A Model for Estimating CO

2
in Aqueous
Alkanolamines
J ostein Gabrielsen, Michael L. Michelsen, Georgios Kontogeorgis, Erling H. Stenby
IVC-SEP, Department of Chemical Engineering, The Technical University of Denmark, Lyngby
To beableto develop moreefficient processes for theseparation of acid gases fromfluegases, thermodynamic modelling of thevapour liquid phaseequilibriumis thefirst step. Most thermodynamic models used
to represent thevapour-liquid equilibriaof CO
2
in an aqueous solution of alkanolamines arevery complex and requirealargeamount of adjustableparameters. This is dueto thefact that thealkanolamines are
weak electrolytes and chemical reactions between alkanolamineand CO
2
occur in theliquid phase. Another problemconcerning therepresentation of thevapour-liquid equilibriais that theexperimental data
existing arenot always plentiful and reliable. Thereis alargescatter particularly at low partial pressures and loadings. In this work avery simplemodel has been developed for representing theVLE of aqueous
alkanolaminesolutions.
References:
[1] J ou, F.-Y.; Mather, A. E.; Otto, F. D. TheSolubility of CO
2
in a30Mass Percent MonoethanolamineSolution. Can. J. Chem. Eng. 1995, 73, 140.
[2] Lawson, J . D.; Garst, A. W.; Gas SweeteningData: EquilibriumSolubility of HydrogenSulfideand Carbon Dioxidein Aqueous Monoethanolamineand Aqueous DiethanolamineSolutions. J. Chem. Eng. Data. 1976, 21, 20.
[3] Lal, D.; Otto, F. D.; Mather, A. E. TheSolubility of H2S and CO2 in aDiethanolamineSolution at Low Partial Pressures. Can. J. Chem. Eng. 1985, 63, 681.
[4] Sidi-Boumedine, R.; Horstmann, S.; Fischer, K.; Provost, E.; Frst. W.; Gmehling, J . Experimental determination of carbon dioxidesolubility datain aqueous alkanolaminesolutions. Fluid Phase Equilib. 2004, 218, 85.
[5] Park S.H., LeeK.B., Hyun J .C., KimS.H., Corellationand prediction of thesolubility of Carbon Dioxidein Aqueous Alkanolamineand Mixed AlkanolamineSolutions, Ind. Eng. Chem. Res., 2002, 41, 1658.
[6] Bishnoi S., RochelleG.T., Absorption of carbondioxideinto aqueous piperazine: reaction kinetics, mass transfer and solubility, Chem. Eng. Sci., 2000, 55, 5531-5543
[7] Liu H.-B., ZhangC.-F., XuG.-W., A Study on EquilibriumSolubility for Carbon Dioxidein Metyldiethanolamine-Piperazine-Water Solution, Ind. Eng. Chem. Res., 1999, 38, 4032-4036
Figure 1 Comparison of model correlation results (solid lines) with
experimental data for CO
2
equilibrium partial pressures over an
aqueous 30 wt % MEA solution, experimental data from [1]
Figure 2 Comparison of model correlation results (solid lines) with experimental
data for CO
2
equilibrium partial pressures over an aqueous 25 wt % DEA
solution, experimental data from [2] and [3].
Figure 3 Comparison of model correlation results (solid lines) with
experimental data for CO
2
equilibrium partial pressures over an
aqueous 46.88 wt % MDEA solution, experimental data from [4].
Figure 4 Comparison of model correlation results (solid lines) with
experimental data for CO
2
equilibrium partial pressures over an
aqueous 30 wt % solution of AMP, experimental data from [5].
Figure 5 Comparison of model correlation results (solid lines) with experimental
data for CO
2
equilibrium partial pressures over an aqueous 5.17 wt % solution of
Piperazine, experimental data from [6].
Figure 6 Comparison of model correlation results (solid lines) with
experimental data for CO
2
equilibrium partial pressures over a
blended aqueous solution of 0.35 M Piperazine and 3.15 M MDEA,
experimental data from [7].
2 3
2H O H O OH
+
+
2 2 3 3
2 CO H O H O HCO
+
+ +
2
3 2 3 3
HCO H O H O CO
+
+ +
2 2 3
' ' RR NH H O H O RR NH
+ +
+ +
2 3
' ' RR NCOO H O RR NH HCO

+ +
( )
2 2
' ' 2 ' . RR NH RR NCOO RR NH CO aq
+

+ +

( )
3 2 2
. RH HCO R CO aq H O
+

+ + +

2
2
2
0
2
2
,
'
2
CO
CO
moleCO amine
loading a initial concentrationof amine
moleamine amine+H O
K combined Henry s lawand equilibriumconstant for partial pressure
of CO over the solution
X molefractionof chemicallybound CO inthe s
= = = =
=
=
( )
olution
T temperature Kelvin =
[ ] ( )
0 2 0
' 1 2 , ' ' RR NH a R RNH RR NCOO a
+
= = =

( ) ( )
2 2 2
0
2
0
1 2
CO CO CO
a
p K X
a

[ ] ( )
0 3 0
1 , R a RH HCO a
+
= = =

( )
2 2 2
0
0
1
CO CO CO
a
p K X
a

2
0 0
ln
CO
B
K A Ca D a
T
= + + +
Thechemical equilibriumtakingplacein theliquid phasewhen CO
2
is
absorbed in aqueous MEA or DEA is described by the following
reactions:
But many simplifications may becarried out, given certain conditions
(loadingbetween 0.02 and 0.48), and the absorption can bedescribed
by onechemical equilibriumreaction:
2 3
2H O H O OH
+
+
2 2 3 3
2 CO H O H O HCO
+
+ +
2
3 2 3 3
HCO H O H O CO
+
+ +
2 3
RH H O H O R
+ +
+ +
Thechemical equilibriumtakingplacein theliquid phasewhen CO
2
is
absorbed in aqueous MDEA or AMP is described by the following
reactions:
But many simplifications may be carried out, given certain conditions
(loading between 0.02 and 0.8 or 0.98), and the absorption can be
described by one chemical equilibrium reaction (it is also used for
Piperazine:
Then defining K
CO2
as a combined Henrys Law and chemical
equilibriumconstant and using the following the partial pressure of
CO
2
over thesolution can beexpressed
Then defining K
CO2
as a combined Henrys Law and chemical
equilibriumconstant and using the following the partial pressure of
CO
2
over thesolution can beexpressed
MEA and DEA
AMP, MDEA, and Piperazine Common Definitions Used in the Model
Thecombined chemical equilibriumand Henrys Law constant is then
fit to experimental VLE data using four adjustable parameters (all
parameters arenot needed for all alkanolamines):
A and B represent the standard temperature dependence of the
chemical equilibriumconstant. The parameters C and D which are
dependent on the total loading is included to approximate an ionic
strength dependence. FurthermoretheB parameter is directly related
theheat of absorption of CO
2
through theGibbs-Helmholtz equation.
Model
Results
Alkanolamines
OH
N
H
H
MEA
Monoethanolamine
HO
N
OH
H
DEA
diethanolamine
OH
N
HO
CH
3
MDEA
Methyldiethanolamine
Piperazine