Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349

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Journal of the Taiwan Institute of Chemical Engineers

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

Investigation of different additives to monoethanolamine (MEA) as a

solvent for CO2 capture
R. Ramazani a,∗, S. Mazinani b, A. Jahanmiri a, S. Darvishmanesh c, B. Van der Bruggen b
a
Department of Chemical Engineering, Chemical and Petroleum Engineering School, Shiraz University, Shiraz Iran
b
ProcESS - Process Engineering for Sustainable Systems, Department of Chemical Engineering, KU Leuven, Celestijnenlaan 200F, B-3001 Leuven, Belgium
c
Department of Chemical and Biological Engineering, Princeton University, Princeton, New Jersey 08544, USA

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

Article history: The influence of various additives including potassium lysinate (PL), potassium glycinate (PG), potassium
Received 1 December 2015 carbonate (K2 CO3 ), 2-(1-piperazinyl)-ethylamine (PZEA), trisodium phosphate (TSP) and tetraethylenepen-
Revised 28 March 2016
tamine (TEPA) to monoethanolamine (MEA) as solvent for carbon dioxide (CO2 ) was evaluated experimen-
Accepted 23 May 2016
tally. In order to determine the absorption rate and solubility of carbon dioxide into aqueous solutions of
Available online 8 June 2016
MEA in the presence of these activators, a vapor-liquid equilibrium (VLE) apparatus was used to measure
Keywords: pressure changes versus time at a constant total blend concentration of 2.5 mol dm−3 (M) and CO2 par-
CO2 solubility tial pressures between 0 and 50 kPa at 313.15 K. In all the experiments, the molar ratio of the additive to
Absorption rate MEA was set to 0.25, 0.66 and 1. The results indicate that the 1.25 M MEA + 1.25 M TEPA system reaches
Activator the maximum loading capacity (mole CO2 /mole solution) of 1.32 and has the highest absorption rate. It
Monoethanolamine can be concluded that the 1.25 M MEA + 1.25 M TEPA blend solution can be a good candidate for CO2
VLE low pressure
capture.
© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.

1. Introduction
The emission of greenhouse gases, generated by human indus-
trial activities, is perhaps the most prominent environmental prob-
lem today. In recent years, CO2 has attracted much attention be-
cause it is the most important human induced greenhouse gas
and is believed to be responsible for approximately 64% of the en-
hanced greenhouse effect [1]. An efficient method to reduce green-
house gas emissions is capture and storage of CO2 from waste gas
streams. Chemical absorption is today still the most cost effective
method for CO2 capture from gas streams [2, 3], in spite of the
emergence of more sustainable technologies based on membrane
separation. For absorption, the selection of a suitable solvent is
one the most important factors, which has a major effect on the
capital and operational cost. The solvent should have a high load-
ing capacity, a high absorption rate, a low regeneration energy and
high stability [4]. MEA was developed more than 60 years ago and
is now the most widely used alkanolamine absorbent for captur-
ing acid gases mainly due to its high reaction rate, low cost, low
molecular weight and low solubility of hydrocarbons. However, it
suffers from disadvantages including its low CO2 loading capacity,
high regeneration energy, high viscosity and vapor pressure [5, 6].
∗
Corresponding author. Tel.: +98 1143 238 339; fax: +98 3216323145.
E-mail address: roozbeh_ramazani@yahoo.com (R. Ramazani).
Recently, much attention has been paid to using blend solu-
tions for CO2 capture. Blending of solvents is a useful technique
to combine the advantages of each solvent into a new product.
Blending can reconcile solvents with different physicochemical
properties to obtain properties superior to those of the individual
solvents. A variety of blend solutions for CO2 capture have been
studied in the literature. In our previous work [7], the solubility
of CO2 in an aqueous blend of sodium glysinate (SG) and MEA
solutions was measured at CO2 partial pressures ranging from
0 to 35 kPa. We examined different blend ratios of SG/MEA at
a constant total blend concentration of 2.5 M in order to find
the optimal ratio of sodium glysinate to MEA. The optimal molar
ratio occurred at 0.6 molar ratio of sodium glysinate. Balsora and
Mondal [8] investigated the CO2 solubility in aqueous blends of
diethanolamine (DEA) with trisodium phosphate at temperatures
and CO2 partial pressures ranging from 303.15 to 333.15 K and
10 to 20 kPa, respectively. It was found that the addition of
trisodium phosphate resulted in a significant increase in the CO2
loading capacity of DEA. Mohd Taib and Murugesan [9] experimen-
tally examined the performance of a blend of two ionic liquids,
bis(2-hydroxyethyl)ammonium acetate (bheea) and 1-butyl-3-
methylimidazolium tetrafluoroborate ([bmim][BF4]), with MEA for
CO2 absorption at pressures between 100 and 1600 kPa and at
three different temperatures (298.15, 303.15 and 313.15 K). The
results showed that the absorption capacity of CO2 in aqueous
[bheaa] + MEA solution is higher than in the mixture of aqueous

http://dx.doi.org/10.1016/j.jtice.2016.05.037
1876-1070/© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
342 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349
[bmim][BF4] + MEA solution. Muraleedharan et al. [10] deter-
mined the equilibrium solubility of CO2 in aqueous of MEA with
2-amino-2-hydroxymethyl-1,3-propanediol (AHPD) at temperatures
between 303.15 and 323.15 K. The results revealed that the ab-
sorption flux decreases when the concentration of AHPD increases
in the blend solutions. Choi et al. [11] used mixed solvents of
2-amino-2-methyl-propanol (AMP) and methyldiethanolamine
(MDEA) with 2-methylpiperidine (2MPD) for CO2 capture. It was
concluded that the absorption capacities of the AMP+2MPD and
MDEA+2MPD blend solutions are greater than that of pure MEA.
Zoghi et al. [12] assessed the effects of several promoters on
the CO2 absorption rate of MDEA solution. It was found that
aminoethylethanolamine (AEEA) has the best performance due
to the fact that the AEEA + MDEA blend solution showed the
highest absorption rate with CO2 . Lee et al. [13] used a dynamic
equilibrium device to investigate the vapor-liquid equilibrium of
CO2 into potassium carbonate with potassium glycinate (as a rate
promoter) at three temperatures (323, 333 and 343 K). Their study
showed that the partial pressure of CO2 decreased significantly as
the concentration of potassium glycinate increased.
This work aims to investigate the performance of 6 different
promoters on the absorption rate and solubility of CO2 in aqueous
MEA solutions (MEA is the most frequently used solvent for CO2
capture). For this purpose, a VLE setup under consistent experi-
mental conditions (CT = 2.5 M, CO2 partial pressure = 0 to 50 kPa
at 313.15 K) was used. The additives considered are classified into
three categories: (1) non-organic solvents such as TSP and K2 CO3 ,
(2) Amino acid salt such as PL and PG, and (3) Amines such as
PZEA and TEPA. TSP and K2 CO3 were selected due to their perfor-
mance for CO2 capture. These salt solutions have some advantages
including their high loading capacity, low cost, low toxicity, low
corrosivity and low absorption heat [14]. Amino acid salts solutions
are now being studied as a possible alternative for alkanolamines.
Glycine and L-Lysine are more expensive, but they have benefits
such as a low vapor pressure, low viscosity, less degradation, lower
toxicity and high chemical reactivity with CO2 [15]. PZEA and TEPA
were also chosen as additive to MEA due to their molecular struc-
tures which can provide several advantages over MEA in terms of
high CO2 loading capacity and rapid carbamate formation. The ob-
jective of the research is to find the most efficient additives with
the highest enhancement absorption rate and capacity for CO2 ab-
sorption, in view of a reduction equipment size and capital and
operating costs.
2. Reaction mechanism
2.1. Reaction of CO2 with aqueous amino acids solution
Amino acids have both amine and carboxylic acid functional
groups and can undertake an internal acid-base reaction. The ini-
tial absorption reaction is the formation of a zwitterion and a car-
bamate. The carbamate undergoes hydrolysis resulting in the for-
mation of a deprotonated amino acid and a bicarbonate/carbonate.
The deprotonated amino acid can then react with CO2 . In this
work, the zwitterionic form of L-lysine and glycine in water were
neutralized with a strong base (KOH) and the resulting aqueous
amino acid salt solution was utilized in CO2 absorption experi-
ments. The reaction of CO2 with L-lysine can be described based
on a zwitterion mechanism [16]:
CO2 + H2 N–CHŔ–COOK ↔ COO+ H2 N–CHŔ–COOK+
C–OO+ H2 N–CHŔ–COO–K+ + B → −
COOHN–CHŔ–COO–K+
+ BH+
The deprotonation of the zwitterions for glycine can be written
as [17]:
+
NH2 R1 R2 COO− + OH− ↔ NHR1 R2 COO– + H2 O (3)
CO2 + NHR1 R2 COO− ↔ − OOCNH+ R1 R2 COO− (4)
2.2. Reaction of CO2 with aqueous K2 CO3 solution
Sherier and Dankwert [18] concluded that at low temperatures,
the addition of a small amounts of amine promoters into K2 CO3
solutions can increase the CO2 absorption rate considerably. Where
both organic (amine) and inorganic compounds used as additives,
the suggested mechanism by Astarita et al. [19] can explain the
promotion of CO2 in carbonate solutions:
CO2(aq) + Promoter  Intermediate (5)
Intermediate + OH− (aq)  HCO3 − (aq) + Promoter (6)
Actually, reaction (6) determines the main difference between
these types of additives. For the inorganic promoters, reaction (6)
is much faster than reaction (5) and follows it, while for the or-
ganic promoters, reaction (6) is very slow compared to reaction
(5) [20]. The chemical reaction of aqueous K2 CO3 solution and CO2
takes place through Eqs. (7)–(12) [21, 22].
CO2(aq) + H2 O(l)  HCO3 − (aq) + H+ (aq) (7)
Dissolution of K2 CO3 (S) in water:
K2 CO3 (S)  2K+ (aq) + CO3 2− (aq) (8)
Hydrolysis of CO3 2− :
CO3 2− (aq) + H2 O(l)  HCO3 − (aq) + OH− (aq) (9)
Bicarbonate formation:
OH− (aq) + CO2(aq)  HCO3 − (aq) (10)
Carbonate formation:
HCO3 − (aq) + OH− (aq)  CO3 2− (aq) + H2 O(l) (11)
The carbonate formation reaction occurs rapidly, therefore the
overall reaction of the K2 CO3 solution with CO2 is as follows:
K2 CO3(l) + H2 O(l) + CO2(aq)  2KHCO3(aq) (12)
2.3. Reaction of CO2 with aqueous TSP solution
The inorganic solvent, TSP has the property to absorb the acidic
gases. It is non-volatile, less corrosive and highly alkaline even at
very low concentration. The overall reaction between carbon diox-
ide and TSP is shown below [23]:
CO2 (g) + Na3 PO4 ·12H2 O ↔ Na2 HPO4 ·7H2 O(s) + NaHCO3(s)
+ 4H2 O (13)
(1) 2.4. Reactions of CO2 with PZEA and MEA
Primary and secondary alkanolamines react with CO2 to form
zwitterions, which are subsequently deprotonated by any base
(2) present in the liquid:
 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349 343

Table 1 bath. The VLE setup is shown schematically in Fig. 2 and techni-
Kinetic constants of each CO2 -amine system.
cal specifications for each device are listed in Table 2. A detailed
Equation k (m3 kmol−1 s−1 ) References description of used apparatus and the method of analysis can be
  found in our previous works [28–31]. Temperature and pressure
1 k = 2.778 × 10 exp −6138
13
[16]
 T  indicators have been placed in the equilibrium cell (with a volume
4 k = 1.22 × 1012 exp −5434 [16]
 T 
of 1500 ml) and the gas storage tank. Before starting the experi-
7 k = 4.07 × 106 exp −5584 [26]
 T  ment, the equilibrium cell was purged by nitrogen gas to remove
10 k = 9.88 × 1013 exp −6956 [26]
 T  trace gases. Then, a known volume of test solution was charged
14 k = 4.5 × 1012 exp −47308 [24]
 −5376
R T  into the cell at the desired temperature. Next, the cell was evacu-
15 k = 3.014 × 10 exp
11
T
[27]
ated by using a vacuum pump, so that the liquid existed under its
own vapor pressure and was allowed to reach the desired tempera-
ture. When the system reached the equilibrium and pressure in the
equilibrium cell remained constant for at least one hour, the vapor
pressure of the solution was recorded. Subsequently, pure CO2 was
delivered from the gas cylinder to the gas storage tank and the ini-
tial pressure in the gas storage tank (P1 ) was recorded. After that,
a certain amount of pure CO2 was transferred from the gas storage
tank to the equilibrium cell, this being considered as the starting
point for the reaction. At the beginning of the experiment (t0 =0)
the total number of moles of CO2 (nCO2 )t0 introduced into the cell
from the gas storage tank was calculated from:
 
Vb P1 P2
(nCO2 )t0 = R T Z1 − Z2 (16 )

where t is the time and subscript 0 denotes the beginning of the

Fig. 1. Molecular structure of additives.
CO2 + R R  NH + b  R R  NCOO− + bH+
This mechanism is applicable to PZEA. The chemistry of the
PZEA system is very complex because it is a tri-amine containing
one primary, one secondary and one tertiary amine group. Thus,
a large number of possible chemical reactions may occur and it is
difficult to know the most important reactions and to exactly de-
termine the effects of these reactions on the overall absorption rate
[24].
The studies on the kinetics of the reaction between CO2 and
the MEA indicate that the reaction is a first order reaction with
respect to the concentration of both MEA and CO2 . The reaction is
described by the overall reaction [25]:
CO2 + 2RNH2 ↔ RNHCOO− + RNH3 +
experiments. Z1 and Z2 are the CO2 compressibility factors at initial
pressure (P1 ) and final pressure (P2 ) in the gas storage tank before
and after transferring the CO2 , and Vb is the volume of the gas
storage tank. The CO2 initial partial pressure in cell was calculated
by subtracting the total pressure of the equilibrium cell (PT ) from
the solvent vapor pressure (PV ):
PCi O2 = PT − PV (17)
(14) As the carbon dioxide is absorbed, the total pressure decreases.
The decrease in cell pressure due to the reaction of the solvent
with CO2 was continuously monitored by the pressure sensor and
the “P vs. t” data were recorded every 0.1 s using the data log-
ger and recorded by Lab View software until the gas–liquid equi-
librium state was reached. The data recorded by the system are
changed to the data of CO2 loading versus time by the same
method proposed in Zoghi et al. [12] and described below. The
equilibrium cell was allowed to reach equilibrium at the desired
temperature. When no changes in the pressure of the cell were
observed (after 2 h), a state of equilibrium was assumed to have
been achieved and the final pressure (Pf ) in the cell was noted.
The equilibrium partial pressure of CO2 is determined by subtract-
ing the final pressure of the cell from the vapor pressure of the
(15) solution.

The reaction rate constant for each CO2 -amine system is sum- PCeO2 = Pf − PV (18)
marized in Table 1. At each time t, the number of moles of CO2 remaining in the
gas phase is calculated from Eq. (19):
3. Experimental section
Vcg Pco2
(nCO2 )t = (19)
3.1. Materials RT
where subscript t denotes time and PCO2 is the partial pressure of
The chemicals used in this work were obtained from Merck CO2 at time t. At each time t, the number of absorbed moles of
Chemical Company (99% assay). CO2 with purity > 99.9%, was CO2 by the solvent is calculated by Eq. (20):
supplied by Avizheh Technology and Development of Middle East
(Iran). The molecular structure of additives is depicted in Fig. 1.
n = (nCO2 )t0 − (nCO2 )t (20)
Consequently, the CO2 loading can be obtained from Eq. (21):
3.2. Solubility n
αCO2 = (21)
The solubility of CO2 in each sample was measured using a VLE nsol vent
apparatus (equilibrium cell). The main compositions of the appara- where nsol vent is the number of moles of solvent; the CO2 loading
tus includes gas storage tank, temperature indicator, pressure indi- capacity (αCO2 ) is the total number of moles of CO2 absorbed per
cator, vacuum pump, data logger, equilibrium cell, stirrer and water one mole of solvent. By the calculations described above the CO2
344 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349
Fig. 2. Schematic of the VLE equipment: (1) gas storage tank; (2) temperature indicator; (3) pressure indicator; (4) data logger; (5) equilibrium cell; (6) water bath.
Table 2
Technical specification of devices used in the VLE setup.
Number Device
1 Gas storage tank
2 Temperature indicator
3 Pressure indicator
4 Water bath
5 Pressure sensor
6 Data logger
loading can be obtained as a function of time. All the experimental
results are the average of three experiments.
3.3. Absorption rate
In each experiment, the valve between the gas storage tank and
the cell was carefully opened for a very short time, and a certain
amount of CO2 from the gas storage tank was rapidly (<2 s) in-
troduced into the cell with a volume of 1500 ml, until the de-
sired initial pressure was reached. The initial pressure of CO2 in
cell has been set to 50 kPa in all the experiments. The rate of de-
cline of gas pressure was recorded every 0.1 s (P vs. t) and the
profile of increasing of CO2 loading in the solution was obtained as
a function of time (α vs. t). These data were plotted for the time
interval between t = 0 s and t = 500 s and the absorption rate
was calculated from the value of the slope CO2 loading versus of
time (d α /dt). In this study, absorption rate refers to the “apparent
absorption rate” in order to compare the performance of the sug-
gested promoters in terms of the CO2 absorption rate. All the ex-
periments have been repeated three times to ensure reproducibil-
ity of the results. This technique has also been used elsewhere
[12, 32, 33].
4. Results and discussion
4.1. Primary-reliability test
To validate experimental method and apparatus used in the
present work, a series of experiments on CO2 solubility in 2.5 M
MEA solution at 313.15 K was carried out. The obtained VLE data
were compared with those published in the literature [34-36] as
shown in Fig. 3. It can be observed that the result obtained in this
work are very close to published data.
Model Company Country Accuracy
Stainless steel Swagelok USA –
Pt-100 Julabo Germany ±0.01 K
TSA GEFRAN Italy ±0.1 kPa
TW Julabo Germany ±0.01 K
TSA GEFRAN Italy ±0.1 kPa
USB-4718 Advantech Taiwan ±0.1%
4.2. Effect of the additive type on the equilibrium solubility
In order to investigate the performance of each activator, the
effect of the addition of suggested additives on the solubility of
CO2 at a total blend concentration of 2.5 M at a molar ratio (ad-
ditive/MEA) 0.25, 0.66 and 1 is shown in Figs. 4–6 and tabulated
in Table 3. It is observed that in the entire range of CO2 partial
pressures (0 to 50 kPa), the addition of TEPA, PZEA, PL and TSP
results in a considerable increase in the CO2 loading capacity of
MEA. However, K2 CO3 +MEA and PG+MEA systems have a higher
CO2 loading than the pure MEA solution at CO2 partial pressures
higher than 20 kPa. It is clear that TEPA presents the best per-
formance compared with other additives because the TEPA+MEA
solution has the highest CO2 loading (1.32). This high performance
of TEPA is because of its structural features where two primary
and three secondary amine sites combine to enhance the CO2
loading capacity of MEA. The addition of PZEA also increased
the CO2 loading capacity of MEA solution significantly. PZEA has
three amine groups, one primary, one secondary and one tertiary.
Its advantages, i.e. its high absorption rate, high CO2 loading
capacity, and rapid carbamate formation are due to the cyclic
diamine structure [29]. It should be mentioned that the increase
of amine groups from 3 (structure of PZEA) to 5 (structure of
TEPA) increased the CO2 loading capacity considerably. This can be
explained by the fact that the increase of amine groups can pro-
vide more available sites for reaction with CO2 . TSP (an inorganic
solvent) is highly alkaline and nonvolatile, which can be a good
candidate as an additive to MEA. From Figs. 4–6, it can be seen
that with increasing concentration of TSP in the blend solution,
the solubility of CO2 increases. Furthermore, the TSP+MEA system
has a greater CO2 loading than PL+MEA, K2 CO3 +MEA, PZEA+MEA
and PG+MEA blends. Potassium carbonate as inorganic solvent has
received much attention for many years [14]. It is obvious that the
 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349 345

Fig. 3. Solubility of carbon dioxide in aqueous 2.5 M MEA solution at 313 K.

Fig. 4. The effect of addition of different additives to MEA on the solubility of CO2 at molar ratio of additive/MEA = 0.25.

addition of K2 CO3 to MEA increases the CO2 loading capacity of
MEA at CO2 partial pressures above 20 kPa.
Amino acids have the same functional group as amines and can
react with CO2 in a similar way. Furthermore, amino acids have
benefits such as their higher loading capacity compared to amines,
less volatility, less degradation, and toxicity. Aqueous amino acids
occur in three states: acidic, zwitterionic and deprotonated. The
deprotonated state is much more reactive with CO2 in compari-
son with other states [17]. The addition of lysinate and glycinate to
MEA increases the pH of the blend solution and thus improves the
CO2 loading capacity of MEA. L-lysine has almost a double load-
ing capacity compared to MEA, because of its two amine groups,
of which one has a high base strength.
As an overall conclusion, additives such as TEPA, TSP, PZEA and
PL have a positive effect on the CO2 loading capacity of pure MEA
solution over the whole range of CO2 partial pressures, while the
additive effect of PG and K2 CO3 on the absorption performance of
MEA at CO2 partial pressures lower than 20 kPa is negative. Blend
solutions have better CO2 loading capacity than pure MEA at CO2
partial pressures higher than 20 kPa in the order: TEPA+MEA >
TSP+MEA > PZEA+MEA > PL+MEA > K2 CO3 +MEA > PG+MEA >
MEA.
The response surface methodology was applied to suggest a
quadratic model to correlate the loading capacity as functions of
temperature, composition, and CO2 partial pressure. The quadratic
model suggested by the software gave the closest fit to the ex-
perimental values. In order to evaluate the operating variables
on the CO2 loading capacity, the central composite design (CCD)
with three factors, temperature (T), partial pressure of CO2 (P),
and molar ratio of the additive to MEA (R) was employed. The
results revealed that the selection of a quadratic model could be
statistically significant for the CO2 loading capacity. The regression
346 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349

Fig. 5. The effect of addition of different additives to MEA on the solubility of CO2 at molar ratio of additive/MEA = 0.66.

Fig. 6. The effect of addition of different additives to MEA on the solubility of CO2 at molar ratio of additive/MEA = 1.00.

coefficient values were evaluated and the subsequent refined
equation is as follows:
C O2 loading capacity = a0 + a1 T + a2 P + a3 R + a4 T × P + a5 T
× R + a6 P × R + a7 T 2 + a8 P 2 + a9 R2
The constant coefficients of each solvent are listed in Table 4.
This equation makes a good visualization of the influences of each
independent variable and their interactions on the response (CO2
loading).
4.3. Effect of the additive type on the absorption rate
The profile of the loading capacity (α ) versus time for each
activator was plotted in order to investigate the effect of the
suggested additives into aqueous MEA solutions in terms of CO2
absorption rate, as shown in Figs. 7–9. The absorption rate is
determined from the slope of the loading capacity (α ) versus time
curves. In this study, the absorption rate refers to the apparent
absorption rate to compare the performance of various absorbents.
As presented in Figs. 7–9, among all the blend solutions, the
TEPA+MEA system shows the highest CO2 absorption rate and
(22) TSP+MEA exhibits the lowest absorption rate. In fact, the addition
of TEPA increases the pH of MEA solution and thus improves the
overall CO2 absorption rate. It can be seen that with increasing
PZEA concentration in the blend solution, the CO2 absorption rate
increases. As discussed earlier, PZEA has shown a good perfor-
mance as an additive due to the rapid carbamate formation with
CO2 . One of the most important limitations of using K2 CO3 is the
low absorption rate for CO2 [37]. At a given temperature, the CO2
absorption rate decreases as the concentration of K2 CO3 in the
solution increases. The results shown in Figs. 7–9 confirm that
potassium lysinate absorbs CO2 slower than sodium glycinate. Con-
sidering the pKa values, this was a predictable result since pKa, Lys
= 8.95 < pKa, Gly = 9.7775. Therefore, PG has a stronger affinity
 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349 347

Table 3
Solubilities (α = mole CO2 /mole blend solution) of CO2 at different molar ratio of additive/MEA at temperature 313.15 K.

PG + MEA PL + MEA PZEA + MEA TEPA + MEA TSP + MEA K2 CO3 + MEA

PCO2 (kPa) α PCO2 (kPa) α PCO2 (kPa) α PCO2 (kPa) α PCO2 (kPa) α PCO2 (kPa) α

Molar ratio = 0.25

07.82 0.273 04.32 0.551 07.76 0.699 04.66 0.801 05.31 0.741 04.37 0.401
11.80 0.367 12.38 0.611 21.15 0.764 12.01 0.840 10.13 0.792 12.67 0.484
21.41 0.494 24.91 0.664 30.18 0.767 23.57 0.902 20.27 0.875 25.10 0.591
28.43 0.557 36.28 0.684 38.56 0.781 31.84 0.954 29.54 0.910 33.26 0.642
34.90 0.644 42.04 0.704 47.83 0.813 48.40 1.014 36.48 0.941 43.86 0.675
Molar ratio = 0.66
06.10 0.333 06.34 0.632 09.18 0.783 03.34 0.893 04.20 0.742 05.50 0.441
14.01 0.443 14.04 0.680 19.37 0.813 14.50 0.950 12.67 0.835 12.36 0.487
20.90 0.512 24.72 0.741 27.95 0.850 27.46 1.083 20.27 0.907 21.68 0.571
28.31 0.561 36.29 0.802 35.20 0.867 37.01 1.102 25.02 0.935 27.92 0.604
34.32 0.689 44.07 0.810 48.01 0.885 47.36 1.180 35.10 0.980 36.46 0.679
Molar ratio= 1.00
03.81 0.297 05.39 0.723 06.23 0.856 03.01 1.040 03.67 0.740 06.27 0.482
08.01 0.386 13.28 0.779 18.76 0.949 08.42 1.111 10.13 0.835 17.34 0.580
19.70 0.557 25.61 0.843 30.46 0.991 17.37 1.160 15.20 0.887 26.57 0.654
27.10 0.603 34.17 0.862 42.37 1.004 32.12 1.273 25.67 0.970 34.18 0.701
33.60 0.737 45.23 0.902 49.10 1.017 47.35 1.322 35.01 1.041 42.65 0.720

Standard uncertainties; U (T) = +/− 0.01 K; U (P) =+/− 0.1 kPa; U (M): 0.001 mol/l; U (α ) =+/− 0.001.

Table 4
The constant coefficients of each solvent.

Coefficient MEA+PL MEA+PG MEA+PZEA MEA+TEPA MEA+K2 CO3 MEA+TSP

a0 −1.5086 24.8607 −9.7478 −12.7011 2.0578 −1.7190

a1 0.0172 −0.1456 0.0733 0.0909 −6.7176 × 10−3 0.0184
a2 0.0136 −0.0105 6.5809 × 10−3 −6.8902 × 10−3 −2.1301 × 10−3 5.0045 × 10−3
a3 0.7026 0.8090 −0.6047 0.4805 0.7754 0.8787
a4 −2.2223 × 10−5 8.333 × 10−5 −4.4444 × 10−6 3.3333 × 10−5 4.4444 × 10−5 1.1111 × 10−5
a5 −2.0 0 0 0 × 10−3 −1.6666 × 10−3 2.1333 × 10−3 2.4205 × 10−16 −2.6666 × 10−3 2.6666 × 10−3
a6 −5.9259 × 10−4 −2.2222 × 10−3 7.7037 × 10−4 8.8888 × 10−4 7.1817 × 10−17 1.7777 × 10−3
a7 −3.4545 × 10−5 2.1272 × 10−4 −1.2863 × 10−4 −1.5409 × 10−4 4.0909 × 10−6 −3.4090 × 10−5
a8 −4.1391 × 10−5 −5.6745 × 10−5 −3.6273 × 10−5 2.8821 × 10−5 −9.7957 × 10−5 −7.5869 × 10−5
a9 0.1354 −0.0976 0.1645 −0.1090 0.1096 0.0113

Standard uncertainties; U (T) = +/- 0.01 K; U (P) =+/- 0.1 kPa; U (M): 0.001 mol/l; U (α ) =+/- 0.001.

Fig. 7. The effect of addition of used additives to MEA on the CO2 absorption rate at molar ratio of additive/MEA = 0.25.
348 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349

Fig. 8. The effect of addition of used additives to MEA on the CO2 absorption rate at molar ratio of additive/MEA = 0.66.

Fig. 9. The effect of addition of used additives to MEA on the CO2 absorption rate at molar ratio of additive/MEA = 1.00.

to accept protons via the deprotonated pathway and results in a 5. Conclusion

faster overall reaction rate with CO2 . Generally, the reaction rate is
an important factor in reducing the size and therefore the capital
costs of the absorber, while a low pKa is necessary to reduce the
energy requirement for CO2 regeneration. The important factors
for the selection of the amino acids subject to this study were
based on their chemical and physical properties, basicity (pKa) and
stability.
It can concluded that additives such as TEPA and PZEA have a
positive effect on the absorption rate of MEA solution, while the
effect of additives like PG, PL, K2 CO3 and TSP on the absorption
rate is negative. In other words, the enhancement effect of ad-
ditives on the absorption rate is listed as follows from the high-
est to the lowest: TEPA+MEA > PZEA+MEA > MEA > PG+MEA >
PL+MEA > K2 CO3 +MEA > TSP+MEA.
In this work, a total of six additives were suggested to enhance
the absorption rate and loading capacity of MEA as the main sol-
vent. The performance of additives was evaluated by using a VLE
apparatus. For better investigation, all the experiments were per-
formed at the same total concentration of 2.5 M and at a temper-
ature of 313.15 K. The results indicate that TEPA had the largest
effect because its blend with MEA (TEPA + MEA) achieved the
fastest absorption rate and highest CO2 loading capacity compared
to other additives. Thus, K2 CO3 has the lowest effect on the ab-
sorption performance of MEA. As an overall conclusion, all sug-
gested promoters improved the performance of MEA in terms of
CO2 loading. However, for practical use of these promoters, their
behavior should be evaluated at different conditions and opera-
tions such as CO2 desorption.
 R. Ramazani et al. / Journal of the Taiwan Institute of Chemical Engineers 65 (2016) 341–349
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