02638762/98/$10.00+0.

00
Institution of Chemical Engineers
Trans IChemE, Vol 76, Part A, November 1998

ANALYSIS OF EQUILIBRIUM DATA OF CO2 IN

AQUEOUS SOLUTIONS OF DIETHANOLAMINE
(DEA), METHYLDIETHANOLAMINE (MDEA) AND
THEIR MIXTURES USING THE MODIFIED
KENT EISENBERG MODEL
M. Z. HAJI-SULAIMAN, M. K. AROUA and A. BENAMOR
Department of Chemical Engineering, University of Malaya, Kuala Lumpur, Malaysia

quilibrium data on the absorption of CO2 in aqueous solutions of single and mixed
amine was analysed using the Modi ed Kent Eisenberg model. The experimental value
of the equilibrium constant for the formation of carbamate, instead of the tted value as
usually used by other investigators, was applied in the analysis. Data on CO2 loading in
aqueous solutions of DEA and MDEA at various temperature (303323 K) and CO2 partial
pressure (0.09100 kPa) obtained from a stirred reactor was tted to generate the different
parameters in the model. Using these constants, the model was applied to predict the CO2
loading in solutions of DEA and MDEA reported in the literature. Prediction was also made on
the loading in solutions of mixed DEA/MDEA obtained from experiments conducted over a
range of composition (DEA:MDEA 0 1) at different temperatures of 303323 K, as well as
those reported in the literature. In all cases, it was found that the model was able to give a
relatively good CO2 loading over a wide range of operating conditions both in solutions of
single and mixed amine using the constants generated from single amine experiments. It also
suggested that the experimental value of the equilibrium constant for the formation of
carbamate obtained from an earlier work can be taken as the true value for the reaction.
Keywords: blended amine; DEA; MDEA; carbon dioxide; absorption

INTRODUCTION

The mechanisms for these reactions have been proposed

by a number of investigators and are available in the
literature1 . It is agreed that similar reaction steps are
involved for all types of amine including the protonation
of amine as well as the ionization of different species in
the solution. However, an additional step, which is the
formation of carbamate ion, has been proposed for a system
involving primary and secondary amines. It is the formation
of this carbamate ion which limits the maximum CO2
loading of 0.5 for these classes of amine.
Several models are available to analyse the solubility of
CO2 in aqueous solution of alkanolamine and to predict the
equilibrium CO2 loading. Among the models which have
been used widely is that of the electrolyte-NRTL model of
Chen and Evans2 , the model of Deshmukh and Mather3 and
Kent and Eisenberg4 . The Chen and Evans model and that
of Deshmukh and Mather were developed based on sound
thermodynamic principles. Non idealities of solution are
taken into consideration by allowing long and short range
interactions between the different species that are present.
The Chen and Evans model used a combination of the
Debye-Huckel theory and the electrolyte-NRTL equation
for calculating the activity coef cients. This model has been
applied among others by Austgen et al.5 . The Deshmukh
and Mather model employed the Guggenheim equation to

The use of aqueous solutions of alkanoalamine to remove

CO2 from process streams is still the choice in industry.
The technique has been proven to be reliable and has
found wide application in many chemical industries such
as ammonia production, coal gasi cation and natural gas
processing. Alkanolamine is broadly classi ed into primary,
secondary and tertiary depending on the number of alkyl
group(s) attached to the nitrogen atom in the structure of
the molecule. Both primary and secondary amines generally
exhibit low CO2 loadings (mol of CO2 captured/mol of
amine) but with a high rate of absorption. In contrast,
tertiary amines showed the opposite behaviour. Recently, a
new class of amine known as sterically hindered amine has
been introduced which shows a high absorption rate and
high maximum gas loading. However, the choice of a
particular amine will depend not only on the absorption
rate and maximum loading that can be achieved, but also
on other factors such as regeneration energy, corrosion
tendency and the cost of the solvent.
The absorption of CO2 in aqueous solution of alkanoalamine couples physical absorption with chemical reaction
which x the CO2 in the solution as carbonates, bicarbonates
and carbamates depending on the type of amine being used.
961

962

HAJI-SULAIMAN et al.

represent activity coef cients and is much simpler to handle

as compared to the previous model. Haji-Sulaiman and
Aroua6 used this model to analyse the CO2 solubility in
DEA and AMP. The Kent and Eisenberg model is the
simplest among these models where the non-idealities that
are present in the system are lumped together into the K
values. This relatively simple model correlates the data
fairly well. Hu and Chakma7 used this model to analyse
solubility data of CO2 and H2 S in the sterically hindered
amine of AMP solutions, in which case no carbamate ions
exist in the system. However, they modi ed the expression
for the equilibrium constant for the protonation of amine,
as originally proposed by Kent and Eisenberg, to include
the dependency on the free gas concentration in the
solution and the amine concentration, as evident from
experimental observation using tertiary amine, MDEA.
Similarly, Kritpiphat and Tontiwachwuthikul8 also tted
their data on the equilibrium of CO2 in AMP using the Kent
and Eisenberg model. By performing a sensitivity analysis,
they also showed that the hydrolysis of carbamate ion is
not important and have ignored the reaction in their system.
When dealing with the solubility of CO2 in systems
involving primary and secondary amines, the uncertainty in
the analysis lies in the chosen value of the equilibrium
constant for the formation of carbamate ion (or the
hydrolysis of carbamate). Investigators who have applied
either the electrolyte-NRTL model of Chen and Evans or
the Deshmukh and Mather model to analyse the solubility
of CO2 in aqueous solutions of primary and/or secondary
amines considered this value as an adjustable parameter
that best t the experimental data. In their original work,
Kent and Eisenberg also performed a similar procedure
when analysing VLE data of CO2 in aqueous solution of
DEA. The approach adopted by these investigators was
mainly due to the unavailability of a reliable experimental
value of the equilibrium constant in the literature. The lack
of published experimental data on the equilibrium constant of carbamate formation is mainly attributed to the
dif culty in measuring the concentration of the different
species in equilibrium, which is required for its evaluation.
From the work conducted in this laboratory, the authors9
have recently proposed a technique to determine the
concentration of all species in an equilibrium system of
CO2 -alkanolamine-H2 O based on titration with a strong
base of NaOH. The method is simple to perform and has
been found to be reliable. Using these values, they were able
to estimate the equilibrium constant at in nite dilution for
the formation of carbamate at different temperatures and
assessed their variations with ionic strength10 . This paper
is an extension of the earlier work and will evaluate the
validity of the equilibrium constant which has been
generated to predict CO2 loadings in DEA and mixtures
of DEA/MDEA and to compare the results with other
experimental data available in the open literature. For this
purpose the Modi ed Kent Eisenberg model will be used.
EXPERIMENTAL
Two different types of amine have been selected in
this work. They are DEA (obtained from Merck with 98%
purity) and MDEA (obtained from Riedel-de-Haen with
98.5% purity). Absorption experiments of CO2 into alkanolamine solution were conducted using a stirred cell reactor

where the amine solution was exposed to a owing gas

consisting of a mixture of CO2 and N2 of known
composition. Details of the experimental apparatus and
procedure are provided by Haji-Sulaiman and Aroua6 . The
experiment was terminated once the equilibrium was
achieved, as indicated by a constant pH value of the
loaded solution, and the liquid was analysed for CO2 loading
and the concentrations of carbamate and other species,
using the procedure described by Haji-Sulaiman et al.9 . In
this study, the partial pressure of CO2 in the owing gas
stream was varied from 0.09 kPa to 100 kPa in the
temperature range of 303 to 323 K.
MODIFIED KENT EISENBERG MODEL
An equilibrium solution of CO2 in aqueous solution of
alkanolamine is governed by the following set of equations:
RR NH2

K1

RR NH

RR NCOO
CO2

H2 O

HCO3
H2 O

K5

K4

H2 O
K3

RR NH

HCO 3

CO3

OH

H
K2

HCO3

Equation (1) represents the protonation of amine, equation

(2) corresponds to the hydrolysis of carbamate and is only
considered in systems consisting of primary and secondary
amines. Equations (3)(5) are the ionization reactions for
the different species in the solutions. In addition to the
above equations, the following set of conditions must also
be satis ed:
Amine balance:
RR NH

RR NH

RR NH2

RN NCOO

6
CO2 balance:
a RR NH

HCO3

RR NCOO

CO3

PCO2 /HCO2

Charge balance:
RR NH2

HCO3

RR NCOO

2 CO3

8
where a is the gas loading. The concentration of carbon
dioxide in the liquid phase can be estimated from Henry s
law, i.e.
PCO2

HCO2 CO2 .

Following Hu and Chakma7 , the apparent equilibrium

constants, K i , for reactions (1) and (2) as de ned in terms
of the concentration of the corresponding species, are taken
to be dependent on the partial pressure of CO2 and the amine
concentration in the solution. Since the equilibrium constant at in nite dilution, Ki , is only a function of temperature, a factor Fi is introduced which takes into account
the effects of CO2 partial pressure and the amine
Trans IChemE, Vol 76, Part A, November 1998

EQUILIBRIUM DATA OF CO2 IN AQUEOUS SOLUTIONS OF DEA, MDEA AND THEIR MIXTURES

963

Table 1. Values of the constants used in equation (11).

Parameter

Range of
validity (C)

6.776904
13.8328
66.8007
35.4819
36.7816
22.4773
11.4519

0
0
0
0
0
0
0.010454

48.7594
87.39717
439.709
220.067
235.482
140.932
94.4914

080
2060
3058
0225
0225
0225
0225

K1, DEA 17
K1, MDEA 18
K2 10
K4 19
K3 19
K5 19
HCO219

3071.15
8483.95
17067.2
12431.7
12092.1
13445.9
6789.04

concentration. Thus
K i Ki F i
10
The dependency of the equilibrium constant, Ki , as well as
the Henry s constant, H, with temperature is expressed as
Ki or H

ai/T

b i ln T ci T d i

11

are taken from the literature, as given in Table 1. In this

work, Fi is de ned in a general form as
Fi

fi
PCO
2

g i ln PCO2

h i PCO2

ji
RR NH

k i ln RR NH

m i RR NH

12

Similarly, fi mi are constants which are to be regressed. For

reactions (3)(5) only the equilibrium constants at in nite
dilution, Ki , were used. Equations (1)(9) can be reduced,
for aqueous solutions of DEA, to a single polynomial
equation in terms of the concentrations of hydrogen
ions, H , and the equilibrium constants as follows:
AH 5 BH 4 CH 3 DH 2 EH
F
where
A
B
C
D

13

PCO2
HCO2

K 1, DEA K 2, DEA K3 K4

K 2, DEA RR NH
K 2, DEA PCO2
H
K 1, DEA
H HCO2
RR NH

A H

B H

PCO2
K4
HCO2

PCO2
RR NH K 1, DEA K 2, DEA
HCO2

RR NH

Trans IChemE, Vol 76, Part A, November 1998

H
14

C H

D H

K 1, MDEA

K3 PCO2

K5

PCO2
HCO2

2 K3 K4

2 K 1, MDEA K3

K5

RR NH

K3 K4
H

K4

where

K5
PCO 2
K4
HCO2

P2CO2
HCO2

15

K 1, DEA

PCO2
K 1, DEA K 2, DEA
HCO2

PCO2
HCO2

For MDEA solutions, no stable carbamates are formed.

Thus reaction (2) does not exist in the system and
RR NCOO was omitted in the charge and mass balance
equations. Thus for this system, equation (13) becomes

R2 NH

K 1, DEA K 2, DEA K2

K 1, DEA K 2, DEA K4

Consequently, the total CO2 loading, a, can be expressed as:

PCO2
HCO2

where ai di are constants. Values of these constants for

all of the reactions (1)(5) and that for the Henry s constant

PCO2
HCO 2 H

2 K 1, DEA K3 K4

K 1, MDEA K5

K 1, MDEA K3

PCO2
HCO2

PCO2
HCO2

Finally the total CO2 loading becomes

K 1, MDEA

K3 PCO2
H
RR NH

K5

PCO2
H HCO2

PCO2
HCO2

16

964

HAJI-SULAIMAN et al.

Equations (14) and (16) were tted respectively to the

experimentally determined gas loading by a non-linear
regression technique to extract the best tting values for
parameters fi and gi using the commercially available
software, REPROCHE. In order to perform this task, a user
subroutine was supplied to determine the roots (values of
H ) of equations (13) and (15). For this purpose, a
modi ed subroutine, RTNEWT 11 , developed based on the
Newton-Raphson algorithm was used. There are respectively ve and four possible roots of equations (13) and (15).
However, only one value of H is valid for each equation
and this could be obtained by limiting the range of H
between 10 6 and 10 12 kmol m 3 which corresponds to the
pH of 7 and 11 respectively for the aqueous solutions of
carbonated and fresh amine.
RESULTS AND DISCUSSION
To ensure the reliability of the experimental data it is
important that the concentration of amine in the solution
is maintained throughout each run. Analysis on the
concentration of amine before and at the end of each
experiment showed that in most cases the variations
between the readings were less than 3%. However, slightly
higher variations of about 5% were obtained for experiments with very low CO2 partial pressures which normally
required 1824 hours to reach equilibrium where evaporation of water is likely to occur. The measured variations
also included errors in the analysis, which has been
estimated to be around 2%. Thus, without introducing any
signi cant errors, it can be concluded that the concentration
of amine in the solution remained constant throughout
each set of experimental run.
The experimental gas loading data at different amine
concentrations, temperatures and CO2 partial pressures as
given in Table 2 was tted simultaneously, using the
Modi ed Kent Eisenberg model as discussed above, to
generate the different parameters fi mi of equation (12).
Sensitivity analyses were conducted to assess the signi cance of these different constants. It was found that for
the protonation of amine, only gi and ki are important.
However, for the formation of carbamate, the contribution
from gi and ji is signi cant. Based on these analyses, Fi is
nally expressed as
Protonation of amine
Fi

gi ln PCO2

ki ln RR NH

17

Formation of carbamate
ji
18
RR NH
Values of these parameters that best t the observed data
with mean residual squares respectively equal to 6.3 10 4
and 9.2 10 4 for aqueous solutions of MDEA and DEA
are given in Table 3. Equation (13) (and equation (15)) is
very sensitive to the initial guess. However, by limiting
the possible root within the range of pH for loaded and
fresh solutions which lies respectively between 7 and 11, the
equation converged to a nal solution within a few
iterations. Using the generated parameters, predicted CO2
loadings were compared with the data of Lee et al.12,13 for

Fi

gi ln PCO2

2M and 8M aqueous solutions of DEA at different

temperatures. The results are given as plots of CO2 partial
pressure against CO2 loading, as shown in Figures 1 and 2.
In general, within the temperature range of 298393 K, both
predicted and published data showed a fairly good
agreement with maximum deviations of about 30% at
very high and very low CO2 partial pressures. Relatively
larger deviations are also shown at the higher temperatures
of 373 and 393 K. The main reason for the observed
differences at these two extreme ends of partial pressure
is that the data used to regress these constants were those
taken within the range of 0.09 and 100 kPa partial pressure
of CO2 . Thus as expected, loadings outside this range could
not be predicted with a high degree of accuracy. Similarly,
predicting CO2 loading at the higher operating temperatures
which are beyond those used to regress the constants also
introduced some errors. However, in the case of 8M aqueous
solution of DEA as shown in Figure 2, it is interesting to
note that even though the estimated parameters were
obtained from data of 2M and 4M DEA, the ability to
predict loadings in 8M solution can be considered excellent
within the range of 0.09 to 100 kPa partial pressure. Similar
comparison was also made for the gas loading in 2M
solution of MDEA using the data published by Jou et al.14 .
For practical purposes and within the range of conditions
employed in this work, it is clear that the modi ed Kent
Eisenberg model together with the various constants which
have been generated is able to predict CO2 loadings
comparable to the experimental results as shown in
Figure 3. As in the case of DEA, relatively large deviations
of about 20% were observed at low partial pressure less
than 0.1 kPa. In this case the formation of carbamate has
not been considered as it is generally agreed that this
reaction does not occur in a system of tertiary amine.
For a solution containing a mixture of DEA and MDEA,
the system is also described by the set of equations (1)(9).
In addition, Reaction (1) must be considered twice, each
for MDEA and DEA in order to account their effects in
the mixture. Using the same parameters generated from
single amine experiments, the predicted CO2 loadings are
compared to those obtained experimentally in this work, as
shown in Figure 4 for 2M mixtures of DEA:MDEA 1 : 3
at different temperatures. Over the entire range of CO2
partial pressure and temperature investigated, the model can
predict well the total gas loadings that could be achieved
with a maximum deviation of about 23%. This observation
reaf rms the validity of the different parameters generated
for equation (12) and the experimental value of the
carbamate equilibrium constant. A similar plot for mixtures
of different ratios of DEA:MDEA at 303 K is given in
Figure 5. In general, the effect of the presence of DEA is
more pronounced at low CO2 pressures. As the pressure
is increased, solutions with a lower proportion of DEA
would exhibit a higher ultimate CO2 loading. Using
the model, the concentrations of the different species in
the system were evaluated. It was found that at low partial
pressure, and therefore at low loading, most of the CO2
absorbed into the solution is in the form of carbamate with a
small amount in the form of bicarbonate. As the loading
increases, the trend is reversed where the presence of
bicarbonate is most signi cant. Over the entire range of CO2
loading, free CO2 is only present in trace amounts. The
formation of carbamate from DEA is very fast and the
Trans IChemE, Vol 76, Part A, November 1998

EQUILIBRIUM DATA OF CO2 IN AQUEOUS SOLUTIONS OF DEA, MDEA AND THEIR MIXTURES

965

Table 2. Experimental and calculated carbon dioxide loading in aqueous solutions of DEA and MDEA.
2M DEA

4M DEA

CO2 Loading a
(mol/mol)
aexpt

PCO2 (kPa)
T
0.098
0.492
1.119
5.355
10.726
32.527
54.213
10.085
T
0.095
0.474
1.039
5.265
10.665
32.147
53.829
104.0.727
T
0.090
0.449
1.040
5.110
10.035
30.358
50.763
98.170
T
1.064
3.130
4.802
10.535
29.756
48.370
95.830
T
1.064
3.069
5.176
10.029
10.349
47.520
93.956
T
0.997
2.938
4.761
9.725
28.435
44.136
91.514

CO2 Loading a
(mol/mol)
acalc

PCO2 (kPa)

303K
0.183
0.325
0.388
0.521
0.591
0.699
0.730
0.786

0.177
0.324
0.393
0.500
0.544
0.631
0.685
0.760

0.098
0.986
4.893
9.863
29.358
48.931
98.628

313 K
0.172
0.278
0.320
0.459
0.538
0.597
0.662
0.727

0.117
0.252
0.325
0.462
0.514
0.604
0.655
0.732

0.095
0.951
5.259
10.413
30.987
52.568
102.119

323 K
0.133
0.152
0.272
0.398
0.473
0.546
0.611
0.688

0.080
0.178
0.256
0.411
0.471
0.567
0.616
0.694

0.095
0.903
4.514
9.028
27.032
46.305
98.673

303 K
0.114
0.244
0.333
0.483
0.673
0.793
0.880

0.112
0.234
0.300
0.452
0.691
0.799
0.905

0.099
0.984
4.918
9.853
29.509
49.100
98.200

313 K
0.103
0.197
0.267
0.374
0.603
0.688
0.805

0.091
0.177
0.243
0.353
0.585
0.698
0.837

0.095
0.954
4.762
9.523
28.521
47.535
95.234

323 K
0.079
0.148
0.194
0.298
0.471
0.590
0.726

0.065
0.133
0.180
0.275
0.483
0.585
0.752

0.090
0.901
4.514
9.028
27.084
45.139
90.279

equilibrium is reached quickly, indicating that at low

pressure, CO2 is preferentially absorbed into DEA. However, due to the stability of the carbamate, the theoretical
stoichiometric loading with DEA is limited to 0.5. A slightly
higher loading of about 0.7 could be achieved in practice
using DEA due to the formation of bicarbonate. As the
CO2 partial pressure is increased, a higher loading, greater
than about 0.7, is only possible through absorption into
MDEA, where the CO2 is xed mainly as bicarbonate. This
Trans IChemE, Vol 76, Part A, November 1998

aexpt

acalc

303 K
0.061
0.309
0.471
0.524
0.588
0.633
0.671

0.131
0.345
0.462
0.505
0.582
0.650
0.687

313 K
0.091
0.281
0.441
0.499
0.561
0.599
0.639

0.087
0.270
0.425
0.477
0.561
0.597
0.674

323 K
0.081
0.193
0.344
0.445
0.498
0.517
0.601

0.054
0.197
0.354
0.419
0.517
0.565
0.641

303 K
0.027
0.061
0.149
0.284
0.516
0.633
0.761

0.014
0.067
0.185
0.276
0.480
0.601
0.758

313 K
0.015
0.052
0.086
0.190
0.384
0.513
0.654

0.011
0.049
0.136
0.207
0.391
0.495
0.653

323 K
0.010
0.037
0.084
0.151
0.251
0.363
0.516

0.007
0.035
0.103
0.159
0.308
0.400
0.548

Table 3. Generated parameters for equations (17) and (18).

Parameter
F1,DEA
F2,DEA
F1,MDEA

gi

ji

ki

0.4559
0.002386
0.03628

0
2.88
0

0.2584
0
0.6262

966

HAJI-SULAIMAN et al.

Figure 1. Comparison between predicted CO2 loading and data of Lee

et al.12,13 in 2M aqueous solution of DEA; Solid lines: model prediction;
(e ) 298 K; (F ) 323 K; (E ) 373 K; ( ) 393 K.

Figure 3. Comparison between predicted CO2 loading and data of Jou

et al.14 in aqueous solution of MDEA; Solid lines: model prediction;
(e ) 298 K; (F ) 313 K; (E ) 343 K; (f ) 373 K; ( ) 393 K.

explanation is in agreement with the observed experimental

data as well as the model predictions in Figure 5, again
suggesting the validity of the model, the different constants
generated and the experimental value of the equilibrium
constant for the formation of carbamate. To support this
conclusion further, comparison is also made with the

available data reported by Austgen et al.15 , as shown in

Figure 6. The data was obtained at two different temperatures of 313 and 353 K in 4M mixtures containing
equal proportion of DEA and MDEA. As in all previous
cases, the predicted values are in good agreement with
the published data.

Figure 2. Comparison between predicted CO2 loading and data of Lee

et al.12,13 in 8M aqueous solution of MDEA; Solid lines: model prediction;
(e ) 298 K; (F ) 323 K; (E ) 373 K.

Figure 4. Comparison between predicted and experimental CO2 in aqueous

solution of 0.5 M DEA 1.5 M MDEA; Solid lines: model prediction; (e)
303 K; ( F) 313 K; ( ) 323 K

Trans IChemE, Vol 76, Part A, November 1998

EQUILIBRIUM DATA OF CO2 IN AQUEOUS SOLUTIONS OF DEA, MDEA AND THEIR MIXTURES

Figure 5. Comparison between predicted and experimental CO2 loading

in 2M aqueous solution of blended DEA/MDEA at different ratios of
DEA/MDEA; Solid lines: model predictions; (E ) DEA/MDEA
1/0;
(e ) DEA/MDEA 3/1; (F ) DEA/MDEA 1/1; ( ) DEA/MDEA 1/3;
(f ) DEA/MDEA 0/1.

It is interesting to note that even for the case of aqueous

solutions containing mixtures of DEA and MDEA, the
apparent equilibrium constants used in the model as given
by equation (12) depend only on CO2 partial pressure and
the total concentration of amine and not on the concentration of the different amines in the system. A series
of analyses were performed to evaluate the possibility
of expressing equation (12) in terms of the concentration of
the individual amine in addition to the CO2 partial pressure.
The results of the evaluation clearly indicate that using
equation (12) as it is written is more appropriate for a
solution of blended amine. For a non-ideal system, the
equilibrium constant, K, depends on the activity coef cient,
c i . Among the commonly used equations to estimate
activity coef cient is that of Debye Huckel which is
expressed as16
ln c i

A z 2i

bi

j bij

19

The equation considers both short and long range interactions of the different species in the system. The contribution
from the second term on the right hand side of the above
equation which represents the long range interaction has
been found to be small10 and can be ignored. Thus for
practical purposes it can be taken that the activity coef cient
only depends on the electrical charges of the species, z, and
the ionic strength of the solution, I, which in turn depend on
the concentration of all ionic species in the system and the
electrical charges of these species. A and bi in the equation
are constants. Regardless of the type, all protonated amines
possess electrical charges of 1. Thus, from the theoretical
view point, the presence of different amine will not affect
Trans IChemE, Vol 76, Part A, November 1998

967

Figure 6. Comparison between predicted CO2 loading and the data of

Austgen et al.15 in aqueous solution of 2M DEA 2M MDEA; Solid lines:
model prediction; ( e) 313 K; (F ) 353 K.

the activity coef cient of the system in question. From this

consideration, equation (12) is still valid when applied to a
system having a mixture of different amines, as supported
by the model prediction on CO2 loading discussed above.
CONCLUSIONS
The modi ed Kent Eisenberg model which takes into
account the effects of CO2 partial pressure and total amine
concentration on the apparent equilibrium constant for the
protonation of amine and the formation of carbamate is able
to give relatively good predictions on the total CO2 loading
in solutions of single and blended amines. The different
parameters expressing the equilibrium constant in terms of
CO2 pressure and amine concentration which were generated from experiments using single amine can be used to
describe the observed data for blended amines and those
published in the literature. The results also showed that the
experimental equilibrium constant at in nite dilution for
the formation of carbamate from DEA obtained from an
earlier work represents the true value for the reaction.
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ACKNOWLEDGEMENT
Financial support for this work was provided by the Ministry of Science,
Technology and Environment, Malaysia through the Seventh Malaysia Plan
IRPA Research Grant.

ADDRESS
Correspondence concerning this paper should be addressed to
Dr M. H. Haji-Sulaiman, Department of Chemical Engineering, University
of Malaya, 5063 Kuala Lumpur, Malaysia. (E-mail: mzaki@fk.um.edu.my).
The manuscript was communicated via our International Editor for
Japan, Professor Seiichiro Koda. It was received 18 February 1998 and
accepted for publication after revision 22 June 1998.

Trans IChemE, Vol 76, Part A, November 1998