International Journal of Greenhouse Gas Control 12 (2013) 390–398

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International Journal of Greenhouse Gas Control

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1D absorption kinetics modeling of CO2 –DEAB–H2 O system

Teerawat Sema a,b , Abdulaziz Naami b , Zhiwu Liang a,b,∗ , Raphael Idem a,b ,
Hussameldin Ibrahim b , Paitoon Tontiwachwuthikul a,b,∗∗
a
Joint International Center for CO2 Capture, and Storage (iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, PR China
b
International Test Centre for CO2 Capture (ITC), Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, Canada

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

Article history: The experimental kinetics data for carbon dioxide (CO2 ) absorption into aqueous 4-diethylamino-
Received 17 April 2012 2-butanol (DEAB) solutions were measured by laminar jet absorber at atmospheric pressure over a
Received in revised form 6 August 2012 temperature range of 298–318 K, a DEAB concentration range of 1–2 M, and a CO2 loading range of
Accepted 13 November 2012
0.001–0.18 mol CO2 /mol amine. These data were interpreted with the aid of 1 dimension comprehensive
Available online 25 December 2012
numerically solved CO2 absorption rate/kinetics model, which takes into account the coupling between
chemical equilibrium, mass transfer, and chemical kinetics of all possible chemical reactions between
Keywords:
CO2 and aqueous DEAB solutions. The partial differential–nonlinear algebraic equations of the model
Absorption
Carbon dioxide
were solved by the finite element method (FEM) based on COMSOL software. The results show that CO2
Kinetics absorption reaction with DEAB is faster than that with MDEA, also comparable with those with AMP and
Modeling DEA, but slower than those with MEA and PZ, respectively. In addition, the reaction kinetics in terms of
enhancement factor was found to increase as DEAB concentration increased, and increase as temperature
increased, but decrease as CO2 loading increased.
© 2012 Elsevier Ltd. All rights reserved.

1. Introduction Almost 60% of CO2 emissions are from coal-fired power generation
plants and other industrial processes, such as refineries and natural
It has been over three decades since the first assessment report gas processing plants. In order to control the CO2 emissions, several
of the Intergovernmental Panel on Climate Change (IPCC) pointed technologies have been applied. However, post-combustion amine
out that the drastically increasing of greenhouse gases, such as car- based CO2 capture technology is recently accepted as one of the
bon dioxide (CO2 ), methane, and chlorofluorocarbons (CFCs), are most cost effective and environmental friendly manner (Devid and
mainly emitted from human activities. The emissions will enhance Herzog, 2000; Rao and Rubin, 2002; Liang et al., 2011).
the greenhouse effect, resulting in the increasing of earth sur- A wide variety of amines such as monoethanolamine (MEA),
face temperature (Houghton et al., 1990; Williams et al., 2012). diethanolamine (DEA), methyldiethanolamine (MDEA) have been
Recently, global warming and climate change issues are receiv- industrially used for capturing CO2 for a number of years (Kohl and
ing attention globally. One of the urgently policies is to control the Nielsen, 1997; Sema et al., 2012a). Recently, Tontiwachwuthikul
greenhouse gas emissions to the atmosphere (Meinshausen et al., et al. (2008), Maneeintr et al. (2009), Sema et al. (2011) have
2009; Ibrahim et al., 2012). CO2 is generally accepted as a major developed and investigated the performances of a newly devel-
greenhouse gas since it responsible for about 57% of the contri- oped amino alcohol solvent, 4-diethylamino-2-butanol (DEAB).
bution on the global warming potential (Lashof and Ahuja, 1990). They found that the absorption capacity of DEAB is competitive
with that of piperazine (PZ) and higher than those of 2-amino-2-
methyl-1-propanol (AMP), MDEA, DEA, and MEA. Moreover, they
∗ Corresponding author at:Joint International Center for CO2 Capture, and Storage also found that the regeneration energy of DEAB is lower than those
(iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha of MDEA, DEA, and MEA, respectively. Regarding to these outstand-
410082, PR China; International Test Centre for CO2 Capture (ITC), Faculty of Engi- ing performances, DEAB is now being considered as a promising
neering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, alternative solvent for capturing CO2 . However, a better solvent
Canada. Tel.: +86 73188573033.
∗∗ Corresponding author at: Joint International Center for CO2 Capture, and Storage for capturing CO2 should not only provide high absorption capac-
(iCCS), College of Chemistry and Chemical Engineering, Hunan University, Changsha ity and low regeneration energy, but should also have fast reaction
410082, PR China; International Test Centre for CO2 Capture (ITC), Faculty of Engi- rate (reaction kinetics), low solvent degradation, and low corro-
neering and Applied Science, University of Regina, Regina, Saskatchewan S4S 0A2, siveness. More importantly, the effective design of the absorber for
Canada. Tel.: +86 13618481627.
amine based CO2 treating plant needs an understanding of reaction
E-mail addresses: zwliang@[Link] (Z. Liang), paitoon@[Link]
(P. Tontiwachwuthikul). kinetics data between CO2 and amine (Astarita et al., 1983).

1750-5836/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
[Link]
 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398 391

both FDM and FEM provide very accurate predicted CO2 absorption
Nomenclature rate. Also, no significant difference between the results obtained
from FDM and FEM were observed.
AMP 2-amino-2-methyl-1-propanol In this study, the experimental kinetics data of CO2 and aqueous
Ce∗ equilibrium concentration of gas at interface, mol/L DEAB solutions were measured using the laminar jet absorber over
or kmol/m3 ranges of temperatures, DEAB concentrations, CO2 loadings, and
Cj0 bulk concentration for species j, kmol/m3 contact times. The obtained experimental data were then used to
CFCs chlorofluorocarbons develop the 1D numerically solved comprehensive CO2 absorption
CO2 carbon dioxide rate/kinetics model (using the FEM based on COMSOL software) for
d jet diameter, m the absorption of CO2 in aqueous solutions of DEAB. The chemical
Di diffusivity of chemical species i, cm2 /s or m2 /s equilibrium, the mass transfer, and the chemical kinetics of all pos-
DEA diethanolamine sible reactions were also taken into account in this comprehensive
DEAB 4-diethylamino-2-butanol model.
E enhancement factor
FDM finite difference method
FEM finite element method 2. Materials and methods
h jet height, cm or m
HeCO2 Henry’s constant, kPa m3 /kmol 2.1. Chemicals
k2i second order forward rate coefficient for reaction i,
m3 /kmol s DEAB was synthesized according to the procedure described by
kL0 liquid phase mass transfer coefficient for physical Tontiwachwuthikul et al. (2008) in our solvent synthesis labora-
absorption of CO2 , m/s tory in the International Test Centre for CO2 Capture (ITC) at the
Ki chemical equilibrium constant for reaction i University of Regina. The purity of synthesized DEAB was deter-
L liquid flow rate, cm3 /s or m3 /s mined by GC–MS and found to be 95%. Aqueous DEAB solutions of
MEA monoethanolamine desired concentrations were prepared by adding a known amount
MDEA methyldiethanolamine of de-ionized water and predetermined amounts of DEAB. CO2 with
N local CO2 absorption rate per unit area, kmol/m2 s purities of 99.9% were supplied by Praxair Inc., Canada.
Nave average CO2 absorption rate per unit area,
kmol/m2 s
2.2. CO2 absorption rate
PCO2 partial pressure of CO2 , kPa
PZ piperazine
The CO2 absorption rate was measured using the laminar jet
RA rate of gas absorption, mol/s
absorber. A detailed description of the laminar jet absorber and its
T temperature, K
operation can be seen in Al-Ghawas et al. (1989) and Aboudheir
TEA triethanolamine
et al. (2004). Briefly, the amine solution was degassed by spraying
u velocity, m/s
it into a vacuum, and then the degassed amine solution was passed
x penetration depth, m
through the temperature-controlled water jacket in order to reach
the desired temperature. The degassed amine solution was then
Greek letters
passed through the jet nozzle in order to continuously generate a
˛ CO2 loading, mol CO2 /mol amine
smooth-surfaced rod-like jet in the absorption chamber. The soap-
 viscosity, g/cm s
film meter (ranging from 0.1 to 10 ml/min with ±1% accuracy) was
 contact time, s
used to measure the rate of absorption (RA ). The two dimensional
microscope was used to measure jet height (h) and jet diameter
(d). Finally, the discharged liquid was collected and liquid flow rate
Laminar jet absorber is one of the apparatuses that provide very (L) was measured. According to the penetration theory for physical
accurate and reliable kinetics data because (i) the interfacial area is absorption, RA can be defined as:
known accurately and (ii) the physical absorption rate has been
RA = 4Ce∗ (DLh)
1/2
shown to agree with the Higbie’s penetration theory prediction (1)
(Astarita et al., 1983; Aboudheir et al., 2003, 2004). One of the very
first numerical comprehensive CO2 absorption rate/kinetics mod- Ce∗ can be determined by:
els for aqueous amine solutions was developed by Hagewiesche
et al. (1995). They studied the absorption of CO2 in aqueous solu- PCO2
Ce∗ = (2)
tions of blended MEA–MDEA using laminar jet absorber based on HeCO2
the Higbie’s penetration theory. However, the experiments were
performed at only 313 K. Recently, more comprehensive kinetics where Ce∗ is the equilibrium concentration of gas at the interface,
model for CO2 absorption into loaded aqueous amine solutions of D is the diffusivity of gas in the liquid, L is the liquid flow rate, h
MEA, blended MEA–MDEA, and blended MDEA–PZ were developed is jet height, PCO2 is partial pressure of CO2 , and HeCO2 is Henry’s
1/2
by Idem et al. (2009), Edali et al. (2009, 2010), and Edali (2010). In constant. A plot of RA and (Lh) at various flow rates and jet heights
their studies, the experimental kinetics data were obtained from should provide a straight line through the origin with a slope of
laminar jet absorber at various temperatures, amine concentra- 4Ce∗ D1/2 .
tions, CO2 loadings, and contact times. Moreover, the chemical The laminar jet absorber was validated with water for the dif-
equilibrium, the mass transfer, and the chemical kinetics of all fusivity of CO2 at 298 K, which was found to be 1.97 × 10−5 cm/s
possible reactions were taken into account in their comprehensive (while Al-Ghawas et al. (1989) and Aboudheir et al. (2004) found to
models. Two numerical techniques, which are the finite difference be 1.95 × 10−5 cm/s and 1.96 × 10−5 cm/s, respectively). Also some
method (FDM) based on Barakat-Clark scheme and the finite ele- CO2 diffusivity measurements were repeated for the repeatability.
ment method (FEM) based on COMSOL software, were used for The results show that the deviation percentage of CO2 diffusivity
solving the CO2 absorption rate/kinetics model. They found that measurement is 0.7%.
392 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398

3. Theory CO2 in the solution or Henry’s constant (He; kPa m3 /kmol). The con-
centrations of C10 − C70 can be obtained by simultaneously solving
Based on the proposed mechanism for the reaction between the mass balance equations, equilibrium constant equations, and
CO2 and DEAB, a vapor–liquid equilibrium (VLE) model and an Henry’s law relationship as shown below:Total DEAB balance:
absorption rate/kinetics model for predicting the kinetics data were
developed. [DEAB]0 = C60 + C70 (11)

Total carbon balance:

3.1. Chemical reaction scheme for CO2 –DEAB aqueous system
˛[DEAB]0 = C10 + C20 + C40 (12)
The chemical reactions in CO2 –DEAB aqueous system are gov-
erned by the following equations: Charge balance:

K3 C50 + C70 = C20 + C30 + 2C40 (13)

RR2 N + H+ ←→RR2 NH+ (3)
K4 ,k24 ,−k24 Independent equilibrium constants:
CO2 + RR2 N + H2 O ←→ RR2 NH+ + HCO−
3 (4)
K5 C20 C70
H2 O + CO2 ←→H+ + HCO− (5) K4 = (14)
3 C10 C60
− K6 ,k26 ,−k26
CO2 + OH ←→ HCO−
3 (6)
C20 C50
K7 K5 = (15)
HCO−
3 ←→H
+
+ CO2−
3 (7) C10
K8
H2 O←→H+ + OH− (8) C20
K6 = (16)
C10 C30
RR2 N represents DEAB where R is (CH2 )2 CH(CH3 )OH and R is
CH2 CH3 . Ki is the chemical equilibrium constant for reaction i. k2i K8 = C30 C50 (17)
is the second order forward rate coefficient for reaction i, DEAB is
considered as a tertiary amine since it has 3 carbon atoms attached Henry’s law relationship:
to the nitrogen atom. In this case, DEAB does not react directly with
PCO2
CO2 but it acts as a base which catalyzed the hydration of CO2 HeCO2 = ∗ (18)
(Hagewiesche et al., 1995; Kohl and Nielsen, 1997) as presented CCO
2
in Eq. (4). Reactions (4) and (6) are considered to be reversible with
The chemical equilibrium constants K4 , K5 , K6 and K8 can be found in
finite reaction rates. Whereas reactions (3), (5), (7), and (8) are con-
the works of Kent and Eisenberg (1976), Edwards et al. (1978), and
sidered to be reversible and instantaneous with respect to mass
Sema et al. (2011). The physical solubility of CO2 into aqueous DEAB
transfer and at equilibrium, since they involve only proton transfer
solutions or HeCO2 can be estimated by the correlation proposed by
(Hagewiesche et al., 1995).
Sema et al. (2012b).
Based on Eqs. (3)–(8) it can be seen that not all of the chemical
The 8 coupled nonlinear algebraic equations, i.e. Eqs. (11)–(18),
equilibrium constants are independent. Only 4 chemical equilib-
were then simultaneously solved for the 8 unknowns, which are
rium constants (K4 , K5 , K6 , and K8 ) are independent. The remaining
C10 − C70 and equilibrium partial pressure (PCO2 ), by inputting the
two (K3 and K7 ) can be obtained by the combination of indepen-
initial guess for each unknown. In the present study, the FEM
dent chemical equilibrium constants as shown in Eqs. (9) and (10).
based on COMSOL 4.1 software with 0D stationary solver mode
Also, water concentration is considered to be constant due to the
was applied. After the software had been operated with the first
presence of excess amount of water in the solution (the water con-
set of initial guess, values of the unknowns were obtained. Then
centration is much higher than DEAB concentration).
these new values are subsequently used as the second set of initial
[RR2 NH+ ] K4 guess for solving of the 8 unknowns. This procedure is repeated
K3 = = (9)
[H+ ][RR2 N] K5 until different percentage deviation of the results of each unknown
for successive attempts is less than 0.01%.
[H+ ][CO2−
3 ] K4
K7 = = (10)
[HCO−
3]
K3 K8 3.3. CO2 absorption rate/kinetics model
The chemical species in Eqs. (3)–(8) have been renamed for conve-
nience in the numerical treatment as follows: A comprehensive CO2 absorption rate/kinetics model was devel-
oped in order to interpret the absorption rate data of CO2 in aqueous
C1 = [CO2 ], C2 = [HCO−
3 ], C3 = [OH− ], C4 = [CO2−
3 ], DEAB solutions, from which the kinetics data were extracted. This
model takes into account the coupling between chemical equilib-
C5 = [H+ ], C6 = [RR2 N], C7 = [RR2 NH+ ]
rium, mass transfer, and chemical kinetics of all possible chemical
Also, the subscripts 1–7 are represented the chemical species of reactions. Also, the model is capable to predict the CO2 absorp-
CO2 , HCO− − 2− +   +
3 , OH , CO3 , H , [RR2 N], and RR2 NH , respectively. tion rate and enhancement factor from the system physiochemical
properties, as well as predicting the kinetics of reaction (which is
3.2. Vapor–liquid equilibrium (VLE) model the second order forward rate coefficient for reaction 4 or k24 or
kDEAB ) from the experimental CO2 absorption rate data.
The bulk concentrations of all chemical species in liquid phase The model was derived from a full 3D cylindrical coordinate sys-
at equilibrium (C10 − C70 ), which are required for the kinetics study, tem, which is the shape of the cylindrical liquid jet generated in the
can be estimated by the VLE model (Shi et al., 2012a). The input laminar jet absorber as shown in Fig. 1. The gas–liquid interface is
parameters for this model are initial concentration of DEAB in the considered as an outer boundary. Also, the diffusion in radial direc-
solution ([DEAB]0 ; kmol/m3 ), equilibrium CO2 solubility in aqueous tion is taken into account. Therefore, the absorption of CO2 into
solutions of DEAB or CO2 loading (˛; mol CO2 /mol DEAB), equilib- the cylindrical liquid jet, with constant density and diffusivity, is
rium constants of involved reactions (Ki ), and physical solubility of governed by Eq. (19) (Astarita et al., 1983). This equation indicates
 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398 393

Total carbon balance:

∂C1 ∂C2 ∂C4 ∂2 C1 ∂2 C2 ∂2 C4
+ + = D1 + D2 + D4 (22)
∂t ∂t ∂t ∂x2 ∂x2 ∂x2
Total DEAB balance:
∂C6 ∂C7 ∂2 C6 ∂2 C7
+ = D6 2
+ D7 (23)
∂t ∂t ∂x ∂x2
Total charge balance:

∂C2 ∂C3 ∂C4 ∂C5 ∂C7 ∂2 C2 ∂2 C3

+ +2 − − = D2 2
+ D3
∂t ∂t ∂t ∂t ∂t ∂x ∂x2
∂2 C4 ∂2 C5 ∂2 C7
+ 2D4 − D5 − D7 (24)
∂x2 ∂x2 ∂x2
All reactions at equilibrium (only the independent equilibrium
constants): including K4 , K5 , and K8 , are given in Eqs. (14), (15) and
(17), respectively.
where R4 and R6 , which are the reaction rate expressions for
reactions (4) and (6), respectively, can be presented as:
k 
DEAB
R4 = −kDEAB C1 C6 + C2 C7 (25)
K4
k 
26
R6 = −k26 C1 C3 + C2 (26)
K6

Fig. 1. Schematic diagram of the liquid jet in the laminar jet absorber. Di is the diffusivity of chemical species i into the solution (m2 /s).
The diffusivity of CO2 in aqueous solution of DEAB (D1 ) can be cal-
culated from the predictive correlation developed by Sema et al.
that the molecular transport is equal to the sum total of convec- (2012b). Hikita et al. (1980) measured the diffusivity of MEA, DEA,
tion term, accumulation term (∂C/∂t), and reaction rate (R). If the and triethanolamine (TEA) in aqueous solution. They reported that
diffusant is being created, R will be negative. the diffusivity affected by the group complexity. Since DEAB is a
tertiary amine as same as TEA, it is reasonable to estimate the dif-
∂C
D∇ 2 C = u · ∇ C + +R (19) fusivity of DEAB from that of TEA (the same assumption has also
∂t
been made in the case of MDEA) (Hagewiesche et al., 1995). Thus,
where D is diffusivity (m2 /s), C is concentration (m3 /kmol), u is the diffusivity of DEAB (D6 ; cm2 /s) can be estimated by:
velocity (m/s), and t is time (s).
D6 = (1.739 × 10−9 )−0.569842 T (27)
The assumption of constant density and diffusivity is valid in the
laminar jet absorber because the change of concentration does not where  is solution viscosity (g/cm s), which can be calculated
represent a substantial variation in the mole fraction of the diffu- based on the predictive correlation developed by Maneeintr et al.
sant due to the short contact time (Aboudheir et al., 2004). Eq. (19) (2008), and T is temperature in K. Also, the diffusivity of HCO− −
3 , OH ,
can be simplified by following assumptions: (a) the penetration CO2− +  +
3 , H , and RR2 NH were assumed to be equal to that of DEAB,
theory is applicable for the transport of the gas into liquid, in which which is the most abundant species in the solution (Hagewiesche
the reaction takes place by unsteady state molecular diffusion in the et al., 1995).
liquid; (b) the penetration depth of the absorbed molecule is much The forward rate coefficient of Eq. (6) (k26 ; m3 /kmol s) was cal-
smaller than the jet diameter due to the short contact time (cre- culated from the correlation developed by Pinsent et al. (1956) as
ated in the laminar jet absorber) between the absorbed gas and the follow:
liquid jet. Therefore, there is no curvature effect. The absorption
of gas into liquid is then considered to be an infinite depth with 2895
log(k26 ) = 13.635 − (28)
flat surface; (c) the diffusion in the flow direction is negligible; (d) T
the liquid jet is quiescent so that no convection movements affect Thus, there are 7 partial differential–nonlinear algebraic equations
the transport of the absorbed gas. Regarding to these conditions, (Eqs. (14), (15), (17) and (21)–(24)), which can be solved for the
Eq. (19) can be simplified to the diffusion equation of Eq. (20). This concentration of chemical species C1 − C7 .
equation governs the variation of time and space of the concentra- Initial conditions:
tion of all reactants and products in the liquid phase (one equation for all chemical species, j = 1, 2, 3, . . ., 7
for each component or material balance).
Cj (x, 0) = Cj0 at t = 0 and 0 ≤ x ≥ ∞ (29)
∂2 C ∂C
D 2 = +R (20)
∂x ∂t Boundary conditions:
for all chemical species, j = 1, 2, 3, . . ., 7
Thus, the partial differential equations (PDEs) and the nonlinear
algebraic equations govern the diffusion-reaction process of Eqs. Cj (∞, t) = Cj0 at x = ∞ and 0 ≤ t ≥  (30)
(3)–(8) can be described as follows:
CO2 balance: for volatile chemical species, j = 1

∂C1 ∂2 C1 Pj
= D1 + R4 + R6 (21) Cj (0, t) = Cj∗ = at x = 0 and 0 ≤ t ≥  (31)
∂t ∂x2 Hej
394 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398

for non-volatile chemical species, j = 2, 3, 4, . . ., 7 absorption surface area can be calculated by measurement of liquid
jet diameter and height using the two dimensional microscope).
∂Cj
(0, t) = 0 at x = 0 and 0 ≤ t ≥  (32) Then, experimental enhancement factor (Eexp ) can be calculated
∂t
using Eq. (37), where kL0 can be calculated by Eq. (34), C1∗ , which is
where C1∗ is the interfacial concentration of CO2 in the solution equilibrium concentration of CO2 at interface can be calculated via
(kmol/m3 ), which is defined as the partial pressure of CO2 in the gas Henry’s law relationship as mentioned in Sema et al. (2012b), and
(P1 ; kPa) divided by the physical solubility of CO2 in the solution or C1∗ can be obtained from the developed VLE model.
Henry’s constant (He1 ; kPa m3 /kmol). Cj0 is the bulk concentration The predicted enhancement factor (Epred ) can also be calculated
of species j in liquid phase (kmol/m3 ), which can be obtained by from Eq. (37). In this case, the rate of CO2 absorption per unit area is
the vapor–liquid equilibrium model. the predicted value from Eq. (36) by integrating (∂C1 /∂t)x=0 over the
For laminar jet absorber, the contact time () is found to be: contact time (). (∂C1 /∂t)x=0 can be obtained from solving Eqs. (14),
(15) and (17) and (21)–(24) simultaneously using FEM based on
d2 h
= (33) COMSOL 4.1 software with 1D time-dependent mode under initial
4L and boundary conditions mentioned in Eqs. (29)–(32).
where d is jet diameter (m), h is jet height (m), and L is volumetric In this calculation process, the second order forward rate coef-
liquid flow rate (m3 /s). ficient for reaction 4 or k24 or kDEAB was considered as an adjusting
From Higbie’s penetration theory, the liquid phase mass transfer parameter. For each experiment (at different initial DEAB concen-
coefficient for physical absorption of CO2 (kL0 ; m/s) is defined as: trations, temperatures, initial CO2 loadings, 
and contact times),
  the value of kDEAB was adjusted until (Eexp − Epred )/Eexp  ≤ 1%
D1 4 D1 L (Hagewiesche et al., 1995). Then the forward reaction rate constant,
kL0 =2 = (34)
 d h kDEAB , was correlated with the reaction rate constant expression as
shown in Eq. (38).
The local CO2 absorption rate per unit area (N; kmol/m2 s) is given
 B
as:
  kDEAB = A · exp − (38)
T
∂Cj
N = −D1 (35) COMSOL is a commercial FEM software, which is widely accepted
∂t
x=0
to be a very powerful and adequate for solving the partial
Thus, the average CO2 absorption rate per unit area (Nave ; differential–non linear algebraic equations for chemical engineer-
kmol/m2 s) is obtained by integrating Eq. (35) over the contact time ing application (Zimmerman, 2006; Pryor, 2009). The numerical
: treatment based on COMSOL software used in the present work
  has been proven to be adequate for developing the CO2 absorp-
D1 ∂C1
Nave = − (0, t) dt (36) tion rate/kinetics model for aqueous amine solutions as reported
 0
∂t
by our previous works (Idem et al., 2009; Edali et al., 2009, 2010;
The effect of chemical reaction in terms of the enhancement factor, Edali, 2010), where CO2 absorption rate/kinetics models for aque-
E, which is defined as the ratio of the absorption rate of CO2 into a ous amine solutions of MEA, blended MEA–MDEA, and blended
reacting liquid to that if there was no reaction, is given by: MDEA–PZ were successfully developed.
Nave
E= (37) 4. Results and discussion
kL0 (C1∗ − C10 )

For each experimental CO2 absorption rate (kmol of CO2 /s) mea- 4.1. Vapor–liquid equilibrium model
sured by the laminar jet absorber at various DEAB concentrations,
CO2 loadings, temperatures, and contact times, one value of CO2 The VLE model for aqueous DEAB solution was developed in
absorption rate per unit area (N; kmol/m2 s) can be obtained (the order to predict the bulk concentrations of all chemical species

Fig. 2. Liquid phase speciation and concentration in aqueous DEAB solutions as a function of CO2 loading (˛) at initial DEAB concentration of 2.0 kmol/m3 and 298 K (dots
are experimental data measured by 13 C NMR obtained from Shi et al. (2012b); solid lines are simulated data obtained from vapor–liquid equilibrium model developed in this
study).
 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398 395

Table 1 The experimental absorption rate data were then interpreted

Species bulk concentration in aqueous DEAB solution of 2 kmol/m3 at 318 K and CO2
by the numerical solved CO2 absorption rate/kinetics model using
loading of 0.10 mol CO2 /mol amine.
FEM based on COMSOL 4.1 software with 1D time-dependent mode
Species Concentration (kmol/m3 ) by considering kDEAB as an adjustable parameter. The kDEAB results
C10 , [CO2 ] 6.96 × 10−6 were correlated with the reaction rate constant expression of Eq.
C20 , [HCO− 3
] 8.27 × 10−2 (38) as:
C30 , [OH− ] 1.22 × 10−5
C40 , [CO2−
3
] 8.27 × 10−2  7527.7 
C50 , [H+ ] 7.60 × 10−13 kDEAB = (4.01 × 1013 )exp − (39)
C60 , [DEAB] 1.682 T
C70 , [DEABH+ ] 0.317
The predicted kDEAB at 298 K compares with that of MDEA, AMP,
DEA, MEA, and PZ are shown in Table 2. By comparing kDEAB and
(C10 − C70 ), which required for the CO2 absorption rate/kinetic mod- kMDEA (both DEAB and MDEA are considered as tertiary amine),
eling. Some simulated results for the bulk concentrations obtained it can be seen that the kDEAB is much higher than kMDEA , which
from the VLE model developed in the present work are shown in means that the reaction kinetics of CO2 absorption into DEAB is
Fig. 2 and Table 1. The comparison of the simulated results and much faster than that into MDEA. Moreover, it can also observed
the experimental values measured by 13 C NMR obtained from the that the kDEAB is comparable with kAMP and kDEA . It is generally
work of Shi et al. (2012b) are shown in Fig. 2. This figure shows the accepted that AMP and DEA are considered to be reactive with CO2
species concentrations at 0–1 CO2 loading for 2.0 M (or kmol/m3 ) of since they are primary sterically hindered amine and secondary
aqueous DEAB solution at 298 K. It can be seen from Fig. 2 that the amine, respectively (Sartori and Savage, 1983; Kohl and Nielsen,
simulated bulk concentrations of all chemical species correspond 1997). However, the kDEAB is much smaller than kMEA and kPZ , since
well with the experimental values. Thus, it can be inferred that the MEA is primary amine, which is very reactive with CO2 , and PZ
VLE model developed in this work is applicable for predicting the is very fast accelerator. Therefore, it can be summarized that the
bulk concentration of all species, and the predictions can then be CO2 absorption reaction with DEAB is faster than that with MDEA,
used for establishing a CO2 absorption rate/kinetics model. More- also comparable with those with AMP and DEA, but slower than
over, it can be observed from Fig. 2 that the DEAB concentration those with MEA and PZ, respectively. This observation is found to
decreases as CO2 loading increases. This due to the DEAB protona- be in good agreement with the mass transfer performance stud-
tion and the CO2 –DEAB–water reaction as shown in Eqs. (3) and ies by Naami et al. (2012). They have found that the mass transfer
(4), respectively. As a result, the protonated DEAB concentration, performance of CO2 absorption in DX structured packed column in
DEABH+ , increases as CO2 loading increases. One of the major prod- terms of KG av and CO2 absorption performance can be ranked as
ucts, which is HCO− 3 , is found to increase as CO2 loading increases. MEA > DEAB > MDEA.
As CO2 loading increases (which means more CO2 is introduced The activation energy can be used for simply prediction of the
to the system), the HCO− 3 is formed due to CO2 reacts with DEAB- kinetics behavior of amine. This due to the fact that the lower acti-
water, water, and OH− as shown in Eqs. (4)–(6), respectively. At vation energy, the easier the reaction can proceed. It can be seen
CO2 loading less than 0.4, [CO2− 3 ] is found to increase due to the from Table 2 that PZ, which is the most reactive amine, is found to
−
CO2−
3 formation by HCO3 as shown in Eq. (7). However, the [CO3 ]
2−
have low activation energy. MEA, which found to have lower reac-
decreases when CO2 loading is higher than 0.4. This is because of tion kinetics than PZ, has higher activation energy than PZ. Lastly,
the acidity of the solution increases as CO2 loading increases. Then DEA and MDEA, which are slower than MEA and PZ, are found to
Eq. (7) is reversed to form HCO− 2−
3 from CO3 . have higher activation energy that that of MEA and PZ.
The experimental enhancement factors, which represent the
4.2. CO2 absorption rate/kinetics model ratio of the absorption rate of CO2 into a reacting liquid to that if
there is no reaction, for CO2 absorption into aqueous DEAB solutions
The CO2 absorption rate in aqueous DEAB solutions was mea- over temperature range of 298–318 K, DEAB concentration range of
sured by laminar jet absorber at atmospheric pressure over 1.0–2.0 M, and CO2 loading range of 0.001–0.18 mol CO2 /mol amine
temperature range of 298–318 K, DEAB concentration range of are shown in Figs. 3 and 4. It can be seen from these figures that
1.0–2.0 M, and CO2 loading range of 0.001–0.18 mol CO2 /mol the enhancement factor increases as DEAB concentration increases
amine. These operating conditions were selected because (i) DEAB over the range of 1.0–2.0 M. This is because at higher DEAB con-
was found to have lower heat of absorption than that from MDEA, centration, more DEAB molecules (which are chemically reactive
DEA, and MEA; thus, lower absorption temperature is applicable in with CO2 ) are introduced to the solutions. Fig. 3 also shown that
the case of DEAB (Sema et al., 2011), (ii) DEAB provides very high the enhancement factor decreases as CO2 loading increases due to
CO2 absorption capacity (competitive with PZ); thus, low DEAB the fact that as CO2 loading increases, the amount of active amine
concentration can achieve the satisfied CO2 absorption capacity decreases, causing the enhancement factor to decrease. It can be
(Tontiwachwuthikul et al., 2008; Maneeintr et al., 2009; Sema et al., observed from Fig. 4 that the enhancement factor increases as tem-
2011), and (iii) the ideal solution assumption is applicable at low perature increases because the reaction rate constant increases as
CO2 loading (Edali, 2010). temperature increases as can be predicted using Eq. (39).

Table 2
Forward second order reaction rate constant (k) and activation energy of MDEA, AMP, DEA, DEAB, MEA, and PZ at 298 K.

k (m3 /kmol s) References (for forward second order reaction rate constant) Activation References (for activation energy)
energy (kJ/mol)

kMDEA 2.33 6.71 Haimour et al. (1987) and Rinker et al. (1995) 47.9 Rangwala et al. (1992)
kAMP 473 570 Saha et al. (1995) and Mandal and Bandyopadhyay (2005) 41.7 Alper (1990)
kDEA 412 576 Rinker et al. (1996) and Zhang et al. (2002) 53.1 Hikita et al. (1977)
kDEAB 429 This work 62.6 This work
kMEA 5939 6209 Versteeg et al. (1996) and Edali et al. (2009) 41.2 Hikita et al. (1977)
kPZ 65,460 70,000 Derk et al. (2006) and Edali et al. (2010) 35.5 Samanta and Bandyopadhyay (2007)
396 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398

Fig. 3. Experimental enhancement factor of DEAB obtained from laminar jet absorber at 298 K over concentration and CO2 loading ranges of 1.0–2.0 M and 0.001–0.18 mol
CO2 /mol amine, respectively.

absorption rate (mol/s) can be obtained from the predicted CO2

absorption rate per unit area (N; kmol/m2 s) since the absorption
surface area was known by measurement of liquid jet diameter
and height using the two dimensional microscope. The predicted
CO2 absorption rate per unit area (N; kmol/m2 s) can be calcu-
lated using Eq. (36) by integrating (∂C1 /∂t)x=0 over the contact
time (). (∂C1 /∂t)x=0 can be acquired as the results of solving par-
tial differential–nonlinear algebraic equations of Eqs. (14), (15),
(17) and (21)–(24) simultaneously by COMSOL software. At this
calculation state, the kDEAB was obtained from the predictive cor-
relation developed in the present work, which is Eq. (39). Also, the
integration over contact time  was done by integration function
in COMSOL software. The predicted CO2 absorption rates com-
pared with the experimental values are shown in Fig. 5 as a parity
chart with an AAD of 6.5%, which is favorably acceptable. Thus,
it can be said that the numerical comprehensive CO2 absorption
rate/kinetics model for aqueous DEAB solution, which is developed
Fig. 4. Experimental enhancement factor of DEAB obtained from laminar jet
in this work, is adequate and provides accurate results.
absorber at CO2 loading of 0.1 mol CO2 /mol amine over concentration and tem-
perature ranges of 1.0–2.0 M and 298–318 K, respectively. The maximum uncertainty of CO2 absorption rates measured
from the laminar jet absorber was found to be 1.8%. By compar-
ing the difference between the prediction of the model and the
In addition, the CO2 absorption rate/kinetics model developed in experiment (which is 6.5%) with the maximum uncertainty of CO2
this study is also able to predict the CO2 absorption rate in aqueous absorption rates (which is 1.8%), it can be seen that the differ-
DEAB solutions at various temperatures, initial DEAB concentra- ence between the prediction of the model and the experiment is
tions, initial CO2 loadings, and contact times. The predicted CO2 larger than the maximum uncertainty of CO2 absorption rates. This

Fig. 5. Parity chart comparing experimental and predicted CO2 absorption rate in aqueous DEAB solution.
 T. Sema et al. / International Journal of Greenhouse Gas Control 12 (2013) 390–398 397

is because of the error caused by (i) the assumptions for simpli- Hagewiesche, D.P., Ashour, S.S., Al-Ghawas, H.A., Sandall, O.C., 1995. Absorp-
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sions from cities: comparison of international inventory frameworks. Local
Environment: The International Journal of Justice and Sustainability 17,
The financial support from National Natural Science Foundation 223–241.
Idem, R., Edali, M., Aboudheir, A., 2009. Kinetics, modeling, and simulation of the
of China (NSFC No. 21276068 and 212111111), Ministry of Science
experimental kinetics data of carbon dioxide absorption into mixed aqueous
and Technology of the People’s of Republic of China (MOST No. solutions of MDEA and PZ using laminar jet apparatus with a numerically solved
2012BAC26B01), Ministry of Hunan Provincial Science and Tech- absorption-rate/kinetic model. Energy Procedia 1, 1343–1350.
nology (No. 2010SK2001), China’s State “Project 985” in Hunan Kent, R.L., Eisenberg, B., 1976. Better data for amine treating. Hydrocarbon
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University–Novel Technology Research and Development for CO2 Kohl, A.L., Nielsen, R.B., 1997. Gas Purification, fifth ed. Gulf Publishing Company,
Capture as well as Hunan University to the Joint International Houston, USA.
Center for CO2 Capture and Storage (ICCS) is gratefully acknowl- Lashof, D.A., Ahuja, D.R., 1990. Relative contributions of greenhouse gas emissions
to global warming. Nature 344, 529–531.
edged. In addition, we would also like to acknowledge the research Liang, Z.H., Sanpasertparnich, T., Tontiwachwuthikul, P., Gelowitz, D., Idem, R., 2011.
supports over the past many years to the Industrial Research Design, modeling and simulation of post-combustion CO2 capture systems using
Consortium–Future Cap Phase II of International Test Centre for reactive solvents. Carbon Management 2, 265–288.
Mandal, B.P., Bandyopadhyay, S.S., 2005. Simulation absorption of carbon dioxide
CO2 Capture (ITC) at the University of Regina. We would also like to and hydrogen sulfide into aqueous blends of 2-amino-2-methyl-1-propanol and
acknowledge the research supports from the followings organiza- diethanolamine. Chemical Engineering Science 60, 64238–66451.
tions: Natural Sciences and Engineering Research Council of Canada Maneeintr, K., Henni, A., Idem, R.O., Tontiwachwuthikul, P., Wee, A.G.H., 2008. Phys-
ical and transport properties of aqueous amino alcohol solutions for CO2 capture
(NSERC), Canada Foundation for Innovation (CFI), Saskatchewan
from flue gas streams. Process Safety and Environmental Protection 86, 291–295.
Ministry of Energy & Resources, Western Economic Diversification, Maneeintr, K., Idem, R.O., Tontiwachwuthikul, P., Wee, A.G.H., 2009. Synthesis, solu-
Saskatchewan Power Corporation, Alberta Energy Research Insti- bilities, and cyclic capacity of amino alcohols for CO2 Capture from flue gas
streams. Energy Procedia 1, 1327–1334.
tute (AERI) and Research Institute of Innovative and Technology
Meinshausen, M., Meinshausen, N., Hare, W., Raper, S.C.B., Frieler, K., Knutti, R.,
for the Earth (RITE). Frame, D.J., Allen, M.R., 2009. Greenhouse-gas emission targets for limiting
global warming to 2 ◦ C. Nature 458, 1158–1162.
Naami, A., Edali, M., Sema, T., Idem, R., Tontiwachwuthikul, P., 2012. Studies of mass
Appendix A. Supplementary data transfer performance of CO2 into aqueous solution of 4-diethylamino-2-butanol
monoethanolamine and N-methyldiethanolamine. Industrial and Engineering
Supplementary data associated with this article can Chemistry Research 51, 6470–6479.
Pinsent, B.R.W., Pearson, L., Roughton, F.J.W., 1956. The kinetics of combination of
be found, in the online version, at [Link] carbon dioxide with hydroxide ions. Transactions of the Faraday Society 52,
10.1016/[Link].2012.11.023. 1512–1520.
Pryor, R.W., 2009. Multiphysics Modeling Using COMSOL: A First Principle Approach.
Jones and Bartlett Publishers, New York.
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