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Energy Procedia 114 (2017) 1841 – 1847

13th International Conference on Greenhouse Gas Control Technologies, GHGT-13, 14-18

November 2016, Lausanne, Switzerland

The Henry Coefficient of CO2 in the MEA-CO2-H2O System

Lichun Lia,b*, Marcel Maedera, Robert Burnsa, Graeme Puxtyb, Sarah Clifforda, and Hai Yub
a
Department of Chemistry, School of Environmental and Life Sciences, The University of Newcastle, Callaghan, NSW 2308, Australia
b
CSIRO Energy, Mayfield West NSW, 2304, Australia

Abstract

The Henry Coefficient of CO2 is a fundamental property and crucial for the accurate simulation of the absorption and desorption
of CO2 in MEA solutions related to post combustion capture (PCC). The free CO2 concentration in amine solutions is very small
and is difficult to be measured since it reacts with the solution. The “N2O analogy” is traditionally applied to estimate the
physical solubility of CO2 based on the assumption that the two gases behave similarly in amine solutions. We propose a direct
way to determine Henry Coefficient of CO2 in MEA solutions as an alternative to N2O analogy. The method only requires vapor
liquid equilibrium measurements of the MEA-CO2-H2O system. Based on the total MEA concentration, loading and known
equilibrium constants the free CO2 can be computed which allows the determination of the Henry Coefficient. A 6-parameter
polynomial is used to approximate the Henry Coefficient as a function of the total MEA concentration and total CO2
concentration at 40 oC.
©©2017
2017TheTheAuthors.
Authors. Published
Published by Elsevier
by Elsevier Ltd.Ltd.
This is an open access article under the CC BY-NC-ND license
Peer-review under responsibility of the organizing committee of GHGT-13.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
Keywords: Henry Coefficient; CO2 absorption; VLE model; MEA solution;

1. Introduction

Accurate simulations of monoethanolamine (MEA) based CO2 capture processes are challenging, but extremely
important towards energy reduction, better column design and plant operation for post combustion capture (PCC).
The Henry Coefficient of molecular CO2 in MEA solutions plays a very important role in modelling and simulating
the CO2 absorption and desorption from MEA solutions. The Henry coefficient defines the equilibrium concentration
of a gas in a liquid and is directly proportional to the partial pressure of the gas above the liquid. However, as a
dissolved gas, aqueous CO2 undergoes several reactions when mixed with aqueous MEA solutions, which makes it

* Corresponding author. Tel.: +61 466 597 148;

E-mail address: lichun.li@uon.edu.au

1876-6102 © 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of GHGT-13.
doi:10.1016/j.egypro.2017.03.1313
1842 Lichun Li et al. / Energy Procedia 114 (2017) 1841 – 1847

extremely difficult to determine the free CO2 concentration via direct measurements. An indirect way, the so-called
“N2O analogy”, was then proposed and has been intensively applied for the estimation of the physical solubility of
CO2 in amine solutions [1-3]. It is based on the assumption that the two gases behave similarly, that the ratio of the
Henry Coefficients are independent of the solution composition, as shown in Equation (1).
H CO2 , A min e
H CO2 , H 2O
R H (1)
H N 2O , A min e
H N 2O , H 2O

The Henry Coefficients for both gases in water can be found in published open literature; determination of the
coefficient for N2O in any amine solution is relatively straightforward as N2O is not reactive and thus the Henry
coefficient of CO2 in amine solutions can be calculated. However, there are some limitations of the “N 2O analogy”
method [4, 5] and this is consistent with a recent published review paper from Svendsen et al. [6] as they state that
there is no sound evidence that, in fact the “N2O analogy” may be restricted to much more dilute system than 5 M
MEA solution in estimating the Henry Coefficient of CO2.
In view of these difficulties, the current study proposes an alternative and direct way to determine the Henry
Coefficient of CO2 in aqueous MEA solutions which avoids the N2O approximation. This method only requires VLE
measurements of the MEA-CO2-H2O system. And it is built on a well-established liquid phase model of the MEA-
CO2-H2O system to calculate the free CO2 concentration, CO2(aq), in MEA solutions. The Henry Coefficient can be
then calculated relating the free CO2 concentration and equilibrium CO2 partial pressure. The main focus of the
current study is to test the validity of the proposed method. Also, a 6-parameter polynomial equation is developed
for the purpose of describe the relationship between the CO2 Henry Coefficient and chemical composition of the
liquid phase, i.e. total MEA concentration and total CO2 concentration at 40 oC.

Nomenclature

H CO , A min e Henry coefficient of CO2 in Amine solutions

2

H N O , A min e Henry coefficient of N2O in Amine solutions

2

H CO , H O 2 2
Henry coefficient of CO2 in water
H N O, H O
2 2
Henry coefficient of N2O in water
Jx Activity coefficient of the species x
zx Charge of the species x
µ Ironic strength of the solution
K Equilibrium/protonation constant
[MEA]tot Total MEA concentration in solution (mol.L-1)
[CO2]tot Total CO2 concentration in solution(mol.L-1)
α CO2 loading (mol CO2/mol MEA)
exp
H CO2 ,i
Henry coefficient of CO2 in MEA solutions calculated from the liquid phase model
mod el
H CO ,i 2
Henry coefficient of CO2 in MEA solutions calculated from the 6-parameter polynomial equation

2. Data Handling

2.1. Data Collection

In this contribution, an extensive collection of vapor-liquid equilibrium (VLE) data of the MEA-CO2-H2O system
at 40 oC was collecteded, covering a wide range of CO2 partial pressure (PCO2), MEA concentration ([MEA]tot), and
total CO2 concentration ([CO2]tot) in solutions [7-24]. VLE data collected from pressures less than 1000 kPa were
believed to be a significant portion of the rather large data base since this conditions are more relevant to the CO 2
 Lichun Li et al. / Energy Procedia 114 (2017) 1841 – 1847 1843

capture using MEA solutions for a conventional PCC plant. The data outside this range were rejected. Also, some
extreme outliers have been removed manually. In total, a data set consisting of 146 data points was collected and
analyzed for determination of the Henry Coefficient of CO2 in MEA solutions at 40 oC.

2.2. Data Analysis

A comprehensive model describing all the equilibrium reactions together with protonation reactions for the
MEA-CO2-H2O system is well established and developed. In the MEA-CO2-H2O system, CO2 reacts with H2O, OH-
and MEA, form multiple species in solution, including MEACO 2-/ MEACO2H, CO32-, HCO3-, H2CO3, and CO2(aq).
All the reactions involved, including all the equilibria and protonation are shown below. The equilibria/protonation
constants values together with the sourced literature are shown in Table S1, Appendix A.
H   OH  mo H 2O (2)
K1

H  CO3 mo HCO3

 2 K2 
(3)
H  HCO3 moCO2  H 2O
  K3
(4)
H  MEAmo MEAH
 K4 
(5)
HCO3  MEAmo MEACO2  H 2O
 K5 
(6)
H   MEACO2 mo
K
MEACO2 H 6
(7)
ReactLab (http://www.jplusconsulting.com) was used to analyses and model the reactions. An activity coefficient
correction was applied to all ionic species for the simulation of the equilibrium concentrations, taking into account
the influence of ionic interactions on the effective concentration of chemical species. As shown in a previous
publication [25], employing a simple model for activity coefficient calculation is quite adequate in describing the
thermodynamic behavior of the amine/CO2 system compared with the complicated models like the Pitzer,
UNIQUAC and eNRTL equations. The Davies equation, as shown in equation (8), was used to estimate the activity
coefficients.

P (8)
logJ x  A u Z x2 (  0.3 u P )
1 P
J x is the activity coefficient of the species x, zx is its charge andv µ is the total ionic strength of the solution. The
parameter A is taken from Manov et al. as a function of temperature [26]. Considering all equilibria (equations (1) to
(6)) and activity coefficients, the equilibrium concentration of all species in CO2/MEA solutions can be simulated,
including the free CO2 concentration, [CO2]aq. The Henry Coefficient can be calculated from the experimental
measured CO2 partial pressure and calculated [CO2]aq. The calculated Henry Coefficient values of the MEA-CO2-
H2O system were fitted using a 6-parameter polynomial as a function of the total CO2 concentration ([CO2]tot), MEA
concentration ([MEA]), as shown in equation (9).

ln H a ˜ [CO2 ]tot
2
 b ˜ [CO2 ]tot  c ˜ [MEA]tot
2
 d ˜ [MEA]tot  e ˜ [CO2 ]tot ˜ [MEA]tot  f (9)

The relative error rather than the absolute error was used because the data vary over orders of magnitude, the
agreement between simulated results and calculated results from experimental data has been expressed as the
average absolute relative deviation as a percentage (AARD%).

n exp
H CO mod el (10)
,i - H CO2 ,i
¦
1
AARD% 100 u 2
exp
%
n H CO
i 1 ,i2
1844 Lichun Li et al. / Energy Procedia 114 (2017) 1841 – 1847

3. Results and Discussion

3.1. 6-Parameter polynomial equation

Based on the calculation from the comprehensive model of the MEA-CO2-H2O system, all calculated Henry
coefficient results were subjected to a liner regression using all parameters in equation (9). The fitted results of all
the parameters are presented in Table 1.
Table 1. All the parameters for equation 9 for estimating Henry Coefficient values
Parameters a b c d e f
Values 5.63E-01 -1.32E+00 6.91E-02 -1.35E-01 -3.29E-01 9.15E+00

8000

7000

6000
Henry Coefficient (kPa.mol-1.L)

5000

4000

3000
1 M MEA
2000

1000 2.5 M MEA

5 M MEA
0
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
α (mol CO2/mol MEA)

Fig. 1. Henry Coefficient values calculated from the liquid phase model together with the calculated results from the 6-parameter polynomial
equation in 1, 2.5 and 5 M MEA solutions as a function of CO2 loading at 40 oC. Puxty et al., (2009) [20] ; Portugal et al., (2009) [18];
∆ Park et al. (1997) [16]; Mazinani et al., (2011) [15]; □ Song et al., (1996) [23]; Shen and Li (1992) [22]; ○ Procheron et al., (2011) [19];
◊ Daneshvar et al., (2004) [8]; x Aroun et al., (2011) [7]; + Austgen et al. (1991) [9]; - Jones et al. (1959) [11]; * Sartori and Savage (1983) [21];
Jou et al. (1995) [19] ; Tong et al., (2012) [24];

The Henry Coefficient values calculated from the liquid phase model together with the predicted results from the
6-parameter polynomial equation of 1, 2.5 and 5 M MEA solutions as a function of CO 2 loading at 40 oC are shown
in Fig. 1. As evident from Fig.1, there is a substantial experimental spread of the VLE data used for the
determination of the Henry Coefficient. Also, as indicated in Fig. 1, the Henry coefficient is clearly depending by
both MEA concentration and CO2 loading. It generally decreases with increasing MEA concentration and shows a
more complex dependence with CO2 loading.

3.2. VLE model

Based on the polynomial equation generated in the current study, a simple vapor-liquid equilibrium model has
been developed that includes all the equilibrium/protonation reactions in the liquid phase and the Davis equation for
the purpose of estimating activity coefficient. By applying the vapor-liquid equilibrium, the CO2 partial pressure is
re-calculated from the chemical composition of the liquid phase, [MEA] tot and [CO2]tot and Henry Coefficient from
the proposed 6-parameter polynomial equation.
 Lichun Li et al. / Energy Procedia 114 (2017) 1841 – 1847 1845

1000

Model Calculated CO2 partial pressure (kPa)

100

10
AARD%=28%

y=x
1

0.1

0.01
0.01 0.1 1 10 100 1000
Experimental CO2 partial pressure (kPa)

Fig. 2. Parity plot of experimental versus model predicted CO2 partial pressure at 40 oC; black line-y=x.

As shown in Fig. 2, by applying the polynomial equation for Henry Coefficient calculation, the VLE model
developed in this study is capable of reasonably adequately the VLE data in the MEA-CO2-H2O system at 40 oC.
The overall average absolute deviation (AAD), of the experimental data from the corresponding data predicted the
VLE model was 28%; which is reasonable and acceptable considering the spread of the experimental VLE data and
that all the equilibria/protonation constants were sourced from open literature. In addition, the data distribution in
Fig. 2 indicates that there are no systematic errors. The CO2 equilibrium partial pressures in 1, 2.5 and 5 M MEA
solutions at 40 oC were predict from the proposed model, together with the experimental CO2 partial pressure as a
function of liquid CO2 loading is presented in Fig. 3.

1000

100 5 M MEA
2.5 M MEA
CO2 Partial pressure (kPa)

1 M MEA
10

0.1

0.01
0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
α (mol CO2/mol MEA)

Fig. 3. Experimental against model calculated CO2 partial pressure data as a function of CO2 loading in 1, 2.5 and 5M MEA solutions at 40 oC.
Puxty et al., (2009) [20] ; Portugal et al., (2009) [18]; ∆ Park et al. (1997) [16]; Mazinani et al., (2011) [15]; □ Song et al., (1996) [23];
Shen and Li (1992) [22]; ○ Procheron et al., (2011) [19]; ◊ Daneshvar et al., (2004) [8]; x Aroun et al., (2011) [7]; + Austgen et al. (1991) [9];
- Jones et al. (1959) [11]; * Sartori and Savage (1983) [21]; Jou et al. (1995) [19] ; Tong et al., (2012) [24];
1846 Lichun Li et al. / Energy Procedia 114 (2017) 1841 – 1847

Fig. 3 shows the plot of the experimental and model calculated CO2 partial pressure as a function of CO2 loading
in 1, 2.5 and 5 M MEA solutions at 40 oC. The experimental and model calculated results show good agreements
across the presented CO2 loading range, from 0.2 to 1. This validates of the proposed VLE model and the Henry
Coefficient calculation.

4. Conclusions

A direct method for the determination of the Henry Coefficient of CO2 in MEA solutions is proposed in the
current study. A 6-parameter polynomial equation for calculating Henry Coefficient of CO2 in MEA solutions was
developed based on published vapour-liquid equilibrium data from MEA-CO2-H2O system at 40 oC. A VLE model
is then developed including the liquid phase model and the polynomial function estimating Henry Coefficient. The
model was used to re-predict the equilibrium CO2 partial pressure and can be used to well-present the VLE data. The
fairly good agreement between experimental and model calculated CO 2 partial pressure data confirm the validity of
the VLE model and the Henry Coefficient calculation. However, this paper only worked at one temperature, 40 oC,
for MEA solution, future work is required to apply this methodology for other temperatures and even other amine
solutions.

Appendix. A

Table S1. The equilibria/protonation constants values for the following reaction at 40 oC
Reactions log K Values Reference
H   OH  mo H 2O 15.3 [27]
K 1

H  CO3 mo HCO3

 2 K2
10.22 [27]
H   HCO3 mo
K
CO2  H 2O
3
8.04 [27]
H  MEAmo MEAH
 K4 
9.022 [28]
HCO3  MEAmo
K
MEACO2  H 2O
5
3.206 [28]
H   MEACO2 mo
K
MEACO2 H 6
6.48 [28]

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