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ScienceDirect
Energy Procedia 63 (2014) 1196 – 1205

GHGT-12

Activity based kinetics and mass transfer of CO2 absorption into MEA
using penetration theory
Koteswara Rao Putta,Hanna Knuutila *,Hallvard F.Svendsen 0F0F

Department of Chemical Engineering, NTNU, Sem Sælands vei 4, 7491 Trondheim, Norway

Abstract

The reaction kinetics of CO2 with loaded aqueous monoethanolamine (MEA) solution is studied over the temperature range from 20 to 70 0C
and CO2 loading from 0 to 0.4 moles CO2/mol amine for 30 weight percent MEA solution. New correlation for reaction kinetic constants of the
carbamate formation reaction are developed taking into account loading, temperature and amine concentration. The correlation is based on
experimental data available in literature. Penetration theory is used to interpret the experimental data. Activity coefficients are calculated with
e-NRTL method. Orthogonal collocation method has been used for solving the governing mass balance equations and kinetic constants are
estimated by the use of optimization routine by minimizing the error between experimental CO2 absorption flux and predicted CO2 flux.
© 2014 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
© 2013 The Authors. Published by Elsevier Ltd.
(http://creativecommons.org/licenses/by-nc-nd/3.0/).
Selection and peer-review under responsibility of GHGT.
Peer-review under responsibility of the Organizing Committee of GHGT-12
Keywords: Aqueous loaded MEA; termolecualr mechanism; activity based kinetics; penetration theory; numerical modeling; optimization; CO2 absorption

1. Introduction

Post-combustion CO2 capture process is based on separating CO2 from the flue gas containing mainly nitrogen, water vapour,
carbon dioxide and excess oxygen. CO2 concentrations vary from 4 volume percent (Natural gas fired turbines) to 15 percent
(coal fired boilers). CO2 is a powerful greenhouse gas, whose presence in the atmosphere causes global warming. Once emitted,
CO2 added to the atmosphere remains for thousands of years. Thus, climate changes forced by CO 2 depend primarily on
cumulative emissions making it more and more difficult to avoid further substantial effects on the environment. CO 2 remains the
major anthropogenic greenhouse gas with 76 percent of total greenhouse gas emissions in 2010 [1]. Energy supply sector is the
largest greenhouse gas emission contributor and the industrial sector being the second largest emissions contributor. Energy
supply sector represents 47 percent and industry sector represents 30 percent of global greenhouse gas emissions in 2010.
Greenhouse gas emissions has grown more rapidly between 2001 and 2010 (3.1 percent per year) than in the previous decade (1.7
percent per year) [1] due to increase in energy demand and coal percentage rise in the global fuel mix. To stabilize the CO 2
concentrations in the atmosphere, low greenhouse gas energy supply technologies are vital in addition to energy efficiency
improvement of fossil power plants and/or feedstock switching from coal to gas. Among several existing technologies to separate
CO2 from flue gas, the most mature processes are the ones based on absorption using liquid solvents. Absorption by means of
chemical solvents, such as monoethanolamine (MEA) is the most commonly used process for CO 2 removal. It can be applied to

* Corresponding author. Tel.: +47 73594119


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

1876-6102 © 2014 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/3.0/).
Peer-review under responsibility of the Organizing Committee of GHGT-12
doi:10.1016/j.egypro.2014.11.129
Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205 1197

exhaust gases of power plants, natural gas and refinery gas. Amine system has several advantages; in particular the chemical
reactions in the liquid phase enhance the mass transfer in the process. Industrially MEA is the most frequently used solvent for
post-combustion carbon capture [2]. In the absorption process CO2 is captured from the flue gas in absorber and released in the
desorber (stripper) by changing the temperature and /or pressure. The main problem is the energy required to release the CO2 in
the desorber. Solvent CO2 capacity, kinetics, the degree of solvent degradation and overall process integration are the other main
factors affecting the efficiency and cost of the process [3].
For accurate design or simulation of absorption column for CO 2 absorption coupled with chemical reactions, the following
data is very crucial.
x Physical, thermal and transport properties of the gases and the liquids in the system
x Vapor-liquid equilibrium data
x absorber internals data
x chemical reaction rate data
A large number of researchers have studied the chemical reaction kinetics of CO2 in aqueous monoethanolamine. Versteeg et
al. [4], Aboudheir et al. [5], Vaidya and Kenig [6] and Luo et al. [7] have reviewed the data available in the literature. As kinetics
play an important role in the absorption process, precise and accurate reaction rate data between aqueous monoethanolamine and
CO2 is essential.
Even though lot of investigators have studied the kinetics of CO2 into aqueous monoethanolamine solutions, only few data is
available on absorption of CO2 into loaded MEA solutions, even though in the process only loaded solutions are present. This
lack of loaded data is due to experimental difficulties at high loadings and need for proper vapor-liquid equilibrium (VLE) model.

Nomenclature

a activity of species in liquid


D diffusivity, m2·s-1
H Henry’s law constant, kmol-1·m3·kPa
kg gas film mass transfer coefficient, kmol·m-2·s-1·kPa-1
kH2O third order kinetic rate constant of H2O, m6·kmol-2·s-2
kMEA third order kinetic rate constant of MEA, m6·kmol-2·s-2
k forward reaction rate constant of carbamate formation reaction, m6·kmol-2·s-2
KG overall mass transfer coefficient, m·s-1 or kmol·m-2·s-1·kPa-1
LMPD logarithmic mean pressure difference between the inlet and outlet of the reactor
M molarity, kmol·m-3
N mole flux, kmol·m-2·s-1
P partial pressure, kPa
Q volumetric flow rate, m3·h-1
r reaction rate, kmol·m-3·s-1
t time, sec
T temperature, K
W circumference of cylinder in wetted wall column, m
Greek letter
Į CO2 loading, moles CO2/ mole MEA
ȝ viscosity, kg·m-1·s-1
ȡ density, kg·m-3
IJ contact time, sec
į liquid thickness, m
Ȗ activity coefficient
ɓ stoichiometric coefficient
Subscripts
0 initial
bulk in the bulk
CO2 carbon dioxide
eq equilibrium
f forward reaction
g gas phase
i at interface
H 2O water
l liquid phase
MEA monoethanolamine
1198 Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205

MEAH+ protonated monoethanolamine


MEACOO- carbamate
b backward /reverse reaction
Superscripts
’ infinite
* in equilibrium
in inlet of wetted wall column
out outlet of wetted wall column
T temperature dependence

All the investigators of kinetics of CO2 with loaded MEA, except Aboudheir et al .[5] assumed the pseudo first order reaction
kinetics and used two film theory to interpret the experimental data. Combining the series resistances and the pseudo first order
assumption assumes that there is no depletion of amine at the gas-liquid interface. Penetration theory was found to represent the
diffusion reaction systems accurately and had been implemented for simulating several processes in the literature [8–13].
In this work the correlations for the reaction rate constants based on concentration and activities are developed by using the
penetration theory. In this work no assumption of pseudo first order kinetics is taken and activities are calculated with eNRTL
model. The results in the present work are compared with the results obtained using correlations available in the literature [5,14].

2. Experimental set-up and procedure

In this work literature data of Luo et al. [14] is used. Luo et al. [14] used the wetted wall column (WWC) reactor for the
experimental measurement of CO2 absorption rate using both loaded and unloaded 5 molar aqueous monoethanolamine
solutions. The experimental apparatus set-up and operating procedure of wetted wall column reactor are given by Luo et al. [7],
so the details are not repeated here.

2.1. Model parameters

Penetration theory based mass transfer and kinetic constants evaluation requires the solution of non-linear partial differential
equations. In order to solve the system of PDEs, several physic-chemical properties values are required and this section will give
the sources from where the correlations or values have been taken for this study.
The viscosity of pure water and pure MEA and heat capacity of water, pure MEA and aqueous MEA solutions have been
calculated using correlation by Cheng et al. [15]. Diffusivity of CO2 in water is calculated using correlation given by Versteeg
and van Swaaji [16] and in aqueous MEA solution using ௗtheௗN2Oௗanalogyௗand StokesíEinsteinௗrelation and diffusivity of MEA
by Snijder et al.[17] correlation. Diffusivity of CO2 in gas phase is taken from Reid et al. [18] and the self-diffusivity of H2O is
taken from Holz et al. [19]. The correlation for calculation of densities of water, pure MEA and loaded aqueous MEA solution,
Henry law constant of CO2 in loaded MEA solution using N2O analogy, viscosity of loaded MEA solution are taken from
Hartono et al. [20]. Activity coefficients of species in the liquid phase are estimated from e-NRTL method and the gas phase
mass transfer coefficients are calculated using the correlations given by Luo et al.[7].

3. Theory and model for kinetic constants estimation

3.1. Theory and reaction mechanism

CO2 from the bulk of gas phase diffuses to the gas-liquid interface and dissolves in the liquid amine solutions and several
chemical reactions occur in the liquid solution. Different reaction mechanisms were proposed for carbamate formation. The
single step reaction mechanism, i.e. termolecular mechanism which was originally proposed by Crooks and Donnellan [21] and
later discussed by da Silva and Svendsen [22] has been used in this work.
The overall reaction for carbamate formation can be given as

CO2  MEA  B MEACOO


MEAC
C   BH  (1)

Where B = MEA and/or H2O.

As per direct reaction mechanism the reaction rate by taking the reversible reaction into account can be expressed as
§ kT ·
rCO2 ^ T
kMEA `
> MEA@  kHT 2O > H 2O@ > MEA@>CO2 @  ¨¨ fT ¸¸ ª¬ MEAH  º¼ ª¬MEACOO  º¼ (2)
© Keq ¹
Equation (2) is used for the concentration based kinetics model and for the activity based kinetics equation (3) has been used in
Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205 1199

the penetration theory model equations (6)-(10).


§ § kT · ·
rCO2 ^k T
MEA `
˜ J MEA > MEA@  kHT 2O ˜ J H 2O > H 2O @ ˜ J MEA > MEA@ ˜ J CO2 >CO2 @  ¨ ¨ fT ¸ ˜ J MEAH  ¬ª MEAH  ¼º ˜ J MEACOO ¬ª MEACOO  ¼º ¸ (3)
¨ ¨ Keq ¸ ¸
©© ¹ ¹
In the above equations (2) and (3), the kinetic constants are expressed with Arrhenius type of temperature dependence.
T E EH O
kMEA kMEA exp( MEA ) and kHT 2O kH 2O exp( 2 ) (4)
RT RT
The kinetic constants will have different values depending on the type of kinetic model (concentration based or activity based).

The equilibrium reaction constant is expressed in terms of activities as

K eqT
k Tf a MEACOO  aMEAH  (5)
T 2
k b a a
CO2 MEA

3.2. Model

The kinetic experimental data from wetted wall column reactor is modeled/interpreted using Higbie’s penetration theory [23].
Mass balance for each species yields non-linear PDEs written below.

w >CO2 @ Solution w 2 >CO2 @


DCO Q CO2 rCO2
wt 2
wx 2 (6)

w > MEA@ w 2 > MEA@


DMEA Q MEA rCO2
wt wx 2 (7)

w ª¬ MEACOO  º¼ w 2 ª¬ MEACOO  º¼
DMEACOO  Q MEACOO rCO2 (8)
wt wx 2

w ª¬ MEAH  º¼ w 2 ª¬ MEAH  º¼
DMEAH   Q MEAH  rCO2 (9)
wt wx 2

w > H 2O @ w 2 > H 2O @
DH 2O (10)
wt wx 2

In the beginning of each penetration cycle, the concentration of each species is uniform throughout the liquid film and the
profile develops during absorption. Contact time is necessary for the correct estimation of concentration profiles in the liquid. In
wetted wall column reactor, the liquid film thickness and contact time are calculated using the following expressions.
1 2
 
3PLQ § U g · 3 § 3Q · 3
GWWC 3 and W WWC 3h ¨ l ¸ ¨ l ¸ (11)
W UL g © Pl ¹ © W ¹

In order to solve the above set of differential equations (6) – (10) uniquely, one initial condition and two boundary conditions are
required for each equation.

Initial condition and boundary condition in the liquid bulk:

At time, t = 0, the concentrations are uniform throughout the liquid and considered the system is in equilibrium for a given CO2
loading and temperature. This is same as the condition in the liquid bulk at any time during absorption.
At t 0; x t 0, and for t ! 0; x f ,
>CO2 @ >CO2 @bulk
> MEA@ > MEA@bulk
(12)
ª¬ MEACOO  º¼ ª¬ MEACOO  º¼
bulk

ª¬ MEAH  º¼ ª¬ MEAH  º¼
bulk

> H 2O @ > H 2O @bulk


1200 Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205

The equilibrium concentrations specified in the initial condition and the boundary condition at the liquid bulk; are obtained using
the e-NRTL model for given CO2 loading and temperature.

Boundary condition at the gas-liquid interface:

The second boundary condition, at the gas-liquid interface, is derived by assuming that MEA, MEACOO- and MEAH+ are non-
volatile and that for CO2 and H2O, the flux in the gas phase is equal to the flux in the liquid phase.

t ! 0, x 0,
w >CO2 @

k g PCO2
g ,bulk
 PCO2
g ,i
Solution
 DCO 2
wx
x 0

w > H 2O @
k P
g H 2O g ,bulk  PH 2O
g ,i
 DH 2O
wx
x 0
(13)

w > MEA@ w ª¬ MEACOO  º¼ w ª¬ MEAH  º¼


0
wx wx wx

CO2 is assumed to be saturated at the gas-liquid interface and henry’s law coefficient of CO2 can be expressed as
PCO2
Solution
H CO g ,i
(14)
2
>CO2 @l ,i
The boundary condition for CO2 at the gas-liquid interface can be re-written as

t ! 0, x 0,
Solution
§ H CO · Solution w >CO2 @ (15)
k g ¨ >CO2 @g ,bulk  2
>CO2 @g ,i ¸  DCO2 x 0
¨ RT x 0¸ wx
© ¹

Orthogonal collocation method is used for discretization of space. In this study ‘ode15s’ solver in MATLAB is used for solving
the system of equations. The kinetic parameters are regressed using the optimization technique (fminsearch) available in
MATLAB. The function ‘fminsearch’ is Multidimensional unconstrained nonlinear minimization routine based on Nelder and
Mead [24] algorithm. The objective of the optimization is to minimize the summation of errors between the model predicted and
experimental flux data. It is defined as
ne
§ (CO2 Exp Model 2
Flux  CO 2 Flux )
·
Objective function ¨
j 1 ©
CO Exp
2 Flux *CO ¦
Model
2 Flux
¸
¹
(16)

Where ne is the number of experimental data points, CO2ExpFlux is the experimental CO2 absorption flux and CO2ModelFlux is the
predicted CO2 absorption flux using penetration theory model.

4. Results and discussion

In this work 95 experimental points of both unloaded and loaded 5 molar MEA solutions were used in the optimization. The
data covered loadings from 0 to 0.4, temperatures from 20 to 70 0C and logarithmic mean pressure difference from 0.8 kPa to 14
kPa. Kinetic constant correlation of Aboudheir et al [5] was used to predict the CO2 absorption flux at experimental points in Luo
et al. [14]. Additionally using the data from Luo et al. [14] kinetic constants (based on activities and concentrations) were
optimized using the model presented in section 3. Thirdly the data was compared with models by Luo et al. [14]. The absolute
average deviations, using the different correlations present are listed in the Table 1.

Table 1 The absolute average deviations of different kinetic models


Absolute average deviation (AARD)
Source
Concentration based kinetics Activity based kinetics

Aboudheir et al. [5] 33.1 --

Luo et al. [14] 21.6 16.7


Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205 1201

Present work 14.7 11.7

From the Table 1 , it’s evident that Aboudheir et al [5] concentration based kinetic constants gives the highest average
deviation of 33% , whereas Luo et al. [14] kinetic constants give average deviation of 21.6 % and present model predicts CO 2
absorption flux with average deviation of 14.7 %. When the non-idealities of species in the liquid are taken into account, activity
based kinetic model by Luo et al. [14] gives average deviation of 16.7 % and the present activity based model predicts with
average deviation of 11.7 %.
These differences can be at least partly explained by different modeling approaches and the fact that the different
experimental data. Aboudheir et al. [5] has used the same penetration theory model as in the present work but different
experimental apparatus. The deviations seen might be due to the experimental data itself, numerical method accuracy and the
different correlations to calculate physical and chemical properties of loaded amine solutions. Luo et al. [14] has used two-film
theory with pseudo-first order assumption for the estimation of kinetic constants in both concentration based and activity based
models and these kinetic constants have been then used in the penetration theory model.
The concentration based kinetic model using penetration theory, developed in this study, is more accurate than the Luo et al.
[14] activity based kinetic model based on two film theory with pseudo-first order assumption, as can be seen from Table 1, and
the activity based model using penetration theory predicts the CO2 flux with smallest deviation. However as seen from the Figure
1, where the parity plot is given, that all of the models under predict the CO2 flux at high CO2 fluxes. The CO2 flux was in
general higher at higher temperature and at higher CO2 loadings.

Fig. 1. Parity plot of CO2 absorption flux using different kinetic models

4.1. Profiles in liquid using penetration theory

Kinetic constants from Aboudheir et al. [5] and Luo et al. [14], are also used in the penetration model presented in this work
for comparison. Figure 2 shows the concentration profile of MEA and Figure 3 shows concentration profile of MEAH + in the
liquid at the end of penetration cycle (time=contact time) at temperature of 41.8 0C, LMPD = 7.7 kPa for unloaded 5 molar MEA
solution. We also observed that, for unloaded solutions, both activity based and concentration based kinetic models of Luo et al.
[14] and this work predicts almost same as experimental CO2 absorption flux with same accuracy and Aboudheir et al. [5] under
predicts the flux. The differences between the different kinetic constant correlations are not clearly visible when looking at
1202 Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205

Figures 2 and 3. Except Aboudheir et al. [5] concentration based correlation, all other models gives the same concentration
profiles in the liquid solution for unloaded MEA solution. Aboudheir et al. [5] models gives higher concentration profile for
MEA and lower profile for MEAH +. Consequently the CO2 absorption flux is under predicted because this model gives lower
reaction rates.

Fig. 2. Concentration profile of MEA in liquid with different kinetic models using penetration theory
Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205 1203

Fig.3. Concentration profile of MEAH+ in liquid with different kinetic models using penetration theory

For loaded solutions and at high temperatures, the differences between the models predictions become more visible. From Figure
4, it can be seen that all the models gives different profiles. Using the kinetic constants from Aboudheir et al. [5], gives the
lowest MEA depletion profile i.e. highest concentration in the gas liquid interface. The activity model from this work on the
other hand show the highest MEA depletion profile. The models of Luo et al. [14] and the concentration based model from this
work give depletion profiles between these extremes. This is also illustrated in Table 2 where the percentage of MEA depletion
due to reaction at the gas-liquid interface at temperature of 65.9 0C and CO2 loading of 0.4 for the driving force (logarithmic
mean pressure difference) of 11.9 kPa is shown. From this we can also see that with the high loadings, temperatures and large
driving forces, the pseudo-first order assumption (models in [14]) gives much lower depletion rate compared to activity based
model of this work. This indicates that the pseudo-first order assumption is maybe not valid at these conditions.

Fig. 4. Concentration profile of MEA in liquid with different kinetic models using penetration theory at high T, LMPD and loading

Table 2. Calculation of Percentage of MEA depletion by different kinetic models at gas-liquid interface
Kinetic model % MEA depletion at gas-liquid interface

Aboudheir et al. concentration model [5] 18

Luo et al. concentration model [14] 21

Present work concentration model 29

Luo et al. activity based model [14] 27

Present work activity based model 35

The selection of correct kinetic model is very important for the process simulations. When the selected model doesn’t predict the
experimental absorption flux correctly, it leads many errors in the simulation like inaccurate estimation of concentration profiles
1204 Koteswara Rao Putta et al. / Energy Procedia 63 (2014) 1196 – 1205

for species and of loading which will in fact leads imprecise calculation of physical and chemical properties while accounted for
loading effect.

5. Conclusions

In this work, kinetic constant correlations for concentration based and activity based models are developed using penetration
theory coupled with optimization. Both the models, concentration based and activity based kinetic models predicts with better
accuracy than the models available in the literature. It is also visible that the non-idealities of species in liquid are strong and by
including the non-idealities in the kinetic model increases the accuracy of the model. All the models except Aboudheir et al. [5]
kinetic model predicts with same accuracy for unloaded 5 molar MEA solutions but the deviations increase with the increase of
temperature, CO2 loading and driving force. The present work also raises the question about the validity of pseudo-first
assumption for loaded MEA solutions. This work also shows the importance of proper kinetic model and physical and chemical
properties correlations considering the effect of loading.

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