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Kinetics of Absorption of Carbon Dioxide in Aqueous

Solution of Ethylaminoethanol Modified with N-
methyl-2-pyrolidone
a a
Rahul R. Bhosale & Vijaykumar V. Mahajani
a
Department of Chemical Engineering , Institute of Chemical Technology , Matunga ,
Mumbai, India
Accepted author version posted online: 18 Jun 2013.Published online: 12 Sep 2013.

To cite this article: Rahul R. Bhosale & Vijaykumar V. Mahajani (2013) Kinetics of Absorption of Carbon Dioxide in Aqueous
Solution of Ethylaminoethanol Modified with N-methyl-2-pyrolidone, Separation Science and Technology, 48:15, 2324-2337,
DOI: 10.1080/01496395.2013.805228

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 Separation Science and Technology, 48: 2324–2337, 2013
Copyright # Taylor & Francis Group, LLC
ISSN: 0149-6395 print=1520-5754 online
DOI: 10.1080/01496395.2013.805228
Kinetics of Absorption of Carbon Dioxide in Aqueous
Solution of Ethylaminoethanol Modified with
N-methyl-2-pyrolidone
Rahul R. Bhosale and Vijaykumar V. Mahajani
Department of Chemical Engineering, Institute of Chemical Technology, Matunga, Mumbai, India
In this paper, kinetics of absorption of CO2 in an aqueous
ethylaminoethanol (EAE) and formulated solvent (aqueous blend
Downloaded by [University of Qatar] at 01:45 29 September 2013
of EAE and N-methyl-2-pyrrolidone (NMP)) was studied in a stirred
cell reactor by using a fall in pressure technique. The reaction path-
ways for CO2–aqueous EAE system were comprehensively described
using both zwitterion and termolecular mechanisms. The physico-
chemical properties such as density (q) and viscosity (l) of aqueous
EAE and formulated solvent and the solubility (HCO2 ) and diffusivity
of CO2 (DCO2 ) in these solvents were estimated experimentally. The
reactive absorption of CO2 in an aqueous EAE was observed to be
first order with respect to both CO2 and EAE concentrations.
Addition of NMP in aqueous EAE enhances the HCO2 by 40%, which
ultimately results into higher CO2 absorption rates in formulated
solvent (
20% higher) compared to that of the aqueous EAE. Effect
of concentration of EAE (0.5 to 2 kmol/m3) and temperature (303 to
318 K) on CO2 absorption kinetics was studied in detail and it was
realized that the rate of absorption of CO2 in aqueous EAE and
formulated solvent was significantly affected by the change in
these parameters. The findings obtained during the temperature
dependency study further indicates that the activation energy of
the absorption of CO2 in aqueous EAE (80.2 kJ/mol) was relatively
lower in comparison with the activation energy of the absorption of
CO2 in formulated solvent (88.95 kJ/mol). The overall reaction of
CO2 with the formulated solvent could be regarded as the reaction
of CO2 with aqueous EAE in parallel with the reaction between
CO2 and aqueous NMP.
Keywords CO2 absorption; ethylaminoethanol (EAE); gas puri-
fication; N-methyl-2-pyrrolidone (NMP); pressure
dependency; stirred reactor
INTRODUCTION
The uninterrupted discharge of greenhouse gases such as
CO2 is considered as one of the major reasons for the global
warming. The concentration of CO2 in earth’s atmosphere
is approximately 392 ppm by volume as of 2011 and rose
by 2 ppm by volume per year during 2000 to 2009. This
rapid upsurge in the CO2 concentration levels in the atmos-
phere is thought to be mainly due to its continuous release
Received 24 December 2012; accepted 10 May 2013.
Address correspondence to Rahul R. Bhosale, Solar
Technology Laboratory, Paul Scherrer Institute, 5232 Villigen,
PSI, Switzerland. E-mail: rrbhosle@yahoo.com
2324
from numerous sources such as synthesis gas, flue gas,
refinery off-gas, natural gas, coke oven gas (1). In this
prospective, considerable efforts are underway towards
the development of CO2 capture technologies, for instance,
physical adsorption (2,3), membrane separation (4), and
closed loop chemical absorption=desorption technique
(CADT). Among these processes, due to its higher
efficiency and lower complexity, CADT is preferred indust-
rially as an effective gas sweetening process for CO2
removal from process gas streams.
CADT is a two-step process where the first step belongs
to the absorption of CO2 by a suitable absorbent at
40–70 C, whereas the second step corresponds to the
desorption of CO2 at 100–150 C (5). Conventionally, aque-
ous alkanolamines and their blends were commonly used as
absorbents for the capture of CO2 during various applica-
tions such as desulfurised natural gas treatment, refinery
processes, etc. Several amines, for example, monoethanola-
mine (MEA), diethanolamine (DEA), di-isopropanolamine
(DIPA), methyldiethanolamine (MDEA), and diglycola-
mine (DGA) have been used industrially for a number of
years (6). A number of researchers have studied the kinetics
of the absorption of CO2 into a variety of alkanolamines
(7–11). Among all previously studied amines, MEA remains
the most popular for CO2 capture owing to its higher
reactivity and lower solvent cost as compared to that of
the other amines (12,13). However, it also possesses high
vapor pressure which makes it unsuitable for low pressure
operations due to the likely vaporization losses (14). In
addition, due to the possibility of the reaction with the
reactor vessels, tubings, and several process compartments,
utilization of highly concentrated MEA solutions for acid
gas sweetening is not feasible (13). The inferior CO2 loading
capacity, elevated solvent regeneration cost, formation of
toxic products due to the degradation in O2-rich environ-
ment (especially in case of flue gas), and reduced scrubber
efficiency due to amine decomposition and corrosion in
the equipments and pipings are few of the other limitations
related to MEA (12,14,15), which induces the quest for
alternative absorbents.
 KINETICS OF ABSORPTION OF CO2 IN EAE
As a substitute for MEA, other alkanolamines such as
DEA and MDEA were considerably examined for CO2
capture; however, the low CO2 loading capacity of DEA
and sluggish reactivity of MDEA with CO2 limits their
utilization. Sterically hindered amines are envisioned as
industrially appealing absorbents for CO2 capture as they
offer higher CO2 loading capacity and absorption rates
and lesser corrosion and energy requirement for regener-
ation in comparison with MEA (16–27). Among the several
sterically hindered amines, ethylaminoethanol (EAE) repre-
sents one of the possible candidates for the bulk removal of
CO2 from process gas streams. The major raw material for
the manufacturing of EAE is ethanol which, in turn, can be
prepared from agricultural products and=or residues; hence
EAE represents a promising absorbent as it can be prepared
from renewable resources (28). In EAE, the hydrogen
atom is replaced by an ethyl group which further enhances
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its basicity and hindrance around the nitrogen atom.
Additionally, it also possesses a number of advantages over
MEA such as less volatility, lower thermal energy require-
ment during CO2 stripping and higher pKa value.
Previously, few researchers have investigated the kinetics
of the reactive absorption of CO2 in an aqueous EAE sol-
ution. For instance, Mimura et al. (19) studied the kinetics
of the reaction of CO2 and aqueous EAE at 298 K and
reported second order rate constant comparable to that of
the CO2–aqueous MEA system. Vaidya and Kenig (28)
reported that the addition of small amounts of EAE to
N,N-diethylaminoethanol (DEAE) enhances the overall
CO2 absorption rate of DEAE. Li et al. (29) explored the
absorption kinetics by using stopped flow technique and
reported that both the zwitterion formation and deprotona-
tion played the key role during the reaction of CO2 with
EAE. Furthermore, these authors also observed that the
absorption of CO2 in an aqueous EAE was much rapid in
comparison with aqueous DEA. By using similar experi-
mental technique Bavbek and Alper (30) reported overall
second order reaction kinetics for the CO2–aqueous EAE
system. It is worth mentioning that most of these studies were
performed by using low amine concentrations (0.02 to
0.1 kmol=m3) and very scarce information is available on
the influence of reaction temperature on absorption kinetics.
In addition to the sterically hindered amines, the utiliza-
tion of mixed solvents, which consists of a blend of chemical
and physical absorbents, is considered beneficial towards
enhancement of the overall CO2 absorption capacity (31).
The mixed solvent owns elevated CO2 absorption capacity
which is not limited by the stoichiometry of the reactions,
especially in case of high CO2 partial pressure. Moreover,
high purity of the treated gas can be achieved with less recir-
culation of these solvents, hence, the required desorption
energy and power requisite for transferring these solvents
in the system is less. The physical solvent behaves like an
activator by increasing the solubility of CO2 in the mixed
2325
solvents. N-methyl-2-pyrrolidone (NMP) is one such
activator that could possibly improve the absorption of
CO2 in mixed solvents. NMP is readily available and it is
used extensively in the refinery and gas sweetening industry
(Lurgi’s Purisol process). Recently, Vaidya and Mahajani
(7) have reported merits of NMP as an attractive physical
solvent, while absorbing CO2 in an aqueous solution of
MEA and diethylene glycol (DEG). These authors also
observed a finite reaction of CO2 with NMP which was simi-
lar with the tertiary amine and in parallel with the CO2 –
MEA reaction. It is well believed by us that the CO2 absorp-
tion capacity of EAE can also be improved by adding NMP
as an activator. Therefore, an aqueous blend of EAE (0.5 to
2 kmol=m3) and NMP (5 kmol=m3) was derived, which
hereafter termed as ‘‘formulated solvent.’’ To the best of
our knowledge, there is no published data available towards
absorption of CO2 in this formulated solvent.
This paper reports the investigation of kinetics of the
absorption of CO2 into aqueous solutions of EAE and for-
mulated solvent. The physico-chemical properties such as
solvent density (q) and viscosity (l) and solubility (HCO2 )
and diffusivity (DCO2 ) of CO2 into these solvents were deter-
mined experimentally. In addition, a linear least-square
multiple regression analysis was performed to formulate
the mathematical expressions for the estimation of physico-
chemical properties. Influence of EAE concentration (0.5
to 2 kmol=m3) and reaction temperature (303 to 318 K) on
absorption kinetics was studied in detail and the activation
energies for the CO2–aqueous EAE and CO2–formulated
solvent systems were determined. Furthermore, the
reaction pathway for CO2–aqueous EAE system was thor-
oughly described using both zwitterion and termolecular
mechanisms.
REACTION MECHANISM
For fundamental understanding of the CO2–aqueous
EAE system, a detailed study of the reaction mechanism
of the CO2 and aqueous EAE is essential. The reaction of
CO2 with this sterically hindered amine can be described
either by a two-step zwitterion mechanism (32,33) or by a
single-step termolecular mechanism (34–36).
Zwitterion Mechanism
Several research articles related to the analysis of the
kinetics of the CO2–aqueous alkanolamines reactions
are available in the published literature (37–40). In case
of CO2–aqueous EAE system, EAE (denoted here as
R1R2NH, where R1 ¼ C2H5 and R2 ¼ CH2CH2OH) reacts
with CO2 through the formation of a zwitterion as an
intermediate:
k1
CO2 þ R1 R2 NH â R1 R2 Nþ HCOO ð1Þ
k1
 2326 R. R. BHOSALE AND V. V. MAHAJANI
Deprotonation of zwitterion takes place due to the reaction
with base B, which results into carbamate formation (33).
_
kB
R1 R2 Nþ HCOO þ B ! R1 R2 NCOO þ BHþ ð2Þ
Dissociation of aqueous EAE may also occur, which can be
represented by:
R1 R2 NH þ H2 O â R1 R2 Nþ H2 þ OH ð3Þ
The rate of absorption of CO2 in an aqueous EAE can
be derived by applying the steady state principle to the
intermediate zwitterion:
k1 ðCO2 ÞðEAEÞ
r¼ ð4Þ
1 þ _k1
kB ðBÞ
Downloaded by [University of Qatar] at 01:45 29 September 2013
_ k1
where k B ðBÞ represents deprotonation of the zwitterion by
base B (H2O, OH or EAE).
If the base B in the reaction represented by Eq. (4) is
EAE itself, carbamate formation can takes place as:
R1 R2 Nþ HCOO þ R1 R2 NH â R1 R2 NCOO
þ R1 R2 Nþ H2 ð5Þ
The overall reaction, which accounts for the carbamate
formation in an aqueous EAE solution, is given by the
sum of the reactions represented by Eqs. (1) and (5):
CO2 þ 2R1 R2 NH â R1 R2 NCOO þ R1 R2 Nþ H2 ð6Þ
Bicarbonate formation can takes place if the zwitterion
reacts more easily with H2O rather than EAE:
R1 R2 Nþ HCOO þ H2 O ! HCO þ
3 þ R1 R2 N H2 ð7Þ
The overall reaction, which accounts for bicarbonate
formation, is given by the sum of the reactions represented
by Eqs. (1) and (7)
CO2 þ R1 R2 NH þ H2 O â HCO þ
3 þ R1 R2 N H2 ð8Þ
In case of EAE, the hydrogen atom of the amino group is
replaced by a larger ethyl group in MEA, which makes
EAE a sterically hindered secondary alkanolamine. Sharma
(41,42) reported that the solidity of the carbamates formed
by the reaction of CO2 and amine can be influenced by the
steric effects. Hence, the carbamates may also readily undergo
hydrolysis to form bicarbonates and free amine molecules:
R1 R2 NCOO þ 
H2 O ! HCO
3 þ R1 R2 NH ð9Þ
As the aqueous EAE solutions exhibit moderate carbamate
stability, the number of bicarbonate ions will increase in
comparison with the carbamate ions due to the reaction
of the free EAE molecule with CO2. The rate of reaction
of CO2 and aqueous EAE represented by Eq. (4) does not
account for the CO2 reactions with OH and H2O and it
exhibits a fractional order between one and two with respect
to the amine concentration.
_
When k1 << k B ðBÞ, zwitterion formation becomes the
rate controlling step and Eq. (4) transformed into:
r ¼ k1 ðCO2 ÞðEAEÞ ð10Þ
Equation (10) suggests that the reaction is overall of the
second order (first order with respect
_ to both CO2 and EAE).
In contrast to this, when k1 >> k B ðBÞ, Eq. (4) turns into:
_
k1 k B ðBÞ
r¼ ðCO2 ÞðEAEÞ ð11Þ
Analogous to Eq. (4), the expression represented by Eq. (11)
indicates a fractional reaction order between one and
two with respect to EAE concentration. However, if the
involvement of the EAE towards zwitterion deprotonation
is substantial as compared with the other bases, the overall
reaction rate will be of the second order with respect to EAE
concentration.
Termolecular Mechanism
Recently, an overview of the termolecular kinetic model
for CO2–aqueous amine reactions has been discussed in
detail by Vaidya and Kenig (36). According to this mech-
anism, the aqueous amine reacts simultaneously with both
CO2 and the base molecules. Furthermore, this mechanism
also believes that the absorption of CO2 in an aqueous
amine proceeds via formation of a slackly bound encounter
complex as an intermediate. For instance, in case of CO2–
aqueous EAE system, the following reaction will occur:
CO2 þ R1 R2 NH þ B â ðEncounter complexÞ !
R1 R2 NCOO þ BHþ ð12Þ
During the course of this reaction, the major portion of the
encounter complex dissociate into CO2 and EAE, while its
small fraction reacts with a second molecule of EAE or
H2O to yield carbamates.
Equation (13) represents the forward reaction rate for
the termolecular mechanism where H2O, OH and EAE
are the dominating bases:


r ¼ kH2 O ðH2 OÞ þ kOH  ðOH  Þ

þ kEAE ðEAEÞ ðCO2 ÞðEAEÞ ¼ kobs ðCO2 Þ ð13Þ
 KINETICS OF ABSORPTION OF CO2 IN EAE
where

of 99.5% was obtained from Inox Air Products Ltd.,
kobs ¼ kH2 O ðH2 OÞ þ kOH  ðOH  Þ
 were also ordered from the same vendor. All the chemicals
þ kEAE ðEAEÞ ðEAEÞ ð14Þ
According to Eq. (13), H2O, OH, EAE, could strongly
affect the CO2–aqueous EAE reaction in parallel. This
equation is analogous with the limiting case of the
zwitterion mechanism represented by Eq. (11) and it can
also indicate fractional and higher order kinetics (34).
For CO2–aqueous EAE system, deprotonation proceeds
mainly via H2O and=or EAE. When H2O is the dominant
base, the reaction is represented by following expression:
_ 7.4  103 m2. The reactor was equipped with a flange made
Downloaded by [University of Qatar] at 01:45 29 September 2013
r ¼ kH2 O ðH2 OÞðCO2 ÞðEAEÞ ¼ k ðCO2 ÞðEAEÞ ð15Þ
_
k ¼ kH2 O ðH2 OÞ ð16Þ
Equations (15) and (16) shows that the CO2–aqueous EAE
reaction is of first order with respect to EAE concentration.
In contrast to this, when EAE is the most dominant
base, the reaction is of the second order with respect to
EAE and the corresponding rate expression will be:
r ¼ kEAE ðCO2 ÞðEAEÞ2 ¼ kobs ðCO2 Þ ð17Þ
kobs ¼ kEAE ðEAEÞ2 ð18Þ
When the contribution of H2O and EAE are comparable,
Eq. (13) can be re-written as:
r ¼ bkH2 O ðH2 OÞ þ kEAE ðEAEÞcðCO2 ÞðEAEÞ
¼ kobs ðCO2 Þ ð19Þ
where
kobs ¼ bkH2 O ðH2 OÞ þ kEAE ðEAEÞcðEAEÞ ð20Þ
It can be understood from Eqs (13) to (20), that the number
of fitting parameters is less in case of termolecular mech-
anism as compared to the zwitterion mechanism.
Furthermore, it is probable that the reaction mechanism
for the CO2–aqueous EAE system can be explained equally
well by both these mechanisms, whereas the kinetic data
can be fitted to either of these.
EXPERIMENTAL
Materials
MEA (99%) and EAE (99%) used in the experiments
were procured from Merck Co., India. NMP (98%) was
purchased from S.D. fine chemicals Ltd., Mumbai, India.
2327
CO2 from a gas cylinder with a minimum stated purity
Mumbai, India. Nitrous oxide (N2O) and nitrogen (N2)
were used without any pretreatment and all the solutions
were prepared using distilled water.
Experimental Set-Up
The experiments pertaining to the kinetics of the absorp-
tion of CO2 in aqueous EAE and formulated solvent were
carried out in a stirred cell reactor (diameter 97 mm, height
187 mm) as shown in Fig. 1. These experiments were carried
out by operating the reactor in a batch mode with flat
horizontal gas-liquid interface. The total volume of the reac-
tor was 1450 mL and the interfacial surface area was
up of SS 316 and fabricated by Sharad Autoclave Engineers,
Mumbai, India. A zero leak variable speed magnetic drive
(Premex Instru., Switzerland) was mounted on this flange.
Provisions were made for the gas and liquid inlet and outlet
ports and the entire stirred cell assembly was tested to
be leak-proof. A pressure transducer (Trans Instruments,
UK, 0–1 bar) was mounted on the flange and coupled with
a data acquisition system which enabled the measurement of
the fall in CO2 pressure during the absorption reaction. The
uncertainty in the pressure measurement was around
1 mbar. The reactor was stirred with two disc blade tur-
bine impellers (six blades, diameter 41 mm) mounted on
the same shaft, one each for the gas phase and the liquid
phase. The stirrer was driven by 1=20 HP geared motor with
a maximum stirring speed of 165 rpm. The speed of
agitation could be adjusted to the desired value with an
accuracy of 1 rpm. The impeller speed during kinetic mea-
surements was limited to a certain rpm so as to ensure that
the gas-liquid interface was undisturbed, which further
results into a geometrically simple and hence exactly known
FIG. 1. Experimental set-up for kinetics and solubility study. (Color
figure available online)
 2328 R. R. BHOSALE AND V. V. MAHAJANI

interfacial area. During the solubility measurements, a
Remi Motor with a maximum speed of agitation of
3000 rpm was used. The stirred cell assembly was immersed
in a constant temperature water bath to ensure isothermal
conditions and the temperature was controlled to within
0.1 C of the set point by means of a temperature indicator
and controller (TIC). A gas feed coil was immersed in the
water bath to enable the solute gas to attain the reactor
temperature prior to being charged inside the reactor.
Experimental Procedure
A series of experiments were performed to study the
kinetics of the absorption of CO2 in an aqueous EAE and
formulated solvent. The reactor was first charged with
250 mL of the absorbing solvent and the reactor contents
were allowed to attain the desired absorption temperature.
CO2 from the gas cylinder was then loaded inside the stirred
Downloaded by [University of Qatar] at 01:45 29 September 2013
CO2 and N2O in water and comparing the results with
the published data. The error between the HCO2 in water
determined during this investigation and the previously
reported HCO2 in water by Versteeg and van Swaalj (43)
was 3%, which is well within the acceptable limit. The
reproducibility of the results was also examined and the
error in all experimental measurements was observed to
be less than 2%.
RESULTS AND DISCUSSION
Estimation of Physico-Chemical Properties
To determine kinetic parameters, estimation of physico-
chemical properties such as density (q) and viscosity (l) of
the absorbing solvent and solubility (HCO2 ) and diffusivity
(DCO2 ) of CO2 in this solvent is necessary. Initially, q and
l of aqueous EAE and formulated solvent was measured
by using a specific gravity bottle and an Ostwald’s capillary

cell reactor at preferred partial pressure which was recorded viscometer. The effect of EAE concentration (0.5 to
with the help of the data acquisition system and this step was 2 kmol=m3) on q and l of these solvents was investigated
considered to be the starting point of the reaction. The reac- at 303 K and the results obtained are shown in Figs. 2a
tor content was then stirred at a pre-determined speed of and 3a. Similarly, the variation in the q and l of solvents
agitation while ensuring that the gas-liquid interface was at different temperatures (from 303 to 318 K) is presented
not disturbed. The decrease in the system pressure due to in Figs. 2b and 3b. From the obtained results, the q and l
reactive absorption of CO2 was monitored with the help of formulated solvent was observed to be always higher as
of pressure transducer and ‘‘PCO2 vs. t’’ data was recorded compared to that of the aqueous EAE at all experimental
for 30 seconds using the data acquisition system. The
‘‘PCO2 vs. t’’ data from t ¼ 5 seconds to t ¼ 25 seconds were
plotted and fitted to a third degree polynomial using the
least squares regression and the rate of absorption of CO2
was calculated with the help of the slope (dPCO2 =dt). This
measurement, which is thoroughly based on the fall in press-
ure of CO2, enables a simple and straight forward esti-
mation of the absorption rate. Further analysis of the
liquid phase is not required and the decrease in the system
pressure is the only factor considered for the evaluation of
kinetic parameters. The reproducibility of the results was
examined and the error in all experimental measurements
was observed to be less than 3%.
All the experiments associated with the measurement of
solubility of N2O in an aqueous EAE and formulated sol-
vent were conducted using the same experimental set-up
shown in Fig. 1. At first, 250 mL of the absorbing solvent
was loaded in the reactor and it allowed attaining the
desired reaction temperature. N2O at a chosen partial press-
ure was charged inside the reactor and the initial pressure
within the stirred cell was recorded with the help of pressure
transducer and the data acquisition system. The reactor
contents were then agitated at higher speeds of 1200 rpm
to ensure an attainment of the equilibrium. The equilibrium
was assumed to be reached when the digital pressure indi-
cator showed a constant reading of the system pressure
for 3 h. This was also confirmed by the ‘‘PCO2 vs. t’’ data FIG. 2. Variation in q of aqueous EAE and formulated solvent
recorded by the data acquisition system. This technique with respect to (a) EAE concentration at 303 K, and (b) temperature at
was validated by performing solubility measurements of (EAE)0 ¼ 2 kmol=m3.
 KINETICS OF ABSORPTION OF CO2 IN EAE 2329
 
2371
DN2 O ¼ ð5:07  106 Þ  exp ð26Þ
T

By using the results obtained via viscosity measurement, the

DCO2 and DN2 O in aqueous EAE and formulated solvent was
estimated using modified Stokes-Einstein correlation (1,12):
   
DN2 O  l0:8 a min e ¼ DN2 O  l0:8 H2 O ð27Þ
   
DCO2  l0:8 a min e
¼ DCO2  l0:8 H2 O ð28Þ

The influence of concentration of EAE and temperature on

DCO2 in these absorbing solvents was experimentally studied
and the results obtained are shown in Fig. 4. The findings
indicate that at all experimental conditions, DCO2 in aqueous
EAE was higher as compared to that of the formulated
Downloaded by [University of Qatar] at 01:45 29 September 2013

solvent. It was further observed that as the concentration

of EAE increases from 0.5 to 2 kmol=m3, the DCO2 in both
these solvents decreases by 24%. However, as the tempera-
ture increases from 303 to 318 K, the DCO2 also increases
by a factor of 1.6. The regression analyses of the results
obtained during this study yields into two different math-
ematical expressions for calculating DCO2 and are as follows:
FIG. 3. Variation in l of aqueous EAE and formulated solvent
with respect to (a) EAE concentration at 303 K, and (b) temperature at ðDCO2  1010 ÞEAE ¼ ð3:8345  1024 Þ
(EAE)0 ¼ 2 kmol=m3.
 ðEAEÞ0:1939
0  ðTÞ9:9074 ð29Þ
conditions. It was also realized that due to the increase in
EAE concentration, q of both these solvents was decreased,
whereas, l was increased. Furthermore, from Figs. 2b and
3b it was understood that q and l of both these solvents
was decreased due to the increase in the temperature. By
using the experimental outputs, mathematical correlations
were derived for the estimation of q and l of aqueous
EAE and formulated solvent using linear least-squares
multiple regression analysis and are shown below:

qEAE ¼ ð4752:98Þ  ðEAEÞ0:0111

0  ðTÞ0:2782 ð21Þ

qFS ¼ ð4107:23Þ  ðEAEÞ0:0137

0  ðTÞ0:2478 ð22Þ

lEAE ¼ ð4:0248  1025 Þ  ðEAEÞ0:2447

0  ðTÞ10:2738 ð23Þ

lFS ¼ ð1:3624  1027 Þ  ðEAEÞ0:2661

0  ðTÞ10:7685 ð24Þ

The DCO2 in aqueous EAE and formulated solvent was

determined using the N2O analogy. The DCO2 and DN2 O
in water was estimated using the following expressions
reported by Versteeg and van Swaalj (43).
  FIG. 4. Variation in DCO2 in aqueous EAE and formulated solvent
2119
DCO2 ¼ ð2:35  106 Þ  exp ð25Þ with respect to (a) EAE concentration at 303 K, and (b) temperature at
T (EAE)0 ¼ 2 kmol=m3.
 2330 R. R. BHOSALE AND V. V. MAHAJANI

ðDCO2  1010 ÞFS ¼ ð5:1980  1021 Þ

 ðEAEÞ0:2124
0  ðTÞ8:5472 ð30Þ

The N2O analogy was also used for the estimation of

HCO2 in aqueous EAE and formulated solvent (43). First,
the HN2 O in these solvents were assessed by performing
the solubility experiments in the stirred cell reactor
(Fig. 1). The initial and final readings of pressure of N2O
within the reactor were recorded using the data acquisition
system and no alteration in the total pressure of the stirred
cell over an extended period is deemed as the attainment
of the equilibrium. Further, the HCO2 can be computed
according to the following correlation:

HCO2 ¼ c  HN2 O ð31Þ

Downloaded by [University of Qatar] at 01:45 29 September 2013

The solubility measurements were validated by compar-

ing the experimentally obtained HN2 O and HCO2 in water
at 303 K with the published literature. To begin with, the
HCO2 in water was estimated experimentally at 303 K
(2.80  104 kmol=m3 kPa) and it matches very well with
the HCO2 in water reported by Versteeg and van Swaalj
(43). Likewise, the experiments were performed to deter-
mine HN2 O in aqueous EAE and formulated solvent and
via N2O analogy, the HCO2 was inferred. The HCO2 in aque-
ous EAE, where (EAE)0 ¼ 2 kmol=m3, was evaluated to be
2.81  104 kmol=m3 kPa at 303 K. Similarly, the HCO2 in
formulated solvent was also determined (4.45  104
kmol=m3 kPa at 303 K) and observed to be considerably
higher in comparison with the aqueous EAE. This enhance-
ment in the HCO2 is because of the addition of NMP to
aqueous EAE and therefore, formulated solvent seems to
be more appealing towards absorption of CO2 compared
to aqueous EAE. Figures 5a and 5b shows the alteration
in HCO2 in aqueous EAE and formulated solvent with
respect to concentration of EAE and temperature. The
results presented indicate that the increase in EAE con-
centration and temperature results into decrease in the
HCO2 in both solvents. Furthermore, Eqs. (32) and (33)
represents the mathematical expressions derived via mul-
tiple regression analysis for computing the HCO2 in aqueous
EAE and formulated solvent.
ðHCO2  104 ÞEAE ¼ ð8:759  1021 Þ
 ðEAEÞ0:0367
0  ðTÞ8:6548 ð32Þ
FIG. 5. Variation in HCO2 in aqueous EAE and formulated solvent
with respect to (a) EAE concentration at 303 K, and (b) temperature at
(EAE)0 ¼ 2 kmol=m3.
Estimation of KL
In case of physical absorption within a stirred cell
reactor, a mass balance for the solute in both the gas and
liquid phase results into the following expression:


PðtÞ  Pfinal m0 VL þ VG
In ¼ kL Yt ð34Þ
Pinitial  Pfinal VL VG
To determine the liquid side mass transfer coefficient (kL),
the physical absorption of CO2 in water at 303 K was
studied and the fall in pressure was recorded via data
acquisition system. To estimate the value of kL, ‘‘ln [(P(t)–
Pfinal) = (Pinitial – Pfinal)] vs. t’’ was plotted and with the help
of the slope which equals to [(m’ VL) þ VG) = (VL VG)] kL
A and other applicable parameters such as m0 ¼ 0.549 mol=
mol, VG ¼ 1200 mL, VL ¼ 250 mL, Y ¼ 7.4  103 m2, the
value of kL was calculated. This value was further corrected
for the aqueous amine solution p using the surface renewal
theory correlation (kL a D) and the corrected kL was
observed to be 2.018  104 m=s.

Reaction Kinetics
4
ðHCO2  10 ÞFS ¼ ð1:093  10 Þ 23 During CO2 absorption experiments, when concen-
tration of CO2 in bulk liquid is negligible and the resistance
 ðEAEÞ0:0998
0  ðTÞ9:011 ð33Þ to mass transfer is entirely in the liquid phase, following
 KINETICS OF ABSORPTION OF CO2 IN EAE
relation controls the absorption kinetics:
RCO2 ¼ kL ðCO2 ÞE
where E corresponds to the enhancement factor, which
describes the enhancing effect of chemical reactions on
mass transport. In order to determine the kinetic para-
meters, it is essential that the CO2–amine system should
confirm the fast reaction regime without depletion of the
amine at the gas-liquid interface and where E equals to
Hatta number (Ha) (44,45). The necessary and sufficient
conditions for the fast reaction regime are:
10 < Ha < ðEi  1Þ
For an irreversible reaction of order m with respect to CO2
concentration and order n with respect to EAE concen-
tration, the Hatta number can be expressed as:
Downloaded by [University of Qatar] at 01:45 29 September 2013
h i1=2
m1
2
ðmþ1Þ DCO2 km;n ðCO2 Þ ðEAEÞn0
Ha ¼
kL
where km,n represents the reaction rate constant for CO2 –
amine system. Furthermore, the enhancement factor for an
instantaneous reaction is:
ðEAEÞ0 DEAE
Ei ¼ 1 þ
zðCO2 ÞDCO2
It is noteworthy that Eq. (38) is valid only if the film theory
is used.
For the fast reaction regime, as E equals to Ha, the rate
of absorption of CO2 in aqueous EAE can be written as:
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

ffi
2
RCO2 ¼ DCO2 km;n ðCO2 Þmþ1 ðEAEÞn0
ðm þ 1Þ
There is an undisputed agreement among all the investiga-
tors that the reaction order with respect to CO2 is unity
(38,39). Therefore,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ffi
RCO2 ¼ ðCO2 Þ DCO2 k1;n ðEAEÞn0
Equation (40) can be re-expressed as:
( )
 n belongs to the fast reaction regime. A plot of log
RCO2 1 n o
log ¼ logðk 1;n Þ þ logðEAEÞ0
ðCO2 ÞðDCO2 Þ1=2 2 2
By examining the change in RCO2 with respect to concen-
tration of EAE, a plot of logfRCO2 =½ðCO2 Þ ðDCO2 Þ1=2 g vs
log(EAE)0 gives the estimation of k1,n and n. Previously,
several researchers used such plots for the investigation
of CO2 absorption kinetics (1,12,25).
2331
CO2–Aqueous EAE System
The kinetics of the absorption of CO2 in an aqueous EAE
ð35Þ
was investigated by using a stirred cell reactor shown in
Fig. 1. At first, the experimental set-up and the data acqui-
sition system was validated using a well known CO2–aque-
ous MEA system. The solubility of CO2 in an aqueous
MEA (where, (MEA)0 ¼ 1 and 2 kmol=m3) was estimated
at 303 K and observed to be 2.85  104 and 2.72  104
kmol=m3 kPa, which agrees very well with the published
literature. The CO2 absorption experiments were carried
out according to the procedure reported in the experimental
section (at 303 K with a speed of agitation equal to 80 rpm).
ð36Þ The fall in pressure of CO2 due to the absorption in aqueous
MEA was recorded with the help of data acquisition system
and the rate of reactive absorption was determined. From
this, the rate constant for the CO2–aqueous MEA system
was calculated and observed to be 7356 m3=kmol s, which
agreed well with the rate constants reported by Vaidya
and Mahajani (7) and Hikitia et al. (46).
ð37Þ After validating the experimental technique, the kinetics
of CO2–aqueous EAE system was investigated over the
ranges of EAE concentrations (0.5–2 kmol=m3), and tem-
peratures (303–318 K). In the fast reaction regime, the
absorption rate is independent of the liquid-side mass trans-
fer coefficient and therefore it should not be influenced by
the speed of agitation. We experimentally studied the effect
ð38Þ
of speed of agitation on rate of CO2 absorption in aqueous
EAE by varying the speed from 60 to 100 rpm. The results
obtained indicated negligible changes in the absorption rate
due to the variation in the agitation speed, which allows us
to conclude that the CO2–aqueous EAE system belongs to
the fast reaction regime. All further experiments related to
the absorption of CO2 in aqueous EAE were performed at
ð39Þ a speed of 80 rpm.
Influence of EAE concentration on rate of absorption of
CO2 in aqueous EAE at 303 K was evaluated experimen-
tally and the results obtained are listed in Table 1. From
these results, an enhancement in the rate absorption of
CO2 was observed with the increase in concentration of
EAE. The parameters, Ha and Ei, were estimated by using
ð40Þ DCO2 and HCO2 in aqueous EAE (Table 1) and the con-
ditions given in Eq. (36) were observed to be satisfied. This
further confirms that the CO2–aqueous EAE system
fRCO2 =½ðCO2 Þ ðDCO2 Þ1=2 g vs log (EAE)0 at 303 K was
drawn (Fig. 6) and the slope of this plot equals to 0.5,
ð41Þ thereby suggesting that the order of the reaction with
respect to EAE concentration is equal to one (n ¼ 1). As
the CO2–aqueous EAE system exhibits complex kinetic
behavior, there is always a conflict between the researchers
about the order of the reaction with respect to EAE concen-
tration (19,28–30). However, by assuming the zwitterion
formation as the rate controlling step, the observations of
 2332 R. R. BHOSALE AND V. V. MAHAJANI

TABLE 1
Equilibrium and kinetic characteristics of CO2–aqueous EAE and CO2–formulated solvent systems
at 303 K (Agitation apeed ¼ 80 rpm, PCO2 ¼ 4:0 kPa)
CO2–aqueous EAE system
(EAE)0 HCO2  104 DCO2  1010 RCO2  106 kEAE
(kmol=m3) (kmol=m3 kPa) (m2=s) (kmol=m2 s) (m3=kmol s) Ha Ei
0.5 2.99 16.51 3.22 8786 133 210
1.0 2.94 15.32 4.31 8768 181 426
1.5 2.89 13.83 4.94 8803 211 649
2.0 2.81 13.15 5.41 8808 238 890

CO2–formulated solvent system

(EAE)0 HCO2  104 DCO2  1010 RCO2  106 kapp
(kmol=m3) (kmol=m3 kPa) (m2=s) (kmol=m2 s) (m3=kmol s) Ha Ei
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0.5 5.11 9.76 4.15 10684 113 122

1.0 4.77 8.42 5.32 9734 141 262
1.5 4.58 7.73 6.08 9418 163 409
2.0 4.45 7.27 6.48 9259 182 562

a first-order dependence of the reaction rates on EAE
concentration is in well agreement with the findings
reported by Vaidya and Kenig (47) and Mimura et al.
(19). Similar observations were realized at different reaction
temperatures of 308 to 318 K.
The intercept of the plot shown in Fig. 6 indicates a
second order rate constant for the CO2–aqueous EAE sys-
tem, which equals to 8770 m3=kmol s. From the previously
reported kinetics studies, the harmony between the rate con-
stants estimated for the CO2–EAE system is inconsistent.
For instance, Li et al. (29) reported the rate constant equal
to 8000 and 9440 m3=kmol s at 298 and 303 K, whereas
Mimura et al. (19) and Bavbek and Alpler (30) observed
the rate constant values as 4170 and 26200 m3=kmol s at
298 and 303 K, respectively. It has to be noted that the
experimental technique used by Mimura et al. (19) (stirred
cell reactor) was different than Li et al. (29) and Bavbek
and Alpler (30) (stopped-flow method). It is worthy of note
that our value of the rate constant for the reaction of CO2
with aqueous EAE is comparable to that of the reaction
with aqueous MEA and also matches very well with the
one reported by Vaidya and Kenig (47).
The effect of temperature on rate of absorption of CO2
in an aqueous EAE was also examined and the results
obtained are reported in Table 2. From the results listed,
it was observed that the absorption rate and kEAE was
increased by 44% and 77%, respectively, as the temperature
increased from 303 to 318 K. The temperature dependency
of the kEAE was further studied by following the Arrhenius-
type expression:
 
EA
kEAE ¼ A exp ð42Þ
RT
A plot of ln kEAE vs. 1=T is shown in Fig. 7a and from the
slope of this plot, the activation energy for CO2–aqueous
EAE system was estimated to be 80.2 kJ=mol. Further-
more, Eq. (42) can be rewritten as:
 
9645
kEAE ¼ 6:013  1017 exp ð43Þ
T

To compare the rate constants of the CO2–aqueous EAE

and CO2–aqueous MEA systems, kMEA is calculated at dif-
ferent temperatures (303 to 318 K) using the correlation
reported by Hikita et al. (46) (Table 2). It was realized that
at all temperatures, kEAE is considerably higher in com-
parison with kMEA. For instance, at 318 K, kEAE is 2.5 times
FIG. 6. A plot of log fRCO2 =½ðCO2 Þ ðDCO2 Þ1=2 g vs. log (EAE)0 at 303 K. higher as compared with kMEA. Typical CO2–amine
 KINETICS OF ABSORPTION OF CO2 IN EAE 2333

TABLE 2
Effect of temperature on equilibrium and kinetic characteristics of CO2–aqueous EAE and
CO2–formulated solvent systems at 80 rpm [(EAE)0 ¼ 2 kmol=m3, PCO2 ¼ 4:0 kPa]
CO2–aqueous EAE system
HCO2  104 DCO2  1010 RCO2  106 kEAE kMEA (46)
T (K) (kmol=m3 kPa) (m2=s) (kmol=m2 s) (m3=kmol s) (m3=kmol s)
303 2.81 13.13 5.40 8808 7722
308 2.50 14.17 6.65 15604 10069
313 2.17 17.49 8.28 26013 13019
318 1.86 21.50 9.68 39367 16699

CO2–formulated solvent system

HCO2  104 DCO2  1010 RCO2  106 kapp kNMP
T (K) (kmol=m3 kPa) (m2=s) (kmol=m2 s) (m3=kmol s) (m3=kmol s)
Downloaded by [University of Qatar] at 01:45 29 September 2013

303 4.45 7.27 6.53 9261 190

308 3.84 8.36 8.17 16944 536
313 3.32 9.59 10.03 29668 1462
318 2.88 10.99 11.97 49039 3869

absorbers are operated in the temperature range of 323 If the two-step zwitterion mechanism is considered
to 343 K; therefore, the higher value of kEAE as compared appropriate for expressing CO2–aqueous EAE reaction
with the kMEA at elevated temperatures is advantageous kinetics, Eq. (4) can be re-expressed as:
and makes the CO2–aqueous EAE system a promising
candidate for commercial application. k1 ðCO2 ÞðEAEÞ
r¼ k1
ð44Þ
1 þ _ _ _
k EAE ðEAEÞþk H2 O ðH2 OÞþk OH  ðOH  Þ

and the observed reaction rate constant, kobs, could be

defined as:
k1 ðEAEÞ
kobs ¼ k1
ð45Þ
1 þ _ _ _
k EAE ðEAEÞþk H2 O ðH2 OÞþk OH  ðOH  Þ

The results obtained in this investigation indicate that the

dependency of the reaction rate on EAE concentration is
of the first order. In this circumstance, it is apparent that
the zwitterion
_ formation is the rate determining step and
k1 << k B ðBÞ, which transforms Eq. (45) into:
kobs ¼ k1 ðEAEÞ ð46Þ

The kobs was calculated over the ranges of EAE concentra-

FIG. 7. Arrhenius plot for (a) CO2–aqueous EAE system and (b) CO2–
formulated solvent system.
tions (0.5 to 2 kmol m3) and temperatures (303 to 318 K)
and the experimental findings are presented in Figs. 8a
and 8b. These results show increase in kobs due the increase
in EAE concentration and temperature.
Instead of zwitterion mechanism, let us assume that the
termolecular model is the suitable one towards explaining
the kinetics of CO2–aqueous EAE system. As the order
of the reaction with respect to EAE concentration is equal
to one, it would be obvious that H2O is the dominant base
 2334 R. R. BHOSALE AND V. V. MAHAJANI
Downloaded by [University of Qatar] at 01:45 29 September 2013
FIG. 8. Plots of kobs vs. a) (EAE)0 at 303 K and b) T at (EAE)0 ¼
2 kmol=m3.
and the reaction rate can be expressed with the help of
Eqs. (15) and (16). Furthermore, using these equations kobs
can be formulated as:
_ concentration was examined and the results obtained are
kobs ¼ k ðEAEÞ ð47Þ
Equations (46) and (47) agrees reasonably well with each
other and hence, the CO2–aqueous EAE system can be signi-
fied evenly by both zwitterion and termolecular mechanisms.
CO2–Formulated Solvent System
Similar to CO2–aqueous EAE system, kinetics of the
absorption of CO2 in formulated solvent was also investi-
gated by using the stirred cell reactor shown in Fig. 1.
The role of NMP towards CO2 absorption in a mixed sol-
vent comprises of MEA þ NMP þ DEG was recently stud-
ied by Vaidya and Mahajani (7). These authors observed
some sort of chemical reaction between CO2 and NMP with
kNMP equal to 190 and 536 m3=kmol s at 303 and 308 K,
respectively. To confirm these outcomes, two experiments
were performed to examine the reactive absorption of
CO2 in an aqueous solution containing 50 wt% NMP at
313 and 318 K. The experimental findings indicate that
the CO2 absorption rates were higher in comparison with
the rates expected solely on the basis of physical absorption,
thereby suggesting that the aqueous NMP is active towards
absorbing CO2 via both physical and chemical absorption.
The kNMP values were calculated and observed to be equal
to 1462 and 3869 m3=kmol s at 313 and 318 K. As per the
results obtained for CO2–aqueous NMP system, the overall
reaction between CO2 and formulated solvent can be con-
sidered as the reaction between CO2 and EAE in parallel
with the reaction of CO2 with NMP. Therefore, the specific
rate of absorption of CO2 in formulated solvent can be
expressed as:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
RCO2 ¼ ðCO2 Þ DCO2 ½kEAE ðEAEÞ þ kNMP ðNMPÞ ð48Þ
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

RCO2 ¼ ðCO2 Þ DCO2 kapp ðEAEÞ ð49Þ
where,
kNMP ðNMPÞ
kapp ¼ kEAE þ ð50Þ
ðEAEÞ
After investigating the CO2–aqueous NMP system, the
absorption of CO2 in formulated solvent was studied over
the range of various EAE concentrations (0.5–2 kmol=m3)
and temperatures (303–318 K). It was observed that the
agitation speed in the range of 60 to 100 rpm does not yield
any change in the CO2 absorption rates. These findings
suggest that the CO2–formulated solvent system also
belongs to the fast reaction regime and therefore, all
further experiments were conducted at a speed of 80 rpm.
The variation in the rate of absorption of CO2 in formu-
lated solvent at 303 K with respect to the change in EAE
listed in Table 1. With the increase in the concentration
from 0.5 to 2 kmol=m3, the absorption rate was increased
by a factor of 1.56. The parameters, Ha and Ei for the
CO2–formulated solvent system were estimated and also
reported in Table 1. These calculated parameters satisfy
the conditions given by Eq. (36), which provide added con-
firmation that this system also belongs to the fast reaction
regime.
The impact of temperature on the rate of absorption was
similarly studied and the results obtained (Table 2) indicate
increase in the rate of absorption and kapp with tempera-
ture. The temperature dependency of kapp was further
investigated by using the Arrhenius-type expression and
the activation energy for CO2–formulated solvent system
was estimated to be 88.95 kJ=mol (Fig. 7b). The results also
reveal that at all experimental conditions, the rate of
absorption of CO2 in formulated solvent is approximately
20% more as compared to that of the aqueous EAE
(Fig. 9a). Likewise, kapp was also observed to be higher
in comparison with kEAE (Fig. 9b).
The kinetic expressions for the specific rate of absorption
of the CO2–aqueous EAE [Eq. (40)] and CO2-formulated
 KINETICS OF ABSORPTION OF CO2 IN EAE
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FIG. 9. Plots of (a) RCO2 vs. (EAE)0 at 303 K and (b) Rate constant vs. T
at (EAE)0 ¼ 2 kmol=m3.
solvent system [Eq. (49)] can be re-written as:
PCO2 1
¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ð51Þ
RCO2 H DCO2 kEAE ðEAEÞ0
CO2
PCO2 1 EAE and formulated solvent was investigated at various
¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 ð52Þ
RCO2 H DCO2 kapp ðEAEÞ0
CO2
By using Eqs. (51) and (52), plots of ðPCO2 =RCO2 Þ vs.
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
1= ðEAEÞ0 were drawn for both CO2–aqueous EAE and
CO2–formulated solvent systems at 303 K, respectively.
The plot yields in two straight lines passing through the
origin and would enable calculation of the combined para-
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
meters HCO2 ðDCO2 kEAE Þ and HCO2 DCO2 kapp . From
the slope of the straight line drawn for CO2–aqueous
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
EAE system, the value of HCO2 ðDCO2 kEAE Þ was found
to be 1.077  106 kmol1=2=m1=2 s kPa. Analogous to this,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
the value of HCO2 DCO2 kapp was observed to be equal
to 1.349  106 kmol1=2=m1=2 s kPa. From these estimated
values the reaction rates for the absorption of CO2 in aque-
ous EAE and formulated solvent can be predicted using the
following correlations:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
RCO2 ¼ PCO2  HCO2 DCO2 ½kEAE ðEAEÞ ð53Þ
2335
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi

RCO2 ¼ PCO2  HCO2 DCO2 kapp ðEAEÞ ð54Þ
The experimental and predicted rates were compared and
observed to be in well agreement with each other. As
mentioned by Vaidya and Kenig (47), in industrial CO2
absorption packed columns, a fast reaction regime met in
the major portion of this apparatus and hence, the column
design will therefore directly depend on the combined
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
parameter, for instance, HCO2 ðDCO2 kEAE Þ, which thereby
suggest that the emphasis should be given to the accurate
determination of this lumped parameter.
The end result of this investigation indicate that the
aqueous EAE and formulated solvent are promising
towards bulk removal of CO2 and therefore can be con-
sidered as the substitutes for aqueous MEA in industrial
CO2 absorption packed columns. However, we strongly
believe that, in addition to the CO2 absorption rates, all
kinds of other properties such as loading capacity, heat of
reclamation, resistance to thermal and chemical degra-
dation, corrosion to carbon steel, solvent recovery from
degraded solution, effluent treatment of the degraded
material, etc., must be taken into account for the best choice
of the effective CO2 absorbents for commercial application.
In this prospective, efforts are underway to study and
compare the degradation of various aqueous solutions of
alkanolamines and their blends in presence of O2 and CO2
and the effect of addition of hydroxyl radical scavengers
towards solvent stability.
CONCLUSIONS
The kinetics of the reactive absorption of CO2 in aqueous
experimental conditions using a stirred cell reactor. The
reaction of CO2 with aqueous EAE was represented equally
well by both the zwitterion and termolecular mechanisms.
The HCO2 and DCO2 in aqueous EAE and formulated sol-
vent was determined using N2O analogy. The value of kL
was also estimated and found to be in line with those typical
for stirred cell reactor. The effect of EAE concentration on
the rate of absorption of CO2 in both these solvents was
examined at 303 K and the obtained results indicate
increase in the absorption rate with the increase in EAE
concentration. Furthermore, the reaction of CO2 with aque-
ous EAE was observed to be of overall second order, that is,
first orders with respect to both CO2 and EAE concentra-
tions. At all experimental conditions, the rate of absorption
of CO2 was observed to be always higher in formulated
solvents as compared to that of the aqueous EAE solution.
Likewise, the kinetic rate constant kapp was observed to be

1.25 times higher in comparison with kEAE during all
kinetic measurements. Furthermore, the temperature
dependency of kEAE and kapp indicate activation energy
equal to 80.2 and 88.95 kJ=mol for CO2–aqueous EAE
 2336 R. R. BHOSALE AND V. V. MAHAJANI

and CO2–formulated solvent system, respectively. This (NMP) concentration of NMP, kmol=m3
investigation further highlights the importance of the n order of the reaction with respect to EAE
aqueous blend of chemical and physical solvents towards PCO2 partial pressure of CO2 in bulk gas phase, kPa
gas purification application. r rate of reaction
RCO2 specific rate of absorption of CO2, kmol=m2 s
ACKNOWLEDGEMENTS R1R2NH ethylaminoethanol
Dr. Rahul R. Bhosale wishes to acknowledge with T temperature, K
thanks the University Grants Commission, Government t time, s
of India, New Delhi for the financial assistance provided VL volume of liquid phase, mL
during the course of this investigation. VG volume of gas phase, mL
Y slope of the curve used for the estimation of kL
NOMENCLATURE Z stoichiometric coefficient
A interfacial surface area, m2
B base assisting in zwitterion deprotonation
(B) concentration of the base B in bulk liquid, ABBREVIATIONS
kmol=m3 DEA diethanolamine
(CO2) concentration of carbon dioxide, kmol=m3 DEG diethyleneglycol
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DEAE diffusivity of EAE in liquid phase, m2=s DEAE diethylaminoethanol

DCO2 diffusivity of CO2 in liquid phase, m2=s DGA diglycolamine
DN2 O diffusivity of N2O in liquid phase, m2=s DIPA diisopropanolamine
E enhancement factor due to chemical reaction EAE ethylaminoethanol
Ei enhancement factor for instantaneous chemical FS formulated solvent
reaction MEA monoethanolamine
EA activation energy, kJ=mol MDEA methyldiethanolamine
(EAE) concentration of EAE, kmol=m3 NMP N-methyl-2-pyrrolidone
(EAE)0 initial concentration of EAE, kmol=m3 N 2O nitrous oxide
HCO2 Henry’s law constant (for CO2), kmol=m3 kPa Greek Symbols
HN2 O Henry’s law constant (for N2O), kmol=m3 kPa
l viscosity, m Pas
Ha Hatta number
q density, kg=m3
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