Applied Energy xxx (2016) xxx–xxx

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Aqueous amine solution characterization for post-combustion CO2

capture process
Nabil El Hadri a, Dang Viet Quang a, Earl L.V. Goetheer b, Mohammad R.M. Abu Zahra a,⇑
a
The Institute Centre of Energy (iEnergy), Masdar Institute of Science and Technology, PO Box 54224, Masdar City, Abu Dhabi, United Arab Emirates
b
Department of Process and Instrument Development, Netherlands Organization for Applied Scientific Research, Leeghwaterstraat 44, 2628 CA Delft, The Netherlands

h i g h l i g h t s

The CO2 solubility of 30 aqueous amine solutions was measured at 30 wt% and 313.15 K.

The CO2 loading of HMD is the highest, and that of TEA is the lowest.

2DMAE, 3DMA1P, 1DMA2P, MDEA, TMPAD and 2EAE have a low heat of absorption with CO2.

2EAE can be used as an alternative to MEA in the CO2 capture process.

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

Article history: This article presents a thermodynamic and kinetic characterization of CO2 absorption by 30 aqueous
Received 15 August 2015 amine solutions. A solvent screening setup (S.S.S.) was used to find the CO2 loading (a) for 30 different
Received in revised form 10 March 2016 aqueous amine solutions (30 wt%) at a pressure of 1 bar with feed gas containing 15 vol% CO2 and
Accepted 13 March 2016
85 vol% N2 at 313.15 K to provide reliable absorber parameters. The structures of various amines (linear,
Available online xxxx
non-linear, polyamines, sterically hindered, etc.) were tested and the S.S.S. results showed that hexam-
ethylenediamine (HMD) has higher CO2 loading at 1.35 moles of CO2/mole of amine, and triethanolamine
Keywords:
(TEA) has the lowest at 0.39 mole of CO2/mole of amine. The heat of absorption indicates that MDEA has
CO2 capture
Amine
the lowest and HMD has the highest at 52.51 kJ/mole of CO2 and 98.39 kJ/mole of CO2, respectively. The
Solvent screening combined data for the CO2 loading and the absorption heat generated 6 amines that have good properties
CO2 loading for the post-combustion CO2 capture process in comparison with that of MEA. These amines are made up
Heat of absorption of one secondary amine (2-ethylaminoethanol, 2EAE) and 5 tertiary amines (N-methyldiethanolamine,
Kinetics MDEA, 1-dimethylamino-2-propanol, 1DMA2P, 2-dimethylaminoethanol, 2DMAE, 3-dimethylamino-1-
propanol, 3DMA1P and N,N,N0 ,N0 -tetramethyl-1,3-propanediamine, TMPDA). In comparison with the
amine reference MEA (DH = 85.13 kJ/mole of CO2 and a = 0.58 mole CO2/mole of amine), the 6 amines
have heats of absorption that are between 68.95 kJ/mole of CO2 and 52.51 kJ/mole of CO2, and their
CO2 loading is between 0.52 and 1.16 mole of CO2/mole amine. The third important parameter, namely
the reaction kinetics between aqueous amine solutions and CO2, was studied by using stopped-flow equip-
ment to measure the pseudo-first order reaction (k0, s1) at different amine concentrations. A determina-
tion of the second order rate constants (k2, m3 mole1 s1) at 298.15, 303.15, 308.15 and 313.15 K was
performed by using the proposed reaction mechanisms. The base catalysis mechanism was used to corre-
late the experimental data of the tertiary amines and the zwitterion mechanism was used to correlate the
experimental data of the primary/secondary amines. The kinetics results show that 2EAE, a secondary
amine, was very high in comparison with MDEA, 1DMA2P, 2DMAE, 3DMA1P and TMPDA, all of which
are tertiary amines that are very close to MEA, which is the reference case. This result shows that 2EAE
is a good candidate for CO2 capture as an alternative to MEA because it has good CO2 absorption, a low heat
of absorption and high kinetic reaction with CO2. Moreover, the outcomes for the thermodynamic and
kinetic properties indicate that the following 5 amine blends have emerged from this study: 2EAE/
MDEA, 2EAE/1DMA2P, 2EAE/2DMAE, 2EAE/3DMA1P and 2EAE/TMPDA.
Ó 2016 Elsevier Ltd. All rights reserved.

⇑ Corresponding author.
E-mail address: [email protected] (M.R.M. Abu Zahra).

http://dx.doi.org/10.1016/j.apenergy.2016.03.043
0306-2619/Ó 2016 Elsevier Ltd. All rights reserved.

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2 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

1. Introduction have a high CO2 absorption and low regeneration energy. Bougie
et al. did a literature review of the entire properties (density, vis-
CCS (carbon capture and storage) post-combustion technology cosity, vapor pressure, heat capacity and heat of absorption, CO2
is the most suitable technological process for decreasing the CO2 and amine diffusivity, CO2 absorption capacity and kinetics, regen-
that is emitted into the atmosphere. This technology can be eration capability) for hindered amines [16]. Their study showed
installed directly to existing power plants [1]. The separation of that AMP is a promising candidate and is the most studied hin-
CO2 from flue gas is based on chemical absorption, and it is suitable dered amine for CO2 capture.
because it can separate CO2 from highly diluted gas streams. Vari- The solubility of CO2 with aqueous amine solutions is the first
ous amine compounds have been tested, and aqueous amines important critical parameter for determining if an amine can be
including monoethanolamine (MEA), a primary amine; diethanola- used for CO2 capture. During a CO2 capture process, CO2 solubility
mine (DEA), a secondary amine; and methyldiethanolamine occurs in the absorber with a specific entrance parameter
(MDEA), a tertiary amine, are the most widely used amines for ðT  40  C=P CO2  10—15% of the total atmospheric pressure). Sev-
CO2 absorption [2]. The primary and secondary alkanolamines eral studies have been performed to find a new amine that could
have a high reaction rate upon CO2 absorption, which begins with have the high CO2 absorption property needed for CO2 capture
the formation of a zwitterion (reaction (1)) that then transfers a applications [17–25]. Bonenfant et al. studied the effects of differ-
proton to an amine to form carbamate (reaction (2)). Their maxi- ent amine structures (amines and polyamines) on the absorption
mum possible CO2 loading is 0.5 mole of CO2/mole of amine (two and desorption of CO2 at an amine concentration of 5 wt% [26].
amine molecules react with one CO2 molecule). At high pressure, Their work was based on eight amines, and their results show that
the carbamate could be hydrolysed to form a free amine and bicar- N-(2-aminoethyl)-1,3-propanediamine (AEPDNH2, polyamines
bonates, and then the free amine will again react with CO2 (reac- with two primary and one secondary amine) and 2-(2-
tion (3) [3]). aminoethylamino)ethanol (AEE, a diamine with one primary and
one secondary amine) have the best characteristics for CO2
R1 R2 NH þ CO2 ðaqÞ $ R1 R2 NHþ COO ð1Þ removal. Chowdhury et al. also studied the effects of amine struc-
ture on the absorption/desorption of CO2 and the reaction heat of
R1 R2 NH þ R1 R2 NHþ COO $ R1 R2 NHþ þ R1 R2 NCOO ð2Þ the hindered amines [9]. The authors show that the CO2 loading
is increased and the reaction heat is reduced for two secondary
R1 R2 NCOO þ H2 O $ R1 R2 NH þ HCO3 ð3Þ amines (IPAE and IBAE) and two tertiary amines (1M-2PPE and
IPDEA) in comparison with the conventional amines (MDEA and
For tertiary amines, the maximum CO2 loading could be 1 mole AMP). Another study by Chowdhury et al. addressed the absorp-
of CO2 per mole of amine (one molecule of amine reacts with one tion/desorption (at 40 and 70 °C, respectively) and the reaction
molecule of CO2) with the formation of bicarbonates (reaction (4)). heats of twenty-four tertiary amines [27]. The authors studied dif-
Although the tertiary alkanolamines have higher CO2 loading, they ferent types of amine structures with different chemical groups at
have low reactivity with CO2 in comparison with the primary or the nitrogen site. The results show that seven tertiary amines have
secondary amines. the potential to be used for CO2 capture. Ma’mun et al. evaluated
the reaction rates and the absorption capacity between CO2 and
R1 R2 R3 þ CO2 ðaqÞ þ H2 O $ R1 R2 R3 NHþ þ HCO3 ð4Þ
five aqueous amine solutions, and they found that AEEA (a diamine
A typical conventional post-combustion CO2 capture process with one primary and one secondary amine) and MMEA (sec-
based on aqueous monoethanolamine (MEA) solution (30 wt%) ondary amine) can be considered for CO2 capture [28]. Prachi
has been used as a reference case. MEA was chosen because of et al. studied different amines (linear, cyclic, polyamines, and
its high reaction rate with CO2, its reasonable CO2 absorption others) to establish a relation between the structure of the amine
capacity and its low cost [4]. However, the regeneration energy and the CO2 loading and absorption rate [29–31]. These results
needed to recover an MEA solution after CO2 absorption is very show the potential that is associated with structural variation,
high causing an increase in the cost of CO2 capture, and this energy and the authors found that 1,6-hexanediamine, N,N-dimethyl has
hinders the conventional post-combustion process from being the best CO2 absorption in comparison with all the studied amines.
used for industrial applications [3,5]. The second major parameter of the post-combustion process
Recently, great effort has been expended to find alternative that should be considered is the regeneration energy in the desor-
amines; a focus on CO2 absorption, reaction kinetics and low ber column. Knowledge of this property is essential for identifying
regeneration energy is the primary challenge in prospective amine the heat that will be provided within the regeneration column. The
solvent performance to reduce the cost of the CO2 capture process. total heat (Eregeneration) required to desorb CO2 from a CO2-amine-
Different amine solvents have been tested in which blends and H2O system is the contribution of three energies as follows:
hindered amine are also considered as a potential alternatives
[6–14]. The use of blends have the particularity to do a combina- Eregeneration ¼ Eheat of absorption þ Esensible heat þ Eheat of v aporization ð5Þ
tion of each amine advantages: a high CO2 absorption of the ter-
tiary amines (e.g. MDEA) coupled with the fast reaction kinetics where Eheat of absorption is associated with the quantity of steam that is
of the primary/secondary amines (e.g. MEA, DEA). Rangwala et al. necessary to regenerate the aqueous amine solution, Esensible heat is
found that a small addition of MEA to tertiary amine increase the the sensible heat required to increase the temperature in the regen-
CO2 absorption rates [15]. Moreover, the combination of the two eration step from the temperature in the absorber, and
properties improves the CO2 capture performance by having a Eheat of v aporization is the energy needed to vaporize the aqueous amine
low regeneration energy cost. In order to decrease the cost of the solution in the regenerator column. The authors specify that
regeneration step in the process, several studies focused on hin- approximately 50–60% of the total regeneration energy comes from
dered amines and found that hindered amines could be good can- the heat of CO2 absorption for MEA 30 wt% [32]. This finding
didate for CO2 capture process [14,16]. Some amine structure, due assumed that the absorption heat is the primary portion of the over-
to the hinderance near or onto the nitrogen site (e.g. AMP), form all regeneration energy. Several studies have been performed to
instable carbamate and their hydrolysis forms preferentially bicar- determine the reaction enthalpy of aqueous amine solution with
bonates which result of a maximum capacity of 1 mole of CO2 per CO2 [33–35]. The heat of absorption is usually high for primary
mole of amine. The particularity of these amines is the capacity to and secondary amines, and therefore, the regeneration energy

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 3

requirements for the CO2 capture process with those amines are During the carbon capture process with an aqueous amine solu-
also high. However, the energy required to regenerate the tertiary tion, the CO2 solubility, the absorption heat of CO2 and the reaction
amine solvents is lower because of their low absorption heat [36]. kinetics are the most critical data for designing the CO2 removal
A determination of the absorption heat could be performed by using process. An ideal aqueous amine solution will have high CO2 load-
the Gibbs–Helmholtz equation from the CO2 solubility data or by ing, high reaction kinetics with CO2 and a low heat of absorption.
making direct calorimetric measurements. The Gibbs–Helmholtz These parameters are related to the cost of the entire process. To
equation was used by Kim et al. to calculate the heat of absorption achieve this objective, a screening method should be used to gain
for MEA and MDEA from the equilibrium constant of each reaction more knowledge within a short time, with different characteriza-
that occurred during the CO2 reaction with the respective aqueous tions in comparison with a classical study. A solvent screening
amine solutions [37]. The direct calorimetric measurements have setup was used to evaluate the CO2 loading, calorimeter equipment
the ability to provide accurate data about the absorption heat was used for the absorption heat determination and stopped-flow
because they incorporate the heat from the physical dissolution of equipment was used to determine the reaction kinetics of amines
CO2 in the aqueous amine solution and the chemical reaction with CO2.
between CO2 and aqueous amines. Mathonat et al. measured the To evaluate the effect of amine structure on the CO2 absorption
enthalpy of absorption for aqueous solutions of MEA and MDEA performance, 30 amines with different structures have been
30 wt% at 40, 80 and 120 °C with a flow calorimeter [38,39]. Arcis selected and characterized to find the most promising candidate
et al. performed calorimetric measurements for aqueous amine for CO2 capture. First, screening for CO2 absorption by the amine
solutions of MEA, MDEA and AMP at different CO2 concentration solvents provided an initial evaluation of some amines (i.e., CO2
ranges, temperatures and pressures [40–42]. Carson et al. measured loading). Furthermore, the effect of the amine structure on the
the absorption enthalpy of CO2 for MEA, DEA, MDEA and an MEA/ CO2 absorption capacity was examined. In parallel, the resulting
MDEA blend at different amine concentrations and 25 °C [36]. aqueous amine solutions were analyzed to obtain the absorption
Kim et al. measured the absorption enthalpy of CO2 in an aqueous heat of CO2. Finally, the promising molecules were studied to
solution of MEA and AEEA in which AEEA is a polyamine with one determine the reaction kinetics of CO2 absorption. The results have
primary amine group and one secondary amino group at tempera- been compared with those of the MEA 30 wt% reference to select
tures ranging from 40 to 120 °C [43]. The authors concluded that the most suitable amine(s) for acid gas removal.
the absorption enthalpy of AEEA is close to that of MEA. In addition,
Dallos et al. measured the absorption enthalpy of CO2 in an aqueous
2. Experimental part
bis-(3-dimethylaminopropyl)amine solution, which is a polyamine
with three amino groups [44]. McCann et al. showed the predicted
2.1. Materials
evolution of CO2 absorption enthalpy for MEA, MDEA, AMP and DEA
in comparison with experimental data [45]. They also provided the
CO2. (P99.5%) and N2 (P99%) were used to simulate flue gas.
contribution of individual reactions to the absorption enthalpy, and
The aqueous amine solutions were prepared with distilled water
they concluded that the high enthalpy of MEA is caused by exother-
on a 30 wt% basis. All the amines (purity P98%) were purchased
mic carbamate formation. The low enthalpy for MDEA is caused by
from Sigma Aldrich. The amines were used on the basis of the pur-
endothermic bicarbonate formation.
ity values given by the supplier. Thirty amines were chosen, and
The third important parameter for considering the suitability of
they had different variations in their structures (Table 1). The
amine candidates for the CO2 capture process is the reaction kinet-
methodology of this present work will be based on the following
ics between CO2 and aqueous amine solutions. These kinetics have
three characterizations:
a strong effect on the absorption rate and on the design of the
absorber that is used for the post-combustion capture process.

The solubility of CO2 absorption by aqueous amine solutions at
The reaction kinetics of CO2 with tertiary amines is commonly
313.15 K when acquired by solvent screening setup (S.S.S.) and
lower than that of primary or secondary amines [46]. Usually,
phosphoric acid titration.
the primary/secondary amines will be able to reduce the solvent

The absorption heat at 313.15 K with a flow micro-reaction
flow, which reduces the height of the absorber column, whereas
calorimeter.
the tertiary amines have a higher solvent flow, which increases

The reaction kinetics for CO2 with aqueous amine solutions at
the height of the absorber column. The reaction kinetics of alka-
298.15, 303.15, 308.15 and 313.15 K and at different amine con-
nolamines were investigated extensively, and different experimen-
centrations ranging from 5 to 800 mole m3 when measuring
tal equipment was used. The different approaches involved a
them with stopped-flow equipment.
laminar liquid jet, a stirred cell wetted wall column and stopped-
flow. The stopped-flow technique was used in several published
studies because it is a direct method for measuring the reaction 2.2. Solvent screening setup (S.S.S.) and phosphoric acid titration (P.A.
kinetics of CO2 absorption by aqueous amine solutions [47]. The T.) used to determine CO2 loading
reaction kinetics of CO2 by aqueous alkanolamine solutions and
polyamines were measured in several studies [47–66]. To improve A description of the solvent screening setup can be found in the
the kinetics of tertiary amines, blends with primary or secondary authors’ previous study [72]. In brief, the setup has six parallel
amines were also considered [6,7,60,67–71]. glass reactors (250 ml ± 0.5) that are operational within a temper-
Many authors have focused on finding more efficient amine sol- ature range from 298.15 K to 423.15 K (±1 K) and a pressure range
vents than aqueous MEA 30 wt% for CO2 capture. Various amines of 0–6 bars (±0.01 bar) (Fig. 1(a)). A magnetic stirrer is used to
have been investigated; however, the effects of different amine ensure homogeneous contact between the solution and CO2 by cre-
structures on their CO2 absorption performance have not been sys- ating a vortex (with a maximum speed of 1500 rpm (±1 rpm)). In
tematically evaluated. Because the amine structure relates directly each experiment, 150 g of each aqueous amine solution at 30 wt
to the reaction mechanism between amine and CO2, CO2 absorp- % was prepared and transferred to the reactors. The absorption
tion capacity, reaction kinetics, and the heat of CO2 absorption, was conducted at 313.15 K with a mixing speed of 500 rpm. A mix-
the objective of the present study is to screen amines with differ- ture of CO2 and N2 (15 vol% and 85 vol%, respectively) was initially
ent structures and to find better candidates for post-combustion fed into a make-up vessel until a pressure of 2 bars was reached,
CO2 capture in comparison with conventional amines (e.g., MEA). and then the mixture was added to each reactor by mass flow con-

Please cite this article in press as: El Hadri N et al. Aqueous amine solution characterization for post-combustion CO2 capture process. Appl Energy (2016),
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4 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

Table 1
List of the 30 amines and their structures.

Name Structure CAS

1 Monoethanolamine (MEA) OH 141-43-5
H 2N

2 N-methyldiethanolamine (MDEA) 105-59-9

3 Diethanolamine (DEA) 111-42-2

4 2-amino-1-methyl-2-propanol (AMP) 2854-16-2

5 Piperazine (Pz) 110-85-0

6 1-amino-2-propanol (1A2P) 78-96-6

7 2-amino-1-butanol (2A1B) 96-20-8

8 2-(methylamino)ethanol (2MAE) 109-83-1

9 2-(ethylamino)ethanol (2EAE) 110-73-6

10 2-(butylamino)ethanol (2BAE) 111-75-1

11 2-(tert-butylamino)ethanol (2TBAE) 4620-70-6

12 2-amino-2-(hydroxymethyl)-1,3-propanediol (AHMPD) 77-86-1

13 2-(dimethylamino)ethanol (2DMAE) 108-01-0

14 1-dimethylamino-2-propanol (1DMA2P) 108-16-7

15 N,N-diethylethanolamine (DEEA) 100-37-8

16 3-dimethylamino-1-propanol (3DMA1P) 3179-63-3

17 Isobutylamine (IBA) 78-81-9

18 Sec-butylamine (SBA) 13,952-84-6

19 Butylamine (BA) 109-73-9

20 N,N,N0 ,N0 -Tetramethyl-1,3-propanediamine (TMPAD) 110-95-2

21 3-(dimethylamino)propylamine (3DMAPA) 109-55-7

22 1,3-diaminopropane (DAP) 109-76-2

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 5

Table 1 (continued)

Name Structure CAS

23 Hexamethylenediamine (HMD) 124-09-4

24 Diethylamine (DA) 109-89-7

25 Triethylamine (TA) 121-44-8

26 Hexylamine (HA) 111-26-2

27 Triethanolamine (TEA) 102-71-6

28 Isopropylamine (IPA) 75-31-0

29 Tert-butylamine (TBA) 75-64-9

30 Benzylamine (BA) 100-46-9

14

12

10

8
CO2 %Vol.

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000
Time (s)
(a) (b)
Fig. 1. Schematic of the solvent screening apparatus (a) and the data obtained from this equipment (b).

troller at a flow rate of 15 L/h. The total pressure inside the reactors of CO2 in % over time. The experiment was repeated three times to
was kept at 1 bar throughout the absorption experiment. The reac- verify the amount of CO2 loading, and an average was calculated.
tion of CO2 with the solution is complete when equilibrium is The CO2 loading was calculated by using the following equation:
reached (i.e., the CO2 % volume is constant, Fig. 1(b)). Classically
aCO2 ¼ nCO2 =namine ð6Þ
speaking, approximately 12 h is needed to reach equilibrium. To
prevent solvent loss, a condenser was used at 279.65 K.
The loaded aqueous amine solution that was obtained for each 2.3. Determining the heat of absorption: Micro Reaction Calorimeter
reactor was used in a phosphoric acid titration to find the CO2 load- (URC)
ing (mole of CO2/mole of amine) [72]. A round-bottom flask con-
taining 85% phosphoric acid solution was used. The temperature A description of the equipment can be found in the previous
was controlled by using a heating mantle (with a maximum tem- study by the authors [3]. A flow micro-reaction calorimeter that
perature of 673.15 K). Phosphoric acid reacts with richly CO2- was supplied by Thermal Hazard Technology (UK) was used to
loaded amines at 453.15 K. A nitrogen flow is used to sweep the evaluate the absorption heat for aqueous amine solutions
CO2 from the system. The CO2/N2 gas mixture goes through an (enthalpy of reaction/DH (kJ/mole of CO2)) (Fig. 2(a)). The system
infrared CO2 analyser to obtain the amount of CO2 that is released can operate at temperatures from 298.15 to 353.15 K (±1 K), and
from the amine-H2O-CO2 system. The software shows the amount the flow gas can be adjusted from 0 to 20 ml/min (±0.1 ml/min).

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6 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

Injection of CO2
into the cell

(a) (b)
Fig. 2. Schematic of the flow Micro Reaction Calorimeter, URC (a) and the data obtained from this equipment (b).

The calorimeter is controlled by URC control software from Ther- tion, a CO2 concentration was prepared by diluting the stock solu-
mal Hazard Technology. In a typical experiment, the sample- tion to keep the CO2 solution approximately 15 times lower than
containing cell was placed inside the calorimeter, and the temper- the aqueous amine solution. The amine is always in excess in the
ature was set to 313.15 K and atmospheric pressure. As the exper- stopped flow system to ensure pseudo-first-order conditions with
iment starts, the variation in power (mW) over time (s) is recorded respect to CO2. The amine solution and the corresponding CO2
by the software. When the signal is stable, CO2 gas is introduced solution are then introduced to reactant-containing cylinders with
into the cell at a rate of 0.5 ml/min (±0.01 ml/min). The CO2 flow syringes. A water jacket is used for a bath to provide a constant
is controlled by a mass flow controller, and the flow passes through homogeneous temperature for the solution. Then, a pneumatic
a desiccant column to remove moisture before entering the sample drive plate pushes equal volumes of the two fresh solutions into
cell. Because the CO2 reaction with the aqueous amine solution is a mixing conductivity cell to initiate the reaction between the
exothermic, the power signal initially increases, and then the sig- aqueous CO2 solution and the aqueous amine solution. The change
nal decrease becomes constant when the reaction is complete in voltages will be converted to the change in solution conductiv-
(equilibrium) (Fig. 2(b)). The sample weight before and after CO2 ities by the calibrated cell voltage from the conductivities of the
absorption was checked to find the mass of absorbed CO2. This standard potassium chloride (KCl) solution. The experimental evo-
value was used to determine the CO2 loading in Eq. (6). The integral lution of the conductivity with time was fitted by using the expo-
heat Q (in kJ) was determined by using URC software. Finally, the nential equation below, and the software calculates the pseudo-
heat of absorption (DH  kJ/mole of CO2) was calculated by divid- first rate constant k0 (s1) (Fig. 3(b) & Eq. (7)) as follows:
ing integral heat Q by the moles of absorbed CO2.
YðtÞ ¼ A exp ðk0  t Þ þ Y 1 ð7Þ

2.4. Stopped-flow technique where Y is the conductance (S), A is the amplitude of the signal (S),
k0 is the pseudo-first order reaction rate constant (s1), t is time (s)
This equipment can be found in the previous study by the and Y1 is the conductance at the end of the observed reaction (S).
authors [73]. To investigate the reaction kinetics of CO2 with an The CO2 and amine solution concentrations should be carefully
aqueous amine solution, a stopped-flow meter (SF-61SX2) sup- selected for use in the stopped flow equipment. In comparison
plied by TgK Scientific suppliers of Hi-Tech Scientific Instruments, with tertiary amines, primary and secondary amines react faster,
UK was used (Fig. 3(a)). First, an aqueous CO2 solution was pre- and to guarantee sufficient values for the observed k0 (s1) con-
pared by bubbling the gas for approximately 2 h in distilled water stant, very low amine and CO2 concentrations should be used.
at a temperature of 298.15 K and atmospheric pressure. Then, dif- There are numerous reaction mechanisms that can be used to
ferent amine concentrations were prepared within the permitted understand the experimental kinetics data, namely, zwitterion, ter-
range for the stopped-flow equipment. For each amine concentra- molecular and base catalysis mechanisms. Both the proposed zwit-

Fig. 3. Schematic diagram of stopped-flow equipment (a) and data obtained from this equipment (b).

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 7

X
terion and termolecular mechanisms are reliable for explaining the rCO2 ¼ ½CO2 ½AmH kBase ½Base ð16Þ
reaction rate of primary and secondary amines. The base catalysis
mechanism is consistent in explaining the reaction rate of tertiary The observed pseudo-first order reaction rate constant k0
amines with CO2. expression is
r CO2
k0 ¼ ð17Þ

Zwitterion mechanism ½CO2 
X
The zwitterion mechanism was originally proposed by Caplow k0 ¼ ½AmH kBase ½Base ð18Þ
and reintroduced by Danckwerts [74,75]. CO2 reacts with amines
with the formation of a zwitterion, and then a base removes a pro- The base can be H2O or another amine in aqueous solution. As
ton from the zwitterion. The two steps of the reaction are shown mentioned for the zwitterion mechanism, the contribution of
below: OH to the reaction rates is assumed to be negligible.

þ  k2 ;k2
CO2 þ AmH








!
AmH COO ð8Þ
Base Catalysis mechanism

kBase The reaction of an amine with CO2 in aqueous amine solution

AmHþ COO þ Base


! AmCOO þ BaseHþ
Dep
ð9Þ produced protonated amine and bicarbonate ions. According to
The base can be H2O or another amine in aqueous solutions. The Donaldson and Nguyen [78], tertiary amines cannot react directly
contribution of OH to the reaction rates is assumed to be negligi- with CO2, and the mechanism that explains the phenomenon is
ble. Versteeg and Van Swaaij showed that the deprotonation reac- known as the base catalysis mechanism, as follows:
tion with OH is not significant, and for this reason, only amines k2
and water would be considered as bases for the deprotonation of
Am þ H2 O þ CO2 ! HCO3 þ AmHþ ð19Þ
the zwitterion [76]. By applying the steady-state principle to the In parallel with that reaction (19), the two following reactions
intermediate zwitterion, the rate rCO2 (the reaction of CO2 in aque- also occur in the aqueous amine solutions:
ous amine solutions) can be termed as follows:
CO2 þ OH $ HCO3 ð20Þ
½AmH½CO2 
r CO2 ¼ 1 ð10Þ
þ P kBase
2 CO2 þ H2 O $ H2 CO3 ð21Þ
k2 k2 ð kDep ½BaseÞ
In aqueous amine solutions, the contribution of the uncatalysed
½AmH½CO2  reaction (21) to the overall reaction is usually negligible. In addi-
r CO2 ¼ 1 ð11Þ tion, the contributions of OH are assumed to be negligible, as
þ P 01
k2 kB ½Base
mentioned in Versteeg et al. and Little et al. [48,57]. Versteeg
et al. noted that the influence of the OH reaction with CO2 is over-
Base
0 k2 kDep estimated because of the presence of other negatively charged ions
where kB ¼ : ð12Þ such as HCO 2
k2 3 and CO3 [48]. H2O is in excess, and the kinetics do
0
not vary; it is described as k2 ¼ k2  ½H2 O, and the reaction rate r CO2
Under pseudo-first-order conditions, the concentration of the
is expressed as
amine [AmH] is always in great excess relative to that of CO2,
0
and the relation can be written as follows: rCO2 ¼ k2  ½H2 O  ½CO2   ½Am ¼ k2  ½CO2   ½Am ð22Þ
rCO2 The expression for the observed pseudo-first-order reaction rate
k0 ¼ ð13Þ
½CO2  constant k0 is as follows:
The observed pseudo-first-order reaction rate constant k0 then r CO2
k0 ¼ ð23Þ
becomes ½CO2 
½AmH 0
k0 ¼ ð14Þ k0 ¼ k2  ½Am ð24Þ
1
k2
þ P k01½Base
B

Termolecular mechanism 3. Results and discussion

A single-step termolecular mechanism could be used to
describe the kinetics reaction between the CO2 aqueous solution 3.1. The CO2 loading (a)
and the aqueous primary/secondary amine solution [77].
The CO2 solubility of an aqueous amine solution is a crucial
CO2 þ AmH    Base $ AmCOO    BaseHþ ð15Þ
parameter because it provides information on the capacity of an
The rate r CO2 (the reaction of CO2 in aqueous amine solutions) aqueous amine solution to absorb more or less CO2 in the absorber.
has the following expression: First, the CO2 solubility of aqueous amine solution at 30 wt% MEA

Table 2
Comparison of the CO2 loading at 30 wt% and 313.15 K with literature data.

Amine solution Concentration T (K) P CO2 (bars) CO2 loading Sources

MEA 30 313.15 0.15 0.58 This work

MEA 30 313.15 0.08–0.36 0.56–0.61 [4]
MEA 30 313.15 0.13–0.29 0.51–0.54 [79]
MDEA 30 313.15 0.15 0.52 This work
MDEA 30 313.15 0.07–0.28 0.40–0.67 [79]

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8 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

and MDEA was completed to validate the equipment. The resulting the ethyl and methyl groups do not have strong effects on the CO2
data were compared with the corresponding literature data, and absorption (0.54 mole CO2/mole amine for 1A2P and 0.59 mole
they are consistent with data from the published literature CO2/mole amine for 2A1B, Table 3). Moreover, Rebolledo-Morales
(Table 2). et al. studied the CO2 solubility of a 0.3 mass fraction of 1A2P at
Table 3 lists the CO2 loading data that were obtained for 30 313.15 K and found a CO2 loading of [0.50–0.65] mole of CO2/mole
aqueous amine solutions at 30 wt%, 313.15 K and P = 1 bar (85% amine at a pressure range from [0.02 to 1.40] bars. These results
N2 and 15% CO2). The results indicate that diamines (TMDAP, are consistent with the data obtained in this work (0.54 mole of
3DMAPA, DAP and HMD), with the exception of Pz (0.81 mole CO2/mole of amine for 0.15 bars) [17]. AMP and 2TBAE contain
CO2/mole amine), have the highest CO2 loading (1.16, 1.20, 1.23 two methyls that are attached to the carbon adjacent to the amino
and 1.35 mole CO2/mole amine, respectively) among all the tested group and one t-butyl group that replaces the hydrogen that is
amines. For monoamines, AMP, 2TBAE, DEEA, 3DMA1P and DA attached to the nitrogen. The presence of these groups increases
have the highest CO2 absorption capacity (P0.80 mole CO2/mole the CO2 loading from 0.58 mole CO2/mole amine for MEA to
amine). Furthermore, although AMP and 2TBAE are secondary ami- 0.80 mole CO2/mole amine for AMP and from 0.58 mole CO2/mole
nes, the measured CO2 absorption (0.80 and 0.87 mole CO2/mole amine for MEA to 0.87 mole CO2/mole amine for 2TBAE. The
amine, respectively) was found to be high and close to the values methyl group acts as an electron donor, and then there is an
of 3DMA1P, DEEA and DA. These results were caused by the steric increase in the CO2 absorption because of the increase of the basic-
hindrance of the different groups that were attached to the carbon ity of the molecule. As shown in Fig. 4, 2TBAE, which has a t-butyl
adjacent to the amino group. This configuration makes an unstable group attached to the nitrogen, has high CO2 absorption in compar-
carbamate, and hydrolysis will occur and form free amines in solu- ison with that of AMP, and two methyls are attached to the carbon
tion that would react with CO2 and then increase CO2 loading [10]. near the amino group. Sartori and Savage discussed the effects of
TEA has the lowest CO2 absorption among all the tested amines, steric hindrance on the CO2 absorption capacity. The authors indi-
with a value of 0.39 mole CO2/mole amine. Moreover, two amine cated that the introduction of steric hindrance to the nitrogen
solutions (TA and HA) were not miscible with water, and three results in high CO2 loading [10]. This observation is also confirmed
aqueous amine solutions (AHMPD, TBA and BA) formed solid after by the 2TBAE result. The results obtained in this study show that
absorption of CO2. the presence of a methyl group in the nitrogen is beneficial in
In considering MEA as a basic structural reference, the effect of terms of high CO2 absorption.
adding functional groups to MEA has been evaluated. The addition From MEA, two hydrogens from the amino group were replaced
of functional groups to the MEA structure could lead to a signifi- by two methyls to obtain 2DMAE, two ethyls were replaced to
cant effect on the CO2 absorption performance of the amines. The obtain DEEA, one methyl and one alcohol were replaced to obtain
modifications on the MEA structure and their impacts on CO2 load- MDEA and two alcohol groups were replaced to obtain TEA (Fig. 5).
ing are shown in Figs. 4–7. The effect of the modification shows that DEEA has a very high CO2
1A2P has a methyl group that is attached to the carbon near the absorption capacity in comparison with that of all the studied
alcohol group, and 2A1B has an ethyl group attached to the carbon amines. When MEA starts at a value of 0.58 mole CO2/mole amine,
near the amino group (Fig. 4). The CO2 loading values suggest that the CO2 loading of DEEA is 0.90 mole CO2/mole amine. The substi-

Table 3
CO2 loading of CO2 in aqueous amine solution at 30 wt%, 40 °C and 1 bar (15% CO2 and 85% N2).

Amine solution Concentration CO2 loading

wt% a ¼ moleCO2 =moleamine
1 Monoethanolamine (MEA) 30 0.58
2 N-methyldiethanolamine (MDEA) 30 0.52
3 Diethanolamine (DEA) 30 0.53
4 2-amino-1-methyl-2-propanol (AMP) 30 0.80
5 Piperazine (Pz) 30 0.81
6 1-amino-2-propanol (1A2P) 30 0.54
7 2-amino-1-butanol (2A1B) 30 0.59
8 2-(methylamino)ethanol (2MAE) 30 0.56
9 2-(ethylamino)ethanol (2EAE) 30 0.67
10 2-(butylamino)ethanol (2BAE) 30 0.69
11 2-(tert-butylamino)ethanol (2TBAE) 30 0.87
12 2-amino-2-(hydroxymethyl)-1,3-propanediol (AHMPD) 30 Formation of solid
13 2-(dimethylamino)ethanol (2DMAE) 30 0.73
14 1-dimethylamino-2-propanol (1DMA2P) 30 0.72
15 N,N-diethylethanolamine (DEEA) 30 0.90
16 3-dimethylamino-1-propanol (3DMA1P) 30 0.89
17 Isobutylamine (IBA) 30 0.59
18 Sec-butylamine (SBA) 30 0.70
19 Butylamine (BA) 30 0.57
20 Tetramethyl-1,3-diaminopropane (TMDAP) 30 1.16
21 3-(dimethylamino)propylamine (3DMAPA) 30 1.20
22 1,3-diaminopropane (DAP) 30 1.23
23 Hexamethylenediamine (HMD) 30 1.35
24 Diethyamine (DA) 30 0.83
25 Triethylamine (TA) 30 Not miscible in water
26 Hexylamine (HA) 30 Not miscible in water
27 Triethanolamine (TEA) 30 0.39
28 Isopropylamine (IPA) 30 0.67
29 Tert-butylamine (TBA) 30 Formation of solid
30 Benzylamine (BA) 30 Formation of solid

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 9

Fig. 4. Modification of the chemical group from the MEA structure to 1A2P, 2A1B, AMP and 2TBAE.

Fig. 5. Modification of the chemical group from the MEA structure to obtain 2DMAE, DEEA, MDEA and TEA.

tution of the two hydrogens that are attached to the nitrogen in and its effect on the nitrogen is to decrease the CO2 loading. This
MEA by two ethyl groups (DEEA) increases the CO2 absorption sig- effect is verified with TEA in which three alcohol groups are
nificantly. The difference between MEA and 2DMAE is the attached to the nitrogen, and the CO2 loading value is 0.39 mole
exchange of two hydrogens at the nitrogen for two methyl groups. CO2/mole amine. When methyl or ethyl groups are attached to
This modification affects the CO2 loading by increasing it from 0.58 the nitrogen, they increase the CO2 absorption of the molecule
to 0.73 mole of CO2/mole of amine, but it is lower than that of more than hydrogen or alcohol groups do.
DEEA. As indicated in Fig. 4, the methyl group is an electron dona- In Fig. 6, when starting from MEA, one hydrogen from the nitro-
tor that is beneficial for increasing the CO2 absorption capacity. The gen was replaced by methyl (2MAE), ethyl (2EAE), butyl (2BAE)
DEEA results show that the ethyl group has more significance in and a tert-butyl groups (2TBAE). The results indicate that the
terms of obtaining high CO2 absorption than the methyl group change of one hydrogen that is attached to the nitrogen of MEA
because the donating inductive effect of ethyl groups is stronger to a methyl to obtain 2MAE does not result in an increase in the
than that of methyl groups. The comparison between 2DMAE and CO2 absorption capacity. The substitution of a hydrogen on the
MDEA is the replacement of two hydrogens at the nitrogen by nitrogen by an ethyl or butyl group leads to a significant increase
one methyl and one alcohol. The result of this difference shows in the CO2 loading, from 0.58 to 0.67 mole of CO2/mole of amine
that the CO2 loading of MDEA is lower than that of MEA, which for 2EAE and 0.69 mole of CO2/mole of amine for 2BAE. The elec-
is lower than that of 2DMAE under the CO2 pressure conditions tron donating effect of a methyl attached to the nitrogen is not pro-
used in this study (Table 3). In contrast to hydrogen, methyl or found in comparison with that of ethyl or butyl groups. The length
ethyl groups, the alcohol group is a strong electron attractant, of the alkyl group that is attached to the nitrogen (2 or 4 carbons)

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10 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

Fig. 6. Modification of the chemical group from the MEA structure to obtain 2MAE, 2EAE, 2BAE and 2TBAE.

Fig. 7. Modification of the chemical group from the MEA structure to obtain SBA and IBA.

Fig. 8. Increase in the carbon chain length from 2DMAE to 3DMA1P and from DAP to HMD.

increases the CO2 absorption capacity. In addition, the result CO2 than IBA (0.70 in comparison with 0.59 mole CO2/mole amine)
obtained for 2TBAE where there is a tert-butyl group that increases because of the presence of a methyl group at the a-carbon, which
the CO2 loading is 0.87 mole of CO2/mole of amine. increases the basicity of the nitrogen. Singh et al. studied the CO2
The effect on CO2 loading by exchanging the alcohol group in loading of different amine structures to establish a relation with
MEA for a methyl group is shown (Fig. 7). A hydrogen on the a- some amine structures. Their experiments were not performed
carbon is replaced by a methyl group to obtain SBA, and a hydrogen under the same concentration and temperature conditions (10 kPa
on the b-carbon is replaced by a methyl group to obtain IBA. The CO2 partial pressure for 1 atm and absorption at 30 °C), but the
impact on the CO2 loading that resulted from the structural modifi- authors show that the evolutionary trend of the CO2 loading for
cation is stronger for SBA than it is for IBA. In fact, SBA absorbs more IBA and SBA are in accordance with one another. In their work, a

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 11

Fig. 9. Change in the nature of the amino group (tertiary, secondary or primary) from TMPAD to 3DMAPA and 3DMAPA to DAP.

CO2 loading of 0.59 mole CO2/mole amine was needed for a concen-
Table 4
tration of 2.53 mole/L in SBA, and a CO2 loading of 0.39 mole CO2/-
Comparison of the absorption heat for MEA and MDEA at 30 wt% and 313.15 K with
mole amine was needed for a concentration of 2.58 mole/L for IBA the literature data.
[31].
Amine Temperature CO2 loading Heat of absorption
The influence of the carbon chain length between 2DMAE (two
solution 30 wt (K) DH (kJ/mole of CO2)
carbons) and 3DMA1P (three carbons) was studied in this work %
(Fig. 8). The increase of the carbon chain length shows that the This Literature This Literature
CO2 loading increases from 0.73 to 0.89 mole CO2/mole amine. This work [9] work [9]
difference comes from the electronic influence that occurs between MEA 313 0.59 0.4–0.6 85.13 86.90
the alcohol group and the amino group. The more the distance MDEA 313 0.74 0.4–0.6 52.51 58.80
between the two groups increases, the smaller the electronic effect DEA 313 0.61 0.4–0.6 74.24 68.90
AMP 313 0.78 0.4–0.6 80.91 79.40
of the alcohol group becomes, and the CO2 loading increases. A par-
allel study was performed on polyamines with two amino groups
in the structure. In comparison with DAP (which has a distance
of three carbons), HMD has the highest CO2 absorption; in HMD, 3.2. Heat of CO2 absorption
the two nitrogens are separated by six carbons. When the distance
between two amino groups is high, the electronic influence The heat that was required to regenerate the aqueous amine
between them is reduced and the CO2 absorption capacity will solution in the stripper column could be approximated as the con-
be high. Moreover, Mondal et al. found a CO2 loading range from tribution of the following three types of energy: the heat of CO2
1.14 to 1.17 mole of CO2/mole amine and a pressure of 0.14 and desorption from the solution, the sensible heat needed to elevate
0.17 bars for HMD at 313 K. Singh et al. used 10 kPa CO2 partial the temperature in the stripper and the heat of evaporation neces-
pressure and 1 atm for absorption at 30 °C, and they found a CO2 sary to produce the stripping steam in the reboiler. The heat of
loading of 0.97 mole CO2/mole amine for a concentration of absorption is associated with the quantity of steam needed to
2.53 mole/L in DAP and a CO2 loading of 1.11 mole CO2/mole amine regenerate the aqueous amine solution. It is assumed that the des-
for a concentration of 2.54 mole/L in HMD. The CO2 loading ten- orption of CO2 from the amine solution in the stripper is the
dencies are in accordance with the findings obtained in this work inverse reaction of CO2 absorption by the aqueous amine solution
for DAP and HMD [31]. that occurs in the absorber. In other words, the heat of CO2 absorp-
An additional study was performed to uncover the influence in tion is considered to be equal to the heat of CO2 desorption. More-
the amino group change (primary, secondary and tertiary) of over, the study on the heat of CO2 absorption by an aqueous amine
polyamines on the CO2 loading (Fig. 9). From TMPAD to 3DMAPA, solution shows that the absorption heat depends strongly on the
one tertiary amino group was changed into a primary amino group, CO2 absorption capacity, the structure of the amine, and the tem-
and the consequence was a small rise in the CO2 absorption capac- perature, but it does not significantly depend on the pressure
ity. The same observation was made between 3DMAPA and DAP, and the amine concentration [81].
when the tertiary amino group was replaced by a primary amino In the present work, the absorption heat is studied at 313.15 K
group. These data indicate that when the methyl groups were under atmospheric pressure in pure CO2. To evaluate the precision
removed from the nitrogen to be substituted by hydrogen, the of the calorimeter equipment used in this work, the heat of the CO2
electronic effect between the two amino groups presented a absorption of MEA, MDEA, DEA and AMP at 30 wt%, 313.15 K and
decrease in the structure and resulted in a small augmentation of atmospheric pressure was measured. These amines could be found
the CO2 loading. Machida et al. also found a value of [0.97–1.16] in the available data in the literature [27,38,39,82,9]. Values of
mole of CO2/mole amine for CO2 pressure range of [0.12–0.26] bars 85.13 kJ/mole of CO2 (aCO2 = 0.59) for MEA, 52.51 kJ/mole of
for TMPAD at 313.2 K, which is in accordance with the values CO2 (aCO2 = 0.74) for MDEA, 74.24 kJ/mole of CO2 (aCO2 = 0.61)
obtained in this work [80]. for DEA, and 80.91 kJ/mole of CO2 (aCO2 = 0.78) for AMP have been
The screening of the CO2 absorption capacity results as acquired found in this study, with 2% uncertainty. The results are consistent
with the S.S.S. equipment show that amines that contain an alkyl with the data in the literature (Table 4).
group (methyl, ethyl or t-butyl) that is attached to or near the The determination of the absorption heat DH (kJ/mole of CO2)
nitrogen have high CO2 loading. The alcohol group near the amino was obtained at 313.15 K and atmospheric pressure, and the
group has a negative effect on the CO2 absorption. Additionally, the results are presented in Table 5. The experiments for all the aque-
polyamines studied in this work showed the highest CO2 loading ous amine solutions were conducted at least 3 times to obtain con-
among all the studied amines. These results are consistent with sistent values, and an average was calculated.
work from Singh et al. in which the impact of the alkyl groups In Fig. 10, the distribution of the experimental absorption heat
and the number of amino groups in the amine molecule enhanced for various amines is compared with the CO2 loading that was
the absorption capacity of the amine-based solvents [29–31]. In obtained by using the micro-reaction calorimeter for the 25 amines.
addition, the screening of the 30 amines shows that 5 amines can- Fig. 10 shows that 4 amines, namely IBA, SBA, DAP and HMD, have
not be considered for the study because there was no miscibility the highest absorption heats, with 97.00 kJ/mole CO2
with H2O or formation of solids during the experiment. The deter- (aCO2 = 0.58), 96.67 kJ/mole CO2 (aCO2 = 0.67), 97.23 kJ/mole
mination of the CO2 solubility for the aqueous amines should be CO2 (aCO2 = 1.03) and 98.39 kJ/mole CO2 (aCO2 = 1.18), respec-
considered together with the determination of the absorption heat tively. The heats of CO2 absorption for MDEA and 3DMA1P are the
for CO2 to select the most promising and suitable amine from this lowest, at 52.51 kJ/mole CO2 (aCO2 = 0.74) and 54.55 kJ/mole
study for the CO2 capture process. CO2 (aCO2 = 0.85). According to experimental data on the absorption

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Table 5
Heat of CO2 absorption in aqueous amine solution at 30 wt% and 40 °C.

Amine solution Concentration wt% CO2 loading Heat of absorption

DH (kJ/mole of CO2)
1 Monoethanolamine (MEA) 30 0.59 85.13
2 N-methyldiethanolamine (MDEA) 30 0.74 52.51
3 Diethanolamine (DEA) 30 0.61 74.24
4 2-amino-1-methyl-2-propanol (AMP) 30 0.78 80.91
5 Piperazine (Pz) 30 0.91 80.58
6 1-amino-2-propanol (1A2P) 30 0.57 85.47
7 2-amino-1-butanol (2A1B) 30 0.60 82.49
8 2-(methylamino)ethanol (2MAE) 30 0.67 73.84
9 2-(ethylamino)ethanol (2EAE) 30 0.71 68.95
10 2-(butylamino)ethanol (2BAE) 30 0.73 74.38
11 2-(tert-butylamino)ethanol (2TBAE) 30 0.79 80.58
13 2-(dimethylamino)ethanol (2DMAE) 30 0.77 63.26
14 1-dimethylamino-2-propanol (1DMA2P) 30 0.83 60.72
15 N,N-diethylethanolamine (DEEA) 30 0.83 73.17
16 3-dimethylamino-1-propanol (3DMA1P) 30 0.85 54.55
17 Isobutylamine (IBA) 30 0.58 97.00
18 Sec-butylamine (SBA) 30 0.67 96.67
19 Butylamine (BA) 30 0.61 94.81
20 N,N,N0 ,N0 -Tetramethyl-1,3-propanediamine (TMPAD) 30 1.32 59.87
21 3-(dimethylamino)propylamine (3DMAPA) 30 1.02 91.33
22 1,3-diaminopropane (DAP) 30 1.03 97.23
23 Hexamethylenediamine (HMD) 30 1.18 98.39
24 Diethyamine (DA) 30 0.83 87.17
25 Triethanolamine (TEA) 30 0.38 66.59
26 Isopropylamine (IPA) 30 0.69 93.16

heat of CO2, amines can be classified into four primary categories,

100
namely A, B, C and D. In group A, there are 14 amines, all of which 17 23
◊ tertiary amines 18 22
are primary or secondary monoamines, except a diamine with one ● primary/secondary amines 19 28
primary and one tertiary amino group. In comparison with cate- 90
21

gories B, C and D, category A has the highest heats of absorption, 24

- ΔH (kJ/mol of CO2)

6
which range between 98.39 (HMD) and 80.58 kJ/mole of CO2 1

4
A
5
(2TBAE). In this group, the sterically hindered amines (AMP and 80 7
11
2TBAE) have a low heat of CO2 absorption because of the formation
of an unstable carbamate, whereas the other amines formed stable 3 8
10
15
B
carbamate, resulting in high absorption heat. Group B consists of 70
9
DEA, 2MAE, 2BAE (all secondary amines) and DEEA (tertiary ami- 27
nes), which have a moderate heat of absorption among all the ami- 13

nes tested in this work, with a value between 74.38 (2BAE) and 60 D 14 20

73.17 kJ/mole of CO2 (DEEA). There are five tertiary amines 16

(2DMAE, 1DMA2P, 3DMA1P, MDEA and TMPAD) and one secondary 2

C
amine (2EAE) in group C. DEEA (group B), a tertiary amine, has an 50
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
absorption heat that is close to that of DEA (group B), which is a sec- CO2 loading
ondary amine and is higher than that of 2EAE (group C), which is a
secondary amine. This result indicates that not all primary or sec- Fig. 10. Heat of absorption DH (kJ/mole of CO2) of aqueous amine solution at
ondary amines have a high heat of absorption in comparison with 313.15 K and atmospheric pressure. The numbers are listed in Table 5.
the tertiary amines, and there are some exceptions that could be
associated with the amine structure. The second result is that the but the most important point is that it has a low heat of absorption
heat of absorption for 2EAE (68.95 kJ/mole of CO2) is lower than (>70 kJ/mole of CO2) in comparison with that of MEA 30 wt%
that of 2MAE (73.84 kJ/mole of CO2), 2BAE (74.38 kJ/mole of (85.13 kJ/mole of CO2).
CO2) and 2TBAE (80.58 kJ/mole of CO2). The evolution is not linear The third parameter that should be studied to find if the amines
with the increased steric hindrance of the amino group. In group C, in group C are potential candidates is a measurement of the reac-
the heat order for CO2 absorption is MDEA < 3DMA1P < TM- tion kinetics between CO2 and the aqueous amine solutions.
PAD < 1DMA2P < 2DMAE, which is in accordance with the work of
Rayer et al. in which the authors found that the absorption heat 3.3. Kinetics of CO2 absorption by aqueous amine solution
order is MDEA < 3DMAP < 1DMAP [83]. The last category D con-
cerns only TEA, which is a tertiary amine. This amine has a low heat The kinetics of CO2 absorption by aqueous solutions including
of absorption as the common tertiary amine, but the CO2 loading is 2DMAE, 3DMA1P, 1DMA2P, MDEA, TMPAD and 2EAE were mea-
also very low. This amine cannot be considered for the CO2 capture sured for temperatures ranging from 298.15 to 313.15 K and con-
process. centrations ranging from 5 to 800 mole m3 with stopped-flow
In this study, the combination of the CO2 loading acquisition equipment. The resulting pseudo-first order reaction kinetics (k0,
with the S.S.S. and the heat of absorption data obtained from a flow s1) were compared with the conventional amine-based solvent
micro-reaction calorimeter show that amines from group C MEA (data are presented in Appendix A, Tables A.1–A.7). The mea-
(2DMAE, 3DMA1P, 1DMA2P, MDEA, TMPAD and 2EAE) could be surement of each (k0, s1) datum was conducted 5 times, and an
considered for CO2 capture. These amines have good CO2 loading, average was used to obtain consistent values.

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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 13

300 300
♦ 289K ♦ 289K
▲ 303 K ▲ 303 K
■ 308 K ■ 308 K
250 ● 313 K 250 ● 313 K
̶ Ali et al. (2005) ̶ Ali et al. (2005)

200 200
k0 (s-1)

k0 (s-1)
150 150

100 100

50 50

0 0
0 5 10 15 20 25 30 35 40 0 50 100 150 200 250 300 350 400
Amine concentration (mole/m3) Amine concentration (mole/m3)
(a) (b)
Fig. 11. Comparison of k0 values for the MEA (a) and AMP (b) obtained in this work at 298.15 (d), 303.15 (j), 308.15 (▲) and 313 K (r) with data from Ali et al. [70].

For an adequate comparison of kinetic data and effective

results, the reactions between CO2 and aqueous MEA and AMP
350
solutions were performed to validate the stopped-flow equipment.
MEA The results were compared with the corresponding literature data
300
and presented in Fig. 11. The values obtained here are consistent
with the data in the literature by Ali et al. for MEA and AMP
250
[70]. Thus, the experimental values validate the experimental
setup used in this study.
200
Fig. 12 shows the plot of the observed pseudo-first order rate
k0 (s-1)

2EAE
constants (k0, s1) against the amine concentration (mole m3) at
150
313.15 K, but the observations are the same for each temperature
(as presented in Appendix A, Figs. A.3–A.7 and 13). For all amines
100
tertiary studied at 313.15 K, the constant (k0, s1) increases when the amine
amines concentration increases. The graph in Fig. 12 specifies that MEA has
50
the highest kinetics in comparison with all the studied amines, and
MDEA MDEA has the lowest. In comparing the values of the experimental
0
0 100 200 300 400 500 600 700 800 900 results for the five tertiary amines (MDEA, 2DMAE, 3DMA1P
Amine concentration (mole/m3) 1DMA2P and TMPAD), the results show that 3DMA1P and TMPAD
have the highest kinetics and the (k0, s1) values are close. The
Fig. 12. Pseudo first-order rate constants (k0, s1) in relation to the amine
longer carbon chain in 3DMA1P could be the reason for the higher
concentrations (mole m3) at 313.15 K for MEA (h), 2EAE (▲), TMDAP (r), 2DMAE
(D), 1DMA2P (d), 3DMA1P (j) and MDEA (}).
kinetics in comparison with those of 2DMAE. In addition, TMPAD
has two tertiary amines, which can increase the kinetics.

40 300

250
30

200
k0 (s-1)

k0 (s-1)

20 150

100
10

50

0
0 100 200 300 400 500 600 700 800 900 0
0 5 10 15 20 25 30 35 40
Amine concentration (mole/m3) Amine concentration (mole/m3)
(a) (b)
Fig. 13. Observed pseudo first-order rate constants (k0, s1) in comparison with the amine concentration (mole m3) at 298.15 (d), 303.15 (j), 308.15 (▲) and 313.15 K (r)
for MDEA (a) and MEA (b). (- - -) dotted lines represent the models.

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14 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx

Table 6 3
Comparison of the second order rate constants (k2, m3 mole1 s1) obtained in this
work with the literature on MEA and MDEA and CO2 from the fitting of the 2
experimental (k0, s1).

Temperature k2 (m3 mole1 s1) 1

(K)
MDEA (this MDEA MDEA MEA (this MEA 0
work) [84] [48] work) [70]

ln k2
-1
298.15 0.0171 0.0073 0.0124 4.7960 5.5200
303.15 0.0256 0.0105 0.0164 6.3550 7.5300
308.15 0.0314 0.0148 0.0215 8.3430 10.2000 -2
313.15 0.0468 0.0207 0.0279 10.8590 13.6000
-3

-4
Three mechanisms have been proposed to correlate the experi-
mental data for the reaction kinetics between CO2 and the aqueous -5
0.0032 0.0033 0.0034
amine solutions. The mechanisms that were proposed to explain
1/T (K)
the CO2 reaction rate for primary and secondary amines are the
zwitterion and termolecular mechanisms. The base catalysis mech- Fig. 14. Comparison of the relation ln k2 = f(1/T(K)) within a temperature range of
anism is proposed for the reaction between the tertiary amine and (298.15–313.15 K) for MEA (h), 2EAE (d), TMDAP (r), 2DMAE (o), 1DMA2P (▲),
CO2. Usually, the mechanism that is used to describe reaction 3DMA1P () and MDEA (j).

kinetics between the primary/secondary amine solution and CO2

is the zwitterion mechanism, and consequently, this model was
selected to investigate the reaction kinetics. The zwitterion and Table 8
Activation energy EA (kJ mole1) of aqueous amine solutions.
base catalysis mechanism are described in the experimental sec-
tion (Section 2.4). Name Activation energy EA (kJ/mole1) Sources
An aqueous solution of MEA with a concentration range of 5– MEA 42.29 This work
34 mole m3 and an aqueous solution of MDEA with a concentra- MDEA 50.03 This work
tion range of 199–800 mole m3 at a temperature range of 2EAE 34.12 This work
2EAE 32.65 [56]
298.15–313.15 K with an interval of 5 K was studied by using a 3DMA1P 72.71 This work
stopped-flow technique. The results of the zwitterion mechanism 3DMA1P 75.55 [66]
for MEA (primary amine) and the base catalysis mechanism for TMDAP 54.65 This work
MDEA (tertiary amine) indicate that the correlation between the 1DMA2P 78.47 This work
1DMA2P 62.55 [66]
experimental pseudo first-order rate constants and the pseudo
2DMAE 55.71 This work
first-order rate constants from modeling are very strong. For the
tertiary amines (2DMAE, 3DMA1P 1DMA2P and TMPAD), the base
catalysis is used, and for 2EAE, the zwitterion mechanism is used.
(k0, s1) with the kinetic models to obtain the (k2, m3 mole1 s1)
The data and graphs are shown in Appendix A (Figs. A.3–A.7). The
could provide this variance.
results show good consistency between the experimental data and
The temperature dependency of the second order reaction rate
the models.
constant (k2, m3 mole1 s1) is correlated with the Arrhenius equa-
The calculated second order reaction rate constant (k2, m3 -
tion (Eq. (25)) as follows:
mole1 s1) from the zwitterion and base catalysis mechanisms
 
for each aqueous amine solution were determined by using Eqs. EA
k2 ¼ A1  exp  ð25Þ
(14) and (24). The k2 data that were obtained by using the corre- RT
sponding model for MEA and MDEA were compared with the data
obtained from the literature (Table 6). The second order rate con- A1 is the Arrhenius constant (m3 mole1 s1), EA is the activation
stants increase with the temperature. The data in this study are energy (kJ mole1) and R is the molar gas constant
consistent with the literature data, although the constant for (8.314 J mole1 K1).
MEA is a bit smaller and that of MDEA is a bit higher in this present The temperature dependency of the Arrhenius relation in the
study. aqueous amine solution obtained from Fig. 14 is determined and
Table 7 shows the calculated second order reaction rate con- presented in Appendix A (Eqs (A.3)–(A.7)). For example, for the
stants (k2, m3 mole1 s1) for 1DMA2P, 3DMA1P, TMDPA, 2DMAE aqueous solution of MDEA and MEA with CO2, the temperature
and 2EAE. The data obtained here for 3DMA1P are consistent with dependency of the Arrhenius equation is given below:
the values obtained in the literature, whereas for 1DMA2P and 1

MDEA : k2 ðm3 mole s1 Þ
2EAE, the data from this study are higher than the values from  
6017:8
the literature. The concentration ranges are different between this ¼ 1:01  107 exp  ð26Þ
present study and the literature, and the fitting of the experimental T

Table 7
Second order rate constants (k2, m3 mole1 s1) of the aqueous amine solution with CO2.

Temperature (K) k2 (m3 mole1 s1)

1DMA2P (this work) 1DMA2P [66] 3DMA1P 3DMA1P [66] TMDPA 2DMAE 2EAE 2EAE [56]
298.15 0.0239 0.0210 0.0370 0.0320 0.0427 0.0322 3.5556 8.0000
303.15 0.0418 0.0310 0.0677 0.0570 0.0653 0.0505 4.4519 9.4400
308.15 0.0709 0.0490 0.1056 0.0910 0.0914 0.0713 5.9055 12.9000
313.15 0.1078 0.0700 0.1517 0.1390 0.1232 0.0946 6.7268 14.5000

Please cite this article in press as: El Hadri N et al. Aqueous amine solution characterization for post-combustion CO2 capture process. Appl Energy (2016),
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 N. El Hadri et al. / Applied Energy xxx (2016) xxx–xxx 15

1

MEA : k2 ðm3 mole s1 Þ because the tertiary amine has a low heat of absorption and high
  CO2 loading, the study of blends will also be needed for a compar-
5086:5
¼ 1:23  108 exp  ð27Þ ison with 2EAE alone. The study of blended amines will be the sec-
T
ond part of this project. The blends that will be used from this
The activation energy from the Arrhenius relation for MDEA study are as follows:
was found to be equal to 50.03 kJ mole1, and it was
42.29 kJ mole1 for MEA.
2EAE + MDEA.
The reaction kinetics of CO2 with an aqueous solution of MEA
2EAE + 1DMA2P.
and MDEA were widely studied, and their activation energies were
2EAE + 3DMA2P.
calculated [46,48–50,58,85]. For MEA, Aboudheir et al. found a
2EAE + 2DMAE.
dependency of the Arrhenius equation at
2EAE + TMDAP.
   4412
1 1 9
3
k2 m mole s ¼ 4:61  10 exp  T , which corre-
sponded to an activation energy of 36.68 kJ mole1 [85]. Versteeg
et al. established the dependency of the Arrhenius equation as Appendix A. Supplementary material
   
1
k2 m3 mole s1 ¼ 4:4  108 exp  5400T
, which corresponds
to an activation energy of 44.90 kJ mole1 [48]. Alper et al. found Supplementary material associated with this article can be
an activation energy of 46.7 kJ mole1 and Hikita et al. calculated found, in the online version, at http://dx.doi.org/10.1016/j.apen-
a result of 41.2 kJ mole1 [50,54]. The value found in this work is ergy.2016.03.043.
consistent with the literature values. For MDEA, Haimour et al.
found an activation energy of 71.5 kJ mole1, Yu et al. published
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Please cite this article in press as: El Hadri N et al. Aqueous amine solution characterization for post-combustion CO2 capture process. Appl Energy (2016),
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