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Kinetics of CO 2 Absorption in to Aqueous MEA Solutions Near Equilibrium

Article  in  Energy Procedia · July 2017

DOI: 10.1016/j.egypro.2017.03.1288

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Energy Procedia 114 (2017) 1576 – 1583

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

November 2016, Lausanne, Switzerland

Kinetics of CO2 absorption in to aqueous MEA solutions near

equilibrium
Koteswara Rao Putta1, Hallvard F. Svendsen1, Hanna K. Knuutila1*
1
Department of Chemical Engineering, Norwegian University of Science and Technology, Sem Sælands Vei 4, NO-7491 Trondheim, Norway.

Abstract

Activity based reaction kinetic model, with the ability to predict the CO2 absorption rates close to equilibrium, is developed for
CO2-aquoues MEA system using mathematical model developed using Penetration mass transfer theory. The non-linear partial
differential equations are solved using orthogonal collocation method on finite elements (OCFE) and implemented in MATLAB
software. The global optimization technique is used to obtain the optimized kinetic constants. The developed kinetic model is
validated with experimental data from independent sources. The developed activity based kinetic model predicted the CO 2
absorption rates with AARD of 13% for data from wetted wall column and laminar jet absorber with CO2 loadings 0.2 – 0.5 and
temperatures 293-343 K. The base contributions from carbonate and bicarbonate species for carbamate formation was found to be
negligible compared to contributions from MEA and H2O. Carbamate reversion reaction has negligible effect on the model
predictions even at high CO2 loadings.
© 2017 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2017 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-reviewunder
Peer-review under responsibility
responsibility of the
of the organizing
organizing committee
committee of GHGT-13.
of GHGT-13.

Keywords: Type your keywords here, separated by semicolons ;

1. Introduction

Currently global warming is a most alarming issue and CO2 is one of the main greenhouse gases. In order to restrict
the global temperature rise to 2o C, capturing CO2 from emitting sources is crucial. Due to a constant increase in energy
demand, the use of coal and gas for energy production is still rapidly growing. Coal is largely used in power production.

* Corresponding author. Tel.: +47-735-94119.

E-mail address: hanna.knuutila@ntnu.no

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.2017.03.1288
 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583 1577

41.1% of the total global electricity was produced using coal in 2014 and coal will remain a principal source of energy
in the future also [1]. The flue gas contains around 14 vol. % of CO2 in coal fired and 4 vol. % in natural gas fired
power plants. Post-combustion capture by chemical absorption using amines is the most mature and promising
technology among the current technologies. Aqueous monoethanolamine (MEA) solution is still one of the most
widely used solvents and is often considered as a reference case for new solvents development. The main challenge in
using amine based processes is the energy requirement for CO2 removal which can cause around 11-23% the power-
plant efficiency reduction [2].

Nomenclature

AARD Absolute average relative deviation (%)

Keq Equilibrium constant
LMPD Logarithmic mean pressure difference between the inlet and outlet of the reactor, kPa
M Molarity of the solution, mole/litre
PCO2 Partial pressure of carbon dioxide, kPa
r Reaction rate, kmol•m-3•s-1
T Temperature, K
VLE Vapour-liquid equilibrium

Greek letter
α CO2 loading, moles CO2/ mole MEA
γ Activity coefficient

Subscripts
a Activity based model
CO2 Carbon dioxide
eq Equilibrium
Exp Experimental
H2O Water
H3O+ Hydronium ion
MEA Monoethanolamine
MEAH+ Protonated Monoethanolamine
MEACOO- Carbamate

Superscripts
T Temperature dependence

Despite MEA being considered as a base case solvent, there are still gaps in the understanding and the precise and
accurate modelling of the process under industrial operating conditions. For example, prediction of reaction kinetics
and mass transfer rates close to equilibrium is a challenge. For optimal operation of a process, reaching the as close
as possible to equilibrium (maximum absorption) is always favourable as regeneration energy required is inversely
related to rich amine loading. As reaction kinetics play an important role in the design, modelling and scale-up of such
processes, understanding and developing a complete kinetic model which describes the absorption process also close
to equilibrium conditions, is essential.

An extensive number of experimental studies have been made in the literature on the kinetics of CO 2 reacting with
aqueous MEA since 1950’s. Different types of experimental set-ups, wetted wall columns, stirred cells, laminar jet
absorbers, string of discs and stopped flow techniques have been used in these kinetic studies. Versteeg et al. [3],
Aboudheir et al. [4], Vaidya and Kenig [5,6], Luo et al. [7] and Ying and Eimer [8] give reviews on the available
literature for kinetics. Also, several kinetic models were proposed for the CO2-MEA reaction in the literature.
1578 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583

Overviews of the reaction rate constants for the CO2 reaction with aqueous MEA from the various literature sources
are given by Aboudheir et al. [4] and Ying and Eimer [8]. The reaction between CO2 and alkanolamines is usually
described using two different reaction mechanisms, the zwitterion mechanism and the termolecular mechanism.
Aboudheir et al. [4] and Luo et al. [9] showed that the termolecular mechanism could be used to explain the observed
kinetic phenomena. It was seen from the study of Razi et al. [10] that the selection of kinetic model influences the
model predictions significantly. The model predictions varied from under-prediction to over-prediction just by
changing the kinetic model.

From a detailed analysis of the kinetic studies in the literature, it was observed that
i) There is a serious limitation in the literature in terms of experimental temperatures and aqueous MEA
solutions concentrations used.
ii) Most of the studies used a simple second order or pseudo-first order kinetic rate constant approach to
interpret experimental absorption data. At low MEA concentrations this simple method could be suitable,
but as the MEA concentration increases, the effect of concentration becomes more significant.
iii) Except few, most of the studies do not consider the effect of CO 2 loading in aqueous MEA solutions.
iv) At temperatures above 313 K, as noted by Versteeg et al. [3] and Aboudheir et al. [4], the experimental
data interpretation becomes more complicated as the regeneration of loaded MEA solutions also needs to
be taken in to account due to the increase in reversibility of the CO 2-aqueous MEA reaction with
temperature. Numerical estimation of the kinetic rate constants is required.
v) As the CO2-MEA-H2O system is highly non-ideal, a VLE model taking non-idealities into account
should be used for estimation of concentration and, if desired, activities of species present in the liquid.
E.g. the Aboudheir et al. [4] kinetic model was developed using a simple Kent-Eisenberg model which
does not consider non-idealities of species in the liquid.
vi) It is very well known that simple kinetic models cannot be extrapolated with confidence beyond the
temperature and concentration ranges of the kinetic data used in their development.

Aboudheir et al. [4] used a simple Kent-Eisenberg model and Luo et al. [9] used the pseudo-first reaction
approximation in the development of their kinetic models. Both these kinetic models do not consider the reversibility
of the reactions and therefore systematic deviations were found at high loadings.
There is strong need for the development of a kinetic model by taking into account the reversibility of the reactions,
the concentration dependency, non-idealities of species in the liquid phase and using a numerical solution method and
physical properties models which consider the CO 2 loading effect.

2. Methodology

In the present work a complete kinetic model is developed by considering base contributions of all bases present
in the solution for carbamate formation and reversibility is considered for all reactions. Kinetic constants are regressed
using lab-scale CO2 absorption data from wetted wall column data published in the literature by Luo et al. [9]. The
developed kinetic model is validated against experimental data from Puxty et al. [11] and Aboudheir et at. [4,12]. The
experimental data considered covers a loading range from 0.2 to 0.5, temperatures from 293 to 343 K and PCO 2 from
0.4 to 100 kPa. Also desorption data are included. The experimental data are chosen in such a way that they cover all
industrial process operating conditions of the absorber column. The termolecular mechanism is used.

According to the termolecular mechanism the complete reaction set will be given as below:
CO2  MEA  B l MEACOO  BH  (1)
here B represents any base present in solution and MEA, H 2O, HCO3 , CO32 are the main bases present in the loaded
MEA solution.

The carbamate reversion reaction considered is given as:

 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583 1579

MEACOO  H 2O l MEA  HCO3 (2)

Bicarbonate formation reaction is:

CO2  OH  l HCO3 (3)

In the present work, a penetration theory based mathematical model was developed by taking into account the
coupling between mass transfer, phase and chemical equilibrium (thermodynamics), heat transfer and kinetics of
reactions. The model equations are the same as given by Putta et al. [13,14]. The governing species material balance
equations including mass transfer and the coupled chemical reaction system yield a non-linear partial differential
equation system.

CO2 absorption into aqueous MEA solutions pose a very stiff problem with a very steep concentration profile for
CO2 as the reaction rate between CO2 and MEA is high. Luo et al. [15] tested a variety of discretization methods,
namely uniform fixed grid methods (Central difference, DSS042, DSS044, DSS020, DSS002, DSS038), non-uniform
fixed grid method (subsection), adaptive moving grid method and the Method of Weighted Residuals (orthogonal
collocation). To solve the model equations the orthogonal collocation method was found to be the fastest and most
accurate method for the CO2-MEA system.
Orthogonal collocation on finite elements (OCFE) has been suggested in the literature to minimize the
computational time and to capture the steep gradients in a particular region precisely [16]. In this work, the model was
implemented in MATLAB and the ‘ode15s’ was used for integration in time.

Optimization techniques are used for the regressing the kinetic constants. In order to avoid a solution at a local
minimum, a global optimization technique, which finds the global minimum using a scatter search mechanism with
multiple starting points, was used. The MATLAB inbuilt ‘global search optimization technique’ was used. The
developed kinetic model was validated with independent source data in order to verify the usefulness.

3. Results

3.1. Carbamate reversion and check for other base contributions to carbamate formation

From a detailed NMR study, spectroscopy data for all species present in the liquid at high loadings (loading > 0.4),
show bicarbonate and carbonate species concentrations at a similar magnitude as for free MEA. The base
contributions of both HCO3- and CO32- for the carbamate formation should therefore be taken into account. In addition
to the carbamate formation reaction from all the significant bases, carbamate reversion reaction was also considered
in the complete kinetic model.
In the present work, experimental data from wetted wall column (WWC) reported by Luo et al. [9] were used in
the kinetic model development using a penetration theory based rate-based model. In addition to fitting the kinetic
constants for contributions of MEA and H2O to carbamate formation reaction, carbamate reversion reaction and
bicarbonate and carbonate species concentrations for carbamate formation were considered as kinetic reactions. Using
the same optimization procedure as used for fitting kinetic constants for the MEA and H 2O base contributions, kinetic
constants for base contributions of HCO3- and CO32- to the carbamate formation were regressed. From the developed
kinetic expressions, it was seen that the base contributions of HCO3- and CO32- to carbamate formation are negligible.
Lastly, the effect of carbamate reversion reaction was studied by considering it as a kinetic reaction and fitting the
kinetic constants using same procedure as used above. The overall effect of carbamate reversion reaction was also
found to be insignificant. So it was concluded that the main bases that contribute to the carbamate formation in loaded
aqueous MEA solutions are MEA and H2O. From the equilibrium constants for each reaction, it was seen that
carbamate formation from the base MEA is irreversible (Keq~10 4-106) and that carbamate formation from the base
H2O is reversible (Keq~10-7-10-6).
1580 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583

3.2. New kinetic model

Figure 1 shows the parity plot between experimental data and predictions using the kinetic model developed in this
work. The present kinetic model has an absolute average relative deviation of 13 % for the WWC data at high CO2
loadings (> .3). From fig. 1, it can be seen that the present kinetic model has very good accuracy. The activity based
kinetic model and the reaction rate expressions were reported in Putta et al. [14] and are given below:

The reaction rate expressions for contributions of MEA and H2O to the carbamate formation reaction are given as:
T
T 2 2 kMEA ,a
rCO2 _ MEA, a kMEA ,a MEA
MEA CO2
CO2 T
MEAH MEACOO
K eq MEAH MEACOO
_ MEA, a
(4)
T
k HT 2O , a
rCO2 _ H 2O , a k H 2O , a H 2O H 2 O MEA MEA CO2 CO2 T
H 3O MEACOO
K eq H 3O MEACOO
_ H 2O , a

The rate constants expressions are given as:

T 5851.7
kMEA ,a 4.5191 x 1011 exp( )
T
(5)
2382.4
k HT 2O , a 2.1105 x 106 exp( )
T

Fig.1 Parity plot of model predictions and experimental data from WWC at high CO2 loadings.

3.3. Validation of developed kinetic model

In the literature, even though the existing kinetic models for the CO2-MEA system may represent
experimental data used for parameter fitting with good accuracy, the accuracy of the models may not be consistent
when the models are used for data from other experimental techniques. Hence, any developed model must be validated
using data from independent experimental studies in order to check its usefulness. In this work, the developed kinetic
model was validated with data from two independent apparatuses reported in literature [4,11]. Figure 2 shows the
prediction capability w.r.t CO2 loading and driving force (LMPD).
 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583 1581

Fig. 2 Model predictions w.r.t. (a) CO2 loading and (b) driving force

As can be seen from figure 2, the developed kinetic model represents the experimental data with good accuracy. For
CO2 loadings above 0.2, the newly developed kinetic model represents the experimental data, excluding desorption
cases, from the WWC work reported by Puxty et al. [11] with an AARD of 12.8 % and the experimental data from a
laminar jet absorber reported by Aboudheir et al. [4] with AARD of 13.2%. From the figures, it can also be seen that
the present kinetic model has the ability to predict experimental data with desorption in addition to absorption with
reasonable accuracy. The experimental data corresponding to desorption cases was found to have large uncertainty
and thus large deviations were observed between experimental and model predicted CO 2 absorption rates. The
developed activity based kinetic model gives predictions with good accuracy over a wide range of temperatures (293-
343 K) also. Figure 3 shows the model predictive ability for 5 M MEA solutions over a temperature range of 293-343
K for different CO2 loadings.
1582 Koteswara Rao Putta et al. / Energy Procedia 114 (2017) 1576 – 1583

Fig. 3 Model predictions w.r.t temperature for 5 M MEA at different CO2 loadings

4. Conclusions

Activity based kinetic model is developed in the present work using a penetration theory based discretized
numerical model and a global optimization technique was used for parameter fitting. The developed kinetic model is
able to represent the experimental data near to equilibrium i.e., at high CO 2 loadings, with good accuracy. The kinetic
model has been validated with two independent experimental data sources and found that the accuracy is good. The
model has predictive capability over a wide range of process conditions like CO2 partial pressure, with and without
gas phase resistance, CO2 loadings, amine concentrations and temperatures. Also it was found that the base
contributions of HCO3- and CO32- to carbamate formation were negligible and the effect of carbamate reversion
reaction on the model predictions was insignificant.

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