chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599

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Effect of methanol addition on waterCO
2
diethanolamine
system: Inuence on CO
2
solubility and on liquid phase
speciation
A. Archane, L. Gicquel, E. Provost, W. F urst

UER Chimie et proc ed es, Ecole Nationale Sup erieure de Techniques Avanc ees, 32 Boulevard Victor, 75739 Paris Cedex 15, France
a r t i c l e i n f o
Article history:
Received 2 October 2007
Accepted 10 March 2008
Keywords:
Absorption
Acid gas
Alcanolamine
Carbamates
Carbon dioxide
EOS
a b s t r a c t
The aim of this study is the characterisation of VLE and chemical equilibria for the sys-
tem CO
2
/diethanolamine (DEA)/H
2
O/methanol. The effect of MeOH composition has been
studied using four compositions (from 0 to 30wt% of methanol with a xed composition
(30wt%) of DEA), the measurement being made at T=298.15K and at various CO
2
loadings
(from 0.2 to 0.8). An original experimental device was used. This device combines a FT-IR
spectroscopy analysis of the liquid phase with a VLE measurement cell.
The data base obtained, including the new solubility data and the liquid phase com-
position, allows the modelling of the system CO
2
/DEA/H
2
O/methanol using an electrolyte
equation of state [F urst, W., Renon, H., 1993, Representation of excess properties of elec-
trolyte solutions using a new equation of state, AIChE J, 39(2): 335343] representing the
equilibrium properties of the system and the liquid phase speciation.
2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
1. Introduction
Absorption of acid gases (CO
2
and H
2
S) in alkanolamine solu-
tion is widely used in many gas purication processes. These
processes are based on chemical absorption. The chemical
equilibria involved in the systems are as follows:
water dissociation : 2H
2
O H
3
O
+
+OH

aminedissociation : R
1
R
2
R
3
N + H
3
O
+
R
1
R
2
R
3
NH
+
+H
2
O
carbondioxidehydrolysis : CO
2
+2H
2
O HCO
3

+H
3
O
+
hydrogen-carbonatehydrolysis :
HCO
3

+H
2
O CO
3
2
+H
3
O
+
carbamates hydrolysis :
R
1
R
2
NH + HCO
3

R
1
R
2
NCOO

+H
2
O
(secondary andprimary amine)

Corresponding author.
E-mail address: Walter.Furst@ensta.fr (W. F urst).
Hence the solutions resulting from the absorption of acid
gases are complex ones and contain ionic as well as molecular
solutes.
In this case, i.e. when the species present in the liquid
phase are connected by chemical reactions, it is known that
the models using parameters adjustedonly onthe pressure vs.
CO
2
solubility data lead to non-realistic representations of the
liquid phase composition. Consequently, even if the represen-
tation of the solubility data is correct, any extrapolation of the
model beyond the range of experimental values used for the
adjustment may conduct to large deviations. Moreover, the
incorporation of such thermodynamic approach in a model
used to represent the absorption kinetics is not very reliable.
The need of speciation data could be illustrated by the
results we obtained studying a much more simple system
(Passarello and F urst, 1996). In the case of waternitric acid
system the data treatment of experimental values for water
and nitric acid partial pressures conducted to a bad rep-
resentation of acid dissociation. But when the speciation
data are included in the database, a precise representa-
tion of both type of data (VLE and speciation) could be
obtained.
0263-8762/$ see front matter 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.cherd.2008.03.005
chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599 593
Nomenclature
A peak area (A.U)
b covolume
c volume translation factor
C concentration (mol/L)
D dielectric constant of the solution
e protonic charge
k response coefcient
n number of moles
N Avogadro number
P pressure (kPa)
R gas constant
T temperature (K)
v molar volume of the solution
V volume (L)
W interaction parameter (dened in Eq. (3))
x mole fraction
x
app
apparent mole fraction
Z ionic charge
Greek letters
loading
1 the shielding parameter (dened in Appendix
B)
z correlation parameter (dened in Eq. (3))
o diameter
o
H
2
O
solvated diameter by water
o
mel
solvated diameter in mixture
t NRTL parameter
Subscripts
c critical property
i,j relative to ionic species
LR long-range term
RF repulsive forces term
SOL solution
SR1 non-electrolyte short-range term
SR2 ionic short-range term
However, although there is a strong link between the devel-
opment of a realistic model and the use of experimental
information about the liquid phase speciation, the equi-
librium data available in the literature are essentially VLE
data (Lawson and Garst, 1976; Lee et al., 1972; Rogers et al.,
1997). Very few are related to the liquid phase composition
(Poplsteinova Jakobsen et al., 2005; B ottinger et al., 2008). This
conducted us to develop an original device that combines a
FT-IR spectroscopic analysis of the liquid phase with a VLE
measurement cell (Sidi-Boumedine, 2003).
Since several years, processes using physical solvents as
well as chemical solvents were developed (Isaacs et al., 1977:
sulnol solution; Henni and Mather, 1995: MDEA+methanol;
Tounsi et al., 2005: DEA+methanol). This explains that, as a
part of our laboratorys experimental work is devoted to the
determination of the speciation in electrolyte systems, we
initiated the determination of the effect of adding a phys-
ical solvent (methanol) on the liquid phase composition of
CO
2
/alkanolamine/water system. This mixed solvent system
has been studied as a possible solvent for acid gas absorption
process and some experimental values for solubility of CO
2
and H
2
S have been already published (Tounsi et al., 2005).
2. Methods and materials
2.1. Apparatus
The experimental device used in this work consists in two
parts: the equilibrium cell, where the solubility of the CO
2
is
measured and anexternal analytical loop, where the composi-
tion of the liquid phase is determined. This device, presented
in Fig. 1, allows the measurement of liquidvapor equilibria
as well as the liquid phase composition for pressure range
from0 to 200kPa and for temperatures between 280 and 350K.
The equilibrium cell is a double-jacketed glass reactor (vol-
ume=460mL), equipped with a pressure transducer (PTX 611
from Druck) and temperature probe (Pt 100, from TC SA). The
uncertainties in pressure and temperature are 0.1kPa and
0.1K, respectively and the maximum pressure is 200kPa as
we are using a glass cell. The stainless lid is maintained at a
temperature slightly higher than the cell temperature to avoid
condensation phenomena. The liquid phase analysis is real-
ized using an infrared spectrometer with an ATR (attenuated
total reectance) cell. During the measurement, the liquid
phase is pumped out from the equilibrium cell to the ATR cell
by HPLC pump, and then returns to the equilibrium cell. The
temperature of the circulation loop (global volume: 3mL) is
maintained at the temperature of the equilibrium cell with an
accuracy of 0.8K.
2.2. Experimental procedure
CO
2
with a purity of 99.9%, supplied by Air Liquide, was used.
The solutions are prepared by weighting, using solvents indi-
vidually degassed. Distilled water and solvents with purity of
+99% were used (methanol and diethanolamine (DEA) from
Sigma Aldrich). The nal degassed solution, containing water,
methanol and DEA, is transferred into the equilibrium cell.
Once the thermal equilibrium is reached, the corresponding
solvent vapor pressure P
vap
sol
is measured. CO
2
, contained in a
reservoir, is then loaded into the cell. Both amounts of CO
2
and alkanolamine solution introduced in the cell are known
by weighting their reservoirs before andafter the introduction.
The precision of weighting is 0.001g. Pressure and IR spec-
tra are regularly checked and when no change occurs within
1h, we assume that the equilibrium is reached. The equilib-
rium pressure and the IR spectra are then recorded, the IR
Fig. 1 Schematic diagram of the apparatus.
594 chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599
spectra being used for the determination of the liquid phase
speciation.
The measurements have been made at T=298.15K and at
various CO
2
loadings (the number of moles of CO
2
in the liquid
phase, divided by the number of alkanolamine moles in the
liquid phase) from 0.2 to 0.8 for every studied system.
2.2.1. Partial pressure and CO
2
loading determination
The CO
2
partial pressure P
CO
2
is calculated from the total
pressure P
tot
and the saturated vapor pressure of the gas-free
solvent P
vap
sol
applying Raoults expression:
P
CO
2
= P
tot
P
VAP
SOL
(1 x
app
CO
2
) (1)
where x
app
CO
2
is the apparent molar fraction of CO
2
in the liquid
phase.
To study the solubility of CO
2
in the solution, the partial
pressure of carbon dioxide in the reactor is presented as a
function of the CO
2
loading
CO
2
. Thus to calculate the CO
2
loading, it is necessary to know the global mole numbers of
amines and CO
2
in the liquid phase from the total amount of
CO
2
in the cell at equilibrium temperature and pressure. As
the amine is a non-volatile compound, the total mole number
of amine in the liquid phase corresponds to what has been
introduced in the cell and is known by weighting. On the other
hand, CO
2
is present inbothvapor andliquidphases anda cor-
rection of vapor phase is necessary for calculation of the CO
2
loading. Finally we have

CO
2
=
n
CO
2
.in
[(V
reactor
V
solution
),V
mol
CO
2
.gas
]
n
Am.in
(2)
where n
CO
2
.in
is the total number of CO
2
introduced, V
reactor
the volume of the reactor, V
solution
the volume of the solution
and V
mol
CO
2
.gas
is the molar volume of CO
2
in the vapor phase
(deduced from the partial pressure of CO
2
in the vapor phase
by applying the ideal gas expression). The accuracy on the
loading is 1%.
2.2.2. IR peak identication and determination of the
concentration
Fig. 2 presents the IR spectrum obtained for a water/DEA solu-
tion loaded with CO
2
. Three peaks are particularly interesting:
the peak observed at 2340cm
1
is specic to molecular CO
2
,
the peak at about 1530cm
1
is representative of carbamates
and the one at 1360cm
1
is characteristic of HCO
3

. In order
to get quantitative results from the treatment of IR spectra, it
Fig. 2 Infrared spectrum of a DEA solution charged with
CO
2
.
is necessary to determine the area of each peak. For HCO
3

and carbamate, a deconvolution is necessary. The concentra-

tion C
i
of a specie i is then proportional to the corresponding
peak area A
i
by: C
i
=k
i
A
i
(mol/L) where k
i
has to be determined
through calibration experiments.
Molecular CO
2
concentration determination
From Fig. 2 it could be observed that the CO
2
peak is located
in spectrum range where no other signicant absorption is
present. It may be easily integrated. The validity of a linear
relationship between the CO
2
peak and the CO
2
concentra-
tion C
CO
2
,molec
= k
CO
2
Area
CO
2
was checked by the analysis
of the water/CO
2
system (Sidi-Boumedine et al., 2005). The
accuracy on C
CO
2
is 15%.
In this system, the dissolved CO
2
concentration (molecular
form) is perfectly known as a function of temperature and
pressure (Carroll et al., 1991). Knowing the peak area and
the concentration, the authors have determined the k
CO
2
value. In the present study, this value is used to determine
the molecular CO
2
concentration from its IR peak area.
HCO
3

and carbamate concentration determination

The study of MDEAH
2
OCO
2
system allows to determine
the coefcient k
HCO
3

connecting the HCO

3

peak area to
its concentration. In this case, the HCO
3

concentration is
the difference between the introduced CO
2
concentration
and the molecular CO
2
. In a second step, the analyses of
the spectra of DEAH
2
OCO
2
system allows to determine
the coefcient k
carbamate
connecting the carbamates peak
area to its concentration. This concentration is calculated
by subtraction of the HCO
3

concentration and the molecu-

lar CO
2
concentrationfromthe apparent CO
2
concentration.
These calibrations have been done and the determination
of the HCO
3

and carbamates peak areas in the systems

containing methanol will make it possible to know their
concentration.
3. Results and analyses
The aim of this work is to study the effect of methanolwater
system on the equilibrium properties in the presence of DEA
and CO
2
. This effect has been studied using different solvent
compositions (from0 to 30wt%of methanol withxedcompo-
sition (30wt%) of DEA), the measurement being made at xed
temperature (T=298.15K):
methanol: 0wt%; water: 70wt%; DEA: 30wt%
methanol: 10wt%; water: 60wt%; DEA: 30wt%
methanol: 20wt%; water: 50wt%; DEA: 30wt%
methanol: 30wt%; water: 40wt%; DEA: 30wt%
3.1. Solubility
In order to compare CO
2
solubility of the various studied sys-
tems, we representedinthe same gure (Fig. 3) the evolutionof
CO
2
partial pressure (determined from the reactor total pres-
sure by application of Eq. (1)) with the CO
2
loading at different
compositions.
Inall the cases, the variationof the CO
2
pressure is very low
for loadings lower than 0.5. Beyond this value, the solubility of
CO
2
decreases (the CO
2
partial pressure increases) with the
increase in the CO
2
loading, even if we remain clearly below
the amine saturation. In fact when the CO
2
loading increases,
the carbamate is transformed gradually into HCO
3

. At xed
chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599 595
Fig. 3 CO
2
solubility in methanolwaterDEA (30wt%)
solution.
CO
2
loading, the solubility of CO
2
decreases when the concen-
trationinmethanol increases inthe solutioninthe considered
loading range (lower than the amine saturation
CO
2
=1). This
can be explained by a less favourable chemical reaction in a
solvent with lower polarity. The increase in methanol concen-
tration involves a strong reduction of the dielectric constant,
which disadvantages the formation of ions and, therefore
the chemical absorption of CO
2
. This result is in agreement
with the results obtained by Henni and Mather (1995) in the
case of the mixture of solvents (MDEA+methanol +water)
as well as by Isaacs et al. (1977) in the case of the mixture
(DIPA+sulfolane+water).
3.2. Liquid phase composition
Fig. 4 shows the evolution of the molecular CO
2
concentra-
tion with the CO
2
loading for different compositions. To take
into account the matrix effect, especially the inuence of
methanol concentration on the relation between peak areas
and species concentration, studies of sub-systems such as
watermethanolCO
2
have been made.
At xed CO
2
loading, the molecular CO
2
concentration
increases when the methanol concentration increases in the
solution. This result illustrates the greater solubility of CO
2
in methanol than in water. The addition of methanol to DEA
aqueous solution results in two opposite effects on CO
2
solu-
bility: the presence of methanol increases the solubility of the
molecular form of CO
2
, whereas it has negative effect on its
ionisation.
Fig. 4 Evolution of the molecular CO
2
concentration with
the CO
2
loading.
Fig. 5 Evolution of the HCO
3

and carbamates molar

fraction with the CO
2
loading.
Fig. 5 shows the evolution of the HCO
3

and carbamates
molar fractions with the CO
2
loading in the methanol: 10wt%;
water: 60wt%; DEA: 30wt% system.
According to Fig. 5, andas one couldexpect, for lowloading,
the formation of carbamates is important. At higher loading
(approximately 0.5) the molar fraction decreases because the
carbamates ions react to form ions HCO
3

.
4. Discussion and conclusion
4.1. Modelling
4.1.1. Model presentation and treatment of data without
methanol
The model used to represent experimental data is an elec-
trolyte equation of state (EOS). A cubic EOS is used for
non-electrolyte interactions, and two supplementary terms
are added to take into account ions. In this work, the non-
electrolyte EOS is the Redlich Kong Soave equation, and the
mixing rule is of Wong Sandler type, with the NRTL model.
For electrolyte part of the EOS, two terms are used: a MSAterm
to represent interactions between ions charges, and a term to
deal with the solvation phenomena. Both terms can be found
in the paper of F urst and Renon (1993).
The main equations dening the model are given in
Appendix B and the ionic parameters used for the representa-
tion of data are detailed in Appendix C.
First, interactions parameters between molecular species
have been tted on the VLE data of binary systems. The
following systems have been considered: watermethanol,
waterDEA, waterCO
2
and methanolCO
2
. The values of k
ij
(in the Wong Sandler mixing rule) and of t
ij
(in NRTL model)
have then be determined, except those for methanolDEA
and CO
2
DEAinteractions because no experimental data have
been found in the literature.
To extrapolate the model to the ternary system
waterDEACO
2
, the determination of new parameters
to represent the interactions between ionic species formed
during the absorption is necessary. As many experimental
data are available for systems containing CO
2
and H
2
S,
the model has been used to represent simultaneously both
ternary systems.
Two types of ionic parameters can be found in the model.
The rst ones deal with the contribution of ions to the covol-
ume (b
i
parameters) and the second ones are interaction
parameters (W
ij
). It has yet been shown that all the covol-
596 chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599
Fig. 6 Representation of the systems waterDEACO
2
and
waterDEAH
2
S with the equation of state of electrolytes.
ume parameters and the ionion and ionsolvent interaction
parameters can simply be correlated to the solvated diam-
eters (F urst and Renon, 1993). For instance W
ca
interaction
parameter could be calculated through:
W
ca
= z
5
(o
c
+o
a
)
4
+z
6
(3)
The list of all correlations used for the calculation of b
or W interaction parameters are given in Table C.4. In this
work, the diameters of solvated ions (DEAH
+
corresponding
to protonated DEA, HCO
3

and HS

) have been tted. b

i
and
W
DEAH
+
.water
have been deduced from correlation with ionic
diameters using the methods already published (Vall ee et
al., 1999). Considering the large size of anions compared to
the cation size, interactions between anion and water have
been neglected. The last parameters to be adjusted from
a data treatment of experimental values relative to system
water/DEA/acidgas are the carbamate formationconstant and
its evolution with temperature because the values found in
literature are not consistent. Finally, 11 parameters have been
tted (4 solvated diameters, 2 parameters for the carbamate
formation constant, 3 W
ij
and 2 z correlation parameters: z
5
and z
6
) on 577 experimental data. It must be noticed that,
except the carbamate formation constant, the parameters are
supposed to be temperature independent.
The results are presented in Fig. 6. The deviations are rel-
atively low, considering the large experimental range and the
experimental deviation.
4.1.2. Extension of the model to the CO
2
solubility when
methanol is added
The second step of this work has been to use the model for the
representation of the CO
2
solubility in water/DEA/methanol
mixture. A mixing rule has been used to take into account
the preferential solvation phenomenon in solvent mixture
water +methanol. In order to reduce the number of param-
eters, the following simple mixing rule has been used:
o
mixture
i
=
x
app
water
o
water
i
+x
app
methanol
o
methanol
i
x
app
water
+x
app
methanol
(4)
All the other parameters, including water solvated diame-
ters, are the same as in the previous part of this work. To apply
the model, only the diameters of ions solvated by methanol
have to be determined. Moreover, anionic diameters in the
mixture are kept at the same value as in water. So, only one
Fig. 7 Calculated and experimental molecular CO
2
peak
area for the systems waterDEACO
2
methanol with
electrolyte EOS.
parameter (the DEAH
+
diameter solvated by methanol) has to
be tted. But, because solventanion interactions have been
neglected, the inuence on anion of the change from water
to water +methanol is not well taken into account. Two fur-
ther parameters have then to be added: W
methanol/HCO
3

and
W
methanol,carbamate
.
The three parameters have beenttedandthe relative devi-
ation between experimental and calculated pressure is from
6.5%to 13%, whichis correct considering the scattering of data
without methanol taken from the literature.
4.1.3. Comparison between measured and calculated
molecular CO
2
peak area
When the model, as described before, is used to calcu-
late the molecular CO
2
peak area, the results are poor. So,
another parameter t
CO
2
.DEA
has been tted, together with
W
methanol/HCO
3

and W
methanol,carbamate
, on equilibrium pres-
sure and CO
2
peak data. The nal result is presented in Fig. 7.
The three systems (containing 10, 20 and 30wt% of
methanol) are correctly represented.
In a last step we have compared the experimental val-
ues of the carbamate peak area to values deduced from the
calculation, using the preceding set of ve parameters. The
experimental and calculated values are presented in Fig. 8.
Their difference is close to the experimental deviation
associated to the carbamate peak area determination.
Fig. 8 Calculated and experimental carbamate area for the
system waterDEACO
2
methanol with electrolyte EOS.
chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599 597
4.2. Conclusion
Original measurements of VLE data coupled to liquid
phase composition data have been obtained for the system
water/DEA/methanol/CO
2
. The use of an equation of state
suited for electrolyte solution leads to a good representation
of pressure data of this system, using the parameters tted
on the systems (water/DEA/CO
2
or H
2
S) and only three new
parameters to take into account the methanol effect. All these
parameters did not allow to obtain a valuable representation
of the molecular CO
2
concentration in the liquid phase. To
determine correctly this concentration, new parameters had
to be tted on both pressure and IR peak area data. This
last set of parameters has led to a good representation of
carbamate composition in the liquid phase, via the prediction
of the carbamate peak area. A new thermodynamic tool has
then been developed in this work, for the realistic representa-
tion of water/alkanolamine/physical solvent/CO
2
.
Acknowledgment
We express our thanks to Agence Nationale pour la Recherche
for its nancial support (convention NT05-2 41583).
Appendix A. Tables of experiment data
x
app
DEA x
app
Eau x
app
CO
2
x
app
MeOH P
CO
2
(kPa) CO
2
area (A.U)
30wt%DEA60wt%H
2
O10wt%MeOH
0.073 0.845 0.000 0.0826 0.000 0.000
0.072 0.831 0.016 0.0813 0.979 0.230
0.071 0.825 0.023 0.0807 1.712 0.329
0.071 0.821 0.028 0.0803 2.435 0.398
0.070 0.817 0.033 0.0799 4.457 0.466
0.070 0.814 0.036 0.0797 7.373 0.513
0.070 0.812 0.039 0.0794 11.185 0.551
0.070 0.810 0.041 0.0792 17.097 0.587
0.070 0.808 0.043 0.0791 24.706 0.616
0.070 0.807 0.045 0.0789 34.616 0.647 0.10
0.069 0.805 0.047 0.0788 45.124 0.673 0.13
0.069 0.804 0.048 0.0786 60.232 0.699 0.17
0.069 0.802 0.050 0.0785 77.641 0.726 0.24
0.069 0.801 0.052 0.0783 98.449 0.751 0.30
0.069 0.800 0.053 0.0783 111.053 0.765 0.35
0.069 0.799 0.054 0.0782 125.257 0.777 0.38
0.069 0.799 0.054 0.0782 134.560 0.786 0.41
0.069 0.798 0.055 0.0781 141.363 0.797 0.45
30wt%DEA50wt%H
2
O20wt%MeOH
0.077 0.751 0.000 0.172 0.000 0.000
0.076 0.744 0.009 0.170 0.761 0.121
0.075 0.736 0.021 0.168 3.236 0.272
0.075 0.728 0.030 0.167 4.998 0.401
0.074 0.722 0.038 0.165 11.752 0.515
0.074 0.719 0.042 0.165 21.580 0.576
0.073 0.716 0.046 0.164 38.707 0.633 0.13
0.073 0.713 0.050 0.163 63.830 0.683 0.24
0.073 0.712 0.052 0.163 91.546 0.719 0.34
0.073 0.710 0.054 0.163 118.659 0.746 0.44
0.073 0.709 0.056 0.162 145.969 0.769 0.54
0.073 0.708 0.057 0.162 165.275 0.781 0.62
0.073 0.708 0.057 0.162 173.978 0.788 0.64
30wt%DEA40wt%H
2
O30wt%MeOH
0.083 0.650 0.000 0.266 0.000 0.000
0.082 0.644 0.010 0.264 0.482 0.124
598 chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599
Appendix A (Continued)
x
app
DEA x
app
Eau x
app
CO
2
x
app
MeOH P
CO
2
(kPa) CO
2
area (A.U)
0.081 0.637 0.021 0.261 1.373 0.262
0.080 0.628 0.035 0.257 5.185 0.439
0.080 0.623 0.043 0.255 14.946 0.537
0.079 0.620 0.047 0.254 27.679 0.590 0.099
0.079 0.618 0.050 0.253 46.307 0.637 0.206
0.079 0.616 0.053 0.252 70.532 0.678 0.306
0.078 0.614 0.056 0.252 97.851 0.710 0.448
0.078 0.613 0.057 0.251 121.265 0.733 0.545
0.078 0.612 0.059 0.251 143.876 0.752 0.680
0.078 0.612 0.060 0.251 161.884 0.765 0.791
0.078 0.611 0.060 0.250 169.688 0.772 0.802
0.078 0.611 0.061 0.250 176.892 0.778 0.870
All the measurements have been made at T=298.15K.
Appendix B. Equations of the model
The model is based on an expression of the molar Helmholtz
energy that contains four contributions:

u u
0
RT

u u
0
RT

RF
+

u u
0
RT

SR1
+

u u
0
RT

SR2
+

u u
0
RT

LR
(B.1)
The term of the rst attractive short-range (SR1) and the
term of repulsive forces (RF), are similar those of the Redlich
Kwong Soave equation of state

u u
0
RT

RF
=

k
x
k
ln

x
k
RT
P
0
(v b)

(B.2)

u u
0
RT

SR1
=
u
SR
RTb
ln

v
v +b

(B.3)
Table C.1 Equilibrium constants
Equilibrium K
a
K
b
K
c
K
d
2H
2
O+CO
2
=H
3
O
+
+HCO
3

231.465 12092.1 36.7816 0

H
2
O+DEAH
+
=H
3
O
+
+DEA 51.021 3302.998 6.7927 0.00357
H
2
O+DEACOO

=DEA+HCO
3

7.5904 4002.8 0 0
The parameters dene the equilibrium constants K in the mole fraction scale (lnK=K
a
+K
b
/T+K
c
lnT+K
d
T).
Table C.2 Solvated diameters (

A)
DEAH
+
DEACOO

HCO
3

Solvation by water 1.461 3.418 3.596

Solvation by methanol 2.557 3.418 3.596
where the covolume b is dened by
b =

s
x
s
b
s
+

i
x
i
b
i
s corresponding to molecular species and i to ions.
On the contrary the a
SR
parameter has no ionic contribu-
tion.
The short-range term (SR2) is specic to solvation interac-
tions and is dened by

u u
0
RT

SR2
=

j
x
i
x
j
W
ij
v(1
3
)
(B.4)
where i or j is an ion, and
3
is dened by

3
=
N
6

i
x
i
o
3
i
v
where i is the over all species.
The last term is the long-range interaction term:

u u
0
RT

LR
=
c
2
N
4
0
DRT

i
x
i
z
2
i
1
1 +1o
i
+
1
3
v
3N
(B.5)
chemi cal engi neeri ng research and desi gn 8 6 ( 2 0 0 8 ) 592599 599
Table C.3 Specic W
ij
interaction parameters (in SI units) between molecular compounds (except water) and DEAH
+
(the
interactions between these molecules and anions being ignored)
With DEA 1.9310
4
With CO
2
9.8610
5
With methanol
a
(Value at T
0
) 2.2010
4
(1/T1/T
0
) +2.3410
4
[ln(T/T
0
) T
0
/T]
a
The value at 298.15K (T
0
) is calculated from the correlations detailed in Table C.4.
Table C.4 Correlations used to get the ionion and the ionsolvent non-zero interaction parameters
Parameter Value
a
(10
6
) Comment
b
i
0.09865 (o
H
2
O
i
)
3
+6.96375 For anions and cations
W
DEAH
+
.H
2
O
or W
DEAH
+
.methanol
77.131 o
mel
DEAH
+
25.007
W
ca
0.064333(o
mel
c
+o
mel
a
)
4
43.0636 For interactions between DEAH
+
and HCO
3

or DEACOO

a
All values are in SI except the diameters (

A).
where D is the dielectric constant of the solution. It is cal-
culated using Pottels expression for taking into account the
effect of ions on its value.
The shielding parameter 1 is obtained from
41
2
=
c
2
N

0
DRT

i
x
i
v

z
i
1 +1o
i

2
Appendix C. Ionic parameters used in the
model
See Tables C.1C.4.
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