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Modeling of CO2 capture via chemical


absorption processes An extensive literature
review
Article in Renewable and Sustainable Energy Reviews October 2015
Impact Factor: 5.9 DOI: 10.1016/j.rser.2015.04.124

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3 authors:
I.P. Koronaki

Loukia Prentza

National Technical University of Athens

National Technical University of Athens

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Vasilis D Papaefthimiou
National Technical University of Athens
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Retrieved on: 05 July 2016

Renewable and Sustainable Energy Reviews 50 (2015) 547566

Contents lists available at ScienceDirect

Renewable and Sustainable Energy Reviews


journal homepage: www.elsevier.com/locate/rser

Modeling of CO2 capture via chemical absorption processes


 An extensive literature review
I.P. Koronaki n, L. Prentza, V. Papaefthimiou
Laboratory of Applied Thermodynamics, School of Mechanical Engineering, Thermal Engineering Section National Technical University of Athens, Heroon
Polytechniou 9, Zografou Campus 15780, Athens, Greece

art ic l e i nf o

a b s t r a c t

Article history:
Received 17 October 2014
Received in revised form
11 March 2015
Accepted 23 April 2015

Climate change mainly due to the release of greenhouse gases into the atmosphere is getting alarming
dimensions. CO2 capture from point source emissions is a promising solution, lately receiving signicant
attention. In particular, chemical absorption of CO2 from ue gases using aqueous solvents (mainly
alkanolamines) is a well-known process, studied in detail. Modern research aims to optimize this
process, maximizing the absorption rates and minimizing the parasitic but not negligible energy
requirements for solvent regeneration. This type of analysis requires considering the coupling of the
absorption with the power plant operation or other source of CO2. The operation uctuations and
disturbances, such as load variations or start-up mode have to be reected in the process modeling,
justifying the emerging need for dynamic modeling. However, dynamic analysis is not always realizable
as dynamic experimental data are scarce in order to enable accurate model validation. Thus, steady state
models are still convenient for certain cases. The current work provides a short description of the main
modeling approaches followed and enlists representative steady state and dynamic models found in
literature. Finally, a primary comparison is performed for some comparable models that used the same
set of experimental data for model validation.
& 2015 Elsevier Ltd. All rights reserved.

Keywords:
Chemical absorption
CCS
Rate-based model
Dynamic modeling
CO2

Contents
1.
2.
3.
4.

5.

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
Chemical absorption process and solvents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 548
Chemical absorption modeling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
4.1.
Modeling requirements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
4.2.
Modeling approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
4.3.
Mass transfer approaches . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 549
4.4.
Thermodynamic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
4.4.1.
Kent  Eisenberg model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
4.4.2.
Electrolyte non-random two-liquid (e-NTRL) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
4.4.3.
EoS/GE models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 550
4.4.4.
SAFT (statistical association uid theory) model . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
4.5.
Kinetic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
4.6.
Absorption column model. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
4.7.
Dynamic modeling. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
Models review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
5.1.
Rational for this review . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551

Corresponding author. Tel.: 30 2107721581; fax: 30 2107723670.


E-mail addresses: koronaki@central.ntua.gr (I.P. Koronaki), prentzaloukia@central.ntua.gr (L. Prentza), vpapaeft@central.ntua.gr (V. Papaefthimiou).

http://dx.doi.org/10.1016/j.rser.2015.04.124
1364-0321/& 2015 Elsevier Ltd. All rights reserved.

548

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

5.2.

Chemical absorption models literature review. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551


5.2.1.
Steady state models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 551
5.2.2.
Dynamic models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 559
5.2.3.
Model comparisons . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 561
6. Conclusions and scope for future work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 563
Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
Appendix A.
List with recent models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 564
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 565

1. Introduction
Facing climatic change as a detrimental result of the increasing
global energy demand, various policies have been adopted aiming to
mitigate the consequences, mainly to the reduction of greenhouse
emissions. During the last years, the penetration of renewable sources
of energy has been mainly promoted as a promising solution.
However, it seems that fossil fuels will still be a predominant
component of the global energy mix, posing the need for more direct
ways of response. At the same time, EU and its member states are
committed to an emission reduction target of 20% by 2020, compared
with 1990 levels. This target could be increased to 30% under
conditions set out by the European Council [1]
Carbon Capture and Storage (CCS) is a promising technique
gaining increasing interest among researchers and policymakers.
In specic, CCS is a process where CO2 is separated from industrial
production or energy conversion, is transported to the storage site
under high pressure and nally geologically stored, aiming to
realize zero emissions in the process of fossil energy extraction,
conversion and usage [2]. CCS refers to the capture of CO2
emissions either before the combustion of the fuel or directly
from the ue gas. Post combustion methods are more applicable as
they have no retrotting requirements for the existing equipment.
The most applied and efcient post combustion method is
chemical absorption. In comparison with other post-combustion
CO2 absorption processes, chemical absorbents ensure higher
absorption efciency and selectivity, and lower energy [3].
In order to enable a wider scale implementation of CCS, detailed
and efcient modeling of the process is a prerequisite. This is because
the study of reactive absorption is mainly based on simulations, as
experimental data are limited and not always reliable. Chemical
absorption of CO2 by aqueous solvents, mainly amines, has been
studied for decades by numerous researchers with satisfying results.
The developed models include both kinetic and thermodynamic
aspects and are aiming to optimize the absorption. It is only recently
though, that these attempts include dynamic characteristics and more
realistic representations of the process.
The current work objective is to outline briey the common
modeling approaches in the eld of post-combustion CO2 absorption and also attempt to list a wide spectrum of specic models,
steady and dynamic, encompassing their assumptions, modeling
and validations tools and main outcome. Finally, the paper aims to
conclude on the prediction efciency of several models, comparing, to the point it is possible, results of different researchers
which are based on the same experimental data.

2. Structure
The article is structured in 5 Sections. Section 1 is the
introductory section providing information about the CO2 emissions problem and the necessity to confront this. In following,
Section 2 outlines the chemical absorption process and certain
commercially used solvents. Section 3 provides the fundamentals,
assumptions and requirements of the reactive absorption

modeling. Different mass transfer models, thermodynamic and


kinetic models are listed. At the end an introduction to dynamic
modeling is included. Section 4 includes the analysis of representative models from literature. Different sub-sections for steady
state and dynamic models are encompassed, providing information for the assumptions made, equations applied and main
outcome. In following in the same Section, three absorption units
are presented that have provided very useful and widely used
experimental results. Based on these data, certain rough comparisons are performed between models. Summarizing, Section 5
outlines the conclusions made by this literature research and
suggest elds for future work.

3. Chemical absorption process and solvents


Chemical absorption (or reactive absorption) is the process
where a gas is absorbed by a liquid phase with combination of
reaction and absorptive mass transport. Amine-based systems,
carbonate-based systems, aqueous ammonia and ionic liquids
based systems are typical systems for chemical absorption.
In specic for CO2 capture, chemical absorption involves the
reaction of CO2 with a chemical solvent forming a weakly bonded
intermediate compound, a process that can be reversed applying heat
and resulting to the original solvent and a CO2 stream [3]. The
regeneration process is the most demanding by means of energy, as it
may cost up to 14% of the power plant efciency [4]. During chemical
absorption the ue gas enters usually an absorption tower where it
contacts countercurrent the solvent under low temperature (40
60 1C). The rich in CO2 solvent is compressed, heated in an exchanger
and inserted in the desorption column (stripper) where it is regenerated under low pressure (close to ambient) and high temperatures
(100140 1C). The regenerated (lean) solvent exits the column and reenters the absorber after dissipating its heat in the rich solvent
through the above mentioned exchanger.
The chemical absorption process was initially performed using
amine aqueous solvents. The most mature and commercially
applied amine is Monoethanolamine (MEA) due to its high
absorptive capacity. MEA is considered an attractive solvent at
low partial pressures of CO2 in the ue gas due to its fast reaction
rates compared to that of secondary and tertiary amines [5]. Other
common amines are Diethanolamine (DEA), Methyl diethanolamine (MDEA), Diglycolamine (DGA), and Diisopropanolamine
(DIPA) and Piperazine (PZ) or mixtures of amines that are
characterized by satisfactory reaction rates and lower regeneration
energy than MEA. Piperazine is usually added as a promoter as it
has been found to have faster reaction rates than MEA. Due to its
high volatility though, its application in CO2 absorption is more
expensive and is still under development [6]. A special category of
amines are sterically hindered amines (SHA) that e.g. 2-Amino-2methyl-1-propanol (AMP). SHA form more unstable carbamates in
comparison with other amines. Thus, they are more efcient
during regeneration, as the unstable carbamates are easier to be
reversed, leading therefore to quicker desorption and less energy

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

requirements [7]. Alternative solvents for chemical absorption are


aqueous ammonia, ionic liquids and potassium carbonate. In
specic, aqueous ammonia is a strongly promising solvent characterized by many assets, as high absorption efciency, high
absorption capacity, low energy requirement for absorbent regeneration and wide distribution of resources [8].

4. Chemical absorption modeling


Within this section the main modeling processses and tools are
provided. The required steps in order to simulate accurately the
process of CO2 absorption are described as well as the dominating
techniques.
4.1. Modeling requirements
Chemical absorption process involves complex mechanisms both of
thermodynamic and chemical nature. This process is described as
reactive absorption considering that reactions and absorptive mass
transport phenomena occur simultaneously. An important characteristic of reactive absorption processes is the variation of reaction
velocities, from very low (slow reactions) up to innitely high
(instantaneous reactions).Thus, the modeling of these mechanisms is
challenging and requires a multi-factor design. The ideal model has to
be rigorous enough to encompass all complex aspects of the problem
and manageable enough in order to enable an easy implementation of
the modeling process [9].
A thermodynamic model has to describe through its differential
equations certain fundamentals: the chemical equilibrium, the
vapour liquid equilibrium, the liquid phase constitution, the
regeneration energy, and the two phases mass [10].
4.2. Modeling approaches
There are two modeling approaches corresponding reactive
processes: the equilibrium models and the rate-based models (or
non-equilibrium models). The equilibrium models assume
vapour liquid equilibrium at each stage [11]. Non-equilibrium
models consider the actual reaction rates and are more accurate as
physical equilibrium is hard to attain.
Equilibrium models assume a quick and cursive mass transfer.
Thus, they are more applicable for solvents with high reaction rates,
e.g. primary amines. Equilibrium models apply MESH (Material
balances, Equilibrium equations, Mole Fractions Sum conditions and
Heat balance) equations. These models are usually based on theoretical stages in which liquid and vapour phases reach equilibrium.
Stages use height equivalent to a theoretical plate (HETP) and assume
the equilibrium state between the streams leaving each stage [12].
These stages correspond either to real column stages, for disc columns,
or equivalent stages, for columns with ller materials.
Non-equilibrium models, as mentioned, estimate the real
reaction rates and mass transfer resistances. These phenomena
are often approached via enhancement factors that amend the
equilibrium computations. The enhancement factor is actually the
chemical mass transfer coefcient to the physical mass transfer
coefcient. It is either obtained by tting experimental data or
theoretically based on simplied model assumptions [13]. This is a
very common approach of modeling reaction kinetics. However,
this approach is often simplied as binary systems are not suitable
to estimate the enhancement factors and theoretical approaches
are based on rough simplications. More complex simulations are
instructed that consider directly the reaction rates.
Rate based models describe the interfacial molar uxes directly.
The mass transfer is usually described through Maxwell Stefan
equations from the kinetic theory of gases modied for binary

549

systems with gas and liquids [9]. The modied equation giving the
generalized driving force is the following:
di

m xlf nlf  xlf nlf


X
i j
j i
j1

C lft Dij

where D is the Maxwell Stefan diffusion coefcient, xlfi and xlfj are
the liquid mole fractions in the liquid lm for i and j components,
nlfj and nlfi are the molar uxes in the liquid lm for i and j
components and C lft is the total molar concentration in the
liquid lm.
The electrolytes effect should be included in this analysis and
for dilute electrolyte systems, the diffusional interactions can be
neglected giving the generalized Maxwell Stefan equations
reduced to the following Nernst Planck equation:
nlfi C lft Dli;ef f



F
xlfi xlfi zi xlfi nlfm
RT

where Dli;ef f is the effective diffusion coefcient, zi the ionic charge


of component i, F Faradays constant, R the gas constant, T the
temperature and the electrical potential.
This approach requires also the assumption of electroneutrality
in each region of the liquid phase expressed by the following
formula:
m
X

xi z i 0

i1

Another method to describe the interfacial mass transfer is


KarhunenLoeve Galerkin (KLG). The KLG method is a Galerkin
method employing the empirical eigenfunctions of the Karhunen
Loeve decomposition as basis functions. [14].
Both equilibrium and rate-based models may consider the reaction
kinetics or not. If the reaction rate is slower than the mass transfer rate,
kinetics should be considered as a dominating factor [13]. Fig. 1 is
widely cited as it clusters reactive absorption models through a very
efcient approach [15]. The lowest level of complexity begins from the
bottom left of Fig. 1 with the simple equilibrium stage model. This
model assumes physical equilibrium and no reactions within theoretical stages. The next level moving rightwards is the equilibrium model
including also reaction kinetics. The model can consider the bulk phase
reaction kinetics or both the bulk and lm reaction kinetics, depending
on its complexity and accuracy. The equilibrium stage extended by the
consideration of kinetically controlled reactions is physically inconsistent; however, this model has often been applied in the literature.
Upwards and beginning from the left, the simplest rate based approach
assumes mass transfer rates and could take into account moving
rightwards, additional factors such as reaction kinetics and electrolytes
inuence. The 5 types of models are numbered from 1 to 5 beginning
from the less complex (equilibrium stage, reaction equilibrium) to the
most complicated (rate based with reaction kinetics, lm reactions and
electrolytes), in order to be referenced later.
4.3. Mass transfer approaches
Different approaches were followed in order to describe the
mass transfer phenomena between the liquid and the gas phase.
The dominant theories are the two lm theory and the penetration
theory.
The two-lm theory [16] suggest that there are two thin areas
(lms) that are adjacent to the two phases interface separating it
from the bulk phases, which are ideally mixed. It is assumed that

550

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Fig. 1. Different modeling approaches [Kenig et al., [9]].

overall mass and heat transfer resistance is concentrated in these


two lms considering that bulk phases are in equilibrium. The two
lm theory is prevailing among rate-based models. An important
factor is the lm thickness that is usually calculated using
empirical correlations. Two-lm theory is described by Ficks rst
law, using mass transfer coefcient correlations for a binary
system A  B.
N A CDA;B

dxA
dC
DA;B A ;
dx
dx

0 o x o n

where N is the ux of each component, is the lm thickness and


D the diffusion coefcient.
These correlations reect the mass transport dependence on
physical properties and process hydrodynamics and are available
from the literature [15]. Models using two-lm theory, often
assume that the reactions take place only within the liquid lm,
when the reaction is characterized as fast [17].
The penetration theory was described by Higbie on 1935 [18]. It
states that diffusion is unsteady state process and the molecules of
the solute are in constant random motion, where clusters of these
molecules arrive at the interface, remaining there for a xed
period of time, and some of them penetrate while the rest mixes
back into the bulk of the phase. The process is described by Ficks
second law with boundary conditions, which is the following for a
binary system A  B.

4.4. Thermodynamic models


A fundamental step towards chemical absorption modeling is the
development of an efcient thermodynamic model to describe the
vaporliquid phase equilibrium. In general, equations of vaporliquid
equilibrium describe the principle of chemical absorption and investigate the effects on gas solubility caused by temperature and pressure
[2022]. In specic for CO2 absorption, the main task of such models is
to determine the partial pressure of CO2 over an aqueous solution of
alkalonamine (or other solvent) and also quantify the energy required
for regeneration. In following, some widely used thermodynamic
models are provided, applied in their initial form or modied by
many researchers.
4.4.1. Kent  Eisenberg model
Kent  Eisenberg model was introduced on 1976 and it was the
rst model describing CO2 absorption by MEA solvents. This model
is an equilibrium model but is still advanced due to its simplicity.
Kent and Eisenberg described the two phase equilibrium through
Henry constants. A basic bottleneck for applying this model is that
it cannot predict the liquid phase composition [10]. The model was
enhanced by Krirpiphat and Tontiwachwuthikul on 1995, predicting the carbon dioxide solubility in aqueous 2-amino-2-methyl-lpropanol (AMP) solutions.

At x 1; C A C Ao 0

4.4.2. Electrolyte non-random two-liquid (e-NTRL) model


A widely accepted and applied Gibbs energy model is e-NTRL,
introduced by Chen et al. [23,24]. It is noteworthy that e-NTRL has
been included in the commercial ASPEN Plus package and has been
modied by various researchers. The eNRTL model is used to correlate
mean ionic activity coefcients of mixed solvent electrolyte systems
[19]. e-NTRL encompasses two main assumptions. It considers local
electro-neutrality and high repulsive forces between ions so that each
ion has an immediate neighborhood consisting of molecular species
and oppositely charged ionic species [19].

When systems with electrolytes are studied (e.g. water, amines),


their inuence cannot be neglected. Electrolyte systems are often
approached by the determination of free (or excess) Gibbs energy (GE
models). Gibbs energy is a result of two contribution terms; longrange interaction contributions attributed to the electrostatic forces
between ions and short-range forces between all species (ion ion,
moleculemolecule, molecule ion) [19]. These models usually compute the ionic activity coefcients through Debye Hunkel equations.

4.4.3. EoS/GE models


A variation of GE models is EoS/GE (equation of state with Gibbs
free energy) models. These models determine the Gibbs energy
through equations of state. The rst EoS/GE model was introduced
by Chunxi and Furst [25] and includes a specially adapted equation of
state considering the electrostatic interactions in the liquid phase.
UNIQUAC is also one of the classical models for EoS modeling of

DA;B

2 C A C A

t
x2

At t 0; C A C Ao 0
At x 0; C A C i

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

activity coefcients. Through UNIQUAC, activity coefcients are calculated in relation to the excess Gibbs free energy. UNIFAC is another
model that can be described as a group contribution method. While
being based on essentially the same model as UNIQUAC it considers
molecules as a set of groups. By obtaining data for segments of
molecules it is possible to predict the activity of any molecule
composed of groups of which parameters are known. This gives
UNIFAC predictive properties that UNIQUAC does not have [26].

551

process. The main common assumptions that most simulations adopt


are the following:

 All reactions are performed within the liquid lm. The liquid
bulk is at chemical equilibrium.

 The column is adiabatic and pressure is constant.


 There is plug ow of gas and liquid
 The gas and liquid ow rates are constant throughout
the column

4.4.4. SAFT (statistical association uid theory) model


SAFT model also uses an equation of state (SAFT equation) but it
determines Helmholtz excess energy instead of Gibbs. SAFT model
does not require the equilibrium constants like other models but is
based on a number of factors. SAFT equations of state are clustered
in the mean eld theories, leading to low accuracy when local
properties of the uid have big uctuations [27].
4.5. Kinetic models
In order to approach the kinetics of chemical absorption of
CO2, the rst step of the researcher is to determine which
reactions are taking place in the liquid bulk. The type of reactions
considered depends on the assumptions for the CO2-solvent
reaction mechanism. There are three main approaches on the
mechanism of CO2 reaction with amine solvents, the zwitterion
mechanism, the termolecular and the based-catalyzed hydration
mechanism.

 The zwitterion mechanism




This reaction mechanism was rst proposed by Caplow and


reintroduced by Danckwerts. Based on this mechanism, the
solvent and CO2 form zwitterions rstly, and then zwitterion is
further deprotonated by a base to form carbamate [8].
The termolecular mechanism
Termolecular mechanism suggests that the formation of the
zwitterions and the deprotonization occur simultaneously.
Base-catalyzed hydration mechanism
Tertiary alkanolamines cannot react directly with CO2. Such
amines have a base-catalytic effect on the hydration of CO2 and
amine dissociation reaction may also occur.

Generally, the reaction of CO2 with primary, secondary and


sterically hindered amines is governed by the zwitterion mechanism, whereas the reaction with tertiary amines is described by the
base-catalyzed hydration of CO2 [28].
The above mentioned reactions occurring within the liquid
phase are clustered in two categories; equilibrium reactions and
kinetically controlled reactions. Equilibrium reactions are fast
enough reactions to consider that the species are in chemical
equilibrium. Kinetically determined reactions should consider the
reaction kinetics. Equilibrium and rate constants (usually given by
temperature dependent correlations) are fundamental parameters
of a reactive absorption model, as they lead to the determination of the liquid phase composition. These constants usually
derive from tting experimental data or other researchers correlations. In literature there are various equations for different
solvents, correlating equilibrium and rate constants with
temperature.
4.6. Absorption column model
Reactive absorption is a complex process making its modeling
challenging. Within a model, a number of assumptions for the
absorption column should be performed in order to simplify the

 The diffusion in the axial direction and the solvent evaporations are negligible.

 The interface temperature is equal to the temperature of the


bulk phase.

 Ideal phases
4.7. Dynamic modeling
The majority of models refer to steady state conditions. However,
the CO2 absorption process should be coupled with the power plant
(or other industry) real time operation. In case of biofuels and coalbased power plants, the parameters of the fuel might vary during
operation leading to uctuations in ue gas composition [29]. The
effect of these uctuations is crucial to be reected by the model. A
dynamic simulation tool can include three factors [30]; optimal
design of the absorption/desorption column often interferes with
each other, the load variation and the emerging technologies that
make the process more complex. Dynamic simulation will play a
pivotal role in identifying any operational bottlenecks at transient
conditions for the integrated power and CO2 capture plants. However, as mentioned, the validation of such models is not always
possible, as dynamic experimental data are very scarce.
5. Models review
An extensive literature review is included in this section,
providing information for a wide range of models examined.
5.1. Rational for this review
During the last decade, an increment of interest on modeling
post-combustion CO2 capture is observed. Numerous researchers
develop models covering all simulation approaches, different
solvents, evaluating different parameters aiming to the optimization of the process and the effective junction with the power plant.
Searching literature there are only few attempts to list these
projects [29,31]. Existing reviews address mainly dynamic modeling and are providing brief descriptions of the studied models. The
current work attempts to describe in detail and compare in a
quantitative approach a number of fundamental models while also
providing tables presenting in short more models.
5.2. Chemical absorption models literature review
An extensive literature survey has been carried out, listing a
number of representative prototype models developed by
researchers based on previous work. The current work aims to
cover the spectrum of different solvents and modeling approaches.
5.2.1. Steady state models
At rst, Table 1 encompasses 7 steady state models that are
going to be further described in following. Following, the models
are further described and tables with main correlations applied are
presented (Tables 214).
Equilibrium models, as mentioned before, are not very applicable as equilibrium is very unlike to be reached. However, a
representative equilibrium stage model is presented.

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I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Table 1
Overview of the studied steady state models.
Researcher

Model
type

Solvent

Simulated Evaluation parameter


equipment

Experimental data for


validation

Sensitivity analysis

[Mores et al.
[32]]

MEA

Absorber/
Desorber

Pilot Plant Study at the


University of Texas, Austin
[Dugas, [38]]

Not performed

[Khan et al.,
[41]]

MEA

Absorber

[Kucka et al.,
[49]]

Amines

Absorber

CO2 concentration and


temperature prole

[Bolhr4
Nordenkampf et al.,
[52]]
[Gabrielsen
4
et al. [5]]

MDEA

Absorber
/Desorber

CO2 and H2S


concentrations along the
column

AMP

Absorber

CO2 concentration, liquid


temperature along the
column

[Puxty et al.,
[57]]

Absorber

[Al-Baghli
et al., [58]]

Amines/
Ammmonia
mixtures
MEA and
DEA

Total heat duty/CO2


recovery and CO2 recovery/
amine solution ow-rate
optimization
CO2 and MEA
concentrations along the
column

Two pilot [Tontiwachwuthikul Different correlations for mass transfer coefcients


et al. [43], Aroonwilas and one
industrial plant [Pintola et al.
[44]]
Pilot [Tontiwachwuthikul et al. Evaluating different correlations for reaction kinetics
[43]], and industrial plant
[Pintola et al. [44]]
A commercially operated
Not performed
selective MDEA plant

Pilot plant [Tontiwachwuthikul Performed for different parameters, model sensitive


et al. [43]
to surface tension of the liquid solution, the Henrys
Law constant for CO2, and the diffusivity of CO2 in
the liquid solution
Calculated versus measured A wetted wall apparatus
Not performed
CO2 absorption ux

Absorber

Column stages in order to


achieve a specic level of
separation

Not available

Not performed

Table 2
Mores model correlations.
Mores model
Parameter

Correlation

Nomenclature

Species mass balance in


stage z

Lz 1xizLzxiz Vz  1yjz  1Vzyjz 0

Energy balance in stage z


Chemical equilibrium
constants

Lz 1hz  Lzhz Vz  1Hz  1  VzHz HR  HH2O 0



v
K m aiz vi xiz iz i

Stage efciency

aiz: activity
D: diffusivity of CO2 in MEA
: enhancement factor
G and L:gas and liquid velocities
kL,G: mass transfer coefcient for liquid and gas phase respectively
kr: forward reaction constant
L: liquid molar ow
V: vapour molar ow
vi: estequiometric coefcient
yniz : equilibrium composition of molecular specie considered leaving the
stage z
iz : coefcient activity
: stripping factor
: gas and liquid densities

z
Enhancement factor

Ez

V z yiz  V z  1 yiz  1
V z yniz  V z  1 yiz  1

1e

h=a



or

G' =RTkG G

 

L' =kL L E

p
DCO2 kr;CO2  MEA MEA kr;CO2  OH CO2 

i !
z

kL

Mores et al. [32] introduced an equilibrium stage model, in


order to simulate CO2 absorption by MEA solvents and optimize
the operating conditions to remove CO2 from ue-gases in a stage
column. The simulation tool determines the optimal operation
through two factors, given the ue gas composition; the ratio
between the total absorbed CO2 and the total heating and cooling
utilities (exchanger, condenser and reboiler heat duties) and the
ratio between total absorbed CO2 and the total amine ow-rate.
The model assumptions include ideal mixtures, equilibrium stages,
neglected solvent vaporization, and two-lm model. Mass and
energy balances are applied for each theoretical stage z. Chemical
equilibrium constants are calculated through activity coefcients
taken from Aboudheir et al. [33]. Electrolytes inuence is considered applying charge and ionic mass balance in each theoretical
stage. Moreover, thermodynamic non-idealities are expressed via
stage efciencies correlations as a function of liquid physical
properties and an enhancement factor. In order to optimize the
operations of the absorber the indicator of CO2 removal efciency
is introduced comparing the CO2 input and output concentrations.

In addition, the effective area of mass transfer is determined, using


equations developed by Onda et al. [34], Wilson [35] and Bravo
and Fair [36]. A similar model for the desorber is applied assuming
the same constraints. The stripper model also includes mass and
energy balances corresponding to the condensers, heaters and
reboiler. Finally, it considers constraints to compute the Henrys
law constant, enthalpies, reaction heats, viscosity, vapour pressures, fugacity coefcients and surface tension among others.
The developed VLE (vapourliquid equilibrium) model was
validated against simulation results by Austgen and Rochelle [37]
and Aboudheir et al. [33]. The CO2 concentration is gured in
relation to the individual species concentrations and partial CO2
pressure. The agreement between the model and literature is
satisfactory. The absorber column is validated compared with
experimental measurements from pilot plant [38] and simulation
results using HYSYS process simulator. Results are presented for
the three approaches mentioned before (Onda et al. [34], Wilson
[35] and Bravo and Fair [36]) and compared with the experimental
data and simulation. Temperature, CO2 and vapour ow rate

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

553

Table 3
Khan model correlations.
Khan model
Parameter

Correlation

Enhancement factor

E 1 h

Nomenclature

1
E1  1

1:35

1

1 1:35
E1  1

where:
C Bl DB
;
E1 1 bD
C Ai
Al

E1

Rate constant

log k2 10:99  2152


T

Overall rate of absorption of CO2

CO
r CO2   2
H

1
kg a

i1=1:35

a: gasliquid interfacial area per unit volume of packing

p
M
p;
tanh M

CAi: CO2 concentration at the gasliquid interface


CBl: MEA concentration in bulk liquid

M 2 DAl k02C2Bl
kl

CMEA: MEA concentration

CCO2,g: molar concentration of CO2 in the gas phase

CO2
k0 aE
1

H CO2 105:3  0:035C MEA  1140=T





Henrys constant
Mass balance equation

d uz C CO2;g

Energy balance equations

dz

GY CO2 C pg

dT g
dz

l
LC pl dT
dz

DAl and DBl: diffusivities of CO2 and MEA in liquid, respectively


G: molar ow rate of gas per unit cross-sectional area of the column

dN CO2;g

SCO2


hg a T g  T l
dz

Hg: gas phase heat transfer coefcient

dT
GY CO2 C pg dzg GHR

HR: heat of reaction


Hs: heat of solution
k2: second-order rate constant
E: enhancement factor
HCO2: is the Henrys law constant

dY CO
H S dz 2

kg and kl : the gas- and liquid-lm physical mass transfer coefcients


NCO2,g( uzCCO2,g GYCO2): molar ux of CO2
pCO2: partial pressure of CO2 in bulk gas phase
SCO2: source term representing the overall rate of absorption of CO2
Tg: gas temperature
Tl: liquid temperature
uz: gas velocity in the axial direction
YCO2: mole ratio of CO2 in the gas phase

Table 4
Kucka model correlations.
Kucka model
Parameter

Correlation

Mass action law

K r e xpv

Bulk mass balance equations

p xvp;r vpp;r
v
ep;r ep;r

Lxlb
i
z

lb l
i
nlb
i a Ac Ri Ac

Gygb
i
z

Bulk enthalpy balance equations

Lhlb
z

Ghgb
z

Film balance equations


Pressure drop in the gas bulk
Heat ux through lms

Nomenclature

i
ngb
i a Ac

qlf ai Ac

qgf ai Ac

nlft 
p
z

clft Dlef f ;i

xlfi
l

xlfi zi RGF T
xlfi nlft
l

f L; G; l; g;
lf

q  l
lf

a: specic area
AC: cross-section area of column
Deff: effective diffusion coefcient
F: Faradays constant
h: molar enthalpy
ni molar ux of component i
p: product index
q: heat ux
RG: gas constant
r: reaction index
R: reaction rate
t: total
: activity coefcients
: lm thickness
: dimensionless lm co-ordinate
: thermal conductivity
: volumetric hold-up

T l

gf

qgf  g

nl
P
i1

T g
g

ng
P
i1

proles are illustrated along the column height. All approaches


provide good predictions for both experimental data and simulation results. In specic, for temperature and vapour ow rate the
correlation of Bravo is in a better agreement with the simulation
results. On the other hand, experimental measurements are better
predicted by Ondas equation. The validation of the stripper is
performed using experimental data by Tobienssen et al. [39];
Freguia and Rochelle, [40] and Dugas [38]. The paper does not
present analytical results for the regenerator but the predictions
are in satisfactory agreement with the model simulations.

lf

nlfi hi

gf

ngf
i hi

Following the model validation, a scenario is tested where the


optimal operating conditions in absorber to maximize the CO2
recovery are investigated. The optimization is oriented towards
two factors: the minimization of total heat duty/CO2 recovery
(OF1) and the maximization of CO2 recovery/amine solution owrate (OF2). Proles of these factors optimal values, heating and
cooling total utilities, amount of CO2 recovered, CO2 lean loading
and amine solution ow-rates are presented along the column
height. From these gures it can be seen that the optimal OF1
value decreases as the absorber height increases. The same

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I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Table 5
Bolhr  Nordenkampf model correlations.
Bolhr  Nordenkampf model
Parameter

Correlation

Nomenclature

Overall mass and energy transfer rates through the interfacial area on
stage k of the column

N i;k yi;k 1 V k 1  yi;k V k aint;k N Vi;k aint:the interfacial area

Mole fractions and at the vapourliquid interface

Hi;k xli;k

Enhancement factor

ECO2 

Ek H k 1 V k 1  H k V k
yl

H: specic enthalpy
Hi: Henry-coefcient of component i

i;k

1
1
E1
Ha3=2

1

Film thickness

2=3

E1 :enhancement factor for innite fast reaction

1
E 1 3=2

q
3wL
3
2 , w  aint  u  sin
L
aint g sin

Ha: Hatta number


Ni: molar ux of component i
u: the average liquid lm velocity
V: vapour ow
the angel of the inclined plane in reference to the
horizontal plane

Table 6
Gabrielsen model correlations.
Gabrielsen model
Parameter

Correlation

Nomenclature

Molar ux of CO2

NCO2 aAc
B
1L dx
L dxH2O L dX CO2
1
 dz 1 dz  1 dz
dG
 N CO2 N H2 O aAc
dz

a: specic wetted area for mass transfer

Stoichiometric relations for the chemical reaction

dyCO
2
dz

AC: cross-sectional area of the column


C 0AMP : concentration of AMP in the bulk liquid

N CO2 aAc yCO  1 N H2 O yCO aAc


2
2
G

C inf
CO2 : concentration of molecular CO2 at the liquid interphase

dyH O
NH O aAc yH O  1 N CO2 yH O aAc
2
2
2
2
G
dz
dL


N
aA
c
CO2
dz

dxCO2
dz

dxH2 O
dz

k2: rate constant

K CO2 :combined Henrys Law and chemical equilibrium constant for

N H2 O X CO2  N CO2 aAc


L

N H 2 O xH2 O  1 N CO2 aAc


L

qaAc
 GC
p;G


N CO2 C p;CO2 N H2 O C p;H2 O aAc T L  T G
dT L

LC p;L
dz
qaAc N CO2 H CO2 N H2 O HH2 O


LC p;L
LC p;L
dT G
dz

Enhancement factor
tanh

where:

E1 1
Equilibrium partial pressure
Heat of absorption

q: heat ux

XCO2: mole fraction of chemically bound CO2 in the bulk of the liquid phase

E1  E
M E1
 E

1
q


CO2 partial pressure


Di,L: diffusivity of component i in the liquid
NCO2: molar ux of CO2

 E
M EE1
1 E

DAMP;L C 0AMP
2DCO2 ;L C inf
CO


k2 DCO2 ;L C 0AMP
, M
2

pnCO2 K CO2 X CO2 1 




CO2 R  8161 47652

kL;CO

HH2O: heat of condensation of H2O


HCO2: heat of absorption of CO2

: loading, mole CO2/mole initial amine

Table 7
Puxty model correlations.
Puxty model
Parameter

Correlation

Nomenclature

Differential equations

ci
t

ci: the concentration of species i


DCO2;W ; DN2O;W :respective diffusion coefcients of CO2 and N2O in water
DCO2; Am , DN2O;Am : respective diffusion coefcients of CO2 and N2O in an aqueous amine
solution
N: the time averaged ux
ri: the rate of formation or destruction of i by chemical reaction
x: the distance from the gas-liquid interface

Averaged CO2 ux across the gas-liquid interface

Di xc2i  r i
DCO R t cCO
N  te 2 0e x 2 dt
2

Ratio of diffusion coefcients between N2O and CO2in DCO2; Am DN2O;Am DCO2; W
DN2O;W
water

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

555

Table 8
Al-Baghli model correlations.
Al-Baghli model
Parameter

Correlation

Enhancement factor

Nomenclature

 DidCi=dzj z 0 ri j z 0
kl Ci; int  Ci;blk



N i;z V in yi;in  V out yi;out kg;i a P i;out  P i;int


0
kl;i aEi C i;int  C i;bulk

Flux of the solute gas

Ci,int and Ci,bulk the interfacial and bulk molar concentration of the solute gas
Di is the diffusivity of solute gas i in the liquid
kg,i and kl,i: gas and liquid phase physical mass transfer coefcients of the solute gas i

Overall rate of absorption of CO2 For MEA


 r CO2 kCO2 C CO2 C RR0 NH 

kCO2 C RR0 NH2 C RR0 NCO2 


K Am
C RR0 NH

For DEA

 r CO2 kH2O C H2O kRR0 NH C RR0 NH


(
)
C '
C RR0 NCO2 
C CO2 C RR0 NH  RR NH2
K Am C RR0 NH

Pi,int the interfacial partial pressure


ri |z 0 the rate of surface reaction at the edge of the liquid lm
R C2H4OH, R H for MEA
and
R R C2H4OH for DEA

Table 9
Overview of the studied dynamic models.
Researcher

Model
type

4
[Kvamsdal
et al.,
[30]]
4
[Ghaemi
et al.
[61]]
[Kenig et al. 5
[15]]
4
[Harun
et al.
[63]]
[Jayarathna 4
et al.,
2013]
[Lawal et al. 5
[70]]

Solvent

Simulated Evaluation parameter


equipment

Data for validation

MEA

Absorber

Temperature prole along the column, effect of


disturbances on temperature and absorption rate

Partially
carbonated
ammonia
Aqueous
ammonia

Absorber

Temperature prole along the column, CO2 concentration


across the lm

Not
Pilot Plant from Separation Research
Program (SRP) at the University of Texas at performed
Austin [Dugas, [38]]
Absorption column pilot plant
Not
performed

Absorber

MEA

Absorber/
Desorber

Pilot plant of the coke plant August


Dynamic and steady concentration proles in the
Thyssena in Duisburg, Germany.
discretized liquid lm, axial proles of the mass transfer
and reaction rates
L/G ratio, CO2 absorption, CO2 loading, gas ow rate in the Simulation results from Aspen Plus
stripper

MEA

Absorber

Time dependency of temperature proles, CO2 loading, CO2 Pilot Plant Study at the University of Texas, Not
removal efciency, re-boiler heat duty
Austin [Dugas, [38]]
performed

MEA

Absorber/
Desorber

Temperature proles along the column height, water mass Pilot plant of Separations Research
Program at the University of Texas at
fraction, lean loading, CO2 capture level, reboiler duty
Austin
through time

approach is followed aiming to OF2 optimization, concluding that


optimal OF2 and amine ow-rate increase with the increasing of
the absorber height. Finally, higher total heating and cooling
utilities are needed to reach the maximum CO2 recovery when
the absorber height is increased.
Khan et al. [41] developed a typical, simple steady state ratebased model simulating CO2 absorption by MEA solvent, using
theoretical column stages. The developed model was validated
compared with two pilot columns [42,43] and one industrial
column [44]. The model applies the two lm theory and uses an
enhancement factor to consider the reaction kinetics. The overall
second order reaction rate is calculated through CO2 and MEA
concentrations as this approach is valid [45] and the rate constant
correlation was taken from [46]. The overall CO2 absorption rate is
calculated through Levenspiel [47] correlation and it is corrected
through the enhancement factor. Gas and liquidlm mass transfer coefcients and the interfacial area for random packings are
obtained from the widely used correlations provided by Onda et al.
[34]. A number of semi-empirical correlations that relate CO2
diffusivity to temperature and viscosity are used. Henrys constant
was used in order to calculate the solubility of CO2 in MEA
solutions as a function of MEA concentration, CMEA, and solution
temperature. Column assumptions include steady-state and adiabatic operations, plug-ow of gas and liquid, negligible diffusion in
the axial direction, constant gas and liquid ow rates throughout

Sensitivity
analysis

Not
performed
Not
performed

Not
performed

the column, negligible evaporation of solvent and constant pressure. Mass and energy balance equations were solved for different
heights of the absorption column to calculate CO2 concentration
prole along the column.
The comparisons of simulation predictions with the experimental data showed the following: for Tontiwachwuthikul pilot
plant (random packing), overall agreement between the prediction
and measurement is satisfactory for CO2 and MEA concentration
along the column. The CO2 concentration is slightly underpredicted for the bottom part of the column and for MEA overpredicted respectively. However, this part is crucial as prediction
results showed that the major absorption process takes place in
the bottom part of the column as the concentrations decrease
rapidly. In addition, in these areas, the predicted solvent temperature deviates from experimental data. This deviation is according
to the authors due to the neglection of the solvent evaporation in
the energy balance. The temperature prole conrms that the
main exothermic absorption occurs in the same column heights, as
a rapid temperature drop is predicted. The predictions are also in a
very good agreement with experimental data for Aroonwilas pilot
plant (structured packing). For the industrial plant experimental
data were not available. Predictions were only validated against
the CO2 exit concentration with very good results.
A sensitivity analysis is also performed using different correlations
for mass transfer coefcients. The correlations for the gas and

556

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Table 10
Kvamsdal model correlations.
Kvamsdal model
Parameter

Correlation

Mass balance equations

dC gi
dt

Species molar ux
Enhancement factor

C i
ug
z  ug z

ag=l :gasliquid interfacial area

 ag=l N i

C nMEA :liquid concentration of free MEA


l dt  ul z ag=l N i




a
dT
T
g=l
g ; l :gas and liquid holdup
C i Cpi g hg=l T l  T g
g dtg  ug zg P

ag=l 
dT g
T l
hg=l : interfacial heat transfer coefcient
l dt  ul z P C i Cpi l




hg=l T l  T g  Hr N CO2  H vap N H2 O  H out T l  T amb
dC li

Heat balance equations

 C gi

Nomenclature

C li



n
 P gi
N i K tot;i P eq;
i
p
kr;CO2 C nMEA DCO2
ECO2
l
kCO

K tot;i : total mass transfer coefcient


kr;CO2 : reaction rate coefcient for the reaction of CO2 with the aqueous MEA

CO2 equilibrium pressure

n
f ree
l
P eq;
CO2 H E;CO2 C tot xCO2 CO2

N i : ux of component i

Equilibrium pressure of MEA


and H2O

n
P eq;
xi i P i
i

n
P eq;
: Equilibrium pressure
i

P gi : partial pressure of
each component
ug ; ul : gas and liquid velocities
H r : heat of absorption of CO2
H vap : Heat of vapourization of H2O
H out : heat transfer coefcient for heat transferred from the absorber to the
surroundings
ree
: free CO2 mole fraction at equilibrium coefcient
xfCO
2

: activity coefcient

Table 11
Ghaemi model correlations.
Ghaemi model
Parameter
Dynamic mass balance equations

Dynamic energy balance equations

Heat transfer rate

Correlation

Nomenclature




d
1
U z
Lj  1 xi;j  1  Lj xi;j nBi;j al RBLi;j L A
dt i;j


U Li;j xi;j U Lt;j xi;j L cLt;j A
h
i 

1
0 z Gj  1 ys;j  1  Gj ys;j nBs;j al RBGi;j G A

A: cross sectional area

h
i 

B
B
1
 z
Lj  1 hL;j  1  Lj hL;j qBL al RBL L oRL A
h
i 

B
B
1
Gj  1 hG;j  1  Lj hG;j qBG al RBG G oRG A
0  z

 P
m
gf
gf
ngf
qgf  gf T i  T gb
i hi

a: specic packing surface

E: specic energy holdup


h: molar enthalpy

dEL
dt

Ha: Hatta number


N: interfacial molar ux

i1


 P
m
lf
lf
nlfi hi
qlf  lf T lb  T i
Molar concentration across the lm

Enhancement factor

C ; t

1
P
n1

i1

i
1 hR
P
t  Q n t 
f n d
0e
hn 1
i
sinn C l t C B t  C l t

e  Q n t sinnn

p
p
k2 DCO2 NH3 
1 Ha2 ; Ha
kL

q: heat ux

R: reaction rate
U: spedic molar holdup
: lm thickness
: volumetric holdup

liquidlm mass transfer coefcients given by Onda et al. [34]


provide better predictions than the penetration theory of Higbie
[18] and the correlation of Bravo et al. [48].
Kucka et al. [49] introduced a rigorous rate-based model to
simulate CO2 absorption by aqueous MEA solvents. Two types of
reactions are considered, namely the kinetically controlled reactions and the instantaneous. In order to consider instantaneous
reactions, the mass action law based on species activities is
applied. Chemical equilibrium constants and reaction constants
are obtained from literature via activity based correlations. Forward and reverse reaction constants lead to the reaction rate

calculation. Contrary to the majority of models using an enhancement factor, this model considers mass and heat transfer resistances according to the lm theory by explicit calculation of the
interfacial uxes. The inuence of electrolytes is also included,
correlating the lm equations with reaction and diffusion kinetics.
The reaction rates are implemented as terms into the mass
transfer equations describing lm phenomena and into the balances describing liquid and bulk behavior. Bulk and liquid balance
equations are solved as well as correlations for enthalpy balance
and pressure drop in the gas bulk phase. In addition, mass transfer
phenomena across the interface are described by MaxwellStefan

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

557

Table 12
Harun model correlations.
Harun model
Parameter

Correlation

Molar balance for the two


phases

dC i;g
dt

dC i;l
dt

 ul

Energy balance for the two


phases

Rate of mass transfer


Enhancement factors

Nomenclature

C i;g ug
z  ag=l N i

ag=l : specic gas-liquid interfacial area

C i;l
z  ag=l N i

A: cross sectional area

h a T  T
T
 ug zg gl glPl g C i;g C p;i

T l
t

agl
l
P
C nCO2 : molar concentration of CO2 at the liquid side interface
C i;l C p;i
 ul T
z 



hgl T l  T g  Hrxn N CO2  H vap N H2 O hout T l  T amb

C p;metal : tube metal specic heat capacity

k1g;i kHiE
l;i
p
k2 C nMEA DCO2
Eabs
k
1
K g;i

C nMEA :liquid molar concentration of free MEA

l;CO2

Estr 1 

DMEACOO 
DCO
2

D

1 2 MEACOO
DCO
2

Reboiler balance equations

Heat exchanger equations

C i;g ; C i;l : the molar concentrations of component i in gas and liquid phases

T g
t

D: diffusivity

K eq C MEA


p
p
p
n
n
K eq C CO

C CO
2

C CO2

dM i;reb
F in xi;in  F v yi;out  F l xi;out
dt
dEreb
F in H in  F v H v  F l H l Q reb
dt
2
M i;reb 4 dc LB m xi
2
Ereb 4 dc LB H l m

Dc: diameter of the column

For tube and shell:

hgl :interfacial heat transfer coefcient


kg;i kl;i :mass transfer coefcients

Eh;x : volumetric specic internal energy


Ereb : energy holdup
F: molar owrate

1 Q
2
 AL
z Q f lux r
Q Tube;f lux U Tube T metal  T tube
Q Shell;f lux ntube U Shell T metal  T Shell
For tube metal:


Q
lux
metal
L  Q Tube;f lux  Shell;f
mmetal C p;metal dTdt
ntube


2
2
mmetal Lmetal 4 do;tube  di;tube
dEh;x
dt

k2: second order reaction order


L: tube length
LB : liquid level of reboiler drum
M i;reb : molar holup
N i : molar ux of the component i
q: interfacial heat transfer
Q: energy ow rate
Q f lux : heat ux
Q Tube;f lux ; Q Shell;f lux :heat ux from tube wall to tube and from tube wall to shell
T amb : ambient temperature
T metal ; T tube ; T Shell : tube metal temperature, tube uid temperature and shell
uid temperature
ug ; ul : gas and liquid velocities
U Tube ; U Shell : overall mass transfer coefcient of the tube and shell
m : molar density
metal : tube metal density

Table 13
Kenig model correlations.
Kenig model
Parameter
Mass balance equations for liquid and gas phases

Correlation


lb
t U i

Nomenclature

lb

lb
i
 z Lxi nlb
i a Ri liq Ac

 

gb
gb i
gb
0
Gyi ni a Ri gas Ac

Driving force
Film balance equations
Reaction kinetics

xlfi

di RT 1lf

xlfi
l

xlfi zi RGF T
xlfi nlft
l


r 3 k3 T cCO2 cNH2  K1eq cH2NCOO  cH3 O

nlft 

equations, assuming local electroneutrality and neglecting diffusion interactions. Through these equations the two lm component uxes and the heat ux are determined. e-NTRL model is
used to describe thermodynamic non-idealities in the liquid phase
and for the gas phase the SoaveRedlichKwong equation of state
[50]. In order to simplify calculations, discretization of the lm
region is performed, dividing it to several balance regions. The

Ac : column cross section


ni molar ux of component i

di
F 1 d
xlfi zi RT
d
lf d

clft Dlef f ;i

ai: specic gas-liquid interfacial area

Ri: total component reaction rate


RG: gas constant
U: specic molar holdup
: lm thickness
: dimensionless lm co-ordinate
: volumetric hold-up

model was validated using two experimental data sets by Tontiwachwuthikul pilot plant and one data set from an industrial
plant. For the rst occasion, the inuence of the number of axial
segments on the gas composition is calculated, showing that the
minimum number of axial segments which provides results of
sufcient accuracy for both data sets is 15. Gas phase composition
and liquid phase temperature prole are presented along the

558

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Table 14
Jayarathna model correlations.
Jayarathna model
Parameter

Correlation

Columns balance equations

clj:Col
t

T lCol
t

U
l
ulCol cj:Col
1 0

zCol nj:Col;trans nj0 :Col;gen0

C vj:Col
t

Nomenclature

ov

T vCol

h Aw
ulCol T lCol
Pn
zCol 3 l
C p:Col

 T lCol

j 1

Condenser equations

Reboiler equations
Buffer tank equations

dclj:BT
dt
dT lBT
dt

ABT

1
ABT Z lBT

P


K ov
CO2

Hj : Henrys law coefcient

clj;Col

BT;Out

BT;In

K vj : local gas side mass transfer coefcient


mlRD;In :mass ow rate of liquid into the reux drum
QRB: reboiler heat duty
rr: vector with overall reaction rates as elements

u: velocity
_ lBT;In
n_ lj:BT;In ABT Z lBT n_ 0j:BT;gen  m

 
 l

P
r
l



l
v: is the stoichiometric matrix
l
l
 H~ r;m r m
P T BT ;In  T BT cl ABT Z lBT C~ p;j  m 1 P
clj:BT C~ p;j
j:BT
clj:BT
l

l
n_ lj:BT;In C~ j:BT;In

 1
1=K vCO

Rate of generation of specie j in


the liquid phase

Ej: enhancement factor



3
Pn
U
0
3
j 1 nj;Col; trans  H vap:j
n0CO2;Col; trans  H abs

P
P
C lp;Col nj 1 clj;Col
C lp;Col nj 1 clj;Col



ov
h Aw T vCol  T lCol
uvCol T vCol
T vCol
P
cvj:Col C vp:j:Col
t  1  zCol 
1 


l
dZ lRD
_ lRD;In  l V_ RD;Out
A 1 l m
dt
RD


dclj:RD
cl
1 l n_ lj:RD:In  j:RD
mlRD;In
dt
l
ARD Z RD

P v
l
n_ j:RB H~ vap:j
Q_ RB mlRB;In C^ p RB H r


l
dZ lBT
_l
1 l m
 l V_
dt

Overall mass transfer coefcient

C: specie concentration

uvCol cj:Col
1

 1 
zCol 1  nj0 :Col;trans0

HCO2 =E CO2 K lCO


2

n_ 0gen vT r r

column. The agreement was satisfactory for both parameters


compared with the experimental data. Validating the model
against industrial experimental measurements, results are also in
a very good agreement compared with methods with enhancement factors. Finally, a sensitivity test was conducted, applying
3 approaches for reaction kinetics from literature (12, 46 and 51).
The rst two approaches provide almost identical results for the
gas phase composition prole, in comparison with Danckwerts
that leads to an underestimation of the column height of 15%.
Bolhr-Nordenkampf et al. [52] developed a predictive tool for
MDEA gas scrubbing processes, modifying Aspen plus RATEFRAC
algorithm. The model is validated compared with a commercially
operated selective MDEA plant in Germany. The approach of stages
is adopted as calculations are made tray by tray and two-lm
theory is considered for the mass transfer phenomena. The overall
mass and energy transfer coefcient rates are calculated through
Khrishnamurthy equations. Henrys law is used to calculate the
mole fraction at the vapourliquid interface. Mass transfer coefcients for the two phases are determined through MaxwellStefan
equations. Within the same work a prediction model for desorption was developed too. Desorption was simulated through an
equilibrium stage model. Equilibrium models are applicable for the
stripper as there are high temperatures and therefore high
equilibrium like reaction rates. Considering the reaction kinetics,
certain reactions are considered as very fast and are described by
equilibrium constants and others reaction rates are taken from
literature provided in a table in the paper. In order to describe the
reaction kinetics, an enhancement factor by Danckwerts equations
was used in order to correlate the physical mass transfer coefcients with the actual reactive transfer coefcients. Predictions for
absorption were obtained for two packing heights using the
developed model and an equilibrium commercial tool. The developed model predicts the measured H2S values far better (21 ppm
average deviation) than the equilibrium approach (88 ppm average deviation) simulation and gives comparable results for the CO2

HAbs, HVap, Hr heat of absorption, vapourization,


reaction
: liquid hold up c, h cold, hot l,v: liquid, vapour
RD: reux drum ov: overall value : per volume gen,
trans: generation, transfer

values (Non-equilibrium: 0.22 vol.%; TSWEET: 0.28 vol.% average


deviation).
A rate based model studying aqueous solution of 2-amino-2methyl-1-propanol (AMP) which is a sterically hindered amine
was developed by Gabrielsen et al. [5]. The model aims to predict
the solubility of CO2 in AMP aqueous solutions as well as the
absorption heat a function of loading and temperature. The
following assumptions were considered in order to model the
packed column: two lm theory, reactions only within the liquid
lm, constant temperature between the interface and the liquid
bulk, neglected axial dispersion and solvent evapouration, adiabatic conditions and ideal phases.
Mass and energy balances are calculated through mass transfer
coefcients and an enhancement factor in order to take into
account the reaction inuence. Mass-transfer coefcients and the
specic gasliquid interfacial area are calculated using correlations
from Billet and Schultes [53]. The enhancement factor is calculated
using the expression proposed by van Krevelen and Hoftijzer [54].
The model assumes a liquid phase ideality and uses one chemical
equilibrium reaction to consider nonidealities combined Henrys
Law and equilibrium constant. Using chemical equilibrium constant, partial pressure of CO2 can be determined through the
vapourliquid equilibrium (VLE) model for aqueous solutions of
alkanolamines, presented in Gabrielsen et al. 2005 [55], as a
function of CO2 loading. This correlation gives satisfactory results
for the partial pressure over the loading range and temperatures
considered, compared with experimental data from Tontiwachwuthikul et al. [1992] including concentration and temperature
proles along the column. In addition, the heat of absorption of
CO2 in the AMP solution (HCO2) was calculated, using the Gibbs
Helmholtz equation [55]. However, there were no experimental
data available to verify the model predictions.
Reaction kinetics is modeled assuming the zwitterion mechanism and using a correlation for the rate constant by Saha [56].
Finally, prediction data are compared with experimental, for

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

concentration proles, liquid temperature proles and liquid


loading in different column heights. The results derived were very
good for the CO2 concentration in both gas and liquid phases,
although the liquid temperature is slightly overpredicted at the
bottom of the column. Sensitivity analysis was also performed,
concluding that the model is most sensitive to the surface tension
of the liquid solution, Henrys Law constant for CO2, and the
diffusivity of CO2 in the liquid solution.
Another steady state model was introduced by Puxty et al. [57]
describing CO2 mass transfer in amine/ammonia single systems or
their mixtures. This model was developed from scratch in Matlab and
was validated against experimental measurements from a wetted-wall
apparatus. Model assumptions include neglected axial dispersion and
heating effects, constant physical properties, two-lm theory. The
system of partial differential equations to be solved is dened by
second Ficks law considering also reaction rates. The reaction kinetics
vary as described in the previous model from fast to kinetically
controlled reactions. The rate and equilibrium constants were taken
from published data and corrected through activity coefcients. The
diffusion ux was calculated by the rst Ficks law for different heights
of the column.
The results from single systems are combined in order to
predict the mixtures results. Thus, complex reactions are not
involved. Single systems are solvents of monoethanolamine
(MEA) piperazine (PZ) and ammonia (NH3). Mixtures studies are
PZ  AMP and PZ  NH3 where PZ is used as a promoter. For single
solvent systems, agreement between predictions and experimental data for calculated versus measured CO2 absorption ux, is very
satisfactory. In particular for aqueous ammonia the data scattering
increases with temperature due to the high volatility that
increases the uncertainty of ammonia concentration in the liquid.
For mixtures studied, the excellent agreement of predicted and
measured values proves that behaviour of these mixtures can be
represented by individual component systems.
Al-Baghli et al. [58] introduced a steady state, rate-based model
applicable for MEA and DEA solvents. Solubility of both CO2 and H2S is
studied. Two-lm theory and stages approach is applied. The model
considers that reactions take place entirely within the liquid lm and
the phases are ideal. The liquid and the gas leaving a tray have the
same temperature and composition as the liquid and the gas on the
tray. Physical equilibrium of the interface is expressed through Henrys
law. This model also uses the enhancement factor to describe the
reaction kinetics. The enhancement factor was calculated through a
system of ve nonlinear differential equations governing diffusion and
reaction in the liquid lm. Moreover, the KentEisenberg equations
are used to calculate the concentrations of the species in the liquid
bulk. The reaction rates are determined through the Danckwerts
approach. In addition, the heat of absorption is predicted for the two
solvents, using correlations for enthalpy and different temperatures.
Tray hydraulics and to obtain the tower diameter, tray spacing, weir
height, and pressure drop across the trays were obtained by Economopoulos algorithm. It was observed that MEA, as expected, requires
fewer stages than DEA in order to achieve a specic level of separation.
In addition, the prole of the enhancement factor for both MEA and
DEA is presented showing that for CO2 the factor increases mildly as
we approach the top of the tower, while for H2S the factor increases
sharply until its concentration is almost zero and then starts decreasing until the top stages of the tower. Finally temperature prole of the
gas or liquid along the tower is presented reecting as expected the
absorption heat transfer phenomena.

5.2.2. Dynamic models


A respective analysis follows for the dynamic models studied
within this work. At this point, should be noted that sensitivity
analysis mentioned below, refers to a specic analysis taking into

559

account the impact of many parameters. The following dynamic


models test different disturbances for the system, but do not
perform a sensitivity analysis as it is dened.
Kvamsdal et al. [59] developed one of the rst dynamic
approaches simulating CO2 absorption by MEA solvents, using
gPROMS tool for model development. The initial tool was rstly
introduced on 2008 and was validated only against steady state
data from a MEA campaign at the University of Texas at Austin
(UT). In a subsequent work [30], the simulation tool was validated
compared with experimental results both for steady (from the
pilot plant at UT) and transient conditions (from a pilot plant at
NTNU/SINTEF). In the context of the same work different
parameter-correlations are studied and compared. The developed
simulation tool tests two scenarios for dynamic operation: startup and load reduction. The model applies the following assumptions for the wetted column: plug ow, axial differential mass and
energy balances for both gas and liquid phases, linear pressure
drop, ideal gas phase, two lm theory, no accumulation in gas and
liquid lms, thermal equilibrium between the liquid and packing
material, condensation of water vapour occurs at gas-liquid interface as well as at the walls and effective contact area is equal to the
specic area of the packing material. Heat and mass balances are
solved for the bulk phases. All the mass transfer coefcients are
determined by correlations given by Onda et al. [34]. An enhancement factor is used to describe the reaction inuence on mass
transfer. The reaction rate coefcient is based on data from Freguia
and Rochelle [40] and is corrected through the activity coefcients.
An equilibrium speciation [60] model is used to determine the free
CO2 mole fraction at equilibrium, the activity coefcient and the
concentration of free MEA and Wilson equation for the activity
coefcients of MEA and H2O. The equilibrium pressure of species is
calculated through activity coefcients. The physical properties
requires, are obtained by literature.
Firstly, steady state validation of the tool was performed,
against experimental measurements by Separation Research Program (SRP) at the University of Texas at Austin. The temperature
prole deriving from the model agrees with the measurements,
with more satisfactory agreement with specic tests.
In following, a dynamic analysis is performed, testing two
scenarios: the change in liquid and ue gas ow rate during the
start-up and the load reduction cases. For the rst case, the liquid
temperature prole during start-up is provided, showing that the
T bulge location changed from the bottom of the column to the top
as the ue gas ow rate increased and the L/G thereby decreased.
Moreover, a decrease of the absorption rate values is observed. For
the second scenario, the upstream cooling tower and the blower
were also considered in a very simplied approach. In addition,
load reduction considered two cases; a reduction in load or
exhaust gas ow rate, without changing the liquid ow rate and
a decrease of the liquid ow rate such that the nal removal rate
was the same as before the gas ow rate reduction.
Ghaemi et al. [61] developed a rate-based model to simulate
carbon dioxide absorption by partially carbonated ammonia solutions. The tool applies the two lm theory and assumes 100 stages
and ideal mixtures. Mass and energy balances equations are solved
for each stage. To describe axial temperature proles, energy
balances are modied including the product of the liquid molar
holdup and the specic enthalpy as energy capacity. In addition,
heat transfer rate is determined. The species concentration is
calculated through an initial boundary value problem considering
unsteady-state mass and heat transfer. Diffusion in the interface is
described by Maxwell-Stefan equations. Within this work the
interfacial compositions are determined through equations based
on the semi-empirical Pitzer equation. Mass transfer coefcients
are taken from Onda [34] and physical properties are obtained by
literature. Reaction kinetics considers reaction between CO2 and

560

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

water, reaction between CO2 and hydroxyl ions and reaction


between CO2 and NH3. The overall rate of reaction is the summation of the aforementioned reaction rates. Rate constants as a
function of temperature, are taken from Danckwerts and
Sharma [51].
The simulation tool was validated against pilot plant experimental data deriving from steady state measurements. Dynamic
model equations are solved both with analytical and numerical
methods. The CO2 concentration was calculated in relation to the
lm coordinates from 0.0001 to 0.1 s. The results vary with time
and justify the need for dynamic simulation. At rst some steady
state results are presented. The CO2 concentration in relation to
the lm coordinates is presented for steady state conditions,
calculated both through the dynamic model and by using an
enhancement factor from literature [62]. The use of the enhancement factor leads to an important relative error compared with
the numerical solution. In addition gas mole fractions over the
column height are presented. CO2 mole fraction decreases along
the column height due to its absorption, whereas NH3 and H2O
concentrations increase as a result of mass transfer from liquid
phase to the gas. Moreover, temperature prole along the column
is given, showing that temperature increases along the column, as
expected for an exothermal process. In order to determine dynamically the overall CO2 concentration in the liquid as a function of
time and stage, both dynamic and enhancement factor approaches
were applied. The same approach is followed for the temperature
proles. The researchers use the relative deviation to compare the
two models. As proved, the enhancement factor leads to higher
deviations almost for all parameters measured.
Another dynamic approach to the CO2 absorption by MEA was
proposed by Harun et al. [63], based on the work by Kvamsdal
et al. [59]. The absorption column was discretized in a number of
stages and the two lm theory is applied. Mass and energy balance
equations are applied for each stage and each component for the
two phases. A correlation for the rate of mass transfer is used,
including an enhancement factor to consider reaction kinetics.
Different equations for the enhancement factor of the absorber
and the stripper are provided.
Moreover, the reboiler is modeled using a simple equilibrium
stage model. P-T ash calculations were used to determine the
compositions of vapour and liquid phases, at given pressure,
temperature and overall compositions. In following, the heat
exchanger is simulated developing a mathematical model, considering it as a counter-current shell and tube heat exchanger. This
model describes the heat exchanged between the hot lean amine
solution and the cold rich amine solution coming from stripper
and absorber, respectively. The simulation tool was validated
against steady state data. For the absorber, experimental measurements by Lawal et al. [64] were used. By the results it is shown
that the model slightly underpredicts the temperature prole
along the column. The stripper model was validated comparing
the results with simulation data from Aspen plus Radfrac model. In
this case, temperature for different column heights is overpredicted by the developed model. The simulation results for the
reboiler and heat exchanger present satisfactory agreement with
those obtained with Aspen Plus.
Dynamic simulations were conducted using a partial load
reduction scenario. The case study assumes a reduction of 50% in
the ue gas ow rate in relation to the initial steady state value.
The liquid to gas ratio (L/G) was calculated through time, concluding that increased as the ue gas ow rate decreased linearly.
This is justied as the lean ow rate remains constant since the
stripper heat duty is the same. The CO2 loading decreased with
time. In addition, the percentage of CO2 absorbed signicantly
increased during the test. This is due to the corresponding
reduction in CO2 available to react with free amine in the absorber.

Finally, it is observed that gas ow rate of CO2 in the stripper was


signicantly reduced during the ramp test.
Kenig et al. [15] based on the steady state model described in the
previous section [49] developed a dynamic model simulating CO2
absorption by aqueous ammonia solvents. Mass balance equations
for the bulk phases include molar holdup terms due to dynamic
nature of the model. However, gas hold-up is neglected. For the lm
region, mass transfer phenomena are reduced to a steady state
problem. The effect of electrolytes is described via the electrical
driving force and the diffusion phenomena using Nernst Planck
equations and assuming local electroneutrality. The thickness of the
lm region is determined by empirical mass transfer coefcient
correlations. The model is validated simulating an innovative purication processes called ammonia hydrogen sulphide circulation
scrubbing (ASCS). The rate of the direct reaction between carbon
dioxide and hydroxyl ions (the most important reaction) is given by
Astarita, Savage and Bisio [65]. In addition, the reaction kinetics of
NH3 and CO2 has been considered in the model equations. The
developed model was compared with experimental data from ASCS
sidestream of the coke plant August Thyssena in Duisburg, Germany.
Concentration proles in the discretized liquid lm are presented.
The interfacial molar uxes are provided both using MazwellStefan
equations without considering the electrical force and using Nernst
Planck equations. Fluxes calculated with the effective diffusion
approach differ only slightly from those obtained by the Maxwell Stefan equations without the consideration of generalized driving
forces. The optimal height of the absorption column was investigated
testing several discretizations of the packing section of the absorber
with different numbers of segments in relation with the mass
transfer and reaction rates. Finally, axial concentration proles are
compared with experimental measurements.
Dynamic simulations include a sudden ammonia concentration
growth in the solvent feed case. Dynamic concentration proles
for the gas and liquid products are given as a function of time. The
results show that increasing solvent concentration reduces the
selectivity of the chemisorption and much of the ammonia gets
lost by the CO2 consumption.
Jayarathna et al. [66] developed a general model for amine
based solvents. Separate sub-models are developed for absorber,
stripper, condenser and reboiler. The main balance equations are
considered the same for the main columns, altering the boundary
conditions of the differential equations deriving from the reux
stream enters the top most section of the stripping tower The
model assumption include constant ow rate, ideal phases,
neglected interfacial mass transfer of N2 and O2, reactions only
in the liquid lm, linear pressure drop, adiabatic system, each
phase in a control volume of the spatially discretized model
behaves as a continuous stirred tank.
The condenser of the stripping tower is modeled as a condenser block followed by a reux drum. The re-boiler is modeled
using a xed vapour-to-feed fraction and the reboiler heat duty is
calculated. The heat exchanger model consists of energy balance
equations for the rich (cold) and lean (hot) amine streams in the
cross heat exchanger and cooling water (cold) and lean amine
(hot) streams in the lean cooler. Additional correlations are applied
for the buffer tank model.
Mass transfer is considered as a concentration driven process.
The equilibrium concentrations are determined by Henrys law
coefcient which is taken from Kent  Eisenberg model. For CO2
the overall mass transfer coefcient is given as a function of the
local mass transfer coefcients, Henrys law coefcient and the
enhancement factor. The forward reaction rate coefcients are
calculated by correlations by Jamal et al. [67] and Freguia and
Rochelle [40], while the equilibrium coefcients for the reactions
are found using the KentEisenberg model [68]. Using these
coefcients the overall reaction rate is calculated.

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

The model was validated compared with experimental data


[38,59,69]. CO2 loadings, CO2 removal efciency, re-boiler duty,
temperature prole and ow Rates are compared with the measurements and are found to be in good agreement. For dynamic simulations, a number of cases of operation disturbances are validated
against steady state data. These scenarios are namely, increase of
molar ow rate of the inlet gas stream into the absorption tower,
increase of the volume ow rate of the inlet MEA stream into the
absorption tower and increase if V/F fraction of the re-boiler.
Lawal et al. [70] introduced a model investigating the operation
of coal-red power plants with post-combustion capture using
dynamic modeling and simulation. The model is a result of
numerous amendments of a dynamic model, simulating both the
absorber and the desorber linked together with recycle. Assumptions for the absorber include adiabatic system, plug ow, linear
pressure drop, negligible holdup in the vapour bulk, solvent
degradation and reactions are assumed to reach equilibrium. The
regenerator model consists of the GasLiquid Contactor model (for
the packed column section) linked with two ash drum models
which represent the condenser and reboiler of the unit. Correlations for the heat of absorption were obtained from the literature.
Mass and energy balance equations are solved for the two
columns. In specic, for the vapour bulk accumulation of mass
and energy holdups are negligible. In following, correlations for
the heat loss and desorption heat are applied as a function of
temperature and other parameters. Mass transfer coefcients in
the liquid and vapour lms were determined by correlations given
by Onda et al. [34]. Phase equilibrium between liquid and vapour
phases is assumed at the interface. The Maxwell Stefan equations
are solved, considering the two lm theory. The equilibrium molar
compositions of the components in the vapour and liquid phases,
are estimated based on the vapour and liquid fugacity coefcients.
Physical property estimations for viscosities, enthalpies and densities were determined using the physical property package Multiash, while the fugacity coefcients and ash calculations in the
reboiler and condenser were determined using the Electrolyte
Non-random-two-liquid (NRTL) model in Aspen Properties and
accessed through the CAPE-OPEN Thermo interface. The steadystate validation of the chemical absorption plant model was
carried out using data from the Separations Research Program at
the University of Texas at Austin [38]. Validation was performed
for stand-alone columns and for the integrated system. Simulation
results were validated using the temperature prole of the
absorber column measured in the pilot plant, with good agreement and higher deviations for the desorber predictions. The
predictions for the integrated system presented higher deviation
from the experimental case for the temperature prole especially
in the regenerator because of certain model limitations. Finally, a
dynamic analysis is performed, testing the behavior of the system
under the following scenarios; switching off water balance control,
increasing ue gas ow rate to the absorber, reducing reboiler heat
duty and increasing CO2 concentration of ue gas to the absorber
column. Dynamic analyses showed that the absorber performance
is more sensitive to the molar L/G ratio than the actual ow rates
of the solvent and ue gas. The performance of the regenerator is
affected by the reboiler duty.

5.2.3. Model comparisons


The current section includes comparisons of key simulated
parameters by models that used the same experimental measurements as reference for validation. As mentioned before, there are
no dynamic experimental data available. Therefore, both for steady
state and dynamic models, validation was performed against
steady state data. Thus, the comparisons consider the models as
steady state. The comparison was made using information

561

included in the cited articles, thus in some cases the comparison


is graphical and includes a wide range of values and in other cases
individual values are compared. The models to be compared are
either described in detail in the previous section or described in
short in this section.
In following, a short description of the pilot plants where the
experiments were conducted is provided.
5.2.3.1. Tontiwachwuthikul pilot plant. Tontiwachwuthikul et al.
[43] carried out a series of experiments in a larger counter
current pilot-plant absorption column consisting of six packed
beds with a total packing height of 6.6 m and 0.1 m in internal
diameter. The column was packed with 12.7 mm ceramic Berl
saddles. Steady-state gas phase CO2 and MEA concentrations and
solution temperatures were measured along the column height for
different gas/liquid ratio, inlet CO2 and MEA concentrations.
Three models were selected for comparison, all of them using a
specic run tests (T22) measurements of Tontiwachwuthikul
plant. Khan model was analyzed in the dynamic models section.
The other models are work of McDowell et al. [71] and Liu et al.
[72]. McDowell uses a rate based approach and applies SAFT-VR
equation of state to describe the thermophysical properties and
uid-phase behaviour of this process instead of using an enhancement factor. The dynamic analysis of the model includes evaluation of the effect of changing the lean solvent ow rate and
thermodynamic state on column behavior. Liu proposes a complex
computational mass transfer model (CMT). The model consists of
the differential mass transfer equation with its auxiliary closing
equations and the accompanied formulations of computational
uid dynamics (CFD) and computational heat transfer (CHT).
Two parameters are presented along the column height, the
CO2 concentrations % (Fig. 2) and the liquid phase temperature
(Fig. 3). As seen by the gures, Khan model slightly underpredicts
experimental measurements while McDowell and Liu predictions
overpredict Tontiwachwuthikuls data especially in the area
between 1 and 3 m height column. At the same area Liu provides
more accurate predictions from McDowell for CO2 concentration.
In Fig. 3, the temperature prole along the column is illustrated
for the three models and the respective experimental data. The
same remarks are observed for the liquid phase temperature
predictions as for the CO2 concentration. However, Mc Dowell
model seems to be the only one predicting the expected temperature bulge. It is known that a temperature bulge can be located in
the bottom of the absorber column [73].
5.2.3.2. Munmorah pilot plant. This pilot plant was jointly constructed
by Australias Common wealth Scientic and Industrial Research
Organization (CSIRO) and Delta Electricity at Munmorah power
station. The pilot plant mainly includes two absorbers in parallel or
series, one heat exchanger and one stripper. The inner diameter and

Fig. 2. Comparison of the CO2 concentration predictions of Khan and McDowell


models and experimental data from Tontiwachwuthikul [T22].

562

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

Fig. 3. Comparison of the temperature prole predictions of Khan and McDowell models and experimental data from Tontiwachwuthikul [T22].

Table 15
Lawal model correlations.
Lawal model
Parameter

Correlation

Mass balance for bulk phases

dMi
dt

Energy balance for bulk phases

Heat Loss (HL)


Heat of absorption
Film equations

Interface model

 L U1A

Nomenclature
A: cross-sectional area

F Li
y N i U Sp U MW i U
V

F
 L U1A yi

dU
dt

 1 F H
L U A y

N i U Sp U MW i U


conv

Sp U U H cond
liq H liq H abs HL


F V
conv
0 LU 1A yH Sp U U H cond
vap H vap
L



 


2
habs R U  14281  1092554
 6800882
32670:01 U


nc xM N  xM N R
M
P
i
k
1 xi
1
T
i
k
i;k
298:15
z ct
k1
1 GT 1 H f lux
z  z
L
V
f i xM;V
f i xM;L
i
i

ct: total molar concentration


f: fugacity coefcient
Fi: component mass ow rate
H: heat ux
HL: heat loss to surroundings
L: length of column section
M: mass holdup
MW:molecular weight
N: molar ux nc: number of components
R: universal gas constant
Sp: specic area
U: energy holdup
: CO2 loading
: lm thickness
: thermal conductivity
: viscosity
: wetted area ratio
Superscripts
Conv:convection
I: interface
L:liquid
Lb:liquid bulk
Lf:liquid lm
M:molar
R:reference
V:vapour
Vb:vapour bulk
Vf:vapour lm
Subscripts
Abs: absorption
H: enthalpy
i: component number
Liq: liquid
Vap: vapour

the packed height of each absorber are 0.6 m and 3.9 m, respectively.
The inner diameter and the packed height of the stripper are 0.4 m and
3.5 m, respectively. The absorbers and stripper are both packed with
25 mm Pall rings.

Two models are compared using the same experimental


measurements by Munmorah pilot plant. In this case, individual
values of parameters were provided so the comparison is performed via Table 15. In order to compare the two values the

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

relative deviation is calculated via the following equation:




X exp:  X pred:
 100
RD%
X exp:
The rst researcher [74] used the commercial RateFrac model of
Aspen plus to simulate the CO2 absorption and regeneration processes
of a research scale pilot plant. The effects of lean solvent ow rate, NH3
concentration, CO2 loading, and temperature on the absorption
process were analyzed. In addition, optimization analysis for the CO2
regeneration process was carried out. The second model was developed by Qi et al. [75] and also aims to simulate CO2 absorption using
aqueous ammonia. The model is based on the RateSep module, a ratebased absorption and stripping unit operation model in Aspen Plus,
and uses the available thermodynamic, kinetic and transport property

Table 16
Comparison of Munmorah simulations.

Case 31
CO2 absorption rate (kg/h)
Model prediction
Experimental
Relative deviation (%)
NH3 concentration in exit gas
Model prediction
Experimental
Relative deviation (%)
CO2 loading of rich solvent
Model prediction
Experimental
Relative deviation (%)
Case 31B
CO2 absorption rate (kg/h)
Model prediction
Experimental
Relative deviation (%)
NH3 concentration in exit gas
Model prediction
Experimental
Relative deviation (%)
CO2 loading of rich solvent
Model prediction
Experimental
Relative deviation (%)
Case 38
CO2 absorption rate (kg/h)
Model prediction
Experimental
Relative deviation (%)
NH3 concentration in exit gas
Model prediction
Experimental
Relative deviation (%)
CO2 loading of rich solvent
Model prediction
Experimental
Relative deviation (%)
Case 39
CO2 absorption rate (kg/h)
Model prediction
Experimental
Relative deviation (%)
NH3 concentration in exit gas
Model prediction
Experimental
Relative deviation (%)
CO2 loading of rich solvent
Model prediction
Experimental
Relative deviation (%)

models for the NH3CO2 H2O system to predict the performance of


CO2 capture. The analysis includes the species concentration prole,
temperature prole, mass transfer rate and coefcient in the gas and
liquid bulk phase along the packing height. Observing the table, it is
not clear which model is more accurate as they are both in good
agreement with the experimental data (Table 16).
5.2.3.3. Pilot plant study at the university of Texas at Austin. The
absorber column of the pilot plant is a packed column with a
diameter of 0.427 m and total packing height of 6.1 m. This column
consists of two 3.05 m packed bed sections with a collector plate
and redistributors between the beds. The models compared are by
Lawal [76] and Jayarathna [66] described in detail before. As seen
by Table 17, in most parameters, Jayarathna model predicts more
efciently the experimental measurements.

6. Conclusions and scope for future work

Munmorah pilot plant simulations


Parameter

563

Model

Qi
77.4
80
3.25

Zhang
83.49
80
4.36

18,589
19,463
4.491

14,415
19,463
25.936

0,338
0.345
2.029

0.36
0.345
4.348

61.8
68.2
9.384

66.2
68.2
2.933

8959
9173
2.333

7936
9173
13.485

0.25
0.34
26.471

0.33
0.34
2.941

80.8
75.44
7.105

75
75.44
0.583

3849
3756
2.476

5132
3756
36.635

0.22
0.42
47.619

0.4
0.42
4.762

(ppm)

(ppm)

(ppm)

87.8
85.6
2.570

87.33
85.6
2.021

8611
10,071
14.497

7740
10,071
23.146

0.284
0.38
25.263

0.38
0.38
0

(ppm)

It is unquestionable that the need for techniques targeting to


polluting emissions reduction, becomes imperative. CCS is as described
a satisfactory solution, especially post-combustion technologies. Chemical absorption is extensively studied, especially amine and ammonia
systems. Various researchers have studied the thermodynamic and
chemical phenomena aiming to the optimization of the system.
Literature includes mainly steady state analysis examining parameters
as species concentration and temperature prole along the column.
Most researchers have mainly dealt with absorption column, while
few models exist for desorption. The papers that include both columns
usually study them separately, not considering their interaction.
Supplementary equipment as reboiler, condenser etc. are usually
simulated with rough simplications. By this spectrum, the columns
operations are well understood.
However, there is a necessity to interconnect the system with
real conditions of the power plant. Disturbances that may occur in
actual operation conditions are usually not reected in the existing
models. In cases that such an analysis is attempted, results cannot
be validated. The target of the developed researches is the
commercialization of the process and this requires a very careful
investigation of its real impact. Thus, during the last years
increasing modeling attempts are observed, that develop dynamic
simulation tools. Dynamic CO2 capture model simulations have
only analysed restricted disturbances as start-up or load uctuations. In addition, dynamic models are validated only in a steady
state approach as dynamic experimental measurements are not
Table 17
Comparisons of Austin pilot plant simulations.
Parameter

Model

CO2 removal efciency (%)


Model prediction
Experimental
Relative deviation (%)

Jayarathna
96
95
1.053

Lawal
99.5
95
4.737

Rich solvent loading (mol/mol)


Model prediction
Experimental
Relative deviation (%)

Jayarathna
0.448
0.428
4.673

Lawal
0.456
0.428
6.542

Lean solvent loading (mol/mol)


Model prediction
Experimental
Relative deviation (%)

Jayarathna
0.285
0.279
2.151

Lawal
0.279
0.279
0

Absorber inlet liquid temperature (K)


Model prediction
Experimental
Relative deviation (%)

Jayarathna
314
314
0

Lawal
331
314
5.414

564

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

currently available. Dynamic models mainly deal with MEA as the


most applied solvent. Concluding, the future works should:

 Develop dynamic models, including all equipment in an inte





grated way, testing more realistic and complex power plant


operation scenarios.
Collect dynamic experimental data in order to be able to
validate simulation tools as verication is necessary to increase
the model reliability and accuracy.
Investigate alternative solvents or blends that increase
efciency.
Perform sensitivity analysis that will examine more parameters
and their effect on the optimization process.

The utmost objective is the optimization of the process,


providing the optimal solution for each case.

The current review could be extended by encompassing latest


future models and also by performing more thorough comparisons
between comparable simulations. More models could be evaluated
in relation to their efciency with different solvents or models
validated against the same experimental data could be compared
using more efciency indicators.

Acknowledgements
The author acknowledge with appreciation the Laboratory of
Applied Thermodynamics, Thermal Engineering Section, School of
Mechanical Engineering, National Technical University of Athens,
for the support of the work on which this paper is based.

Appendix A. List with recent models

Researcher Model Dynamic/ Solvent


type
Steady

Simulated Evaluation parameter


equipment

4
[Pintola
et al.,
[44]]
[Aboudheir 4
et al.,
[77]]
[Nittaya
4
et al.,
[78]]

MEA

Absorber

AMP

Absorber

MEA

Absorber/
Desorber

MEA and PZ

Absorber

MEA

Absorber
/Desorber

Alkanolamines Absorber

[Moioli
5
et al.,
[82]]
[Sema et al., 4
[84]]

PZ

Absorber

DEAB

Absorber

[Dugas and 5
Rochelle,
[79]]
[Saimpert
4
et al.,
[80]]
[Gaspar
et al.,
[81]]

Data for validation

MEA concentration, enhancement factor, Pilot plant


CO2 concentration, temperature along
the column
Concentration and temperature proles Two pilot plants (University of
along the packed column
British Columbia and
University of Regina)
Pilot plant [Dugas, [38]]
The performance of different control
schemes was evaluated under different
scenarios, e.g. changes in ue gas ow
rates, set point tracking, and valve
stiction
Mass transfer coefcients in relation to Pilot plant [Dugas, [38]]
CO2 loading, temperature and amine
concentrations
CSIROs PCC Process
CO2 and temperature proles, CO2
Development Facility and a
loading, outlet liquid ow rate, water
absorbed, CO2 desorbed, reux ow rate, pilot plant (Tarong Power
Station)
loading for different operating points
CO2 molar fraction, liquid phases
Pilot plants Aroonwilas and
temperature, L/V ratio along the column Veawab [42], Tobiesen and
height. CO2 molar fraction through time Svendsen [39] and
Tontiwachwuthikul et al. [43]
Temperature and CO2 vapour molar
Pilot plant [Plaza, [83]]
fraction along the column
Liquid phases speciation and
concentration in aqueous DEAB
solutions as a function of CO2 loading,
absorption rate, second order reaction
rate constant k2

Pilot plant [Shi et al. [85]]

I.P. Koronaki et al. / Renewable and Sustainable Energy Reviews 50 (2015) 547566

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