Fuel 356 (2024) 129607

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Full Length Article

Comparison of CO2 absorption in DETA solution and [bmim]-[PF6] using

thermodynamic and process modelling
Morteza Afkhamipour a, Ebad Seifi b, Arash Esmaeili c, Mohammad Shamsi d, Tohid
N. Borhani e, *
a
National Iranian Gas Company (NIGC), South Pars Gas Complex (SPGC), Asaluyeh, Iran
b
Research Centre for Membrane Separation Processes, Faculty of Chemical Engineering, Iran University of Science and Technology, Narmak, Tehran, Iran
c
Department of Applied Science and Technology (DISAT), Politecnico di Torino, Corso Duca degli Abruzzi 24, 10129 Torino, Italy
d
Process Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, Tehran, Iran
e
School of Engineering, Center for Engineering Innovation and Research, School of Engineering, Computing and Mathematical Sciences, University of Wolverhampton, UK

A R T I C L E I N F O A B S T R A C T

Keywords: Non-conventional amines are being research around the world to overcome the problems associated with
CO2 absorption traditional and conventional amines such as monoethanolamine (MEA) and methyldiethanolamine (MDEA).
DETA solution Having appropriate and specific process and thermodynamic models for these amines is vital to recognize their
Ionic liquid
applicability and performance for CO2 absorption. However, studies on process modelling of these types of
Rate-based model
Thermodynamic model
amines are very limited. In this study, the rate-based modelling was utilized for a packed column to obtain
Sensitivity analysis profiles of operating variables for CO2 absorption by Diethylenetriamine (DETA) solution. Deshmukh-Mather (D-
M) method as thermodynamic modelling was incorporated in the rate-based model. The process model was
validated using experimental data from the literature. Additionally, a sensitivity analysis of mass transfer cor­
relations was performed on the temperature and concentration profiles. The effect of different operational pa­
rameters on the CO2 removal efficiency was studied, and the CO2 absorption efficiency of DETA solution was
compared with that of an ionic solvent, 1-n-butyl-3-methylimidazolium hexafluorophosphate ([bmim]- [PF6]).
The effect of different parameters on the CO2 removal efficiency highlights the need to find optimum operating
parameters for absorber column to achieve the maximum absorption efficiency. Although the absorption effi­
ciency of CO2 by ionic solvent was higher than that of DETA solution under the same operational conditions, the
advantages, and the disadvantages of each solvent in CO2 capture processes should be considered without
compromising the solvent performance.

There are two solutions to address the issue of increasing greenhouse

1. Introduction
Greenhouse gases (GHGs) emissions have become one of the most
challenging environmental issues over the last few decades, and the
rising CO2 concentration in the past 200 years has contributed signifi­
cantly to the global warming. The International Energy Agency, the
Intergovernmental Panel on Climate Change, and the UK government,
among others, suggest that carbon capture and storage (CCS) is crucial
for decarbonisation of the power and industrial sectors. This is because
CCS can provide clean, flexible power generation and industrial capac­
ity, which can increase the resilience of these sectors to fluctuations in
market conditions. Human releasing almost 40 billion tons of CO2 to the
atmosphere every year [1,2].
gas emissions. One short to mid-term solution is carbon from sources
such as power plants, cement industries, chemical manufacturing, etc
and storage of the captured CO2. The long-term solution is utilisation of
renewable energies and utilisation of carbon and conversion of CO2 to
value added products. There are different approaches/technologies to
capture CO2 which are pre-combustion, post-combustion, and oxy-
combustion carbon capture, and direct air capture (DAC) [3]. In each
of these approaches, several processes/methods can be applied. The
most known processes are absorption, adsorption, and membrane.
CO2 absorption using amine solutions is one of the most mature
processes in the world and this method has been used for many years.
Different types of solvents are introduced based on the gas stream
containing CO2 (flue gas, natural gas, synthesis gas, etc.) [4]. However,

* Corresponding author.
E-mail address: t.borhani@wlv.ac.uk (T.N. Borhani).

https://doi.org/10.1016/j.fuel.2023.129607
Received 7 June 2023; Received in revised form 30 July 2023; Accepted 21 August 2023
0016-2361/© 2023 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
M. Afkhamipour et al.
Nomenclature
CDETA DETA concentration, kmol/m3
DCO2 − i CO2 diffusivity in component i, m2/s
HCO2 Henry’s constant of CO2, for ionic liquid MPa and for
DETA solution kPa.m3/kmol
kr Second-order rate constant, 1/s
kL Physical mass transfer coefficient in the liquid phase,
m/s
kDETA,P Third-order reaction rate constant contributed by
primary amino group of DETA, m3.kmol/s
kDETA,S Third-order reaction rate constant contributed by
secondary amino group of DETA, m3.kmol/s
kH2 O Third-order reaction rate constant contributed by
water, m3.kmol/s
KGav Volumetric overall mass-transfer coefficient, kmol/m3.
kPa.hr
K Equilibrium constant
PH2 O Water partial pressure, kPa
PCO2 CO2 partial pressure, kPa
P*CO2 CO2 equilibrium partial pressure, kPa
Greek Letters
α CO2 loading, mole CO2/mole Amine
β Adjustable molecule–molecule, ion-ion, and molecule-
ion interaction parameters, Kg/kmol.K
μ Viscosity, Pa.s
ρ Density, g/cm3
γ Activity coefficient
conventional amine solutions such as MEA and MDEA showed several
weaknesses such as high energy requirements for solvent regeneration
and corrosion problems [4]. Researchers tried to propose several solu­
tions to overcome the weaknesses of conventional solvents such as
developing new type of solvents [5], mixing chemical solvents together
[6,7], mixing chemical solvents with physical solvents [8], and appli­
cation of additives and catalysts in regeneration unit [9]. Mixture of
solvents have been used to benefit from the positive characteristics of
each solvent in the mixture.
In addition to amines, green solvents, including ionic liquids, have
gained significant attention in CO2 absorption processes due to their
potential for improved environmental sustainability and efficiency.
Ionic liquids (ILs) are a class of solvents consisting entirely of ions,
typically with low melting points below 100 ◦ C. When it comes to CO2
absorption, ILs offer several advantages over conventional organic sol­
vents: high CO2 solubility, low volatility, thermal stability, and reduced
environmental impact. Despite these advantages, there are still chal­
lenges associated with the use of ionic liquids in CO2 absorption pro­
cesses. Some of these challenges include high viscosity, cost, and
potential toxicity of certain ILs. Additionally, the regeneration of the
solvent and separation of CO2 from the absorbed ILs can be technically
challenging [10].
Non-conventional amines attracted much attention, and many re­
searchers are working in this area to design more beneficial solvents for
CO2 absorption. Therefore, some amines, such as diethylenetriamine
(DETA), 4-(diethylamino)-2-butanol (DEAB) and 2-(1-piperazinyl)-eth­
ylamine (PZEA), have been considered as promising alternative solvents
for CO2 absorption [11,12]. Diethylenetriamine (DETA) is an aliphatic
ethylene amine with two primary and one secondary amine groups. Its
CAS number is 111-40-0 and molecular weight is 103.17 and has
chemical formula of C4H13N3. This amine appears as a yellow liquid
with an ammonia-like odour, less dense than water, corrosive to metals
and tissue, vapours heavier than air, burns, although possibly difficult to
2
Fuel 356 (2024) 129607
ignite. Toxic oxides of nitrogen produced during combustion. This
amine can be used as a solvent for plastics and dyes and in chemical
synthesis. Most studies related to DETA solution are kinetic and mass
transfer studies. The study presented by Hartono et al. [13] can be
considered as pioneer research that focused on different aspects of
application of DETA solution for CO2 absorption and started by exper­
imental determination of concentration of species in the DETA solution.
They also reviewed and collected the density, viscosity and excess
properties of DETA aqueous solution in another study [14]. The same
group measured the solubility of N2O in DETA solution which can be
used to determine the physical solubility and henry’s constant of CO2 in
the DETA solution [15]. Hartono et al. [16] also used a string of discs
contactor to measure the kinetics of CO2 absorption in unloaded
aqueous solution DETA by concentrations in the range of 1.0 to 2.9 mol/
L and at temperatures ranging between 298.1 and 332.3 K. They also
represented the CO2 solubility in 2.5 M DETA solution and used
Deshmukh-Mater model to predict the CO2 partial pressures against
loading for different temperatures [17]. The zwitterion and termolecular
mechanisms were used to correlate the rate constants. Salvi et al. [18]
studied the kinetics of CO2 reactions with EDA and DETA using a stirred
cell reactor. Fu et al. [19] studied experimentally the mass transfer
performance of CO2 absorption into aqueous DETA solutions in a
randomly packed column with Dixon rings at 303–303 K and atmo­
spheric pressure. The authors presented the mass transfer performance
in terms of volumetric overall mass-transfer coefficient (KGav) and
compared the results with MEA. They have reported that KGav of DETA
was found to be higher than that of MEA. In a subsequent study, the
authors repeated the measurements in a column packed with Sulzer DX-
type structured packing over a temperature range of 30–50 ℃ and at
atmosphere pressure [11]. They also used an ANN model to predict the
mass transfer performance. Solubility of CO2 in aqueous mixture of
DETA and PZ (at 30 wt% total amine concentration) was reported by
Chang et al. [20]. The authors also presented the solubility data in the
aqueous DETA solutions with 20, 30 and 40 wt% concentrations. They
have found that the CO2 solubility in aqueous solutions of DETA were
significantly higher than in typical amine solvents. Different thermo­
dynamic properties such as surface tension were measured for several
non-conventional amines including DETA [21]. The vapour pressure and
total pressure of aqueous DETA solution was measured and correlated to
Antoine equation and some thermodynamic models such as NRTL and
UNIQUAC [22]. Fan et al. [23] investigated the influences of the DETA
solution, temperature and the solution concentration on CO2 absorption
and desorption performances. They compared the performance of DETA
solution with MEA and DEA solutions. They reported the regeneration
capacity of DEA is higher than DETA and for DETA is bigger than MEA.
Sheng et al. [24] applied DETA solution in rotating packed bed (RPB).
They measured the overall volumetric mass-transfer coefficient in a lab-
scale RPB and used BPNN model to predict the results.
It is crucial to study and simulate the CO2 absorption process using
amines. For optimisation, scale-up, process analysis, configuration
analysis, and determining the ideal operating parameters, a validated
and reliable process model can be employed [25]. However, the number
of process modelling studies using more recently and non-conventional
amines such as DETA is negligible in comparison to conventional and
commercial amines, and this can be considered an important drawback
for the utilisation of non-conventional solvents in industrial-level ap­
plications. It must be noted that DETA has been reported to exhibit
degradation. This can potentially pose significant challenges when it
comes to the industrial use of this amine [26].
When DETA undergoes oxidative degradation, it reacts with oxygen
or other oxidizing agents, leading to chemical transformations. One of
these degradation products that can be formed during this degradation
process is ammonia [27]. It’s important to note that the specific con­
ditions under which DETA undergoes oxidative degradation, such as the
presence of oxidizing agents, temperature, and other environmental
factors, can influence the extent and rate of ammonia formation. By
M. Afkhamipour et al. Fuel 356 (2024) 129607

Table 1 the rate-based model.

Chemical reactions of CO2 absorption in DETA solution [20].
Reaction Type No 2.1.1. Chemical reactions
The chemical reactions occurring in CO2 absorption using DETA
+ K1
DETAH ↔ DETA + H+ Equilibrium R (1)
solution are presented in Table 1. It must be mentioned that there is not
K2 Equilibrium R (2)
CO2 + H2 O ↔ HCO−3 + H+ any chemical reaction between CO2 and ionic liquid and CO2 absorption
HCO−3 ↔ CO2−
K3 Equilibrium R (3) on [bmim]- [PF6] is physical absorption.
3 + H
+

K4
H2 O ↔ OH− + H+ Equilibrium R (4) All equilibrium constants for each of the equilibrium reactions are a
CO2 + 2DETA ↔ DETCOO− + DETAH+ Kinetic R (5) function of temperature by the following format:
CO2 + DETA + H2 O ↔ DETCOO− + H3 O+ Kinetic R (6)
A
ln(Ki /HCO2 ) = + Bln(T) + C(T) + D (1)
(T)
studying the degradation pathways of amines and their byproducts,
The adjustable parameters A–D for K1-K4 were taken from literature
researchers can develop strategies to mitigate degradation and improve
and presented in Table 2. It should be noted that K1 is calculated based
the stability of these systems. Various strategies can be employed to
on the method described in previous study [12].
mitigate the formation of ammonia during amine regeneration, such as
Because DETA has three amino groups, the overall reaction rate for R
optimizing process conditions, utilizing additives or inhibitors to mini­
(5) and R(6) can be considered to be a combination of CO2 reaction with
mize degradation.
primary and secondary amino groups [24]:
This study aims to present process modelling and simulation of CO2
absorption using DETA as a promising solvent in a packed bed column. − rCO2 − DETA = (kDETA,P CDETA + kDETA,S CDETA + kH2 O CH2 O )CDETA CCO2 (2)
⏟̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅⏞⏞̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅⏟
The rate-based model is developed in MATLAB software. To the best of Kr
our knowledge, there is not any published study which performed pro­
( )
cess modelling and simulation of CO2 absorption using DETA solution. − 3869.3
kDETA,P = 7.4692 × 109 exp
In addition to process model, thermodynamic modelling is also carried T
out using Deshmukh-Mather method. After validation of process model,
( )
sensitivity analysis is performed to reveal the impact of different pa­ − 4092.8
kDETA,S = 4.6294 × 108 exp
rameters on the system. In addition to above-mentioned studies, the CO2 T
removal efficiency of an ionic liquid 1-n-butyl-3-methylimidazolium
( )
hexafluorophosphate ([bmim]- [PF6]) was studied and compared with − 3450.4
kH2 O = 2.0384 × 107 exp (3)
DETA solution at the similar operational conditions. T

2. Methodology where kDETA,P is the third-order reaction rate constant contributed by

primary amino group of DETA, kDETA,S is the third-order reaction rate
In this part of study, information about thermodynamic modelling, constant contributed by secondary amino group of DETA, kH2 O is the
process modelling, sensitivity analysis, and parametric study is pre­ third order reaction contributed by water, all m3.kmol/s.
sented. All the relevant equations and details are presented.
2.1.2. Thermodynamic model equations
The Deshmukh and Mather method is used in previous studies and
2.1. Thermodynamic modelling had a great performance in aspect of prediction of VLE. The total devi­
ation of the model was better than other methods such as Extended
The objective of thermodynamic modelling study for CO2 absorption UNIQUAC [33]. In addition, implementation of the model is easier than
systems is to perform speciation modelling and vapour-liquid equilib­ other thermodynamic methods. equations for CO2 absorption in DETA
rium (VLE) modelling. In the speciation modelling, the model will help solution can be written as follow:
to determine the concentration of different species in the solution. In the Four equilibrium constants based on the chemical reactions (1)–(4)
VLE modelling, the model will assist to explain the behaviour of species presented in Table 1:
in the vapour and liquid phases in the equilibrium condition. There are
[H + ][DETA] γH+ γDETA
many methods for each of speciation and VLE modelling [28]. K1 = (4)
[DETAH + ] γDETAH +
The speciation and VLE modelling can be done using an iterative
method and root-finding problem which is presented for the first time by
[H + ][HCO−3 ] γH+ γHCO−3
Deshmukh and Mather [29]. In this method, the physical and chemical K2 = [ ] (5)
CO2(aq) γCO2
equilibriums based on the material and charge balances, as well as
equilibrium constants of the reactions are solved simultaneously by
[H + ][CO2−3 ] γ H+ γ CO2−3
considering an activity coefficient model [28]. For the case of K3 = (6)
[HCO−3 ] γ HCO−3
CO2+([bmim]- [PF6]) system, a solubility correlation developed by
[30] as thermodynamic modelling was used to predict CO2 solubility in

Table 2
Equilibrium constants and the Henry’s constant.
Ki Temp. Range (◦ C) A B C D Ref.

K1 25–60 − 5622.077 0 0 − 9.012 Current Study

K2 0–225 − 12092.1 − 36.7816 0 235.482
[31]
K3 0–225 − 12431.7 − 35.4819 0 220.067
[31]
K4 0–225 − 13445.9 − 22.4773 0 140.932
[31]
HCO2 0–100 − 8477.71 − 21.9574 0.00578 170.7126
[32]

3
M. Afkhamipour et al. Fuel 356 (2024) 129607

Table 3 extended Debye-Hückel equation is employed in this study to determine

The binary interaction parameters of the extended Debye–Hückel thermody­ the species’ activity coefficients in the DETA solution [29]:
namic equation. √̅̅
AZi2 I ∑
βij f (kg/kmol.K) g (kg/kmol) lnγi = − √̅̅ + 2 βij mj (12)
1+B I j∕
=w
βDETAH+ − 0.919 3.984 ⏟̅̅̅̅̅̅̅⏞⏞̅̅̅̅̅̅̅⏟ ⏟̅̅̅̅̅⏞⏞̅̅̅̅̅⏟
CO2
electrostatics forces
βDETAH+ − HCO−3 0.012 0.140 short− range van derWaals forces

βDETAH+ − CO2−
3
5.081 − 0.002
βDETA− CO2 10.477 − 5.871 A = [1.131 + 1.335 × 10 − 3 × (T − 273.15) + 1.164 × 10 − 5
βDETA− HCO−3 − 7.301 0.096 × (T − 273.15)2] (13)
βDETA− CO2−
3
3.090 2.410
βCO2 − HCO−3 1.125 0.311 B = 1.2 (14)
βCO2 − CO2− 0.986 − 3.304
3

+
K4 = [H ]γH+ [OH ]γOH− −
Three material/species balances:
[ ]
Charge balance : [H+ ] + [DETAH+ ] = HCO−3 + [OH− ] + 2[CO2−3 ]
Amine balance : [DETA]0 = [DETA] + [DETAH + ]
[ ]
Carbon balance : αCO2 [DETA]0 = [CO2 ] + HCO−3 + [CO2−3 ]
[DETA]0 are initial concentrations of DETA based on experimental
data. DETA is considered as solute and water as solvent in the thermo­
dynamic modelling. DETA is considered as involatile component and
Henry’s law is used to account the physical solubility of CO2. αCO2 is CO2
loading. The partial pressure of CO2 and Henry’s law for CO2 can be
related to each other:
PCO2 = HeCO2 [CO2 ]
As can be seen in Eqs. (4)–(6), activity coefficients have been used to
account the non-ideality of the liquid phase for mixture of water, CO2,
and amines. Different activity coefficient based on the thermodynamic
models can be used to calculate the activity coefficients in these equa­
tions [28]. Similar to the study by Deshmukh and Mather [29], the
1∑
I= mj Zj2 (15)
2 i
(7)
βij = f + gT (16)
Here, Zi is the electrical charge of the ions and mj is the molality
(8)
concentration of species j. The term βij represents the adjustable mole­
(9) cule–molecule, ion-ion, and molecule-ion interaction parameters. There
are 9 species involved in the interaction between CO2 and the DETA
(10) solution. A total of 64 interaction parameters between chemical species
were evaluated independently, excluding water from consideration. It
must be mentioned that βij are equal to βji , all molecule–molecule
interaction parameters, including those involving self-interaction, were
disregarded, except for CO2 – DETA, all like-charged interaction pa­
rameters were ignored. Therefore, finally 8 binary interaction parame­
ters are calculated and presented in Table 3.
(11) 2.1.3. Thermodynamic model solution method
The fminsearch function in MATLAB was employed to implement the
Neldere-Mead simplex direct search technique, an optimisation pro­
cedure, and discover the model parameters (Table 3). This optimisation
procedure, which uses a heuristic search approach, minimises the non-
linear functions of several real variables by using only their function
values. In a prior study, this method is described. [34].

Table 4
Physical properties used for gas and liquid phase in the process modelling.
Property Comment/Equation Ref
3
Gas density (kg/m ) Soave–Redlich–Kwong equation presented in 1972 [36]
Specific heat of liquid solution (J/K.mol) Linear mixing presented by Chiu and Li (1999) [36]
Specific heat of gas components (J/K.mol) DIPPR method presented in DIPPR (2005) [36]
Thermal conductivity of the gas (W/m.K) DIPPR method for pure compounds, Mason and Saxena method for mixture [36]
Diffusivity of CO2 and water in the gas phase (m2/s) Fuller equations [36]
Gas viscosity (Pa.s) Chapman-Enskog for pure compounds and mixing rule for mixture [36]
Diffusivity of CO2 in water in the liquid phase (m2/ − 2119
DCO2 − H2 O = 2.35 × 10− 6 ( ) [37]
s) T
DETA density (kg/m3) The data for regression are extracted from [14]
[38]
ρ = 1000.3 +0.14w2 +0.11w3 − 0.12T2 w is wt.% and T is K
DETA Viscosity (Pa.s) The data for regression are extracted from [14]
[ ] [ ] [38]
0.00049 0.00088
lnμ = ( 2.00131 + +0.00017w +0.00100w2 − 0.00024 − − 0.00066w T2 )/1000w is wt.% and T is K
T T
[bmim][PF6] viscosity (Pa.s) The data for regression are extracted from Liang-Liang Zhang
( ) [10]
1 1052.377
μ = exp − 2.4474 +
1000 T − 167.518
[bmim][PF6] density (kg/m3) ρ = − 0.8259T + 1613.5
[10]
Diffusivity of CO2 in [bmim][PF6] (m2/s) DCO2 − = 10− 14 2
T − 4 × 10− 12
T + 3 × 10− 10
[bmim][PF5]
[10]
( )
Henry’s constant of CO2 in [bmim][PF6] (MPa) HCO2 = 0.0042T3 − 3.7734T2 +1132.5T − 113406 The Henry’s constant for ionic liquid is based on mole fraction
[39]
Henry’s constant (kPa.m3/kmol) The method is known as N2O analogy
[40]
HCO2 in H2 O
HCO2 in DETA = HN O in DETA The Henry’s constant for DETA solution is based on Molarity
HN2 O in H2 O 2
The data for HN2 O in DETA are extracted from [15]
( ) ( ) [15]
− 1952.6 − 2284
HN2 O in DETA = 999.50 × 106 exp HN2 O in H2 O = 8.55 × 106 exp
T T
( )
− 2044
HCO2 in H2 O = 2.82 × 106 exp [40]
T

4
M. Afkhamipour et al. Fuel 356 (2024) 129607

2.2. Process modelling Table 5

Different mass transfer correlations for performing sensitivity analyses in the
The objective of process modelling is to simulate the real absorption rate-based model.
process to capture CO2. Therefore, here the absorber column is modelled Authors Correlations Ref.
and related input information (operating parameters) are used to Onda et al. ( ) ( )1/3
2DG,i ρG UG 0.7 μG
simulate the model. Hence, a rate-based model which was built for CO2 kG,i =( 2
)
ap dP μG ap ρG DG,i
[42]
absorption into other amine solutions in previous studies [35] is used in Onda et al. ( )1/3 ( ) ( )
μL g ρL UL 2/3 μL − 1.2
( )0.4
[42]
this study. For the purpose of calculating the concentration and tem­ kL,i = 0.0051 ap dp
ρL μL ae ρL DL,i
perature profiles along the height of the packed column, differential Onda et al. ae
ap
= [42]
equations of mass and energy conservation are applied. Here, to calcu­ ( )0.75 ( ) ( )− 0.05 ( )0.2
late the outcomes for CO2 absorption into DETA solution, we have σC ρL UL 0.1 ap U2L ρL U2L
1 − exp[− 1.45 ]
μL ap g ap σL
exclusively concentrated on rate-based model sub-models and do not σL
Van Krevelen (
0.2DG,i ρL UL 0.8
) ( )1/3
repeat the main governing/conservation equations. The sub-models and kG,i = ( )
μG [43]
dp μ L ap ρG DG,i
contain mass transfer correlations, enhancement factor, and physico­ Hoftijzer
chemical properties. In addition to these sub-models, the thermody­ Van Krevelen 0.015DL,i
(
ρL UL
)2/3 (
μL
)1/3
kL,i = [43]
namic models developed in Section 2.1 is also used in the process and (μL /ρL g) 1/3 μL ae ρL DL,i
Hoftijzer
modelling. ( )0.49 (
Kolev )0.196
ae ρL g ap U2L ( )0.42 [44]
= 0.583 ap dp
ap σ L ap
2 g
2.2.1. Physical properties used in the process model ( )0.392
Bravo and ρg UG μl UL
The physical properties used in the process model are listed in Fair
ae
= 0.496 (σL )0.5 (Zt)− 0.4 [45]
Table 4. It should be noted that selection of physical properties has a ap μg ap σL
considerable impact on accuracy of the model.
2.2.3. Mass transfer correlations
2.2.2. Enhancement factor
Different known and frequently used correlations are selected in the
One of the main methods to account the effect of chemical reaction
rate-based model to perform the sensitivity analysis and listed in
on the CO2 absorption, is application of enhancement factor [25]. The
Table 5. These correlations are used in the calculation of the overall
following enhancement factor is used in current study:
mass-transfer coefficient KG,CO2 . Based on the two-film model, the
√̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅̅
equation for overall mass-transfer coefficient can be written as:
kr Cbulk
DETA DCO2 ,DETA
ECO2 = (17) 1 1 HCO2
kL = + ◦ (19)
KG,CO2 kG,CO2 ECO2 kL,CO2
where kr is the second-order rate constant for the chemical reaction
between CO2 and DETA solution which is presented in Eq. (2), 1/s. 2.2.4. Experimental data used for process modelling
DCO2 ,DETA is the CO2 diffusivity in DETA solution, m2/s. kL is the physical The experimental data presented by Fu et al. [19] used in this study.
mass transfer coefficient in the liquid phase, m/s. Cbulk
DETA is DETA con­ The authors’ absorption column was a randomly packed acrylic plastic
centration in the liquid bulk, kmol/m3. column that was covered in thermal insulation material. A Dixon ring
The diffusivity of CO2 in DETA solution was calculated according to (made of 304 stainless steel) was loaded into the column. The authors
the modified Stokes-Einstein equation [37]: also used a liquid redistributor in the middle of packed bed to minimize
( ) the unfavourable effect of wall flow. In addition to the packed column,
μH2 O 0.8
DCO2 − DETA = DCO2 − H2 O (18) auxiliary tools such an air compressor, a CO2 cylinder, a constant liquid-
μDETA
flow pump, a thermostatic water bath, a gas mixer, and storage tanks
In the Eq. (17), it is assumed that the enhancement factor is the same were used in their investigation. These tools also had accuracy ratings of
as the Hatta number [41]. The Hatta number is a dimensionless less than 1%, 0.3%, and 1 K.
parameter used to characterize the mass transfer performance of an The range of 14.8% to 15.8%, which corresponds to the CO2 con­
absorption process. It is defined as the ratio of the actual mass transfer centration for the post-combustion process of the flue gas from coal-fired
rate to the mass transfer rate that would occur in the absence of any power plants, was tested for the input CO2 concentration. Also, the CO2
chemical reaction. If the Hatta number is equal to the enhancement loading range of DETA used in their work was 0.051–0.819 mol CO2/
factor in CO2 absorption by amine solution, it suggests that the mass mol DETA. The diameter of the column was 24 mm, height of packing
transfer performance of the absorption process is primarily governed by was 1.4 m, inert gas load was 28.78–46.62 kmol/m3.h, DETA concen­
the physical mass transfer (diffusion) rather than the chemical reaction. tration 1–4 kmol/m3, feed temperature was 303–323 K and pressure of
In other words, the rate at which CO2 is absorbed by the amine is mainly the system was 103 kPa.
controlled by the diffusion of CO2 through the gas–liquid interface. This
condition can occur when the mass transfer resistance due to the 2.2.5. Process model solution method
chemical reaction is negligible compared to the mass transfer resistance The mass transfer and heat transfer equations described in our pre­
caused by diffusion. It may happen when the reaction rate between CO2 vious study for rate-based model [46] were applied for CO2 absorption
and the amine is fast or when the concentration of CO2 is relatively low. into DETA solution in randomly packed column. The main equations of
It’s worth noting that the Hatta number and enhancement factor are the model solved simultaneously with the help of sub-models (described
two different parameters that describe different aspects of the absorp­ in Sections 2.2.1–2.2.3) to calculate concentration and temperature
tion process [30]. However, when they are equal, it indicates a specific profiles along the height of packing column. At the outlet of the absorber
behaviour in the CO2 absorption by amine system. Here, as the reaction column, unknown variables were estimated using the finite difference
is fast between CO2 and DETA solution [16,18] and partial pressure of along with a shooting method, and model equations were solved. In this
CO2 is low, we assumed that Hatta number is equals to the enhancement method, the overall height of the packing of the absorber column
factor and Eq. (17) was used. divided into 100 differential heights (segments). It should be noted that
the number of segments cannot be determined in specific procedure in
the rate-based model. When experimental data are available, the

5
M. Afkhamipour et al. Fuel 356 (2024) 129607

Table 6 calculated for each number of segments. Then, the optimum number of
Five different cases for mass transfer correlations sensitivity analysis. segments was determined by comparison of simulation results and
Cases kG kL ae experimental data.
The Simplex algorithm in the MATLAB software was used to predict
1 Onda et al. Onda et al. Onda et al.
2 Van Krevelen and Van Krevelen and Onda et al. the adjustable parameters in rate-based sub-models, such as thermody­
Hoftijzer Hoftijzer namic and physicochemical property models. This algorithm minimises
3 Onda et al. Onda et al. Kolev the difference between experimental and estimated values for variable i.
4 Van Krevelen and Van Krevelen and Kolev The objective function for minimization is as follows:
Hoftijzer Hoftijzer
5 Onda et al. Onda et al. Bravo and
⃒
N ⃒ Est
⃒
1 ∑ φi − φExp ⃒
(20)
i
Fair OF = Exp
N j=1 φi

modelling results can be compared with experimental data and the
optimal number of segments can be determined. To perform sensitivity
analysis of the segments for packing column, following procedure was
followed-the number of segments in the rate-based model was varied
from 10 to 150 and the CO2 concentration and temperature were
φ is showing any parameters. The Newton’s method was utilised to solve
the nonlinear algebraic equations in the physicochemical properties and
thermodynamic models after determining the regression parameters for
sub-models.

Fig. 1. Equilibrium concentration profiles of species at temperature of 298.15 K and an initial DETA concentration of 3 M.

Fig. 2. Validation of the D-M model for the CO2 loading data in the CO2-DETA-H2O system using reported experimental data.

6
M. Afkhamipour et al. Fuel 356 (2024) 129607

1.4

Volumetric overall mass-transfer coefficient

1.2
AARD=6.0%
1

(kmol·m−3·h−1.kPa-1)
0.8

0.6
Exp data
0.4 Model result

0.2

0
2 3 4 5 6 7 8
Liquid flow rate ( m3 ·m−2·h−1)

Fig. 3. Comparison between model result and experimental data of KGav. Effect of liquid flowrate on the KGav data.

2.3. Sensitivity analysis of mass transfer correlations 3.1. Thermodynamic modelling results

The significant part of rate-based modelling is the sensitivity analysis
of mass transfer correlations for the absorber column [47]. In order to
perform sensitivity analysis of mass transfer coefficients, different cases/
scenarios are considered by combining the correlations presented in
Table 6.
2.4. Parametric study
A parametric analysis of the packed column was used to evaluate the
rate-based model’s performance. We have chosen the following eight
parameters: amine content, partial pressure of CO2 in the inlet gas, inlet
gas and liquid flow rates, inlet gas and liquid temperatures, partial
pressure of H2O in the inlet gas, and CO2 loading of amine. The effects of
these parameters were studied and discussed on the CO2 mole fraction
profiles, temperature profiles as well as CO2 removal efficiency.
3. Results and discussion
In order to perform calculation of the mass transfer flux in the ki­
netics model, having knowledge about concentrations of ions and mol­
ecules in CO2-DETA-H2O system is important. Fig. 1 shows the
prediction of the chemical species profiles in the CO2-DETA-H2O system.
The prediction was obtained for DETA concentration of 3 M, tempera­
ture of 298.15 K, and for CO2 partial pressure ranges of 0.005–2000 kPa.
As can be seen by increasing the CO2 loading the free concentration of
DETA decreased which is due to chemical reaction between CO2 and
DETA. Therefore, concentration of HCO−3 and DETAH+ increased.
Similar to previous study for 1DMA2P solution [46], the enhancement of
acidity followed by increasing the CO2 loading causes a small bulge for
the CO2−3 in the middle value of CO2 loading.
Fig. 2 illustrates the D-M model’s validation using data on CO2
loading in the CO2-DETA-H2O system. The model results were compared
with the Chang et al. [20] experimental data. An AARD of 7.8% was
obtained between the D-M model and experimental data for the CO2-
DETA-H2O system.

In this part of study, thermodynamic model validation and result,

process model validation and result, and sensitivity analysis results will 3.2. Process modelling results
be presented with relevant discussions.
As it mentioned before, in order to validate the process model, the
data presented by Fu et al. [19] is used. Validation results for CO2

Fig. 4. Comparison between model result and experimental data of KGav. Effect of amine concentration on the KGav data.

7
M. Afkhamipour et al.
Volumetric overall mass-transfer coefficient
0.9
0.8
0.7
(kmol·m−3·h−1.kPa-1)
0.6
0.5
0.4
0.3
0.2
0.1
0
0 0.1
Fig. 5. Comparison between model result and experimental data of KGav. Effect of CO2 loading on the KGav data.
Fig. 6. Prediction of volumetric overall mass-transfer coefficient (KGav) along the height of packed column.
capture by Diethylenetriamine (DETA) solution in a Dixon-ring packed
column done based on the volumetric overall mass-transfer coefficient
(KGav) data. The authors performed experimentally the effect of changes
for liquid flow rate, amine concentration, and CO2 loading on KGav data.
These data are used to validate the model as presented in Figs. 3-5. In
these figures, the results between the model and the experimental data
are in good agreement and the errors are 6%, 6.12% and 8.47%,
respectively for the liquid flowrate, concentration, and CO2 loading
data. Corresponding data of KGav along the height of the packed column
for different values of liquid flow rate also presented in Fig. 6. In this
figure, zero value shows bottom of the column and 1.4 m is for the top of
the column.
The CO2 and H2O concentration profiles along the height of packed
column also illustrated in Fig. 7. Unfortunately, experimental data for
the CO2 concentration during the length of the column were not avail­
able and the experimental data in the inlet and outlet is shown in Fig. 7.
As can be seen the CO2 concentration in the inlet is 15% and it will reach
Fuel 356 (2024) 129607
AARD=8.47%
Model result
Exp data
0.2 0.3 0.4 0.5 0.6 0.7 0.8
CO2 loading (mol CO2/mol amine)
to less than 2% in the outlet of the column. For obtaining the profile of
water in gas phase, it was assumed that the gas stream inserted to the
absorber column is in the wet condition. Due to chemical reaction be­
tween CO2 and amine solution and formation of bulge temperature in
gas phase at the bottom of packed column, the concentration of water
increased and stayed constant during the length of the column. This
means that by increasing the gas temperature at the bottom of column,
partial pressure of water increases, and gas phase is saturated along the
column in contact with amine solution.
The flowrate and temperature profiles for gas and liquid phases along
the height of packing column obtained by the rate-based model (Figs. 8
and 9).
Fig. 8 shows the flowrates of gas and liquid phase along the packing
column height. At the beginning of the column the gas flowrate reaches
to a maximum and then decrease drastically. The liquid phase flowrate
decreases dramatically. As can be seen in Fig. 9, there is a bulge for the
gas phase temperature at the bottom of absorber column which is due to
8
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 7. Mole fraction profiles of CO2 and H2O along the column.

Fig. 8. Flowrate profiles for liquid and gas phases along the column.

Fig. 9. Temperatures profiles in gas and liquid phases predicted by the rate-based model.

9
M. Afkhamipour et al. Fuel 356 (2024) 129607

0.45
0.4

Operating CO2 loading (mol CO2/mol

0.35
0.3
0.25

Amine) 0.2
0.15
0.1
0.05
0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Packing column height (m)

Fig. 10. Operating CO2 loading profile along the packing height.

0.16

0.14 Operating CO2

CO2
Concentration (mole fraction)

0.12 Equilibrium CO2 Solubility

0.1

0.08

0.06

0.04

0.02

0
0 0.2 0.4 0.6 0.8 1 1.2 1.4
Packing column height(m)

Fig. 11. CO2 concentration profiles (operating and equilibrium) along the height of the column.

combination of exothermal CO2 absorption and endothermal H2O terms of CO2 mole fraction at the bottom of column can be seen than the
vaporization. Although, the location of bulge temperature is related to top of column. This is due to mass transfer with chemical reaction which
the liquid to gas ratio. As profiles of Fig. 8 shown that the liquid to gas take place for CO2 absorption by amine solution. As removal efficiency
ratio is high and it leads to the temperature bulge inclines to the bottom decreases along the packing height of column the equilibrium conditions
of the column. In Fig. 9, the exothermic nature of the reaction between take place and following these conditions, driving force decreases.
CO2 and DETA solution was demonstrated by the differences between
values of entrance gas temperature and outlet liquid temperature at the
3.3. Sensitivity analysis results for mass transfer correlations
bottom of the column. This is because the bottom of the column expe­
riences greater mass and heat driving forces than the top, where equi­
The sensitivity analysis is done to find the optimum results by the
librium conditions prevail. As a result, the temperature of the gas and
mass transfer correlations presented in Table 5 in the rate-based model.
liquid increased towards the bottom of the column, and from the top of
The results are presented in terms of CO2 concentration profile, water
the packing column’s 0.6 m height, their temperature profiles matched.
concentration profile, and temperature profiles for liquid and gas pha­
These findings demonstrated the model’s capability to accurately
ses. Fig. 12 shows the different CO2 concentration profiles in the gas
anticipate the profiles.
phase based on cases 1–5. As can be seen the best results is obtained by
The CO2 loading profile along the column is presented in Fig. 10. As
case 2. The experimental data are only available at inlet and outlet of the
it expected the CO2 loading of the solution will be maximum in the
column not along the length of the column. The Onda et al.’s interfacial
bottom of the column as the solution is saturated with CO2 and leave the
area correlation [42] had the most impact on the CO2 profiles. This can
column for regeneration. As can be seen the CO2 loading at the top of the
be seen also by considering cases 3 and 5 which another interfacial area
column is 0.051 and the loading is increasing gradually to 0.4 at the
correlation was used with mass transfer coefficients of Onda et al. [42].
bottom of the column. Fig. 11 shows the CO2 concentration profile
Fig. 13 presents the water concentration profile in the gas phase along
which is obtained by mass transfer correlations of Onda et al. [42]. In
the column for different cases 1–5. It should be noted that there is not
addition to operating CO2 concentration profile, the equilibrium CO2
any experimental data to compare these profiles with them. At bottom of
solubility profile also presented in this figure which showing almost
the column the gas stream enters the column at wet conditions (yH2O =
stable value along the column. In this figure, the higher driving force in
0.01). When the gas flow upward in the column some amount of water

10
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 12. Sensitivity analysis of mass transfer correlations on the CO2 concentration profile in the gas phase.

Fig. 13. Sensitivity analysis of mass transfer correlations on the water concentration profile in the gas phase.

will transfer from liquid phase to the gas phase, and it remains almost
constant till the top of the column that the gas phase is leaving the
column. As there is not any experimental data for water profile in the gas
phase, we cannot conclude exactly which cases represent the best results
for this profile.
Fig. 14 shows the sensitivity analysis on the temperature profiles in
the (A) gas and (B) liquid phases along the length of the column. In this
figure for gas phase temperature profile (A), temperature bulge can be
seen for all cases except for case 3 does not show bulge at the bottom of
the column which should not be correct. As seen from liquid phase
temperature profiles in Fig. 14 (B), the trend of the liquid temperature
after the bulge of the gas phase temperature gets closer to each other and
this shows that case 2 has a better prediction than the rest of the trend
cases. It is clearly shown also in Fig. 9 (Case 2) that the temperature of
both phases at the top of the column almost reaches to equilibrium
conditions considering that the removal efficiency of CO2 is complete.

11
M. Afkhamipour et al.
Fig. 14. Sensitivity analysis of mass transfer correlations on the temperature profile for (A) gas and (B) liquid phases.
3.4. Parametric study results
3.4.1. Effect of liquid and gas temperatures on the absorption efficiency
Fig. 15 shows the effect of inlet gas temperature to the absorber on
the liquid temperature profile along the column at three different gas
temperatures. The effect of this parameter can have a significant effect
on the liquid temperature profile as well as CO2 removal efficiency
during CO2 absorption by amine solution. In this figure, as gas tem­
perature to the absorber increases the outlet liquid temperature in­
creases. When the gas temperature is high for example here 323 K, it can
cause the amine solution to heat up and to result in an increasing of the
liquid temperature leaves the bottom of column. As also shown the
trends for profiles for CO2 removal efficiency along the height of packing
column in Fig. 16 that by increasing the liquid inlet temperature it de­
creases CO2 removal efficiency. This is because the reaction between
12
Fuel 356 (2024) 129607
CO2 and amine is exothermic, meaning it releases heat. Therefore,
increasing the temperature increases the reaction rate based on the
Arrhenius equation but it decreases the solubility of CO2 in amine so­
lution. Therefore, it is important to maintain a proper balance between
the gas and liquid temperatures to optimize CO2 absorption efficiency.
This can be achieved through proper control of theses temperatures for
design of the absorber column. Fig. 17 shows the effect of inlet gas
temperature on the gas temperature profiles. As seen from this figure
that the bulge temperature occurs at the bottom of the column. As
increasing the inlet gas temperature to the absorber, this bulge shifts to a
higher point at the bottom of absorber column. In this figure, from the
top of the packing column’s 0.6 m height, profiles changes are large for
three different temperatures, after that, due to approaching the gas
temperature to the liquid phase temperature, these changes are less
along the length of the column and the trend is almost the same for all
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 15. Effect of inlet gas temperature to the absorber on the liquid temperature profile along the column at three different gas temperatures.

Fig. 16. Effect of inlet liquid temperature on the CO2 removal efficiency.

Fig. 17. Temperature profile for the gas phase along the column at three different inlet gas temperatures.

13
M. Afkhamipour et al.
Fig. 18. Operating CO2 loading profile along the column.
Fig. 19. The effect of operating lean loading (mole CO2/mole Amine) on the CO2 removal efficiency.
profiles. By referring to Fig. 9, it can be seen that the profile of the gas
phase approaches the liquid phase at the top of the column, and the
changes will be less due to lower absorption rate.
3.4.2. Effect of operating CO2 loading of amine on the absorption efficiency
Fig. 18 shows the operating CO2 loading profiles along the height of
packing column at different values of the lean CO2 loading. As seen from
this figure, by increasing the input lean loading to the absorber column
(at top of the column) from 0 to 0.4 (mol CO2/mol amine) the values of
rich loading increase at the exit of the column (bottom of the column). It
is obvious that by increasing CO2 loading in amine solution, it decreases
the existing active amine concentration. This means that the amine so­
lution becomes saturated with CO2 and reaches its capacity. Also results
for effect of CO2 lean loading on the CO2 removal efficiency was ob­
tained and it shown in Fig. 19. As can be seen in loading of 0.8 the max
value of CO2 removal efficiency at the top of the column is 52%. The
higher loading showing lower removal efficiency along the column.
Nevertheless, in loading of 0.2 the max value of CO2 removal efficiency
14
Fuel 356 (2024) 129607
at the top of the column is 97.2%. A decrease in the loading at lower
values may need to increase the demanded energy for regeneration of
amine solution which increases the cost of plant for CO2 capture pro­
cesses. Therefore, it is important to optimize this parameter to achieve
the maximum absorption efficiency without increasing the operational
costs.
3.4.3. Effect of CO2 and H2O partial pressure on the absorption efficiency
Figs. 20 and 21 show the CO2 partial pressure profiles for different
values of inlet CO2 partial pressure in the gas feed for CO2-H2O-DETA
system and CO2–([bmim]- [PF6]) system, respectively. As seen from
these figures, profiles have a downward trend along the height of the
packed column. From the point of view of comparing the two systems,
by increasing the CO2 partial pressure at the inlet of the absorber col­
umn, CO2 partial pressure at the outlet increases for CO2-H2O-DETA
system, but for CO2–([bmim]- [PF6]) system, the values of CO2 partial
pressure approach to zero at a small height from the column, which
indicates the high absorption rate of this system. Increasing CO2 partial
M. Afkhamipour et al.
Fig. 20. CO2 partial pressure profiles for different inlet partial pressures to the absorber column for CO2-H2O-DETA system.
Fig. 21. CO2 partial pressure profiles for different inlet partial pressures to the absorber column for CO2–([bmim]- [PF6]) system.
pressure at the inlet of the absorber column has two effects on CO2 ab­
sorption efficiency. A higher value of inlet CO2 partial pressure in the gas
feed leads to a higher absorption rate due to the increased deriving force
for mass transfer. However, this can also result in a decrease in the
amine solution efficiency which becomes saturated with higher CO2
partial pressure. Fig. 22 shows the equilibrium CO2 partial pressure
profiles for different values of inlet CO2 partial pressure in the gas feed
along the column for CO2-H2O-DETA system. This figure shows that the
values of equilibrium CO2 partial pressure decrease similar to trends of
CO2 partial pressure profiles. In order to better show the driving force of
mass transfer at the inlet and outlet as well as along the length of the
column, Fig. 23 is shown for both profiles. The profile with higher values
is for operating partial pressure and the corresponding lower trend is for
equilibrium values. As the figure shows, at the bottom of the column, we
have the most driving force, this is due to the high absorption at the
bottom of the column, which continuously decreases from the bottom of
15
Fuel 356 (2024) 129607
the column to the top of the column. When these two profiles (operating
CO2 partial pressure and its equilibrium) meet at the top of the column,
the absorption efficiency is completely done. Therefore, the model has
correctly shown these trends in this study. Fig. 24 shows the effect of
CO2 partial pressures on the CO2 removal efficiency profiles for CO2-
H2O-DETA and CO2–([bmim]- [PF6]) systems. As seen from this figure,
at two different values of CO2 partial pressures, CO2 removal efficiency
of CO2–([bmim]- [PF6]) system has higher values than CO2-H2O-DETA
system and this happens at lower part of the column. Although CO2
removal efficiency is more for CO2–([bmim]- [PF6]) system, but
considering the higher viscosity and higher price of this solvent than
DETA solution, it seems that its use in industrial systems will face with
operational problem.
Fig. 25 shows the effect of H2O partial pressure in the inlet of
absorber on the profiles through the column and outlet of H2O partial
pressures. By flow up of the gas from bottom to top of the column, with
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 22. CO2 equilibrium partial pressure profiles for different inlet partial pressures to the absorber column for CO2-H2O-DETA system.

Fig. 23. CO2 partial pressure and CO2 equilibrium partial pressure profiles for 3 kPa of the inlet CO2 partial pressure to the absorber for CO2-H2O-DETA system.

evaporation from the amine phase, the H2O partial pressure increases
near the bottom of the column and then with condensation from the gas
phase remains almost constant till the top of the column that the gas
phase is leaving the column. For other H2O partial pressures trends at
different conditions out of dry case, similar trends can be seen in Fig. 25.
With increasing the H2O partial pressure at the inlet of absorber, the
values of partial pressure increase along the packing height of column as
well as at the outlet of column. In general, the presence of water in the
inlet gas to absorber creates resistance to mass transfer and reduces the
diffusivity of CO2 into the amine solution. Accordingly, increasing the
amount of water at the exit of the column causes an increase in the
separation costs in the downstream of the unit. However, the presence of
water in the inlet gas is unavoidable in the CO2 capture processes.
3.4.4. Effect of amine flowrate and amine concentration on the absorption
efficiency
Fig. 26 shows the effect of different amine concentrations (2,3, and 4
M) on the CO2 removal efficiency profiles along the height of packing
column. As seen from this figure, with increasing the amine concen­
tration in the inlet of absorber, it increases the CO2 removal efficiency.
This is due to the presence of a large amount of amine molecules at the
gas–liquid interface for CO2 absorption, and this factor causes an in­
crease for CO2 to react with amine solution on a larger active surface
area. However, increasing the concentration of amine solution in the

16
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 24. Effect of CO2 partial pressures on the CO2 removal efficiency profiles for CO2-H2O-DETA and CO2–([bmim]- [PF6]) systems.

Fig. 25. H2O partial pressure profiles for different of inlet H2O partial pressures to the absorber.

inlet of absorber cause increasing of amine viscosity. This may decrease
the diffusivity of CO2 in amine solution, and as a result, absorption ef­
ficiency will decrease. Therefore, it is important to optimize this
parameter to achieve the maximum absorption efficiency without
compromising the solvent performance (minimizing solvent degrada­
tion and operational costs).
Fig. 27 shows the effect of different amine flowrates on the CO2
removal efficiency profiles along the height of packing column. The
effect of amine circulation flowrate on the CO2 removal efficiency in an
absorber column depends on several factors, including the type of amine
used, the concentration of the amine solution, the gas flowrate, and the
column design. As seen from this figure, with increasing the amine cir­
culation flowrate in the absorber column, it increases the CO2 removal
efficiency. However, there is a limit to this enhancement, beyond which
further increase in the amine flowrate may not result in significant
improvement in mass transfer. This is because excessive amine flowrate
can lead to flooding or channelling in the column, and increasing
regeneration energy for amine solution which can decrease the effi­
ciency of absorption. Therefore, it is important to optimize the amine
circulation flowrate based on the specific conditions of the absorber
column.
4. Conclusion
DETA solution is used to absorb CO2 in this study. Thermodynamic
modelling performed using Deshmukh-Matter method to determine the
concentration of different species in the solution contains water, DETA
and CO2. Process modelling using rate-based model also applied to

17
M. Afkhamipour et al. Fuel 356 (2024) 129607

Fig. 26. The effect of amine concentration on the CO2 removal efficiency profiles along the height of packing column.

Fig. 27. The effect of amine flowrate on the CO2 removal efficiency profiles along the height of packing column.

examine the performance of DETA as a solvent. Different scenarios are
considered by changing the mass transfer correlation modelling in
which four combination of mass transfer correlation models are exam­
ined. The accuracy of the results was done, and the errors were 7.8% for
thermodynamic model and the errors between the experimental data
and the rate base model for the volumetric overall mass transfer coef­
ficient were 6%, 6.12% and 8.47%, for liquid flowrate, concentration,
and CO2 loading data, respectively. Sensitivity analyses of mass transfer
correlations showed that the correlations of Van Krevelen and Hoftijzer
for mass transfer coefficients in gas and liquid phases and Onda’s cor­
relations for effective interfacial area (case 2) provide better results for
profiles of concentrations and temperatures in absorber packing column
with Dixon rings type. Effect of different operation parameters on the
CO2 removal efficiency show that increasing of the liquid inlet
temperature to the absorber it decreases CO2 removal efficiency, and
increasing the CO2 partial pressure, CO2 loading, and partial pressure of
H2O also decreases CO2 removal efficiency. With increasing concen­
tration and liquid flowrate of DETA solution, it increases the CO2
removal efficiency. Therefore, it is important to optimize operating
parameters to achieve the maximum absorption efficiency without
increasing the operational costs in absorber column. Also, a comparison
was made between the DETA solution and the ionic solvent, and results
show that the CO2 removal efficiency by the ionic solvent was higher
than DETA. But considering the disadvantages of ionic solvent, such as
high viscosity and its price, there is a need to further investigate the CO2
capture process for using this type of solvent compared to amines.

18
M. Afkhamipour et al.
CRediT authorship contribution statement
Morteza Afkhamipour: Writing – original draft, Methodology,
Investigation. Ebad Seifi: Validation, Investigation, Formal analysis.
Arash Esmaeili: Writing – review & editing, Validation, Investigation.
Mohammad Shamsi: Software, Resources, Methodology. Tohid N.
Borhani: Writing – review & editing, Writing – original draft, Valida­
tion, Supervision, Conceptualization.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
No data was used for the research described in the article.
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