Kinetics of Carbon Dioxide Removal by Ethylenediamine and

Diethylenetriamine in Aqueous Solutions

Anuj P. Salvi,1 Prakash D. Vaidya1 and Eugeny Y. Kenig2*

1. Department of Chemical Engineering, Institute of Chemical Technology, Nathalal Parekh Marg, Matunga, Mumbai 400019, India
2. Faculty of Mechanical Engineering, Chair of Fluid Process Engineering, University of Paderborn, D‐33098 Paderborn, Germany

The polyethyleneamines ethylenediamine (EDA) and diethylenetriamine (DETA) can be considered as promising CO2‐capturing solvents, producible
from renewable resources. In the present work, kinetics of CO2 reactions with EDA and DETA was investigated by using a stirred‐cell reactor.
The molarities of EDA and DETA in the aqueous solutions were varied from 0.1 to 0.4 and 0.1 to 0.5, correspondingly. The observed pseudo‐first‐order
reaction rate constants were measured at 303, 308, and 313 K. The zwitterion and termolecular mechanisms were used to correlate the rate
constants. DETA was found to have higher reactivity with CO2 than EDA. Second‐order rate constants for the reactions with EDA and DETA were equal
to 15770 and 21480 m3/(kmol s) at 303 K. The activation energy values for EDA and DETA were found to be 57.7 and 30.2 kJ/mol, respectively.

Keywords: ethylenediamine, diethylenetriamine, carbon dioxide, absorption, kinetics

INTRODUCTION et al.[8] used different indirect methods for studying reaction

kinetics (e.g., competitive reaction, liquid jet and rapid mixing).

C
arbon dioxide (CO2) capture from gaseous streams currently
represents an essential step in the performance of electric
power stations, petroleum refineries, chemical fertilizer
plants, coal gasifiers, cement factories, and the steel industry. A
wide variety of chemical solvents (e.g., alkanolamines, carbonate‐
bicarbonate buffers, and amino acid salts) can be used to absorb
CO2. Among alkanolamines, the primary amines, monoethanol-
amine (MEA) and diglycolamine (DGA), the secondary amines,
diethanolamine (DEA) and diisopropanolamine (DIPA), and the
tertiary amines, triethanolamine (TEA) and N‐methyldiethanol-
amine (MDEA), are industrially important.[1]
Due to the presence of two or more primary or secondary amino
groups in their structure, solvents containing polyamines have a
good potential for CO2 capture. Their reactivity with CO2 and
equilibrium capacity is expected to be higher than those of
conventional amine‐based solvents. In our previous study, the
CO2 reactions with two diamines, N‐(2‐aminoethyl)ethanolamine
(AEEA) and piperazine (PZ), were investigated.[2] The present
work was undertaken to examine the kinetic characteristics of two
polyethyleneamines, viz., ethane‐1,2‐diamine (or ethylenedi-
amine, EDA) and N‐(2‐aminoethyl)ethane‐1,2‐diamine (or dieth-
ylenetriamine, DETA).
EDA is industrially manufactured by the reaction of ammonia
with MEA or ethylenedichloride (EDC). MEA is made up from
ethylene oxide (obtained from the oxidation of ethylene which, in
turn, can be produced by dehydration of ethanol), whereas EDC is
prepared by the chlorination of ethylene. DETA is a by‐product
of EDA production from EDC. Ethanol, which is the major raw
material for the manufacture of EDA and DETA, can be prepared
from agricultural products or residues. Thus, EDA and DETA
represent promising absorbents, as they can be prepared from
renewable resources. Moreover, according to Zhou et al.,[3]
Mangalapally and Hasse,[4] and von Harbou et al.,[5] solvents
with EDA as the CO2‐capturing component are more efficient for
flue gas cleaning than MEA.
Literature data on the reaction between CO2 and EDA is
summarized in Table 1.[6–12] It is worthy of note that, in earlier
works, Jensen and Christensen,[6] Weiland and Trass,[7] and Hikita
This can explain why the agreement between the second‐order
reaction rate constants (k2) estimated in these works is poor. Later,
Sada et al.[9] investigated reaction kinetics in non‐aqueous solvents
using a stirred‐cell reactor. More recently, Li et al.,[10] Rayer
et al.,[11] and Kadiwala et al.[12] used the direct stopped‐flow
technique. Kadiwala et al.[12] investigated kinetics in two polar
solvents, methanol and ethanol. The k2 values reported by Li
et al.[10] are in line with those of Hikita et al.[8] (see Table 1). As
evident from these two investigations, EDA reacts faster with
CO2 than MEA; however, there exists no kinetic data at EDA
concentrations higher than 0.1 M.
DETA has three amine functionalities (viz., two primary and one
secondary amine group), and it would be interesting to investigate
its reactivity with CO2. Up until now, information on the chemical
kinetics of the CO2‐DETA system available in the literature was
scarce. A recent work by Hartono et al.[13] using a string of discs
contactor is the only investigation on the kinetic characteristics. It
follows from their work that DETA has higher reactivity with CO2
than AEEA, EDA, and MEA.
In the present work, kinetics of CO2 reactions with EDA and
DETA was investigated by using a stirred‐cell reactor in the 303–
313 K temperature range. The molarities of EDA and DETA in the
aqueous solutions were varied from 0.1 to 0.4 and 0.1 to 0.5,
correspondingly. The zwitterion and termolecular mechanisms
were used to describe the reaction pathway. The values of the
reaction order, rate constant, and activation energy were deter-
mined. The outcome of this investigation will facilitate the design
and operation of gas treating plants using polyethyleneamines for
CO2 capture.
*Author to whom correspondence may be addressed.
E‐mail address: eugeny.kenig@upb.de
Can. J. Chem. Eng. 92:2021–2028, 2014
© 2014 Canadian Society for Chemical Engineering
DOI 10.1002/cjce.22064
Published online 9 October 2014 in Wiley Online Library
(wileyonlinelibrary.com).

VOLUME 92, DECEMBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 2021
 Table 1. Literature data on the reaction between CO2 and EDA

Temp. K (EDA) kmol/m3 Experimental Technique Solvent k2 (m3/(kmol s)) at T ¼ 303 K Reference

303 — Competitive reaction Water 22300 Jensen and Christensen[6]

303 — Liquid Jet Water 138000 Weiland and Trass[7]
278–313 0.0074–0.0284 Rapid mixing Water 17880 Hikita et al.[8]
303 — Stirred‐cell Methanol 3680 Sada et al.[9]
Ethanol 2280
298–313 0.026–0.067 Stopped Flow Water 17700 Li et al.[10]
298–313 0.02–0.10 Stopped Flow Water — Rayer et al.[11]
293–313 0.02–0.12 Stopped Flow Methanol 3960 Kadiwala et al.[12]
Ethanol 4360
303–313 0.1–0.5 Stirred‐cell Water 15770 This work

THEORY CO2 in aqueous amine solutions can be expressed in general

as
In an aqueous amine solution, CO2 may simultaneously react with
an amine (here denoted as AmH), OH
and H2O. For an amine with k2 ðCO2 ÞðAmHÞ
a stable carbamate, the following reaction takes place: rAmH ¼ ; ð6Þ
k
1
1þ
^ B ðBÞ
k
CO2 þ 2AmH $ AmCOO
þ AmHþ
2: ð1Þ
where the kinetic constant k ^ B ðBÞ represents deprotonation of the
If the carbamate is unstable, it may readily undergo hydrolysis zwitterion by any base, such as H2O, OH
or AmH, or by a
forming bicarbonates and releasing free amine molecules as combination of bases. The contributions of the CO2 reactions with
follows: OH
and H2O to the overall rate are assumed to be negligible. The
reaction rate represented by Equation (6) exhibits a fractional order
AmCOO
þ H2 O $ AmH þ HCO

3: ð2Þ between one and two with respect to the amine concentration.
Equation (6) can be written as
If the tendency of the amine to form carbamates is low, the
following reaction is predominant: rAmH ¼ kobs ðCO2 Þ; ð7Þ

CO2 þ AmH þ H2 O $ AmHþ

2 þ HCO3 : ð3Þ where kobs is the observed reaction rate constant, which can be
measured and is given by
CO2 reacts with EDA and DETA in aqueous solutions to form
monocarbamate.[10,14] Also, according to Katchalski et al.,[15] an ðAmHÞ ðAmHÞ
intramolecular salt is formed during the reaction with EDA. kobs ¼ ¼ ; ð8Þ
1 k
1 1 1
þ þ
In our recent papers, we presented comprehensive overviews on ^ B ðBÞ k2 kB ðBÞ
k2 k2 k
the kinetics of the CO2 reaction with amines.[16,17] The reaction of
CO2 with EDA and DETA can be described either by the two‐step
zwitterion mechanism (originally proposed by Caplow[18] and later ^ B =k
1 . When deprotonation is very fast as compared
with kB ¼ k2k
reintroduced by Danckwerts)[19] or by the single‐step termolecular to the reverse reaction in Equation (4) ðk
1  k ^ B ðBÞÞ and
mechanism (originally proposed by Crooks and Donnellan[20] zwitterion formation is rate‐determining, Equation (6) becomes
and recently revisited by da Silva and Svendsen[21]).
rAmH ¼ k2 ðCO2 ÞðAmHÞ; ð9Þ
Zwitterion Mechanism
There are two comprehensive reviews on the zwitterion mecha- thereby suggesting that the reaction is of the first order with
nism available.[22,23] Assuming this mechanism, the reaction respect to both CO2 and AmH, and hence, overall of the second
between CO2 and the amine proceeds through the formation of a order. When zwitterion deprotonation is rate‐determining
zwitterion as an intermediate: ðk
1  k^ B ðBÞÞ, Equation (6) becomes

k2 ;k
1
CO2 þ AmH ! AmHþ COO
: ð4Þ ^ B ðBÞ
k2 k
rAmH ¼ ðCO2 ÞðAmHÞ: ð10Þ
k
1
This zwitterion undergoes deprotonation by a base (or bases) B to
form carbamate:
Similar to Equation (6), the latter expression suggests a
^B
k fractional reaction order between one and two with respect to
AmHþ COO
þ B ! AmCOO
þ BHþ : ð5Þ AmH concentration. In the limiting case, when the contribution of
AmH to zwitterion deprotonation is much more significant than
Applying the steady‐state principle to the intermediate that of other bases, such as H2O and OH
, the overall reaction is of
zwitterion in Equation (4), the overall rate of reaction of the second order with respect to AmH.

2022 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, DECEMBER 2014
Termolecular Mechanism
The termolecular mechanism assumes that the amine reacts
simultaneously with one molecule of CO2 and one molecule of a
base. This can be represented as
CO2 þ AmH    B $ AmCOO
   BHþ :
where the enhancement factor E is used to describe the enhancing
effect of chemical reactions on mass transport. To study the
reaction kinetics, it is essential that the system belongs to the fast
reaction regime, in which E equals the Hatta number.[25,26] The
necessary conditions for the fast reaction regime are
ð11Þ
10 < Ha  ðEi
1Þ: ð19Þ

The reaction proceeds in a single step via a loosely‐bound

For an irreversible reaction of mth‐order with respect to CO2 and
encounter complex as the intermediate (rather than a zwitterion).
nth‐order with respect to the amine, the Hatta number is given by
This complex breaks up to form reactant molecules (CO2
and amine), while its small fraction reacts with a second molecule qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
m
1
of the amine or a water molecule to yield ionic products mþ1 DCO2 km;n ðCO2 Þ
2
ðAmHÞn
(carbamates). The forward reaction rate for this mechanism, for Ha ¼ ; ð20Þ
kL
the case that H2O, OH
, and AmH are the dominating bases, is
given by where km,n denotes the reaction rate constant. The enhancement
factor for an instantaneous reaction reads as
rAmH ¼ ½kH2 O ðH2 OÞ þ kOH
ðOH
Þ þ kAmH ðAmHÞðAmHÞðCO2 Þ
 
ð12Þ ðAmHÞ DAmH
Ei ¼ 1 þ : ð21Þ
z ðCO2 Þ DCO2
¼ kobs ðCO2 Þ; ð13Þ
It is worthy of note that Equation (21) is valid only if the
where kobs is expressed by
film theory is used. Using Equations (18) and (20), the rate of
absorption in aqueous amine solutions can be expressed as
kobs ¼ ½kH2 O ðH2 OÞ þ kOH
ðOH
Þ þ kAmH ðAmHÞðAmHÞ: ð14Þ
rffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
2


Equation (12) suggests that H2O, OH , AmH, and any other RCO2 ¼ DCO2 km;n ðCO2 Þmþ1 ðAmHÞn : ð22Þ
mþ1
bases can influence the reaction in parallel. Its form is similar to
that of the limiting case of the zwitterion mechanism represented
by Equation (10), and it can describe fractional and higher‐order There is unanimous agreement among all researchers that the
kinetics, too.[21] In aqueous solutions, deprotonation proceeds reaction order with respect to CO2 is one. Therefore, Equation (22)
mainly via water and the alkanolamine.[24] When the solvent can be rewritten as
(water) is the dominant base, the reaction is of the first order with qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
respect to the amine, and the rate is given by RCO2 ¼ ðCO2 Þ DCO2 k1;n ðAmHÞn ; ð23Þ

^
rAmH ¼ kH2 O ðH2 OÞðCO2 ÞðAmHÞ ¼ kðCO2 ÞðAmHÞ; ð15Þ where (CO2) ¼ HCO2 PCO2. Equation (23) can be expressed in the
following form:
where k ^ ¼ kH O ðH2 OÞ. When AmH is the most dominant base, the
2
( )   n
reaction is of the second order with respect to the amine, and the
RCO2 1 n o
rate is given by log pffiffiffiffiffiffiffiffiffiffi ¼ logðk1;n Þ þ logðAmHÞ : ð24Þ
ðCO2 Þ DCO2 2 2
rAmH ¼ kAmH ðCO2 ÞðAmHÞ2 : ð16Þ
If the variation in RCO2 with (AmH) is studied, a plot of
pffiffiffiffiffiffiffiffiffiffi
For the intermediate case when the contribution of water is logfRCO2 =½ðCO2 Þ DCO2 g vs. log (AmH) enables the estimation of
comparable to that of AmH, Equation (14) can be rewritten as the value of k1,n and n. Shen et al.[27] used such plots to investigate
follows: kinetics of the reaction between CO2 and 2‐piperidineethanol in
aqueous solutions. For the case when n ¼ 1, Equation (23) is
kobs ¼ ½kH2 O ðH2 OÞ þ kAmH ðAmHÞðAmHÞ: ð17Þ transformed into the following form:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
RCO2 ¼ ðCO2 Þ DCO2 kobs ¼ PCO2 HCO2 DCO2 kobs ; ð25Þ
It is clear from Equation (14) that the number of fitting
parameters for the termolecular mechanism is fewer than that
where kobs ¼ k2 (AmH).
for the zwitterion mechanism.

Kinetics Measurement
When CO2 concentration in the bulk liquid is negligible and the
resistance to mass transfer is entirely concentrated in the liquid
phase, it can be shown, based on the two‐film theory of mass
transfer,[25] that the following relation holds:
RCO2 ¼ kL ðCO2 Þ E; ð18Þ
EXPERIMENTAL
Materials
Ethylenediamine and diethylenetriamine (purity 98 %) were
purchased from S. D. Fine Chemicals Pvt. Ltd., Mumbai. CO2,
nitrogen (N2) and nitrous oxide (N2O) cylinders, with a given
purity of 99.95 %, were purchased from Inox Air Products Ltd.,
Mumbai.

VOLUME 92, DECEMBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 2023
Experimental Setup
A glass stirred‐cell reactor with a plane, horizontal gas‐liquid
interface was used for the absorption rate measurements. The main
advantage of the stirred‐cell is that the rates of absorption can be
measured using a liquid with a single, known composition. This
easy‐to‐use experimental device was operated batchwise. The total
volume of the reactor was 1.21 dm3, inner diameter 97 mm, and
the interfacial surface area was 7.4  10
3 m2. The reactor was
equipped with two flanges made of stainless steel. A pressure
transducer (high pressure limit 1 bar) mounted on the gas‐side
flange, coupled with a data acquisition system (Jekins Electro
Control, Mumbai), enabled measurement of the total pressure
inside the reactor, the uncertainty in this measurement being
1 mbar. Two temperature sensors were used to measure the gas
and liquid temperatures. The reactor was also equipped with inlet
and outlet ports for the gas and liquid phase. The entire assembly
was proven to have no leak. The gas and liquid were stirred
separately by two impellers. The speed of stirring could be adjusted
to the desired value with an accuracy of 1 rpm. Water at the
desired temperature circulated through the reactor jacket to ensure
isothermal conditions. The temperature was adjusted to the desired
value with an accuracy of 0.1 K. The setup was supplied by two
reservoirs (equipped with heat exchangers), one for the gas phase
and one for the liquid phase. The entire setup was constructed by a
local vendor (Sharad Autoclave Engineers, Mumbai). A similar
apparatus was earlier used in our previous works.[28–30] The
stirred‐cell reactor can also be applied to estimate the physical
solubility of the solute in the liquid phase, and it was used to
measure the solubility of N2O in the amine solutions, too.
Experimental Procedure
A series of experiments was conducted over wide ranges in
temperature and amine concentration for studying reaction
kinetics. In each experiment, the liquid reservoir was filled with
the fresh amine solution and kept in a N2 atmosphere to prevent
contamination. The gas storage tank was filled with CO2 and both
vessels were heated to the desired temperature. The reactor was
purged with N2, evacuated and charged with 0.4 dm3 of liquid
solution. After the desired temperature was attained, CO2 from the
gas cylinder was charged inside the reactor, this being considered
as the starting point for the reaction. The reactor content was
stirred at the desired speeds of agitation. The liquid‐side impeller
speed during kinetic measurements was limited to 60 rpm in order
to ensure that the gas‐liquid interface was undisturbed. By this
way, the mass transfer interfacial area has a simple geometry and
hence is exactly known. The gas‐side impeller speed was higher
(1000 rpm). The decrease in system pressure due to reaction was
monitored by the pressure transducer and the “PCO2 vs. t” data
were recorded during 30 seconds using the data acquisition system.
These data were plotted for the time interval between t ¼ 5 s and
t ¼ 25 s and fitted to a third degree polynomial using the least‐
square regression. It was found that a linear fit resulted in a poor
R‐squared value, and hence the relationship was non‐linear.
In contrast, a fit of the data to a third degree polynomial provided
the best R‐squared value (R2 ¼ 0.99, where R is the correlation
coefficient). From the initial value of the slope
dPCO2/dt, which
was also the maximum value, the absorption rates were calculated
using the relationship
 
VG dPCO2
RCO2 ^a ¼
: ð26Þ
^
VL RT dt
2024 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING
This measurement method based on the fall‐in‐pressure
technique enabled a simple and straightforward estimation of
the absorption rates. Furthermore, no analysis of the liquid phase
was required, and the pressure decrease was the only factor
necessary for the evaluation of the kinetic parameters. The
reproducibility of experiments was checked, and the relative
error in the absorption rate measurements was found to be less
than 3 %. To verify the measurement technique, CO2‐MEA reaction
kinetics was investigated. The second‐order rate constant
(7311 m3/(kmol s)) at 303 K was in line with that reported by
Hikita et al.[8] (7721 m3/(kmol s)).
A similar procedure was used to determine N2O solubility. The
reactor was charged with the liquid solution, then N2O gas was
introduced and the reactor content was vigorously stirred. The gas‐side
and liquid‐side impeller speed was kept at 1000 rpm. From a record of
“PN2 O vs. t” data, it was found that equilibrium was achieved within
4 h. Knowing the initial and final values of PN2 O , the solubility was
found using the ideal gas law and the solute mass balance.
Mass Transfer Considerations
It was found that, at the high gas‐side agitation speed used, the
mass transfer rate was independent of the gas‐side mass transfer
coefficient kG. Therefore, we concluded that the CO2 absorption
process was liquid‐phase‐controlled. To estimate the liquid‐side
mass transfer coefficient kL, a procedure earlier outlined by Littel
et al.[31] was used. For the case of physical absorption in a stirred‐
cell reactor, a solute mass balance for both the gas and the liquid
phase yields the following expression:
   
PðtÞ
Pfinal ^ L Þ þ VG
ðmV
ln ¼
kL At: ð27Þ
Pinitial
Pfinal VL VG
The physical absorption of CO2 in water at 303 K was studied,
and the fall‐in‐pressure due to absorption was recorded. After-
h i
PðtÞ
P
wards, ln Pinitial
Pf inal was plotted vs. time, t, to estimate the value
f inal
h i
^ L ÞþVG
of kL. The slope of this graph equals
ðmV VL VG kL A. From the
value of the slope and from the knowledge on other relevant
parameters (m ^ ¼ 0.58 mol/mol, VG ¼ 0.81 dm3, VL ¼ 0.4 dm3, A ¼
7.4  10
3 m2), the value of kL was found to be 4.6  10
5 m/s. This
is in line with those typical for stirred‐cell reactors. The solubility of
CO2 in water at 303 K was found to be 3.1  10
4 kmol/(m3 kPa),
which agrees well with the published value.[32]
In the fast reaction regime, the rate of absorption is independent
of the liquid‐side mass transfer coefficient, and hence, it should not
depend on the agitation speed. This effect was experimentally
studied for both amines (i.e., EDA and DETA), and it was found
that there is practically no change in the absorption rate, when the
stirring speed is varied in the range 40–100 rpm at 313 K. Hence,
we concluded that the CO2‐EDA and CO2‐DETA systems belong
to the fast reaction regime systems. All further experiments were
conducted at a speed of 60 rpm.
Estimation of Physical Properties
Knowledge of physical properties is essential for the estimation of
kinetic parameters. Density and viscosity of aqueous EDA and
DETA solutions were measured at 303, 308, and 313 K using a
commercial densitometer and a capillary viscometer. These values
are represented in the Supplementary Material. The diffusion
coefficients of N2O and CO2 in water, viz., 2.03  10
9 and
2.15  10
9 m2/s at 303 K, were earlier reported by Versteeg and
van Swaaij.[32] Based on our viscosity measurements, the values of
VOLUME 92, DECEMBER 2014
N2O diffusivity in the aqueous solutions of amines were estimated
using the modified Stokes‐Einstein correlation:

ðDN2 O m0:80 ÞAmine ¼ const ¼ ðDN2 O m0:82 ÞWater : ð28Þ

Furthermore, the solubility of N2O in aqueous EDA and DETA

solutions was measured. These values are given in the Supple-
mentary Material. The values of DCO2 and HCO2 in solutions were
found using the N2O analogy.[32]

RESULTS AND DISCUSSION

CO2 absorption rates in EDA and DETA are represented in Table 2.
Plots of RCO2 vs. PCO2 at T ¼ 303 K for both amines are shown in
Figure 1. As expected, the reaction exhibits first‐order kinetics for
CO2 concentration. As seen in Figure 1, DETA reacts faster with
CO2 than EDA. Thus, the increase in the number of amine groups
results in a rise in reaction rates. A similar observation was earlier
reported by Hartono et al.[13] To reaffirm the reaction regime, we
plotted RCO2 versus (AmH) at 303 K. The molarities of EDA in Figure 1. Plots of RCO2 vs. PCO2 at T ¼ 303 K (AmH ¼ 0.1 M).
the aqueous solutions were varied from 0.1 to 0.4; for DETA, they
were varied from 0.1 to 0.5. It was found that the relationship is
agreement with the previous work by Li et al.[10] Since
non‐linear (see Figure 2). As a result, the instantaneous reaction
deprotonation proceeds mainly by EDA and water, Equation (8)
regime can be considered as improbable.
pffiffiffiffiffiffiffiffiffiffi can be represented as
Plots of logfRCO2 =½ðCO2 Þ DCO2 g versus log (AmH) at 303 K for
both amines are shown in Figure 3. The slopes equal 0.6 and 0.5,
ðEDAÞ
correspondingly, thereby suggesting that the reaction order with kobs ¼ : ð29Þ
respect to EDA and DETA is 1.2 and 1. Li et al.[10] reported a similar
1
k2 þ kEDA ðEDAÞþk
1
H ðH2 OÞ
2O
value (n ¼ 1.07) for EDA concentrations lower than 0.1 M. On the
contrary, Hartono et al.[13] suggested a higher reaction order with If the termolecular model were appropriate, the contribution of
respect to DETA (1.73) in the amine concentration range 1–2.9 M. water to deprotonation would be comparable to that of EDA. In this
It thus appears that the reaction order with respect to DETA case, Equation (17) is represented as
increases with rising amine concentration.
EDA exhibits fractional order between 1 and 2. If the two‐step kobs ¼ ½kH2 O ðH2 OÞ þ kEDA ðEDAÞðEDAÞ: ð30Þ
zwitterion mechanism is appropriate, it is obvious that both
zwitterion formation and deprotonation steps affect reaction rates
for the CO2‐EDA system (see Equation (6)). This observation is in Zwitterion formation is the rate‐determining step in the CO2‐
DETA system (see Equation (9)). If zwitterion formation were not
rate‐limiting, first‐order behaviour with respect to DETA would
Table 2. CO2 absorption rates in aqueous EDA and DETA solutions at not be observed. For the termolecular model, water would be
T ¼ 303 K

Amine (AmH) kmol/m3 PCO2 kPa RCO2  106 kmol/(m2 s)

EDA 0.1 2.85 1.57

3.37 1.78
3.98 2.13
4.76 2.35
0.2 3.26 2.74
4.07 3.35
4.70 3.81
6.28 4.96
0.3 2.51 2.35
3.75 3.44
4.69 3.57
5.44 4.96
0.4 3.76 3.48
4.07 4.18
5.16 4.75
6.02 5.35

DETA 0.1 3.23 2.13

3.86 2.44
4.57 2.87
4.98 3.31 Figure 2. Plots of RCO2 vs. (AmH) at T ¼ 303 K (PCO2 ¼ 4kPa).

VOLUME 92, DECEMBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 2025

pffiffiffiffiffiffiffiffiffiffi
Figure 3. Plots of logfRCO2 =½ðCO2 Þ DCO2 g vs. log (AmH) at T ¼ 303 K.
obviously the dominant base (cf. Equation (15)). At high DETA
concentrations, both water and DETA influence the reaction in
parallel.[13]
The equilibrium and kinetic characteristics of the two investi-
gated systems at different temperatures are represented in Tables 3
and 4. The rate constant at 303 K for the reactions with EDA and
DETA were estimated as 15770 and 21480 m3/(kmol s). Our k2
value for the CO2‐EDA system is close to those reported by Hikita
et al.[8] and Li et al.[10] (see Table 1). For the CO2‐DETA system,
Hartono et al.[13] reported much bigger k2 values which were not
meaningful. Thus, no reliable literature data to compare our k2
values with is available. Using the values of DCO2 and HCO2 listed
in Tables 3 and 4, the parameters Ha and Ei were estimated. The
conditions given by Equation (19) are satisfied, thereby confirming
that both reactive systems belong to the fast reaction regime.
The dependence of k2 on temperature is represented in Tables 3
and 4. Arrhenius plots for the CO2‐EDA and CO2‐DETA systems are
shown in Figure 4. The activation energy values for EDA and DETA
were found to be 57.7 and 30.2 kJ/mol. These values are close to
those reported in literature, i.e., 50.6 (Li et al.)[10] and 32.2 kJ/mol
(Hartono et al.)[13] The observed reaction rate constants were
measured. Plots of kobs vs. (EDA) at 303 K and comparison with
literature data are shown in Figure 5. As expected, the increase in
EDA concentration results in a rise in the value of kobs. Again,
DETA concentrations used by Hartono et al.[13] were much higher
than those used in this study; thus, a comparison of the values of
kobs was not possible.
CONCLUSIONS
Kinetics of the CO2 reactions with two polyethyleneamines, viz.,
EDA and DETA, was investigated in a stirred‐cell reactor. DETA

Table 3. Equilibrium and kinetic characteristics of CO2‐EDA system

Temp. K (EDA) kmol/m3 HCO2  104 kmol/(m3 kPa) DCO2  109 m2/s kobs (1/s) k2 m3/(kmol s) Ha Ei

303 0.1 3.06 2.15 1382.6 13825.8 37.0 91.6

0.2 2.98 2.13 3518.5 17592.4 59.7 156.1
0.3 2.76 2.12 4832.2 16107.4 69.6 289.2
0.4 2.60 2.10 6225.6 15564.0 78.9 336.1

308 0.1 2.79 2.40 2209.9 22099.0 50.3 101.6

0.2 2.68 2.38 4588.8 22944.3 71.9 162.0
0.3 2.57 2.36 6840.1 22800.5 87.5 266.1
0.4 2.36 2.35 9542.0 23855.0 103.0 381.2

313 0.1 2.45 2.68 3116.7 31167.0 63.0 128.8

0.2 2.34 2.67 6165.2 30826.1 88.5 234.6
0.3 2.19 2.66 9905.5 33018.3 112.0 358.4
0.4 2.12 2.65 13497.4 33743.6 130.0 410.6

Table 4. Equilibrium and kinetic characteristics of CO2‐DETA system

Temp. K (DETA) kmol/m3 HCO2  104 kmol/(m3 kPa) DCO2  109 m2/s kobs (1/s) k2 m3/(kmol s) Ha Ei

303 0.1 3.03 2.16 2112.0 21120.0 46.6 82.6

0.2 2.93 2.15 4238.1 21190.4 65.9 151.7
0.3 2.68 2.15 6506.1 21686.9 81.6 210.3
0.4 2.53 2.14 8847.6 22119.1 94.9 327.1
0.5 2.41 2.13 10640.4 21280.7 103.7 501.3

308 0.1 2.85 2.16 2462.4 24623.9 50.3 86.5

0.2 2.69 2.15 5075.1 25375.5 72.2 194.6
0.3 2.43 2.15 7666.0 25553.3 88.5 288.4
0.4 2.23 2.14 10561.1 26402.7 103.5 423.4
0.5 2.13 2.12 13249.8 26499.6 115.7 553.4

313 0.1 2.70 2.18 3131.0 31309.6 56.9 99.6

0.2 2.30 2.16 6212.0 31060.0 79.9 223.9
0.3 2.00 2.15 9479.8 31599.3 98.5 393.4
0.4 1.90 2.14 12619.0 31548.5 113.5 377.3
0.5 1.60 2.13 15926.6 31853.3 127.2 600.2

2026 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, DECEMBER 2014
 NOMENCLATURE
^a Gas‐liquid interfacial area per unit volume of liquid
(m2 m
3)
A Interfacial surface area, m2
AmH Amine (i.e., EDA or DETA)
(AmH) Amine concentration (kmol m
3)
B Base assisting in zwitterion deprotonation
(B) Concentration of base B in liquid (kmol m
3)
(CO2) Interfacial concentration of CO2 (kmol m
3)
DAmH Diffusivity of amine in liquid (m2 s
1)
DCO2 Diffusivity of CO2 in liquid (m2 s
1)
DN 2 O Diffusivity of N2O in liquid (m2 s
1)
(DETA) Initial concentration of DETA in liquid (kmol m
3)
E Enhancement factor due to chemical reaction
Ei Enhancement factor for an instantaneous reaction
(EDA) Initial concentration of EDA in liquid (kmol m
3)
HCO2 Solubility of CO2 in liquid (kmol m
3 kPa
1)
Ha Hatta number
(H2O) Concentration of water (kmol m
3)
Figure 4. Arrhenius plots for the CO2‐EDA and CO2‐DETA systems. ^
k Rate constant in Equation (15)
k2 Forward reaction rate constant in Equation (4)
(m3 kmol
1 s
1)
reacted faster with CO2 than EDA. Both the amines exhibited k
1 Reverse reaction rate constant in Equation (4)
reaction order close to unity. Reaction pathways were described (m3 kmol
1 s
1)
using the zwitterion and termolecular mechanism. Both zwitterion kAmH Deprotonation constant for amine
formation and deprotonation steps affected the rate of the reaction kB Rate constant in Equation (8)
^B
k Rate constant in Equation (5)
between CO2 and EDA. Zwitterion formation was the rate‐
determining step in the CO2‐DETA system. Analysis using the kG Gas‐side mass transfer coefficient (kmol m
2 s
1 kPa
1)
termolecular mechanism suggested that the contribution of water kH2 O Deprotonation constant for water
to deprotonation was comparable to that of EDA. In contrast, water kL Liquid‐side mass transfer coefficient (m s
1)
was the dominant base for the CO2‐DETA system. Second‐order km,n Reaction rate constant
rate constants for the reactions with EDA and DETA were equal to kobs Observed reaction rate constant (s
1)
15770 and 21480 m3/(kmol s) at 303 K. The activation energies kOH
Deprotonation constant for OH

^
m Dimensionless solubility (mol/mol)
were found to be 57.7 and 30.2 kJ/mol, correspondingly. From
the results obtained in this work, it can be concluded that m,n Reaction order with respect to CO2 and amine
solvents containing polyethyleneamines are promising for the (OH
) Hydroxyl ion concentration (kmol m
3)
enhancement of CO2 capture. PCO2 partial pressure of CO2 in bulk gas phase (kPa)
P(t) Partial pressure of solute gas at time t (kPa)
Pinitial Initial partial pressure of solute gas (kPa)
Pfinal Partial pressure of solute gas at equilibrium (kPa)
rAmH Reaction rate in aqueous solution of AmH (kmol m
3 s
1)
R correlation coefficient
^
R Gas constant (m3 kPa kmol
1 K
1)
RCO2 CO2 absorption rate (kmol m
2 s
1)
T Temperature (K)
VG, VL Volume of gas and liquid inside reactor (m3)
z Stoichiometric coefficient
m Viscosity of amine solution (mPa s)

Glossary
AEEA N‐(2‐aminoethyl)ethanolamine
DEA Diethanolamine
DETA Diethylenetriamine
DGA Diglycolamine
DIPA Diisopropanolamine
EDA Ethylenediamine
EDC Ethylenedichloride
MDEA N‐methyl diethanolamine
MEA Monoethanolamine
PZ Piperazine
Figure 5. Plots of kobs vs. (EDA) at T ¼ 303 K. TEA Triethanolamine

VOLUME 92, DECEMBER 2014 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING 2027
ACKNOWLEDGEMENTS [30] P. D. Vaidya, E. Y. Kenig, Ind. Eng. Chem. Res. 2008, 47, 34.
The authors are grateful to University Grants Commission, New [31] R. J. Littel, G. F. Versteeg, W. P. M. van Swaaij, Chem. Eng.
Delhi, for the financial assistance (Grant: UGC/Major Research Sci. 1991, 46, 3308.
Project in Science/No. F. 39‐851/2010 (SR)). [32] G. F. Versteeg, W. P. M. van Swaaij, J. Chem. Eng. Data 1988,
33, 29.
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2028 THE CANADIAN JOURNAL OF CHEMICAL ENGINEERING VOLUME 92, DECEMBER 2014