step for amines to absorb CO2 in
zwitterion mechanism (Caplow, 1968; Danckwerts, 1979). When re-
acting with CO2, the amine with different conformer leads to different
reaction configuration. In this work, the typical conformers of MEA, PZ,
AMP and DEA are used (Arstad et al., 2007; da Silva et al., 2007; Stowe
et al., 2016; Yamada et al., 2011), see Fig. 1 for their molecular
structures. During CO2 absorption, the amine molecule first reacts with
Fig. 1. The typical structure for the discussed amines (blue atoms-N, grey atoms-C, red atoms-O, white atoms-H). (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
International Journal of Greenhouse Gas Control 74 (2018) 119–129
(12) CO2 to form zwitterion as shown in Eqs (1)–(4). This process is bimo-
(13) lecular and involves one amine molecule, thus no interactive reaction
occurs. The atom movements in zwitterion formation for the discussed
(14) amines are similar, which are, C in CO2 moves close to N in amine
(MEA/PZ/AMP/DEA) and the bond angle of O]C]O shrinks. A tran-
(15)
sition state appears with one imaginary frequency for each reaction
(16) process and the imaginary frequency is shown in Table S1 in the
Supporting Information.
(17)
Fig. 2 shows the energy analysis of intrinsic reaction energy (IRE)
(18) and Gibbs free energy in zwitterion formation. In the histogram, data in
one column reflect the relative energies for one reaction process. The
(19)
energies of the reactants are set as zero baselines for each process. The
(20) data that at the top of the columns show the relative energies of the
transition states, which also represent the forward energy barriers for
the reactions. The data at the bottom of the columns indicate the re-
lative energies of the products. The energy difference between the
transition state and the product is the backward energy barrier. In
Fig. 2, the calculation results show that the forward Gibbs free energy
barrier for MEA, DEA and AMP are 38.78 kJ/mol, 33.93 kJ/mol and
44.98 kJ/mol, respectively, which are in well agreement with the ex-
perimental results of 40 kJ/mol, 32.2 kJ/mol and 41.9 kJ/mol (ALI,
2005; Arstad et al., 2007) with the deviation of 3.05%, 5.37% and
7.35%, respectively. For PZ, the forward Gibbs free energy barrier is
31.33 kJ/mol, this value is very close to the experiment result of
33.6 kJ/mol (Bishnoi and Rochelle, 2000). These data validate the ac-
curacy of the calculating model. The Gibbs free energy barriers show
that AMP has the highest forward barrier, followed by MEA, DEA and
PZ. For the backward process, MEA has the highest one, followed by
DEA, PZ and AMP, and the energy barrier for AMP is 39% lower than
(21) that of MEA. All the forward energy barriers are higher than that of the
backward processes, hence, the reaction energies for Gibbs free energy
(22) (ΔEreaction,Gibbs) are all positive values, and PZ has the smallest value of
(23) 24.42 kJ/mol, indicating that the configuration for PZ zwitterion is the
most stable one.
The intrinsic reaction energy (IRE) analysis during the zwitterion
formation shows that AMP has the highest forward energy barrier of
24.91 kJ/mol, followed by MEA, DEA and PZ. The barrier for PZ is 39%
lower than that for AMP. For the backward process, MEA has the
highest energy barrier of 21.52 kJ/mol, followed by AMP, PZ and DEA.
The barrier for DEA is 18.5% lower than MEA. For the reaction energy
(ΔEreaction,IRE), it is negative value for MEA, PZ and DEA, and the
zwitterion formation for PZ has the smallest ΔEreaction,IRE of −4.01 kJ/
mol, while it is 4.00 kJ/mol for AMP. Compared with other amines, the
PZ zwitterion has the most stable configuration than the reactant and
the AMP zwitterion has the most unstable one. The PZ complex with
lower relative energy reveals the reaction inclination for PZ over other
amines in CO2 absorption. The relative energy for AMP zwitterion re-
veals the easy regeneration in CO2 capture process over other amines.
Combining the analysis of IRE and Gibbs free energy, PZ has the
lowest forward IRE and Gibbs free energy barrier, followed by DEA,
MEA and AMP. For the backward process, MEA has the highest energy
barriers for both IRE and Gibbs free energy, and the energy barrier of
PZ is in between DEA and AMP. Hence, in zwitterion formation, PZ has
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T. Zhang et al.
Fig. 2. The energy barriers for zwitterion formation of RNH+COO−.
the lowest forward energy barrier and the second lowest backward
energy barrier compared with MEA, DEA and AMP. As the forward
energy barrier influences the CO2 absorption process, PZ has the best
absorption performance during zwitterion formation. Tan and Chen
(2006) conducted some experimental works and obtained the similar
conclusions.
3.2. Hydrogen transfer process
The subsequently reaction following zwitterion formation
(RNH+COO−) is the intermolecular hydrogen transfer process
RNH+COO− + B, where RNH+COO− is the hydrogen proton donator
and the amine molecule B is the proton acceptor. In this reaction, the
hydrogen atom moves from N in RNH+COO− to N in B, at the same
time, the bond length of N(RNH)-C(CO2) becomes shorter and the bond
angle of O]C]O (CO2) becomes smaller. Finally, the carbamate an-
ions RNCOO− and ammonium cations BH+ are produced. Each reac-
tion has a transition state with which the imaginary frequency is cal-
culated and its vibrational mode is checked. The imaginary frequency
of the transition state is shown in Table S2 in the Supporting
Information. In this paper, the configurations of the transition states for
the discussed intermolecular hydrogen transfer are given and shown in
Fig. 4. Moreover, the bond length of NeH and NeC and bond angle of
O]C]O as shown in Fig. 3 are investigated to characterize the reac-
tion process. It is worth mentioning that the energy we used is the
calculated value for the ion-pair product after the proton transfer rather
than the values separately for carbamate and protonated amine.
Fig. 3. The sketch for the discussed bond length of NeC and NeH and bond
angle of O]C]O during the reactions.
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International Journal of Greenhouse Gas Control 74 (2018) 119–129
3.2.1. The intermolecular hydrogen transfer processes of MEA+COO− + B
MEA is one of the most commonly used alkanolamines in CO2
capture. In the mixed solutions containing MEA, the formed zwitterion
MEA+COO− reacts with MEA (purebred process) or PZ/AMP/DEA
(hybrid process) to finish the intermolecular hydrogen transfer pro-
cesses of MEA+COO− + B, as presented in Eqs (5)–(8). Fig. 5 shows the
energy changes of IRE and Gibbs free energy. The intrinsic reaction
energy (IRE) shows that the process of MEA+COO− + PZ has the
lowest forward energy barrier of 2.22 kJ/mol, which is 41% lower than
that of MEA+COO− + MEA. For both MEA+COO− + AMP and
MEA+COO− + DEA, the forward energy barriers are higher than that
of MEA+COO− + MEA. For the backward process, the purebred pro-
cess of MEA+COO− + MEA has the lowest IRE barrier, followed by
AMP, DEA and PZ. Thus in the IRE analysis, PZ has an enhancing effect
on MEA in forward process but shows a hindering effect in backward
process. AMP and DEA show hindrance effect on MEA for both the
forward and backward processes. As for the reaction energy
ΔEreaction,IRE, all the results have negative values. The ΔEreaction,IRE of
MEA+COO− + PZ is the smallest, which means that the configuration
of the product for MEA+COO− + PZ is the most stable one.
For Gibbs free energy, the forward energy barrier is 0.84 kJ/mol for
MEA+COO− + MEA, and it decreases to 0.71 kJ/mol when PZ is the
proton acceptor. This changing tendency is consistent with that of IRE.
As for the processes of MEA+COO− + AMP and MEA+COO− + DEA,
the calculated forward barriers are negative values which mean that the
processes could occur spontaneously for the given conditions. For the
backward process, the energy barrier is 28.55 kJ/mol for
MEA+COO− + PZ, which is much higher than that of
MEA+COO− + MEA. When AMP and DEA are proton acceptors, the
energy barriers for both of them are lower than that of MEA. Hence, the
Gibbs free energy shows that PZ enhances the forward process for MEA
but hinders the backward process. As for DEA and AMP, lower energy
barriers are observed than that of MEA for both forward and backward
processes. At the same time, the ΔEreaction,Gibbs of MEA+COO− + AMP
has the largest value, which indicates an easy regeneration process. The
reaction energy ΔEreaction,Gibbs of MEA+COO− + PZ has the lowest
value, which is consistent with the result of IRE, indicating that the
reaction process may be thermodynamically more favorable than the
others.
For the hydrogen transfer processes of MEA+COO− + B, the bond
length of NeH increases from reactant to product through the transition
state (TS), at the same time, the bond length of NeC and the bond angle
T. Zhang et al. International Journal of Greenhouse Gas Control 74 (2018) 119–129

Fig. 4. The configurations of the transition states for the intermolecular hydrogen transfer process.

Fig. 5. The energy barriers for intermolecular hydrogen transfer of MEA+COO− + B.

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Fig. 6. The structural changes for the reaction configurations during MEA+COO− + B.

of O]C]O decrease as shown in Fig. 6. The changes of bond length of during the hydrogen transfer process in IRE analysis, however, the
NeH and the bond angle of O]C]O from reactant to TS and TS to Gibbs free energy analysis shows that they have promotion effects.
product are different for different proton acceptors. During the process
of reactant to TS, DEA has the largest increase in NeH bond length and
3.2.2. The intermolecular hydrogen transfer processes of PZ+COO− + B
decrease in O]C]O bond angle, followed by MEA/AMP, PZ (the in-
PZ is a cyclic diamine, and is usually used as a promoter in the
crease/decrease for MEA and AMP are nearly the same). These struc-
mixed solutions (Freeman et al., 2010; Nakai et al., 2016; Stowe et al.,
tural change tendencies are consistent with the energy changes of IRE,
2016). In this part, the reaction processes of PZ+COO− + B are dis-
i.e., PZ has the lowest and DEA has the highest forward barrier. During
cussed. The proton acceptors here include PZ, MEA, AMP and DEA, as
the process of TS to product, PZ has the largest increase in NeH bond
shown in Eqs (9)–(12). The reaction energies and structural changes of
length and decrease in O]C]O bond angle, followed by DEA, AMP
reaction configurations are shown in Figs. 7 and 8, respectively. The
and MEA. These changing tendencies are also in accordance with that of
results of IRE show that the forward energy barrier for PZ+COO− + PZ
the backward IRE barriers. In the whole process, no significant differ-
is the lowest. The process of PZ+COO− + MEA has the highest value
ences are observed for the change of NeC bond length among the dif-
and it is 88% higher than that of PZ+COO− + PZ. However, the
ferent amine bases. The analysis above shows that the structural
purebred reaction process has the highest backward energy barrier,
changes of the reaction configurations have close relationship with the
followed by MEA, AMP and DEA. Hence, according to IRE analysis,
IRE barriers.
MEA, AMP and DEA all have hindering effects on PZ in forward reac-
The results above show that PZ has an enhancing effect on MEA in
tion process but show enhancement effects in the backward process in
the forward hydrogen transfer process of MEA+COO− + B, but shows a
the intermolecular hydrogen transfer of PZ+COO− + B.
hindering effect in the backward process. This reveals that, compared
For Gibbs free energy, PZ+COO− + MEA has the highest energy
with MEA, PZ is a better proton acceptor and acts more active in CO2
barrier for both the forward and backward process and
absorption. For AMP and DEA, hindering effect is observed on MEA
PZ+COO− + DEA has the lowest ones. The forward energy barrier of

Fig. 7. The energy barriers for intermolecular hydrogen transfer of PZ+COO− + B.

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T. Zhang et al.
Fig. 8. The structural changes for the reaction configurations during PZ+COO− + B.
PZ+COO− + AMP is 56% higher than that of PZ+COO− + PZ. For the
backward process, the energy barrier of PZ+COO− + PZ is higher than
that of PZ+COO− + AMP. These results show that MEA has a hindering
effect on PZ+COO− for the whole process compared with PZ. AMP
inhibits the forward but activates the backward process for PZ+COO−
in the hydrogen transfer process. For DEA, an enhancement effect is
observed on PZ in the backward process, while for the forward process,
the results of IRE and Gibbs free energy are different.
As for the reaction energy, it is observed that PZ+COO− + PZ has
the lowest ΔEreaction,IRE and ΔEreaction,Gibbs as compared to the others.
This shows that the product of PZ+COO− + PZ has the most stable
configuration and is thermodynamically more favorable than the hy-
brid reactions.
Fig. 8 presents the typical structure changes of the reaction con-
figurations during the process of PZ+COO− + B. It is observed that in
the process of reactant to TS, both the bond length change of NeH and
bond angle change of O]C]O for PZ (PZ is the proton base) is the
smallest, followed by AMP, DEA and MEA. These structural change
tendencies are consistent with those of the forward IRE energy barriers.
Fig. 9. The energy barriers for intermolecular hydrogen transfer of AMP+COO− + B.
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International Journal of Greenhouse Gas Control 74 (2018) 119–129
In the backward process, PZ+COO− + MEA has the largest increase in
NeH bond length and the smallest decrease in O]C]O bond angle,
while for the other three processes, the structural changes are similar.
No significant differences are observed for the bond length change of
NeC for different amines.
Compared with PZ, both MEA and AMP have hindering effects on
PZ during the forward reaction processes of PZ+COO− + B, while AMP
and DEA show enhancement effect on PZ during the backward reaction
processes by lowering the reaction energy barriers.
3.2.3. The intermolecular hydrogen transfer processes of AMP+COO− + B
AMP is a typical sterically hindered amine and has been studied
extensively (Ismael et al., 2009; Yamada et al., 2011). In this part, the
processes of AMP+COO− reacting with different amine bases, AMP, PZ,
MEA and DEA, as shown in Eqs (13)–(16), would be discussed. The
energy analysis and structure changes are exhibited in Figs. 9 and 10,
respectively. The results show that the forward energy barriers of
AMP+COO− + MEA and AMP+COO− + PZ are all lower than that of
AMP+COO− + AMP for both IRE and Gibbs free energy. The barrier of
T. Zhang et al.
Fig. 10. The structural changes for the reaction configurations during AMP+COO− + B.
AMP+COO− + PZ is lower than that of AMP+COO− + MEA. Here, the
energy barrier for AMP+COO− + PZ is negative, which shows that the
process could occur spontaneously. Thus, MEA and PZ can activate the
forward reaction process of AMP+COO− + B. For the process of
AMP+COO− + DEA, the IRE barrier is higher while the Gibbs free
energy barrier is lower than that of AMP+COO− + AMP in the forward
process. For the backward process, the IRE energy barrier of
AMP+COO− + PZ is the highest, followed by DEA, AMP and MEA. For
Gibbs free energy, the energy barrier of AMP+COO− + DEA is the
highest, followed by AMP, MEA and PZ. Hence, it is concluded that
MEA has an enhancement and DEA has a hindrance effect on AMP in
the backward process of AMP+COO− + B.
The analysis of reaction energy shows that the ΔEreaction,IRE of
AMP+COO− + PZ is the lowest, indicating that the product of
AMP+COO− + PZ has the most stable reaction configuration. While
the ΔEreaction,Gibbs of AMP+COO− + DEA is the lowest, and this is dif-
ferent from that of IRE.
The structure changes of the reaction configurations in Fig. 10 in-
dicate that PZ (AMP+COO− + PZ) has the smallest changes in NeH
bond length and O]C]O bond angle, followed by MEA, AMP and DEA
during the process of reactant to TS. These are consistent with the trend
of the forward IRE barriers. During the process of TS to product, MEA
has the smallest change of NeH bond length, followed by PZ and AMP/
DEA (the changes for AMP and DEA are nearly the same). And for
O]C]O bond angle, MEA has the smallest change, followed by AMP/
DEA, and PZ. These results are consistent with the backward IRE bar-
riers that AMP+COO− + MEA is the lowest, followed by
AMP+COO− + AMP, AMP+COO− + DEA and AMP+COO− + PZ.
An overall analysis of IRE and Gibbs free energy indicates that,
compared with AMP, both MEA and PZ can reduce the forward barriers
in the process of AMP+COO− + B. Hence, MEA and PZ show enhan-
cing effects on AMP in the hydrogen transfer processes, and PZ has
better enhancement effect than MEA. Also, MEA shows an enhancement
effect on AMP in the backward reactions. For DEA, a hindering effect is
observed on AMP in the backward reaction, while it shows a hindering
effect for IRE but an enhancing effect for Gibbs free energy on AMP in
the forward process.
3.2.4. The intermolecular hydrogen transfer processes of DEA+COO− + B
DEA is a commonly used secondary alkanolamine and has good CO2
absorption properties, but the reaction rate is lower than that of MEA
(Versteeg and Swaaij, 1988). The reaction processes of
DEA+COO− + B (B represents DEA, PZ, MEA and AMP) as shown in
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International Journal of Greenhouse Gas Control 74 (2018) 119–129
Eqs (17)–(20) are discussed in this part. The reaction energies and
structure changes of the reaction configurations are shown in Figs. 11
and 12, respectively. The energy analysis shows that the process of
DEA+COO− + PZ has the lowest forward barrier, followed by
DEA+COO− + DEA, DEA+COO− + MEA and DEA+COO− + AMP for
both IRE and Gibbs free energy. The energy barrier of
DEA+COO− + PZ is 60% lower than that of DEA+COO− + DEA. Thus,
compared with the purebred process, when DEA+COO− reacts with PZ,
the forward energy barrier is largely reduced and the hydrogen transfer
process is significantly enhanced. However, the energy barriers of
DEA+COO− + MEA and DEA+COO− + AMP are much higher than
that of DEA+COO− + DEA, indicating that MEA and AMP show hin-
dering effects on DEA+COO−. During the backward reaction process,
the energy barrier of DEA+COO− + AMP is much higher than that of
DEA+COO− + DEA. For DEA+COO− + MEA, the IRE barrier is
4.73 kJ/mol higher (14%) while the Gibbs free energy barrier is 0.2 kJ/
mol lower (less than 0.8%) than that of DEA+COO− + DEA. For the
process of DEA+COO− + PZ, the IRE energy barrier is 0.95 kJ/mol
higher (2.8%) than that of the purebred process, while the Gibbs energy
barrier is largely reduced to 6.22 kJ/mol which is 75% lower than that
of DEA+COO− + DEA. Combing the forward and backward energy
analyses, the results show that PZ has a significant enhancement on
DEA in the intermolecular hydrogen transfer process, while both MEA
and AMP show hindering effects on DEA, and the hindering effect for
AMP is stronger than that of MEA.
The ΔEreaction,IRE of DEA+COO− + PZ is lower than that of
DEA+COO− + DEA/MEA, which is consistent with the analysis in
previous sections that the ΔEreaction,IRE of RNHCO2 + PZ (RNH re-
presents MEA, PZ and AMP) is lower than the others. However,
ΔEreaction,Gibbs of DEA+COO− + PZ has the highest value, indicating the
reaction process is thermodynamically more favorable than the other
processes. It is worth mentioning that the ΔEreaction of
DEA+COO− + AMP is the lowest one for both IRE and Gibbs free en-
ergy. With the aforementioned highest reaction energy barriers, AMP
shows a hindering effect on DEA in the hydrogen transfer process.
As for the structure changes of the reaction configurations during
DEA+COO− + B, the results show that in the process of reactant to TS,
when PZ is the proton base, the process has the smallest changes of
NeH bond length and O]C]O bond angle, followed by DEA, MEA and
AMP. This changing is consistent with that of the forward IRE barriers.
During the backward process, PZ (DEA+COO− + PZ) has the smallest
change in NeH bond length, followed by MEA, DEA and AMP. For the
bond length of NeC and the bond angle of O]C]O, AMP has the
T. Zhang et al.
Fig. 11. The energy barriers for intermolecular hydrogen transfer of DEA+COO− + B.
Fig. 12. The structural changes for the reaction configurations during DEA+COO− + B.
largest changes compared with others. These results are consistent with
the largest backward energy barrier of DEA+COO− + AMP.
Given above, the IRE and Gibbs free energy analyses show that PZ
has an enhancing effect on DEA by reducing the energy barriers, while
both MEA and AMP show hindering effects and the hindering effect for
MEA is weaker than AMP.
The above given analyses of energy and structure changes on the
reaction processes of RNHCO2 + B show that PZ has an enhancement
effect on MEA, AMP and DEA in the forward process and turns out to be
a good activator in blended amine solutions for CO2 absorption. MEA
shows an enhancement effect on AMP. However, Both MEA and AMP
show hindering effects on PZ and DEA. Moreover, one self-contra-
dictory phenomenon is observed in the simulations. According to IRE
analysis, DEA has a hindering effect on MEA, PZ and AMP, while the
Gibbs free energy analysis shows that DEA has an enhancement effect
on them. To explain such a phenomenon, more work needs to be con-
ducted in future researches.
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International Journal of Greenhouse Gas Control 74 (2018) 119–129
3.2.5. The effect of intermolecular hydrogen transfer on the blended
solutions
In the previous sections, we have systematically analyzed the in-
termolecular hydrogen transfer processes of RNH+COO− + B and
analyzed the energy and structural changes. In this part, we would
make a detailed analysis of the interactive reactions in the specific
blended amine solutions.
In the blended solutions of (MEA + PZ), there are two extra reac-
tions as compared with the pure MEA or PZ solution, i.e., the processes
of (MEA+COO− + PZ) and (PZ+COO− + MEA). During the inter-
molecular hydrogen transfer processes, the forward energy barriers are
in the order of (MEA+COO− + PZ) < (MEA+COO−
+ MEA) < (PZ+COO− + PZ) < (PZ+COO− + MEA) for both IRE
and Gibbs free energy. Thus one can conclude that PZ activates the
hydrogen transfer for MEA, and the MEA+COO− based reactions have
lower energy barriers than those of PZ+COO−. Similarly, in the
blended system of (AMP + PZ), the activation energy barriers for the
T. Zhang et al.
hydrogen transfer processes are in the following order,
(AMP+COO− + PZ) < (PZ+COO− + PZ) < (PZ+COO− + AMP)
< (AMP+COO− + AMP) for both IRE and Gibbs free energy. This
indicates that, compared with pure AMP solution, adding PZ in it could
improve the CO2 absorption property. As in the blended solution of
(DEA + PZ), the activation energy barriers are in the order of
(DEA+COO− + PZ) < (PZ+COO− + PZ) < (PZ+COO− + DEA)
< (DEA+COO− + DEA) for IRE, and (DEA+COO−
+ PZ) < (PZ COO + DEA) < (PZ COO + PZ) < (DEA+COO−
+ − + −
+ DEA) for Gibbs free energy. The results show that blending PZ in
DEA could enhance the hydrogen transfer process, i.e., the blended
solutions perform better in CO2 chemical absorption.
As for the blended system of (MEA + AMP), in the intermolecular
hydrogen transfer processes, the calculated forward energy barriers are
in the order of (MEA+COO− + MEA) < (MEA+COO−
+ AMP) < (AMP+COO− + MEA) < (AMP+COO− + AMP) for IRE,
and (MEA+COO− + AMP) < (MEA+COO− + MEA) < (AMP+COO−
+ MEA) < (AMP+COO− + AMP) for Gibbs free energy. The results show
that MEA has an enhancement effect on AMP, which is consistent with the
experimental results (Xiao et al., 2000). The IRE barriers for
MEA+COO− + MEA and MEA+COO− + AMP are 3.78 kJ/mol and
3.88 kJ/mol, respectively, and the Gibbs free energy barriers are 0.84 kJ/
mol, −0.35 kJ/mol, respectively. These results show that the energy bar-
riers are similar in quantity grade for MEA and AMP, indicating that AMP
has comparable reaction property as MEA. Hence, the blended solution of
(MEA + AMP) has better performance than the pure AMP/MEA solution in
CO2 absorption capacity. However, the reaction rate is considered to be
lower than that of the pure MEA solution.
For the system of (MEA + DEA), the activation energy barriers are
in the following order, (MEA+COO− + MEA) < (MEA+COO−
+ DEA) < (DEA+COO− + DEA) < (DEA+COO− + MEA) for IRE,
and (MEA+COO− + DEA) < (MEA+COO− + MEA) < (DEA+COO−
+ DEA) < (DEA+COO− + MEA) for Gibbs free energy. The results
show that MEA has a hindering effect on DEA while DEA shows a
hindrance effect on MEA for IRE but an enhancement effect for Gibbs
free energy. However, limited studies have been found on the perfor-
mance of the blended solution of (MEA + DEA).
As for the blended solutions of (DEA + AMP), the activation bar-
riers are in the order of (AMP+COO−
− −
+
+ AMP) < (AMP COO + DEA) < (DEA COO + DEA) +
< (DEA+COO− + AMP) for IRE, and (DEA+COO−
+ DEA) < (AMP+COO−
+ DEA) < (AMP+COO− + AMP) < (DEA+COO− + AMP) for Gibbs
free energy. These results show that AMP has a hindering effect on DEA
while DEA also shows a hindering effect on AMP for IRE. However, the
experimental results show that the addition of small amounts of DEA to
AMP results in significant improvement in CO2 absorption rates
(Mandal et al., 2003), which is similar to the results of Gibbs free en-
ergy analysis that DEA shows an enhancement effect on AMP.
When compared all the discussed intermolecular hydrogen transfer
processes, it can be seen that the forward energy barriers for
MEA+COO− based reactions are lower than the others. As to the
backward processes, the energy barriers for AMP+COO− based reac-
tions are lower than the others. Hence, the blended solutions of
(MEA + AMP) show good absorption and desorption performance
theoretically, indicating a good choice for the binary amine solutions.
To sum up, PZ has an enhancement effect on the discussed amines in
CO2 absorption, followed by MEA. For AMP, it has similar absorption
performance but a little inferior than MEA. For DEA, the results be-
tween IRE and Gibbs are in contrast to each other, i.e., it shows a
hindering effect on PZ/MEA/AMP for IRE but an enhancement effect
for Gibbs free energy. And the (MEA + AMP) blended solutions show
good CO2 capture performance.
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International Journal of Greenhouse Gas Control 74 (2018) 119–129
4. Conclusions
In this paper, we computationally studied the chemical reactions of
CO2 absorption in mixed solutions of MEA/PZ/AMP/DEA. Six binary
systems, (MEA + PZ), (MEA + AMP), (MEA + DEA), (PZ + AMP),
(PZ + DEA) and (AMP + DEA) were analyzed. In total, 20 reactions
were involved including 4 zwitterion formation processes and 16 in-
termolecular hydrogen transfer processes (MEA+COO− + B,
PZ+COO− + B, AMP+COO− + B and DEA+COO− + B). Simulations
were performed by ab initio method using Density Functional Theory.
The reaction energies (IRE, Gibbs free energy) and structure changes of
the configurations were analyzed. The results showed that, in zwit-
terion formation, PZ has the lowest forward energy barrier compared
with MEA, AMP and DEA, while the backward energy barrier is the
second lowest. This holds true for both IRE and Gibbs free energy. In the
following process of intermolecular hydrogen transfer, the interactive
reactions play an important role in CO2 capture in blended amines. The
interactive hydrogen transfer is a key factor for the interactive effect
between different amines. According to energy analysis, the following
conclusions have been obtained,
(1) PZ shows an enhancement effect on MEA/AMP/DEA, as the energy
barrier of the process RNH+COO− + PZ is lower than the purebred
process RNH+COO− + RNH (RNH represents MEA, AMP and
DEA).
(2) MEA has an enhancement effect on AMP, but shows a hindering
effect on PZ and DEA.
(3) DEA has a self-contradictory property, i.e., it shows a hindering
effect for IRE but enhancing effect for Gibbs free energy on PZ, MEA
and AMP.
(4) The MEA+COO− based reactions have good absorption property,
and the AMP+COO− based reactions show favorable desorption
property.
Acknowledgements
National Natural Science Foundation of China (Nos. 21736008 and
51276141) is gratefully acknowledged. This work is also supported by
the Natural Science Basic Research Plan in Shaanxi Province of China
(No. 2015JQ5192) and “Fundamental Research Funds for the Central
Universities”. Additionally, the authors are grateful to Ms. Maimoona
Sharif in our university for her carefully proof-reading.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at https://doi.org/10.1016/j.ijggc.2018.04.023.
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