1st Post Combustion Capture Conference

Equilibrium in the H 2 O-MEA-CO 2 system:

new data and modeling
Ugochukwu E. Aronua, Shahla Ghondala, Erik T. Hessena, Tore Haug-Warberga, Ardi
Hartonoa, Karl A. Hoffb, Hallvard F. Svendsena *
a
Department of Chemical Engineering, Norwegian University of Science and Technology,
N-7491 Trondheim, Norway
b
SINTEF Materials and Chemistry, N-7465 Trondheim, Norway

CO 2 absorption, Vapor-liquid equilibrium, N 2 O solubility, Thermodynamics, Extended UNIQUAC

1. Introduction

Several studies have been carried out on the solubility of CO 2 in aqueous MEA solution. The experimental data
of Jou et al., 1995 covers a wide range of temperatures, pressures and loadings, however it is available only for 30
mass % MEA. Of all the numerous work on MEA, only Mason and Dodge(1936) and Atadan (1954) measured CO 2
solubility in MEA at concentrations higher than 30mass %. These data are old and quite few. There is also a strong
need for more data in the very low loading and pressure regions for modeling purposes. Thus an up-to-date VLE
data set for the H 2 O-MEA-CO 2 system, spanning a large concentration range, is clearly needed. All model
implementations of H 2 O-MEA-CO 2 system were based on data of not more than 30 mass % MEA concentration,
except for Hessen (2010) who applied the r-e-NRTL model to predict experimental VLE results of 60mass % MEA
up to 80oC. None of the existing models have used the solubility of N 2 O in MEA which by utilizing the so-called
N 2 O analogy (originally proposed by Clarke, 1964) gives a measure of the physical solubility, or Henry’s law
constant, of CO 2 in the aqueous MEA solution. Through the physical solubility of CO 2 , the activity coefficient of
CO 2 can be calculated. Hessen (2010) showed that existing models give CO 2 activity coefficients which are far from
the N 2 O analogy derived values.
The objectives of this work are to present a consistent VLE data set for MEA through experimental VLE
measurements for 15, 30, 45 and 60 wt% MEA in the low and high CO 2 loading regions from 40 to 120oC, and to

* Corresponding author. Tel.: +47-73594100; fax: +47-73594080.

E-mail address: ugochukwu.aronu@chemeng.ntnu.no (U.E. Aronu);
hallvard.svendsen@chemeneg.ntnu.no (H.F. Svendsen).
2

use these data together with CO 2 solubility data based on the N 2 O analogy, to provide a rigorous equilibrium model
based on the extended UNIQUAC model framework (Thomsen and Rasmussen, 1999).

2. Equilibrium experiments and model parameters regression

VLE experiments for preloaded aqueous MEA solutions were conducted from 40 to 80oC using a low
temperature/atmospheric vapor-liquid equilibrium apparatus while equilibrium total pressure data at 100 and 120oC
for the systems were obtained using a high temperature apparatus. The data set used for regression of model
parameters are; the experimental determined CO 2 partial pressures and total pressure measurements from this work
as well as data for solubility of N 2 O into 30wt% MEA from Hartono, 2009.

3. Results

The extended UNIQUAC model results for the N 2 O (physical) solubility of 30 wt% MEA are shown in figure 1.
The average absolute relative deviation (AARD) value of 2.7% indicates a very good representation of experimental
data. Sample model results and experimental CO 2 partial pressures from this work as functions of loading and
temperature are given in figure 2. The model correlates well CO 2 partial pressures over MEA solutions for 15, 30,
45 and 60 wt% MEA and adequately predicts pCO 2 down to 0.5wt% MEA. The AARD of 18.8 % for the fit to own
data shows that the model gives a good representation of the experimental data. Figure 3 shows the concentration
dependency of CO 2 partial pressure for the MEA system. It is clear from the figure that CO 2 partial pressures over
MEA solution are strongly dependent on the MEA concentration.
4
x 10
1.8
○ 25oC
1.6 □ 40oC
+ 49oC
1.4
Δ 59oC
HCO2 (Pa.m .mol )
-1

× 68oC
1.2
● 78oC
HCO2Model

4
10
MEA
3

◊ 87oC
1
MEA

0.8

0.6

0.4
a b
0.2
0 0.1 0.2 0.3 0.4 0.5 4
10
CO2 loading (mol CO2/mol MEA) MEA
HCO2Experiment

Figure 1: (a) Solubility of N 2 O in 30wt% MEA partialy loaded with CO 2 . Experimental points, Hartono 2009; ,
e-UNIQUAC this work. (b) Parity plot between experimental and model predicted N 2 O solubility in 30wt% MEA.

4 4
10 10

3 3
10 10

2 2
10 10

1 1
10 10
PCO2 (kPa)
PCO2 (kPa)

0 0
10 10

-1 -1
10 10

-2 -2
10 10

-3 -3
10 10
a b
-4 -4
10 10
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0 0.1 0.2 0.3 0.4 0.5 0.6
CO2 loading (mol CO2 / mol MEA) CO2 loading (mol CO2/mol MEA)

Figure 2: CO 2 partial pressure as function of loading for MEA. Experimental data; ○, 40oC; ◊, 60oC; □, 80oC; Δ,
100oC; ∇ , 120oC; —, e-UNIQUAC. (a) 30wt% MEA. (b) 60wt% MEA.
 Author name / Energy Procedia 00 (2011) 000–000 3

50
60wt%
60wt%
45
45wt%
40 45wt%
0 35 30wt%
10
PCO2 (kPa)

PCO2 (kPa)
30
15wt%
25
15wt%
20 6wt%
-2
10 30wt% 15 3wt%
10

5
0.5wt%

0
0.1 0.2 0.3 0.4 0.5 0.4 0.45 0.5 0.55 0.6 0.65
CO2 loading (mol CO2/mol MEA) CO2 loading (mol CO2/mol MEA)

(a) (b)
Figure 3: Concentration dependency of equilibrium CO 2 partial pressure of MEA at 40oC

4. Conclusions

New experimental data for vapor-liquid equilibrium of CO 2 in aqueous monoethanolamine solutions are
presented for 15, 30, 45 and 60 mass % MEA and from 40 to 120oC. CO 2 partial pressures over loaded MEA
solutions were measured using a low temperature equilibrium apparatus while total pressures were measured with a
high temperature equilibrium apparatus. The extended UNIQUAC model framework was applied; model parameters
were fitted to the new experimental VLE data and physical solubility data from the literature. The model gives a
good representation of the experimental VLE data for all MEA concentrations with an average absolute relative
deviation (AARD) of 18.8 % and also of the physical solubility data with an average absolute relative deviation
(AARD) of 2.7 %. Further, the model predicts well liquid phase speciation results determined by NMR and
experimental data for freezing point depression and excess enthalpy.

Acknowledgment
This publication forms a part of the BIGCO2 project, performed under the strategic Norwegian research program
Climit. The authors acknowledge the partners: Statoil AS, GE Global Research, Statkraft, Aker Clean Carbon, Shell,
TOTAL, ConocoPhillips, ALSTOM, the Research Council of Norway (178004/I30 and 176059/I30) and Gassnova.

References
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