Chemical Engineering Science 61 (2006) 5440 – 5447

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Absorption of carbon dioxide into aqueous blends of

2-amino-2-methyl-1-propanol and monoethanolamine
B.P. Mandal a,∗ , S.S. Bandyopadhyay b
a Department of Chemical Engineering, Indian Institute of Technology Guwahati, North Guwahati-781039, India
b Separation Science Laboratory, Cryogenic Engineering Centre, Indian Institute of Technology Kharagpur, Kharagpur-721302, India

Received 18 February 2006; received in revised form 29 March 2006; accepted 1 April 2006
Available online 21 April 2006

Abstract
This work presents an investigation of CO2 absorption into aqueous blends of 2-amino-2-methyl-1-propanol (AMP) and monoethanolamine
(MEA). The acid gas mass transfer has been modeled using equilibrium-mass transfer-kinetics-based combined model to describe CO2
absorption into the amine blends according to Higbie’s penetration theory. The effect of contact time and relative amine concentration on
the rate of absorption and enhancement factor were studied by absorption experiment in a wetted wall column at atmospheric pressure. The
model was used to estimate the rate coefficient of the reaction between CO2 and monoethanolamine at 313 K from experimentally measured
absorption rates. A rigorous parametric sensitivity test has been done to identify the key systems’ parameters and quantify their effects on the
mass transfer using the mathematical model developed in this work. The model predictions have been found to be in good agreement with the
experimental rates of absorption of CO2 into (AMP + MEA + H2 O).
䉷 2006 Elsevier Ltd. All rights reserved.

Keywords: Gas absorption; CO2 removal; Modeling; Blended amines; 2-Amino-2-methyl-1-propanol; Monoethanolamine

1. Introduction
The removal of acid gas impurities such as CO2 and H2 S
from natural, refinery and synthesis gas streams is a sig-
nificant operation in gas processing. The amines that have
proved to be of commercial interest for acid gas removal
by chemical absorption are monoethanolamine (MEA), di-
ethanolamine (DEA), N -methyldiethanolamine (MDEA) and
di-isopropanolamine (DIPA).
Primary and secondary amines react rapidly with CO2 to
form carbamates. By the addition of a primary or secondary
amine to a purely physical solvent such as water, the CO2 ab-
sorption capacity and the rate is enhanced manifold. However,
because there is a relatively high heat of absorption associated
with the formation of carbamate ions, the cost of regenerating
primary and secondary amines is high. Primary and secondary
amines also have the disadvantage of requiring 2.0 mol of amine
∗ Corresponding author. Tel.: +91 3612582256; fax: +91 3612690762.
E-mail address: bpmandal@iitg.ernet.in (B.P. Mandal).
0009-2509/$ - see front matter 䉷 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2006.04.002
to react with 1.0 mol of CO2 . Thus, their loadings are limited to
0.5 mol of CO2 per mol of amine. Tertiary amine lack of N–H
bond required to form the carbamate ion and therefore do not
react directly with CO2 . However, in aqueous solutions, tertiary
amine promotes the hydrolysis of CO2 to form the bicarbonate
and the protonated amine. The advantages of MDEA, a tertiary
amine, over primary or secondary amine include its high equi-
librium loading capacity (1.0 mol of CO2 per mole of amine)
and its low heat of reaction with CO2 , which leads to lower
energy requirement for regeneration. A recent advancement in
gas-treating technology is the application of sterically hindered
amine e.g., 2-amino-2-methyl-1-propanol (AMP), which offer
absorption capacity, absorption rate, selectivity and degrada-
tion resistance advantages over conventional amines for CO2
removal from gases (Sartori and Savage, 1983).
The use of mixed amine solvents in gas-treating processes
is of increasing interest today. Blends of primary and tertiary
amines (such as mixtures of MEA and MDEA) or secondary
and tertiary amines (such as mixtures of DEA and MDEA),
which combine the higher equilibrium capacity of the ter-
tiary amine with the higher reaction rate of the primary or
 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447 5441

K5
secondary amine, have been suggested for industrial gas- RNH2 + H+ ←→ RNH+
3, (5)
treating processes. Compared to MDEA, AMP has the same
K6
high equilibrium capacity for CO2 , but has a higher rate con- R NH2 + H+ ←→ R NH+
3, (6)
stant for reaction with CO2 (Saha et al., 1995). Since sterically
hindered amine, AMP, does not form stable carbamate (Saha K7
H+ + OH− ←→ H2 O, (7)
et al., 1995), bicarbonate and carbonate ions may be present
in the solution in larger amounts than the carbamate ions. where Ki(i=1,...,7) is the equilibrium constant for reaction (i),
Hence, the regeneration energy costs when aqueous solutions and k2j (j =1,...,3) is the second-order forward rate coefficient for
of AMP is used to absorb CO2 may be lower as in the case reaction (j ). Reactions (1)–(3) have finite reaction rates and are
of using aqueous MDEA solutions. Hence, aqueous blends of reversible and reactions (4)–(7) are considered instantaneous
AMP and MEA may be an attractive new alternative solvent and reversible and at equilibrium.
to (MDEA + MEA + H2 O) for the gas-treating processes. In the above reaction scheme not all the reaction equilib-
Absorption rates of CO2 into aqueous blends of MEA and rium constants are independent. Only six equilibrium constants
MDEA were studied by Glasscock et al. (1991), Rangwala et (K2 , K3 , K4 , K5 , K6 and K7 ) are independent. The remaining
al. (1992), Hagewiesche et al. (1995), and Mandal et al. (2001). one can be obtained by appropriate combination of the indepen-
Relative to the work on CO2 –(MDEA+MEA+H2 O), available dent equilibrium constants. Hence, we have K1 = K2 K5 /K7 .
literature on CO2 absorption in aqueous mixture of AMP and The interaction between the protonated and unprotonated
MEA is very limited. Recently, Xiao et al. (2000) investigated amines, shown in Eq. (8) involves only a proton transfer and is
the kinetics of CO2 absorption into (AMP + MEA + H2 O) with considered to be instantaneous and at equilibrium.
1.7 and 1.5 kmol m−3AMP mixed with various quantities of
MEA (0.1, 0.2, 0.3, and 0.4 kmol m−3 ). They observed signifi- R NH+  K8 +
3 + RNH2 ←→ R NH2 + RNH3 . (8)
cant enhancement of CO2 absorption rates with the addition of
small amounts of MEA into aqueous AMP. They claimed that Reaction (8) is implicitly included in the reaction scheme above.
a hybrid reaction rate model with first-order reaction for MEA K8 can be obtained by properly combining the instantaneous
and a zwitterion mechanism for AMP satisfactorily explained equilibria of reactions (5) and (6) as K8 = K5 /K6 .
the CO2 absorption data. The hydration of CO2 may occur as follows:
In this work a mathematical model is presented to describe
K9 ,k29
the absorption of CO2 into (AMP + MEA + H2 O). The dif- CO2 + H2 O ←→ HCO− +
3 +H . (9)
fusion reaction processes are modeled according to Higbie’s
penetration theory with the assumption that all reactions are re- This reaction is very slow (k29 = 0.026 s−1 at 25 ◦ C) (Pinsent
versible. The effect of contact time and relative amine concen- et al., 1956) and may usually be neglected (Blauwhoff et al.,
tration on the rate of absorption and enhancement factor were 1984).
studied by absorption experiment in a wetted wall column at
atmospheric pressure. The rate coefficient of reaction between 2.2. Reaction mechanism
CO2 and MEA at 313 K was estimated using the mathematical
model developed in this work. A rigorous parametric sensitiv- The zwitterion mechanism has recently become one of the
ity test has been done to identify the key systems’ parameters most widely accepted mechanisms for primary amine reactions
and quantify their effects on the mass transfer using the math- with CO2 (Blauwhoff et al., 1984; Versteeg and van Swaaij,
ematical model developed in this work. 1988; Versteeg et al., 1990; Versteeg and Oyevaar, 1989; Glass-
cock et al., 1991; Littel et al., 1992; Mandal et al., 2003a). The
2. Reaction scheme and mathematical model rate coefficients k21 and k23 are viewed as the global rate coef-
ficients for the formation of bicarbonate and carbamate, respec-
2.1. Reaction scheme tively. Hence, this representation does not rule out the possible
formation of a zwitterion reaction intermediate.
The following reactions may take place when CO2 is ab-
sorbed into an aqueous blended amine solution of AMP (RNH2 ) 2.3. Bulk liquid equilibrium model
and MEA (R NH2 ) (where R = C(CH3 )2 CH2 OH and R =
CH2 CH2 OH). For convenience, the chemical species are renamed as fol-
lows:
K1 ,k21
CO2 + RNH2 + H2 O ←→ RNH+ −
3 + HCO3 , (1) u1 = [CO2 ], u2 = [RNH2 ], u3 = [RNH+ −
3 ], u4 = [HCO3 ],
K2 ,k22 u5 = [OH− ], u6 = [CO2−
3 ], u7 = [H+ ],
CO2 + OH− ←→ HCO−
3, (2) 
u8 = [R NH2 ], u9 = [R 
NH+
3 ], u10 = [R NHCOO− ].
K3 ,k23
R NH2 + CO2 ←→ R NHCOO− + H+ , (3) The initial liquid bulk concentrations of all chemical species
can be estimated from the initial concentrations of AMP and
K4
HCO− + 2−
3 ←→ H + CO3 , (4) MEA, the initial CO2 loading (
) and the assumption that all
5442 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447
reactions are at equilibrium. For the 10 liquid bulk concentra-
tions u01 .u010 , the 10 non-linear algebraic equations have been
presented in our previous work (Mandal et al., 2001). To solve
this we have used IMSL Library, FORTRAN Developer Studio
version 4.0.
2.4. Diffusion-reaction model
Higbie’s penetration model is used to set up the diffusion-
reaction partial differential equations which describe the ab-
sorption of CO2 into aqueous blends of a sterically hindered
amine RNH2 and a primary amine R NH2 . All reactions were
treated as reversible reactions. The partial differential equations
along with the rate expressions for reactions (1)–(3), which de-
scribe the diffusion-reaction process, have been presented ear-
lier (Mandal et al., 2001). The instantaneous reactions assumed
to be at equilibrium are as follows:
u 6 u7
K4 = , (10)
u4
u3
K5 = , (11)
u2 u7
u9
K6 = , (12)
u7 u8
1.0
K7 = . (13)
u7 u5
Thus, there are ten partial differential-algebraic equations
for the blended amine solvent, (AMP + MEA), which can be
solved for the concentrations of 10 chemical species, u1 .u10 .
Initial condition and boundary conditions at x = ∞:
At t = 0 (for all x
0) and at x = ∞ (for all t
0), the
concentrations of all chemical species are equal to their liquid
bulk concentrations.
Boundary conditions at gas–liquid interface (x = 0):
At x = 0 (gas–liquid interface), the fluxes of the nonvolatile
chemical species are equal to zero except for CO2 . For the
volatile component (CO2 ), the mass transfer rate in the gas near
the interface is equal to the mass transfer rate in the liquid near
the interface. For the case of pure gas, the interfacial partial
pressure of the gas is the same as the bulk partial pressure of
the gas, and there is no mass transfer resistance in the gas phase
(kg,i → ∞). The detailed discussion on the initial and boundary
conditions are presented earlier (Mandal et al., 2003a).
The differential equations are integrated from t = 0 to , the
contact time. The contact time, the liquid-phase mass transfer
coefficient for physical absorption of CO2 , the time-averaged
rate of absorption of CO2 per unit interfacial area, and the
enhancement factor for absorption of CO2 are computed from
the equations as presented elsewhere (Mandal et al., 2003a;
Mandal and Bandyopadhyay, 2005).
3. Method of solution
The partial differential equations are transformed into set of
ordinary differential equations in time variable t by discretizing
the spatial variable x. Central difference formulae are used
to approximate the spatial derivative (Mandal et al., 2003a).
Equally spaced nodes are used to discretize the spatial vari-
able, x. Typical number of nodes used is 200 and correspond-
ing nodal spacings are of the order 10−7 .10−8 m. The resulting
systems of ordinary differential equations coupled with alge-
braic equations are solved by using the subroutine DDASSL
(Petzold, 1983; Brenan et al., 1989) in double precision FOR-
TRAN on a Pentium IV processor.
4. Physicochemical properties and model parameters
Knowledge of the physicochemical and transport properties
of the alkanolamines and CO2 e.g., density and viscosity of
the aqueous amine solutions and diffusivity and physical sol-
ubility of CO2 in the aqueous amine solutions were necessary
for analyzing the results of absorption studies using the nu-
merical model developed in this work. Density and viscosity
of the aqueous amine solutions were needed to find out the
liquid-film thickness w and the contact time  in the wetted
wall column. Values of  along with the values of diffusiv-
ity of CO2 in the amine solutions enable the determination
of the corresponding values of the liquid side mass transfer
coefficient kL .
The density and viscosity of aqueous alkanolamine solutions
were found out by standard methods, and presented elsewhere
(Mandal et al., 2003b). The solubility and diffusivity of CO2 in
aqueous amine solutions cannot be found out directly because
CO2 undergoes reaction with the amines. Hence, these proper-
ties were estimated by the “N2 O-analogy” (Mandal et al., 2005)
and presented in Table 1.
The equilibrium constants are needed to interpret the results
of CO2 absorption measurement into alkanolamines. Values of
the independent equilibrium constants have been found out us-
ing reliable correlations and the dependent ones have been es-
timated by appropriate combination of the independent equi-
librium constants. These are calculated from the correlations
as presented in Table 2. The correlation for the reaction rate
constants k21 and k22 are also given in Table 2.
In view of the difference in the reported value of the reaction
rate constant k23 for CO2 –MEA, it was thought desirable to
estimate the value of k23 at 313 K from our experimental data.
This was done by reasonably adjusting the value of k23 in the
model until the model predicted rates were in good agreement
with measured rates of absorption.
5. Experimental
The stainless-steel wetted wall contactor used was similar
to our earlier work (Mandal et al., 2003a; Mandal and Bandy-
opadhyay, 2005). The outer diameter of the column was 2.81 ×
10−2 m. The length of the absorption surface could be varied
between 50×10−3 and 120×10−3 m. Absorption measurements
were done with 30 wt% AMP, 28.5 wt% AMP +1.5 wt% MEA,
27 wt% AMP + 3 wt% MEA and 25.5 wt% AMP + 4.5 wt%
MEA at 313 K. Pure CO2 was used. The temperature of ab-
sorption was controlled within ±0.2 K of the desired level with
a circulator temperature controller (JULABO FP 55, FRG).
 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447 5443

Table 1
Density and viscosity of the aqueous AMP + MEA solutions studied and the diffusivity and Henry’s law constants of CO2 in these solutions at 313 K

MEA (mass%) AMP (mass%) [MEA] (kmol/m3 ) [AMP] (kmol/m3 )  (kg/m3 )  × 103 (kg/m s) DCO2 × 109 (m2 /s) HCO2 (kPa m3 /kmol)

0 30 0.0 3.326 988.72 2.24 1.46 4720

1.5 28.5 0.243 3.163 989.19 2.19 1.52 4622
3 27 0.487 2.999 990.08 2.16 1.57 4576
4.5 25.5 0.730 2.835 991.06 2.13 1.67 4521

Table 2
Equilibrium and forward rate constant correlations used for model calculations

Equilibrium Correlation Temperature Reference

and forward range (K)
rate constant


log10 K1 = 8909.483 − 142613.6
T − 4229.195 log10 (T ) + 9.7384T
K7 7 273–573 Olofsson and Hepler (1975)
−0.0129638T 2 + 1.15068 × 10−5 T 3 − 4.602 × 10−9 T 4


K
K2 log10 K2 = 179.648 + 0.019244T − 67.341 log10 (T ) − 7495.441
T 273–523 Read (1975)
7
K4 log10 (K4 ) = 6.498 − 0.0238T − 2902.4
T 273–323 Danckwerts and Sharma (1966)


K
K5 ln K5 = −7261.78 − 22.4773 ln(T ) + 142.58612 313–353 Silkenbäumer et al. (1998)
7
T
K1 K5 3635.09
K3 log10 K = 2.8898 − T 298–393 Li and Mather (1994)

3
K6 log10 K = −2.1211 − 8189.38
1
T + 0.007484T 273–333 Li and Mather (1994)
6
k21 ln k21 = 25.815 − 5801.7
T 293–313 Mandal and Bandyopadhyay (2005)
k22 log10 (k22 ) = 13.635 − 2895
T 273–313 Danckwerts and Sharma (1966)

Reagent grade MEA and AMP of 98% purity were obtained
from E. Merck. Pure CO2 (99.995%) cylinder was obtained
from Hydrogas India. Distilled water degassed by boiling was
used for making amine solutions.
The liquid flow rate was 2 × 10−6 m3 /s. The total amine
concentration of the solutions were determined by titration with
standard HCl using methyl orange indicator. Carbon dioxide
content in the liquid samples after absorption was determined
by acidulating a known volume of the sample and measuring
the volume of evolved gas, as described earlier (Mandal et al.,
2003a).
All absorption experiments were done at atmospheric pres-
sure with partial pressure of CO2 near atmospheric and with
initial CO2 loading of the solutions before absorption equal to
zero. The total amine concentration in the solution was kept at
30 mass% in view of commercial interest in using concentrated
amine solutions in gas treating. Absorption measurements for
CO2 into 30 mass% AMP, 28.5 mass% AMP+1.5 mass% MEA,
27 mass% AMP + 3 mass% MEA and 25.5 mass% AMP +
4.5 mass% MEA at 313 K were interpreted according to the
model developed.
6. Results and discussion
Table 3 presents the measured and model predicted
rates and enhancement factors for absorption of CO2 into
(AMP + MEA + H2 O). As shown in Table 3 and Fig. 1,
the addition of small amounts of MEA to an aqueous
solution of AMP results in increase in the enhancement
of the rates of absorption. For contact time,  = 0.5 s,
for example, the enhancement factor for aqueous solutions
of 30 mass% AMP, 1.5 mass% MEA + 28.5 mass% AMP,
3 mass% MEA + 27 mass% AMP, and 4.5 mass% MEA and
25.5 mass% AMP are about 38.6, 45.3, 50.3 and 57.0, re-
spectively. So by replacing 1.5 mass% AMP with an equal
amount of MEA, the enhancement factor increased by about
17%. Replacing an additional 1.5 mass% AMP with MEA
increased the enhancement factor by an additional 11%. A
further replacement of 1.5 mass% AMP with an equal amount
of MEA resulted in increasing the enhancement factor by
additional 13%.
For each composition of the blended amine solution the ef-
fect of contact time on the rate of absorption was studied by
performing the absorption experiments for three different film
lengths—5 × 10−2 , 7 × 10−2 and 10 × 10−2 m. These results
are presented in Fig. 2. It is evident from these results that the
specific rate of absorption of CO2 into aqueous blends of AMP
and MEA remains essentially unchanged with the variation in
contact time, that is, with the variation in the liquid-film mass
transfer coefficient, kL . This observation signifies that under
the conditions of present work the absorption, in general, con-
formed to the fast pseudo-first-order regime.
The measured rates and the predicted rates from the model
are compared in the parity plot shown in Fig. 3. As shown in
Fig. 3, the model predicted rates of absorption of CO2 into
(AMP + MEA + H2 O) are in excellent agreement with the
experimental results, the average absolute deviation between
the experimental and model results being about 4%. The value
of k23 was obtained for a particular contact time and amine
concentration by trial and error procedure by matching the
5444 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447

Table 3
Experimental data and model results for the absorption of CO2 into aqueous solutions of AMP + MEA in the wetted wall contactor at a total pressure of
1 atm (T = 313 K, PCO2 = 93.5 kPa)

[MEA] (kmol/m3 ) [AMP] (kmol/m3 )  (s) kL,CO2 × 105 (m/s) Experimental Model results

RCO2 × 105 (kmol/m2 s) E RCO2 × 105 (kmol/m2 s) E

0.0 3.326 0.369 7.096 4.75 33.8 4.43 31.5

0.0 3.326 0.516 6.001 4.66 39.2 4.25 35.8
0.0 3.326 0.737 5.021 4.64 46.7 4.15 41.7

0.243 3.163 0.366 7.270 5.75 39.1 5.79 39.4

0.243 3.163 0.512 6.147 5.69 45.8 5.65 45.4
0.243 3.163 0.731 5.144 5.62 54.0 5.56 53.4

0.487 2.999 0.364 7.409 6.70 44.3 6.55 43.3

0.487 2.999 0.509 6.266 6.49 50.7 6.46 50.5
0.487 2.999 0.728 5.239 6.48 60.5 6.35 59.3

0.730 2.835 0.362 7.663 7.80 49.2 7.41 46.8

0.730 2.835 0.507 6.475 7.68 57.4 7.29 54.4
0.730 2.835 0.724 5.418 7.65 68.3 7.17 64.0

65 10
mass% AMP + mass% MEA
30+0
60 28.5+1.5
9
Rate of Absorption x 105 (kmol/m2s)

27+3
25.5+4.5
55
8

50
ECO2

7
45

6
40

5
35

30 4
0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.30 0.35 0.40 0.45 0.50 0.55 0.60 0.65 0.70 0.75 0.80
[MEA]/[AMP] θ (s)

Fig. 1. Effect of molar ratio of MEA/AMP on the enhancement of CO2 Fig. 2. Effect of contact time on specific rate of absorption of CO2 into
absorption into 30 mass% aqueous blends of MEA and AMP.  = 0.5 s. aqueous AMP + MEA at 313 K.

measured rate in the experiment to the rate from the model to
within 1%. However, since k23 is unlikely to be a function of
concentration or contact time, the final k23 is the average of
the various values of k23 obtained for different concentrations
and/or contact times. The estimated reaction rate constant k23
value for the reaction CO2 and MEA in this work has been
found to be 9500 m3 /(kmol s) at 313 K. Hagewiesche et al.
(1995), Xiao et al. (2000) and Mandal et al. (2001) reported
the values of k23 as 10, 090 m3 /(kmol s), 11, 743 m3 /(kmol s)
and 8300 m3 /(kmol s), respectively, at 313 K. Thus, the value
of k23 obtained in this work is in close agreement with the value
reported in the literature.
Typical calculated concentration profiles for absorption of
CO2 into 28.5 mass% AMP + 1.5 mass% MEA is shown in
Fig. 4. It is interesting to note that the CO2 concentration pro-
file in Fig. 4 is concave downwards from the interface and be-
comes convex above a x/ value of 0.2, instead of being con-
sistently concave downwards with respect to the dimensionless
distance. This may be due to the fact that the higher CO2 par-
tial pressure (93.5 kPa), as in the present case, results in higher
interfacial concentration of CO2 and a consequential slight de-
pletion of hydroxyl ion in the film (as shown in Fig. 4) and a
resultant reduction of contribution of hydroxyl ion towards the
enhancement factor.
Rigorous parametric sensitivity test is often needed to iden-
tify the key systems’ parameters and quantify their effects on
the mass transfer, as well as quantify the effects of possi-
ble errors in the pertinent model parameters on the prediction
 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447 5445

8.0 100
Predicted Rate of Absorption x 105 (kmol/m2s)

95
7.5
90
7.0
85

Enhancement Factor
6.5
80

6.0 75

70
5.5
65
5.0
60
4.5
55

4.0 50
4.0 4.5 5.0 5.5 6.0 6.5 7.0 7.5 8.0 1E-6 1E-5 1E-4 1E-3 0.01
Experimental Rate of Absorption x 105 (kmol/m2s) Interfacial Concentration of Carbon Dioxide (kmol/m3)

Fig. 3. Comparison of model predicted rates of absorption to the experimental Fig. 5. The effect of interfacial concentration of CO2 on the predicted
rates of absorption of CO2 into aqueous AMP + MEA. rate of absorption of CO2 into aqueous AMP + MEA. T = 313 K,
[AMP] = 3.163 kmol/m3 , [MEA] = 0.243 kmol/m3 , PCO2 = 93.5 kPa,
t = 0.731 s, kL,CO2 = 5.144 × 10−5 m/s, kCO2 .AMP = 1400 m3 /kmol s,
DCO2 = 1.52 × 10−9 m2 /s, HCO2 = 4622 kPa m3 /kmol with a rate of absorp-
10 10 tion of 5.56×10−5 kmol/m2 s. Solid line: considering k22 =24, 311 m3 /kmol s
1 AMP AMPH+ 1 and dotted line: considering k22 = 0.
0.1 0.1
HCO3-
0.01 MEACOO- 0.01 100
Concentration (kmol/m3)

% Deviation in the Predicted Rate of Absorption

1E-3 2- MEAH+ 1E-3

1E-4
CO3 MEA OH- 1E-4
80

1E-5 1E-5 60
CO2
1E-6 1E-6
1E-7 40
1E-7
1E-8 1E-8 20
1E-9 1E-9
1E-10 0
H+ 1E-10
1E-11 1E-11 -20
1E-12 1E-12
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 -40
Dimensionless distance from interface, x/δ
-60
Fig. 4. Calculated concentration profiles in the film for absorption
of CO2 into an aqueous AMP + MEA. T = 313 K, [AMP] = -80
3.163 kmol/m3 , [MEA] = 0.243 kmol/m3 , PCO2 = 93.5 kPa, t = 0.731 s,
-100
kL,CO2 = 5.144 × 10−5 m/s. -50 -40 -30 -20 -10 0 10 20 30 40 50
% Deviation for Henry's Law Constant for Carbon Dioxide
accuracy of the absorption rates and enhancement factors. The
Fig. 6. The effect of errors in Henry’s law constant on the predicted
pertinent parameters considered for the analysis are CO2 inter- rate of absorption of CO2 into aqueous AMP + MEA. T = 313 K,
facial concentration (CO2 partial pressure), Henry’s law con- [AMP] = 3.163 kmol/m3 , [MEA] = 0.243 kmol/m3 , PCO2 = 93.5 kPa,
stant for CO2 , diffusion coefficient of CO2 , and reaction rate t = 0.731 s, kL,CO2 = 5.144 × 10−5 m/s, kCO2 .AMP = 1400 m3 /kmol s,
coefficient (rate constant) of the CO2 –AMP reaction. k22 = 24, 311 m3 /kmol s, DCO2 = 1.52×10−9 m2 /s, HCO2 = 4622 kPa m3 /
Fig. 5 shows the effect of the CO2 interfacial concentration kmol with a rate of absorption RCO2 = 5.56 × 10−5 kmol/m2 s.
(CO2 partial pressure) on the enhancement factor. It is clear
that the enhancement factor at lower interfacial concentrations
(lower partial pressures) is greater than that at higher interfacial shown in Fig. 5 neglecting CO2 /OH− reaction at much lower
concentrations (higher partial pressures). This is because as partial pressure than 100 kPa will result in marginal error, while
the CO2 interfacial concentration decreases, the contribution of neglecting CO2 /OH− reaction shall not result in much error
physical absorption to the overall absorption of CO2 decreases for CO2 at partial pressure close to 100 kPa.
and the contributions of the chemical reactions between CO2 Fig. 6 shows the effect of errors in Henry’s law constant for
and AMP, CO2 and MEA, and CO2 and OH− increase. As CO2 on the predicted rate of absorption. Here, errors of −50%
5446 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447

100 100

% Deviation in the Predicted Rate of Absorption

% Deviation in the Predicted Rate of Absorption

80 80

60 60

40 40

20 20

0 0

-20 -20

-40 -40

-60 -60

-80 -80

-100 -100
-50 -40 -30 -20 -10 0 10 20 30 40 50 -50 -40 -30 -20 -10 0 10 20 30 40 50
% Deviation for Diffusivity of Carbon Dioxide % Deviation in kCO2-AMP

Fig. 7. The effect of errors in the diffusion coefficient of Fig. 8. The effect of errors in kCO2 .AMP (the rate constant of the
CO2 on the predicted rate of absorption of CO2 into aqueous CO2 +AMP reaction) on the predicted rate of absorption of CO2 into aqueous
AMP +MEA. T =313 K, [AMP]=3.163 kmol/m3 , [MEA]=0.243 kmol/m3 , AMP +MEA. T =313 K, [AMP]=3.163 kmol/m3 , [MEA]=0.243 kmol/m3 ,
PCO2 = 93.5 kPa, t = 0.731 s, kL,CO2 = 5.144 × 10−5 m/s, kCO2 .AMP = PCO2 = 93.5 kPa, t = 0.731 s, kL,CO2 = 5.144 × 10−5 m/s, kCO2 .AMP =
1400 m3 /kmol s, k22 = 24, 311 m3 /kmol s, DCO2 = 1.52 × 10−9 m2 /s, 1400 m3 /kmol s, k22 = 24, 311 m3 /kmol s, DCO2 = 1.52 × 10−9 m2 /s,
HCO2 = 4622 kPa m3 /kmol with a rate of absorption of 5.56 × HCO2 = 4622 kPa m3 /kmol with a rate of absorption of 5.56 ×
10−5 kmol/m2 s. 10−5 kmol/m2 s.

7. Conclusions
to +50% have been introduced into the value of Henry’s law
constant and the corresponding errors in the rate of absorption The absorption of CO2 into aqueous solutions of mixtures
have been determined to range from +42% to −22%, respec- of small amounts of fast reacting MEA, a primary amine, and
tively. It is evident that the rate of absorption is very sensitive much larger amounts of AMP, a sterically hindered amine,
to the value of Henry’s law constant. This is because Henry’s were studied experimentally and theoretically. It has been
law constant determines the amount of CO2 , which dissolves found that the addition of small amount of MEA to an aque-
into the liquid for the given pressure, temperature, and AMP ous solution of AMP significantly enhances the enhancement
and MEA concentration. Hence, it is very important to have factor and rate of absorption over conventional single amine
accurate values for the Henry’s law constant in order to get ac- solvents. This establishes the importance of the blended amine
curate and reliable predictions for the rate of absorption and solvent (AMP + MEA) as a potential alternative for CO2 ab-
enhancement factor. sorption. The rate coefficient (k23 ) for the reaction CO2 and
Fig. 7 shows the effect of errors in the value of the diffusion MEA at 313 K was determined from the experimental data.
coefficient of CO2 on the predicted rate of absorption. Here, The estimated k23 value obtained by adjustment in the model
errors of −50% to +50% have been introduced into the value for the reaction of CO2 with MEA in this work has been found
of the diffusion coefficient of carbon dioxide, and the corre- to be 9500 m3 /(kmol s) at 313 K. In general, the experimen-
sponding errors in the rate of absorption have been determined tal data and the model results are in good agreement for the
to be in the range of −18% to +12%, respectively. Thus, it is blended amine solvents studied. This indicates that the com-
also important to have accurate values for the diffusion coeffi- bined mass transfer-reaction kinetics-equilibrium model can
cient of CO2 in order to obtain accurate predictions for the rate effectively represent CO2 mass transfer in the blended amine
of absorption. solvent (AMP + MEA + H2 O). The model is used for paramet-
Fig. 8 shows the effect of errors in the rate coefficient of ric study to identify the key systems’ parameters and quantify
the reaction of CO2 with AMP on the predicted rate of absorp- their effects on the mass transfer, as well as quantify the effects
tion. Errors of −50% to +50% have been introduced into the of possible errors in the important model parameters on the
value of the rate coefficient, and the corresponding errors in the prediction accuracy of the absorption rates and enhancement
rate of absorption have been determined to range from −15% factors. Sensitivity analyses allow for process optimization
to +8%, respectively. Thus, in order to obtain accurate pre- by parameter identification of the key parameters of these
diction for the rate of absorption, it is very important to have processes. Such a tool can be of great interest and worth for
accurate values for the rate coefficient of the reaction of CO2 industrial applications, notably in the treatment of sour natural
with AMP. gas streams, refinery off-gas streams and polluted tail gases.
 B.P. Mandal, S.S. Bandyopadhyay / Chemical Engineering Science 61 (2006) 5440 – 5447 5447

Notation Li, Y.-G., Mather, A.E., 1994. Correlation and prediction of the solubility
of carbon dioxide in a mixed alkanolamine solution. Industrial and
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[AMP] concentration of 2-amino-2-methyl-1- Littel, R.J., Versteeg, G.F., van Swaaij, W.P.M., 1992. Kinetics of CO2
propanol in the aqueous solution, kmol/m3 with primary and secondary amines in aqueous solutions-II. Influence of
[AMP]initial initial liquid bulk concentration of 2-amino- temperature on zwitterion formation and deprotonation rates. Chemical
2-methyl-1-propanol, kmol/m3 Engineering Science 47, 2037–2045.
Mandal, B.P., Bandyopadhyay, S.S., 2005. Simultaneous absorption of
Di diffusion coefficient of species i in the aque- carbon dioxide and hydrogen sulfide into aqueous blends of 2-amino-2-
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Hi physical equilibrium constant (Henry’s law Mandal, B.P., Biswas, A.K., Bandyopadhyay, S.S., 2003a. Absorption of
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kL,i physical mass transfer coefficient for gaseous Mandal, B.P., Guha, M., Biswas, A.K., Bandyopadhyay, S.S., 2001. Removal
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[MEA] concentration of monoethanolamine in the in aqueous MDEA/MEA and AMP/MEA solutions. Chemical Engineering
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Acknowledgement Saha, A.K., Bandyopadhyay, S.S., Biswas, A.K., 1995. Kinetics of absorption
of CO2 into aqueous solutions of 2-amino-2-methyl-1-propanol. Chemical
The financial support by the Centre for High Technology Engineering Science 50, 3587–3598.
Sartori, G., Savage, D.W., 1983. Sterically hindered amines for CO2 removal
(CHT), New Delhi, India, is gratefully acknowledged.
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