In: Carbon Dioxide Capture ISBN: 978-1-63485-321-7

Editor: Jonathan Albo Sánchez © 2016 Nova Science Publishers, Inc.

Chapter 4

MASS TRANSFER IN AMINE-BASED CO2

ABSORPTION PROCESS: THEORY AND ITS
APPLICATIONS TO PLANT DESIGN AND OPERATION

Adisorn Aroonwilas
and Amornvadee Veawab*
University of Regina, Canada

ABSTRACT
This book chapter reviews mass-transfer fundamentals associated with CO2-amine
absorption systems and demonstrates how theoretical knowledge is used for design and
operation of large-scale CO2 absorption columns. The chapter begins with mass-transfer
basics presenting mass-flux equations, Two-film theory with an integration of Henry’s
law, and compilation of Henry’s law constant data and/or equations available for various
CO2-amine absorption systems. Three theories, i.e., film, penetration and surface-renewal
are described and used to determine mass-transfer coefficient in the liquid film residing
next to the gas-liquid interface. The role of chemical reactions between CO2 and amine
on mass transfer is reviewed by compiling series of absorption reactions, kinetic rate
constants, reaction regimes and enhancement factor equations. Role of vapor-liquid-
equilibrium on mass-transfer driving force in the CO2 absorption process, including
mass-flux analysis and mass-transfer limits due to equilibrium, is discussed. Furthermore,
the chapter includes the knowledge of exothermic process operations leading to changes
in temperatures and physical properties of both gas and liquid phases within the
absorption column and their impacts on mass-transfer efficiency and limits. At the end of
this book chapter, a design procedure for gas absorption column in CO 2-amine
application and column design simulation results are provided.

Keywords: mass transfer, CO2 capture, CO2 absorption, amines, kinetics

*
Corresponding Author address: 3737 Wascana Parkway, Faculty of Engineering and Applied Science, University
of Regina, Regina, Saskatchewan, Canada. Email: [email protected].
70 Adisorn Aroonwilas and Amornvadee Veawab

INTRODUCTION
The removal of carbon dioxide (CO2) from industrial gas streams has been an important
step in many process operations such as ammonia production, natural gas purification, and oil
refining. In these processes, CO2 is considered as an impurity that must be removed in order
to enhance the quality of gas products. Recently, the CO2 removal has become one of the
crucial strategies that help to reduce the emissions of greenhouse gases generated from fossil-
fuel combustion. The removal of CO2 can be achieved by a number of processes. Among
these, gas absorption into amine solutions is the most promising and cost-effective approach
for removing CO2 from high-volume gas streams.
The purpose of this book chapter is to review mass-transfer fundamentals associated with
CO2-amine absorption systems and also to demonstrate how theoretical knowledge is used for
design and operation of large-scale CO2 absorption columns. This book chapter is organized
into six sections including i) mass-transfer basics, ii) liquid-side mass-transfer coefficient, iii)
role of chemical reactions between CO2 and amine on mass transfer, iv) role of vapor-liquid-
equilibrium (VLE) on mass transfer, v) exothermic energy and mass-transfer operation, and
vi) demonstration of the design and operation of CO2 absorption columns. The section of
mass-transfer basics presents mass-flux equations, Two-film theory with integration of the
Henry’s law, and compilation of Henry’s law constant data and/or equations available for
various CO2-amine absorption systems. The section of liquid-side mass-transfer coefficient
describes film, penetration and surface-renewal theories used for determination of mass-
transfer coefficient in the liquid film residing next to the gas-liquid interface. The section of
role of chemical reactions between CO2 and amine on mass transfer summarizes types of
amines available for CO2 absorption process, and their absorption reactions. A review on
kinetic rate constants, reaction regimes and enhancement factor equations together with their
application ranges for individual amines is also provided. The section of vapor-liquid-
equilibrium discusses the role of vapor-liquid-equilibrium on mass-transfer driving force in
the absorption process, mass-flux analysis that combines both equilibrium data and actual
operating conditions in CO2 absorption process and mass-transfer limits due to the
equilibrium. The section of exothermic energy and mass transfer operation provides
knowledge of the exothermic process operations leading to changes in temperatures and
physical properties of both gas and liquid phases within the absorption column and their
impacts on mass-transfer efficiency and limits. The last section is dedicated to the design
procedure for gas absorption columns in CO2-amine application, role of packing
hydrodynamic features on mass-transfer activities in the full-length absorber. It describes two
approaches of the adiabatic column design and presents column design simulation results that
generate a comprehensive set of mass-transfer and temperature column profiles along the
absorber. A comparison between simulated results and a pilot plant data currently reported in
literature was also made.

MASS TRANSFER BASICS

Mass transfer is the phenomenon characterized by the movement of chemical substances
from one location to another on a molecular basis. The molecular transport occurs in many
 Mass Transfer in Amine-Based CO2 Absorption Process 71

chemical engineering processes, including CO2 absorption and CO2 stripping, where the
transferring component (CO2 in this case) travels across the interface between gas and liquid
phases. The mass transfer rate and its direction take place by means of diffusion driven by
CO2 concentration gradient being developed over the two insoluble fluids. Mass transfer flux
of CO2 (NCO2) can be written as:

𝑁𝐶𝑂2 = 𝑘𝐺 𝑃 (𝑦𝐶𝑂2,𝐺 − 𝑦𝐶𝑂2,𝑖 ) = 𝑘𝐿𝑜 (𝐶𝐶𝑂2,𝑖 − 𝐶𝐶𝑂2,𝐿 ) (1)

where 𝑘𝐺 and 𝑘𝐿𝑜 are the gas-side mass transfer coefficient and the liquid-side mass transfer
coefficient, respectively; 𝑃 is the total system pressure; 𝑦𝐶𝑂2,𝐺 and 𝑦𝐶𝑂2,𝑖 are the CO2 mole
fractions in the gas bulk and the gas-liquid interface, respectively; and 𝐶𝐶𝑂2,𝐿 and 𝐶𝐶𝑂2,𝑖 are
the CO2 concentrations in the liquid bulk and the interface, respectively. Note that Equation
(1) is for mass transfer activity in an absence of chemical reactions. It is commonly assumed
that the mass transfer resistances are those residing in the fluids themselves; there is then no
resistance to the transfer across the interface [1]. This suggests that the mole fraction 𝑦𝐶𝑂2,𝑖 in
the gas phase is in equilibrium with the concentration 𝐶𝐶𝑂2,𝑖 in the liquid phase. The CO2
equilibrium can be expressed by Henry’s law [2].

𝑃 𝑦𝐶𝑂2,𝑖 = 𝐻𝐶𝑂2 𝐶𝐶𝑂2,𝑖 (2)

where HCO2 is the Henry’s law constant for CO2 in the unit of kPa m3 kmol-1.
In the actual absorption operation, it is rather difficult to precisely determine CO2
concentration at the gas-liquid interface. Thus, it becomes more practical to express the mass
transfer flux as a function of bulk concentrations (𝑦𝐶𝑂2,𝐺 and 𝐶𝐶𝑂2,𝐿 ) that can be directly
measured from the process operation. This leads to an alternative mass flux equation written
in terms of the overall mass transfer coefficients 𝐾𝐺 and 𝐾𝐿 .

𝑃 𝑦𝐶𝑂2,𝐺
𝑁𝐶𝑂2 = 𝐾𝐺 (𝑃 𝑦𝐶𝑂2,𝐺 − 𝐻𝐶𝑂2 𝐶𝐶𝑂2,𝐿 ) = 𝐾𝐿 ( 𝐻𝐶𝑂2
− 𝐶𝐶𝑂2,𝐿 ) (3)

The relationships between the overall coefficients and the individual-phase coefficients
can be derived from the two-film theory with an integration of the Henry’s law as shown
below.

1 1 𝐻𝐶𝑂2
= + (4)
𝐾𝐺 𝑘𝐺 𝑘𝐿𝑜

1 1 1
= + (5)
𝐾𝐿 𝐻𝐶𝑂2 𝑘𝐺 𝑘𝐿𝑜

For the Henry’s law constant, CO2 absorption into pure water has been commonly used
as the reference system since there is no chemical reaction taking place during mass transfer
process. The typical Henry’s law equations for pure water were proposed by Versteeg and
van Swaaij [3].
72 Adisorn Aroonwilas and Amornvadee Veawab

−2040
𝐻𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 = 2.825 × 106 𝑒𝑥𝑝 ( 𝑇
) (6)

where is the Henry’s law constant in kPa m3 kmol-1; T is the system temperature in
Kelvin. The Henry’s law constant of CO2 in water can also be calculated from a semi-
empirical equation by Harvey where the constant is in unit of pressure. [4] The equation by
Harvey shown in Equation (7) is applicable up to 631.7 K.

∞ 𝑠𝑎𝑡 𝑇 𝑇 0.355 𝑇𝑐
𝐻𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 [𝑙𝑛𝑝𝐻2𝑂 − 9.4234 𝑇𝑐 + 4.0087 (1 − 𝑇 ) 𝑇
+
𝑐
𝑇 𝑇 −0.41
10.3199𝑒𝑥𝑝 (1 − ) ( ) ] (7)
𝑇 𝑇𝑐 𝑐

Recently, Equation (7) was modified by Monteiro and Svendsen [5] to Equations (8) and
(9) for low pressure (up to 1 MPa) and high pressure (up to 20 MPa) ranges, respectively.

∞ 𝑠𝑎𝑡 𝑇𝑐 𝑇 0.355 𝑇𝑐
𝐻𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 [𝑙𝑛𝑝𝐻2𝑂 − 7.4455 + 3.6456 (1 − ) +
𝑇 𝑇 𝑐 𝑇
𝑇 𝑇 −0.41
8.7600𝑒𝑥𝑝 (1 − ) ( ) ] (8)
𝑇 𝑐 𝑇 𝑐

∞ 𝑠𝑎𝑡 𝑇 𝑇 0.355 𝑇𝑐
𝐻𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 [𝑙𝑛𝑝𝐻2𝑂 − 10.16975 𝑇𝑐 + 4.4824 (1 − 𝑇 ) 𝑇
+
𝑐
𝑇 𝑇 −0.41
10.6583𝑒𝑥𝑝 (1 − 𝑇 ) (𝑇 ) ] (9)
𝑐 𝑐

It should be noted that the Henry’s law constant for CO2 absorption into amine solutions
cannot be measured directly as CO2 undergoes chemical reactions with amine solutions.
Based on the fact that N2O does not react with amines, the so-called N2O analogy, first
introduced by Clarke [6], has been commonly used to estimate the constant of CO2 in amine
solutions. It was assumed that the ratio of CO2 Henry’s constant to N2O Henry’s constant
in water is equivalent to the Henry’s constant ratio in the amine solution as shown
in the following relation [3]:

𝐻 𝐻
(𝐻 𝐶𝑂2,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ) = (𝐻 𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 ) (10)
𝑁2𝑂,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟

The Henry’s law constant for N2O absorption into pure water can be calculated from the
following equations.
Versteeg and van Swaaij, 1988 [3]:

−2284
𝐻𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 = 8.547 × 106 𝑒𝑥𝑝 ( 𝑇
) (11)

Penttilä et al. 2011 [7]:

9048.596
𝐻𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 (158.245 − 0.00252𝑇 − 𝑇
− 20.860𝑙𝑛𝑇) (12)
 Mass Transfer in Amine-Based CO2 Absorption Process 73

Similar to the Henry’s law constant of CO2 in water, the Henry’s constant of N2O in
water can also be calculated (in pressure unit) from a semi-empirical equations by Monteiro
and Svendsen [5] as shown in Equations (13) and (14) for low pressure (up to 1 MPa) and
high pressure (up to 20 MPa) ranges, respectively.

∞ 𝑠𝑎𝑡 𝑇 𝑇 0.355 𝑇𝑐
𝐻𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 [𝑙𝑛𝑝𝐻2𝑂 − 9.9118 𝑇𝑐 + 3.2644 (1 − 𝑇 ) 𝑇
+
𝑐
𝑇 𝑇 −0.41
11.4552𝑒𝑥𝑝 (1 − 𝑇 ) (𝑇 ) ] (13)
𝑐 𝑐

∞ 𝑠𝑎𝑡 𝑇 𝑇 0.355 𝑇𝑐
𝐻𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 = 𝑒𝑥𝑝 [𝑙𝑛𝑝𝐻2𝑂 − 16.4928 𝑇𝑐 + 4.8133 (1 − 𝑇 ) 𝑇
+
𝑐
𝑇 𝑇 −0.41
16.3786𝑒𝑥𝑝 (1 − ) ( ) ] (14)
𝑇 𝑇 𝑐 𝑐

The Henry’s constants of N2O and CO2 in various amine solutions reported in the
literature are summarized in Table 1.

Table 1. Henry’s constant in various amine solutions

Amine system Temperature Amine concentration Data / Equation Reference

(K)
MEA 298 10, 20, 30 wt% 4299.5 – 7406.3 kPa m3 kmol-1 Browning and
DEA 10, 20, 30, 40 wt% 4548.2 – 8033.2 kPa m3 kmol-1 Weiland, 1994
MDEA 20, 30, 40, 50 wt% 4845.0 – 9654.9 kPa m3 kmol-1 [8]
MEA+MDEA 10%MEA/40%MDEA 5679.6 – 9331.6 kPa m3 kmol-1
MEA+MDEA 20%MEA/30%MDEA 5464.8 – 8781.5 kPa m3 kmol-1
DEA+MDEA 10%DEA/40%MDEA 5544.9 – 7772.9 kPa m3 kmol-1
DEA+MDEA 20%DEA/30%MDEA 5501.5 – 7507.4 kPa m3 kmol-1

𝑙𝑜𝑔(𝐻) = (ℎ+ + ℎ− + ℎ𝑔 )𝐼 + 𝑙𝑜𝑔 ( 𝑚𝑖 𝐻𝑖′ )

MEA, DEA, TEA, 298 - 333 Up to Versteeg and van
DMMEA, 3.0 kmol/m3 for MEA 1 Swaaij, 1988 [3]
𝐻𝑁2𝑂 =
MDEA, MIPA, 3.1 kmol/m3 for DEA (𝑅𝑇)(𝑎0 + 𝑎1 𝐴𝑚𝑖𝑛𝑒 + 𝑎2 𝐴𝑚𝑖𝑛𝑒 2 + …)
DIPA 2.9 kmol/m3 for TEA
2.4 kmol/m3 for DMMEA where 𝐻𝑁2𝑂 = Henry’s constant in kPa m kmol 3 -1

2.8 kmol/m3 for MDEA 𝐴𝑚𝑖𝑛𝑒 = amine concentration in mol/m3

3.7 kmol/m3 for MIPA
4.1 kmol/m3 for DIPA
MEA 288-393 Up to 36.8 wt% For single amine: Penttilä et al.,
DEA 288-393 Up to 37.2 wt% 2 2011 [7]
𝑇
DIPA 293-333 Up to 54 wt% 𝐻𝑁2𝑂,12 = (𝐻𝑁2𝑂,𝑖 𝑥𝑖 ) + 𝐴12 𝑥1 𝑥2 2 [1 − ] 𝑒𝑥𝑝 −𝐶12 𝑥2
𝐵12
MDEA 288-393 Up to 50 wt% 𝑖=1
AMP 289-393 Up to 50 wt% For blended amine:
3
MEA+MDEA 293-393 1.5-24%MEA/6-28.5%MDEA
MEA+AMP 293-393 1.5-24%MEA/6-28.5%AMP 𝐻𝑁2𝑂,123 = (𝐻𝑁2𝑂,𝑖 𝑥𝑖 )
DEA+MDEA 293-393 1.5-24%DEA/6-47.9%MDEA 𝑖=1
3 2
DEA+AMP 293-393 1.5-24%DEA/6-28.5%AMP
DIPA+MDEA 298 4.5-10.6%DIPA/6-31.9%MDEA + 𝐴123 𝑥1 𝑥𝑖 . [1
MDEA+AMP 283-333 3.6-41.5%MDEA/0.7-40%AMP 𝑖=2
3
𝑇 𝐸𝑋
− ] . 𝑒𝑥𝑝 −𝐶123 𝑥𝑖 + 𝐻𝑁2𝑂,23
𝐵123
𝑖=2

DEEA 298, 308, 11.82 wt% 4257 – 9662 kPa m3 kmol-1 Monteiro et al.,
318, 328, 23.75 wt% 4712 - 8026 kPa m3 kmol-1 2015 [5]
338 35.82 wt% 4433 - 6398 kPa m3 kmol-1
48.16 wt% 3666 - 5047 kPa m3 kmol-1
61.35 wt% 2817 - 3822 kPa m3 kmol-1
100 wt% 957 - 1597 kPa m3 kmol-1
MEA 298-360 10, 20, 30 wt% 𝐻𝑁2𝑂,𝑀𝐸𝐴−𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 Dugas and
Up to 0.5 mol/mol CO2 loading Rochelle, 2011
= 𝑒𝑥𝑝 [(8.3194 + 452 × 10−3 (𝑀𝐸𝐴) − 4.78
[9]
× 10−2 (𝐶𝑂2 𝐿𝑑𝑔) + 4.56 × 10−2 (𝑀𝐸𝐴)(𝐶𝑂2 𝐿𝑑𝑔))
1 1
− 1905 ( − )]
𝑇 298.15
74 Adisorn Aroonwilas and Amornvadee Veawab

LIQUID-SIDE MASS TRANSFER COEFFICIENT

In CO2 absorption applications, the rate of mass transfer is controlled by mass transfer
coefficient in liquid phase. There are three important theories commonly used to describe the
phenomenon: i) film theory, ii) penetration theory and iii) surface renewal theory.

Film Theory

The film theory established by Lewis and Whitman [12] is considered to be the oldest
and the most obvious picture describing mass transfer in gas-liquid system. The theory is
based on the assumption that mass transfer activity takes place by molecular diffusion from
gas phase through a stagnant liquid film located at the gas-liquid interface. The diffusion in
this case is a steady state process where the concentration profile of the transferred
component in the film is linear as shown in Figure 1. In the absence of chemical reaction, the
differential equation for steady state mass transfer can be written as:

𝜕2 𝐶𝐶𝑂2
𝐷𝐶𝑂2,𝐿 =0 (15)
𝜕𝑥 2

where is the diffusivity of CO2 in liquid; and x is the distance from the gas-liquid
interface. Based on the boundary conditions (at x = 0, = ; at x = film thickness ,
= ), the mass flux equation can be written as:

𝐶𝐶𝑂2,𝑖 −𝐶𝐶𝑂2,𝐿
𝑁𝐶𝑂2 = 𝐷𝐶𝑂2,𝐿 ( ) (16)
𝛿

Combining Equations (1) and (16), the mass transfer coefficient without reaction ( ) can
be expressed as:

𝐷𝐶𝑂2,𝐿
𝑘𝐿𝑜 = (17)
𝛿

According to Astarita et al. [13], mass transfer predictions based on the film theory were
questionable because the available experimental data on mass transfer coefficient tended to be
proportional to the square root of the diffusivity.

Penetration Theory

The penetration theory proposed by Higbie [14] is associated with the motion of liquid
elements at the gas-liquid interface as shown in Figure 2. It is assumed that small liquid
elements (clusters of liquid molecules) are constantly brought from bulk liquid to the
interface, exposed to the gas for a fixed time period (known as contact time tC), and then
swept back to the bulk liquid. Each liquid element at the interface essentially behaves as a
 Mass Transfer in Amine-Based CO2 Absorption Process 75

rigid body with no internal motion, allowing mass transfer to take place by molecular
diffusion. This transient diffusion is an unsteady state process as the gas-liquid contact time is
so short that the concentration gradient of the transferred components within the liquid
elements would have no time to develop. The partial differential equation for unsteady CO2
diffusion to the liquid element can be written as [14]:

𝜕2 𝐶𝐶𝑂2 𝜕𝐶𝐶𝑂2
𝐷𝐶𝑂2,𝐿 = (18)
𝜕𝑥 2 𝜕𝑡

Figure 1. Film theory for mass transfer.

Figure 2. Penetration theory for mass transfer.

76 Adisorn Aroonwilas and Amornvadee Veawab

It should be noted that all liquid elements are assumed to remain at the interface for the
same length of contact time. Based on the boundary conditions i.e., at t = 0, 𝐶𝐶𝑂2 = 𝐶𝐶𝑂2,𝐿
for all distances from the interface, and at t > 0, 𝐶𝐶𝑂2 = 𝐶𝐶𝑂2,𝑖 at the interface, mass transfer
coefficient for physical absorption of CO2 is defined as:

𝐷𝐶𝑂2,𝐿
𝑘𝐿𝑜 = 2√ (19)
𝜋𝑡

The penetration theory has been used extensively in a number of research works since it
has been found to accurately represent the diffusion reaction systems. The recent use of the
penetration theory is for the interpretation of kinetic data in the single amine systems such as
CO2-loaded MEA and AHPD as well as blended amine systems such as monoethanolamine
(MEA)+2-amino-2-methyl-1-propanol (AMP), piperazine (PZ) + AMP, PZ + methyl
diethanolamine (MDEA), and AMP + diethanolamine (DEA) [15-20]. Furthernore, it was
also employed in the simulation of CO2 absorption in packed columns by Khan et al. and
Sebastia-Saez et al. [21, 22].

Surface Renewal Theory

Danckwerts proposed in 1951 an extension of the penetration theory known as the

surface renewal theory. [23] The theory is base on the assumption that the liquid elements are
exposed to the interface for different random periods of time. Distribution of the contact time
in this case is characterized by the fraction of liquid surface renewed per unit time (s). This
theory is also considered the unsteady state form of mass transfer. The mass transfer
coefficient is expressed as:

𝑘𝐿𝑜 = √𝐷𝐶𝑂2,𝐿 𝑠 (20)

This theory is not as popular as the penetration theory since it requires the information on
the rate of surface renewal (s), which is rather difficult to obtain.

Diffusivity of CO2 in Amine Solution

It is clear from all three theories that diffusivity of CO2 in liquid phase ( ) is the
essential component for determining the liquid-side mass transfer coefficient. Similar to the
Henry’s law constant, the diffusivity of CO2 in amine solution can be estimated by the N2O
analogy presented in the following relation [3]:

𝐷 𝐷
(𝐷 𝐶𝑂2,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 ) = (𝐷 𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 ) (21)
𝑁2𝑂,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟
 Mass Transfer in Amine-Based CO2 Absorption Process 77

The diffusivity of CO2 and N2O in pure water can be determined from the following
equations [3]:

2119
𝐷𝐶𝑂2,𝑤𝑎𝑡𝑒𝑟 = 2.35 × 10−6 𝑒𝑥𝑝 ( 𝑇
) (22)

2371
𝐷𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 = 5.07 × 10−6 𝑒𝑥𝑝 ( ) (23)
𝑇

The diffusivity of N2O in amine solutions can be calculated according to the modified
Stokes-Einstein relation given below.

𝜇𝑤𝑎𝑡𝑒𝑟 0.8
𝐷𝑁2𝑂,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = (𝐷𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 ) (𝜇 ) (24)
𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

where and are the viscosity of water and amine solution, respectively. In
2009, Dugas conducted a series of experiments with loaded MEA and PZ solutions and
proposed the new relation with viscosity dependence of 0.72 [24].

𝜇𝑤𝑎𝑡𝑒𝑟 0.72
𝐷𝑁2𝑂,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛 = (𝐷𝑁2𝑂,𝑤𝑎𝑡𝑒𝑟 ) ( ) (25)
𝜇𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

ROLE OF CHEMICAL REACTIONS ON MASS TRANSFER

Chemical reactions start to play a role in the mass transfer process when a gas stream is
brought into contact with a liquid solution containing amine, which can react with the
diffusing CO2. All associated reactions take place only in the liquid side. In general, the
chemical reaction influences mass transfer behavior of the system in two ways. First, CO2 is
consumed by chemical reactions in the liquid phase, resulting in a low concentration of CO2
in the liquid main body (CCO2,L). The driving force for the chemical mass transfer then
becomes higher than it would be in the absence of chemical reaction. Second, at a given level
of the driving force, the actual rate of mass transfer with chemical reaction may be
considerably larger than that without chemical reaction. The ratio of the actual rate with
chemical reaction to that which occurs without the reaction under the same driving force is
defined as an enhancement factor E [13].

𝑘𝐿
𝐸= 𝑘𝐿𝑜
≥1 (26)

where is the liquid-side mass transfer coefficient with chemical reaction. Thus, the mass
transfer flux of CO2 can be written as:

𝑁𝐶𝑂2 = 𝑘𝐺 𝑃(𝑦𝐶𝑂2,𝐺 − 𝑦𝐶𝑂2,𝑖 ) = 𝐸 𝑘𝐿𝑜 (𝐶𝐶𝑂2,𝑖 − 𝐶𝐶𝑂2,𝐿 ) (27)

with chemical reaction, Equations (4) and (5) can then be respectively rewritten as:
78 Adisorn Aroonwilas and Amornvadee Veawab

1 1 𝐻𝐶𝑂2
= + (28)
𝐾𝐺 𝑘𝐺 𝐸 𝑘𝐿𝑜
1 1 1
= + (29)
𝐾𝐿 𝐻𝐶𝑂2 𝑘𝐺 𝐸 𝑘𝐿𝑜

To determine the enhancement factor E, several approximate numerical and analytic

solutions have been proposed. [2, 13, 25-28] The most commonly used relation is as follows:

𝐸 −𝐸
√𝑀( 𝐸∞ −1 )
∞
𝐸= 𝐸 −𝐸
(30)
tanh √𝑀( ∞ )
𝐸∞ −1

where

𝐷𝐶𝑂2,𝐿 𝐷𝐴𝑚𝑖𝑛𝑒,𝐿 𝐶𝐴𝑚𝑖𝑛𝑒 𝐻𝐶𝑂2,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(for penetration theory) 𝐸∞ = √𝐷 +√
𝐷𝐶𝑂2,𝐿
(
𝑧
)(
𝑃𝐶𝑂2,𝑖
) (31)
𝐴𝑚𝑖𝑛𝑒,𝐿

𝐷𝐴𝑚𝑖𝑛𝑒,𝐿 𝐶𝐴𝑚𝑖𝑛𝑒 𝐻𝐶𝑂2,𝑠𝑜𝑙𝑢𝑡𝑖𝑜𝑛

(for film theory) 𝐸∞ = 1 + ( 𝐷𝐶𝑂2,𝐿
)(
𝑧
)(
𝑃𝐶𝑂2,𝑖
) (32)

The parameter M can be calculated from Hatta number (Ha) in the following equation:

𝑀 = 𝐻𝑎2 (33)

where

√𝐷𝐶𝑂2,𝐿 (𝑘𝑎𝑝𝑝 + 𝑘𝑂𝐻− 𝐶𝑂𝐻− )

𝐻𝑎 = (34)
𝑘𝐿𝑜

Note that Equation (34) includes chemical reaction of CO2 with hydroxyl ion (OH-), the
component commonly found in all aqueous amine solutions. The term and are the
-
second order rate constant for CO2-OH reaction and concentration of hydroxyl ion,
respectively. The is the apparent reaction rate constant corresponding to all reactions
associated with the CO2-amine system, which can be related to the reaction rate and
concentration of CO2 in the following relationship;

−𝑟𝐶𝑂2 = 𝑘𝑎𝑝𝑝 𝐶𝐶𝑂2 (35)

The apparent rate constant can be estimated according to a number of reaction

mechanisms. It is commonly known that the chemical reactions for CO2 absorption into
aqueous amine solutions are remarkably complex. According to Astarita et al. [13], the
following three main reactions are considered for primary and secondary amines ( ).
Carbamate formation:
 Mass Transfer in Amine-Based CO2 Absorption Process 79

𝐶𝑂2 + 2𝑅𝑅 ′ 𝑁𝐻 ↔ 𝑅𝑅 ′ 𝑁𝐻2+ + 𝑅𝑅 ′ 𝑁𝐶𝑂𝑂− (36)

Bicarbonate formation:

𝐶𝑂2 + 𝑅𝑅 ′ 𝑁𝐻 + 𝐻2 𝑂 ↔ 𝑅𝑅 ′ 𝑁𝐻2+ + 𝐻𝐶𝑂3− (37)

Carbamate reversion:

𝐶𝑂2 + 𝑅𝑅 ′ 𝑁𝐶𝑂𝑂− + 2𝐻2 𝑂 ↔ 𝑅𝑅 ′ 𝑁𝐻2+ + 2𝐻𝐶𝑂3− (38)

where RR’NH2+ and RR’NCOO- are the protonated amine and amine carbamate, respectively.

Table 2. Kinetic correlations for common amines

Amine correlation Reference

MEA 2152 Hikita et al., 1977 [30]
log(𝑘2 ) = 10.99 −
𝑇
AMP 5176.49 Saha et al., 1995 [31]
log(𝑘2 ) = 23.69 −
𝑇
MDEA 7
−2152 Rinker et al., 1995 [32]
𝑘2 = 2.91 × 10 𝑒𝑥𝑝 ( )
𝑇
PZ − 3.5 × 104 1 1 Samanta and Bandyopadhyay, 2007
𝑘2 = 5.8 × 104 𝑒𝑥𝑝 ( − ) [33]
𝑅 𝑇 298
AHPD −6465 Bougie and Iliuta, 2009 [16]
𝑘2 = 5.08 × 1011 𝑒𝑥𝑝 ( )
𝑇
DEAB −7527.7 Sema et al., 2012 [34]
𝑘2 = 4.01 × 1013 𝑒𝑥𝑝 ( )
𝑇
OH- 2895 Pinsent et al., 1956; Danckwerts and
log(𝑘2 ) = 13.635 −
𝑇 Sharma, 1966 [35-36]
1
In general, the carbamate formation predominates when the CO2 loading in amine
solution is less than 0.5 mol CO2/mol amine, and the carbamate reversion plays a major role
when the CO2 loading exceeds 0.5 mol CO2/mol amine. The carbamate formation is made up
of two steps commonly referred to as zwitterions mechanism [29]:

𝑘2 ,𝑘−1
𝐶𝑂2 + 𝑅𝑅 ′ 𝑁𝐻 ↔ 𝑅𝑅 ′ 𝑁𝐻 + 𝐶𝑂𝑂− (39)

𝑘𝑏
𝑅𝑅 ′ 𝑁𝐻 + 𝐶𝑂𝑂− + 𝐵 ↔ 𝐵𝐻 + + 𝑅𝑅 ′ 𝑁𝐶𝑂𝑂− (40)

where B represents base species that could be either amine (𝑅𝑅 ′ 𝑁𝐻), hydroxyl ion (𝑂𝐻 − ) or
water (𝐻2 𝑂). With the above mechanism, the apparent rate constant for primary and
secondary amines can be written as:

𝑘2 𝐶𝐴𝑚𝑖𝑛𝑒
𝑘𝑎𝑝𝑝 = (41)
𝑘−1
(1+ )
∑𝑖(𝑘𝑏,𝑖 𝐶𝐵,𝑖 )
80 Adisorn Aroonwilas and Amornvadee Veawab

Equation (41) has been commonly used for analyzing kinetics data for MEA, DEA,
DIPA, PZ and AHPD.
For tertiary and hindered amines such as MDEA, AMP, and DEAB, the reaction
mechanism is simpler. Bicarbonate formation is considered to be the primary reaction.

𝑘2
𝐶𝑂2 + 𝑅𝑅 ′ 𝑅 " 𝑁 + 𝐻2 𝑂 ↔ 𝑅𝑅 ′ 𝑅" 𝑁𝐻 + + 𝐻𝐶𝑂3− (42)

The apparent rate constant in this case can be written as:

𝑘𝑎𝑝𝑝 = 𝑘2 𝐶𝐴𝑚𝑖𝑛𝑒 (43)

Based on the above equation, the second order rate constant (k2) is the crucial parameter
for estimating the enhancement factor E. Table 2 summarizes kinetic correlations developed
for a number of common amines.

ROLE OF VAPOR-LIQUID-EQUILIBRIUM ON MASS TRANSFER

The relationship between CO2 content in an amine solution and CO2 partial pressure in
the gas phase under equilibrium conditions is one of the most important information required
for the design of a CO2 absorption unit. This vapor-liquid-equilibrium establishes the CO2
concentration gradient between the two fluids, driving mass transfer process to occur. For a
gas absorption application, it is common to represent mass transfer driving force in terms of
pressure gradient. Therefore, mass flux for CO2 absorption into amine solution can also be
written as:

∗
𝑁𝐶𝑂2 = 𝐾𝐺 (𝑃𝐶𝑂2,𝐺 − 𝑃𝐶𝑂2,𝐿 ) (44)

where is the CO2 partial pressure in the gas phase, and is the CO2 partial
pressure in equilibrium with the content of CO2 in amine solution. To allow the CO2
absorption into the amine solution, the gas-phase CO2 partial pressure must be greater than
the corresponding equilibrium .
The equilibrium data for CO2-amine system are available and presented in terms of “CO2
loading” (in a unit of mole CO2 per mole amine) representing the relationship between gas-
phase CO2 partial pressure and CO2 content of amine solution. Such equilibrium data have
been reported for decades as a function of temperature, type of amine used, and concentration
of amine. A comprehensive data collection for common amines such as MEA, DEA, DIPA,
MDEA, AMP, and their blends can be found in the book by Kohl and Nielsen [37]. The
equilibrium data for newly developed amines can also be found in recent literature. It should
be noted that, for the CO2 absorption from a low pressure flue gas, CO2 partial pressure in the
gas phase is kept below atmospheric pressure (e.g., 101.3 kPa). Figure 3 shows a summary of
equilibrium data applicable to flue gas conditions.
For the design and operation of CO2 absorption columns, the equilibrium data are used in
combination with the operating data commonly known as “operating line.” This operating
 Mass Transfer in Amine-Based CO2 Absorption Process 81

line represents a relationship between partial pressure of CO2 in the gas stream and CO2
content in the amine solution that is derived directly from material balance around the
absorption column. Figure 4 shows a schematic diagram of a packed absorption column in
which the entire height is divided into a series of sections with a differential height of dz.

Figure 3. Equilibrium data for CO2-amine system at 40oC.

Figure 4. Schematic diagram of a packed column.

82 Adisorn Aroonwilas and Amornvadee Veawab

For each column section, the amount of CO2 removed from the gas phase is equivalent to
the amount of CO2 absorbed into the amine solution. Therefore, the material balance of CO2
can be written as:

𝑃𝐶𝑂2 𝑜
𝐺𝐼 (𝑑𝑌𝐶𝑂2 ) = 𝐺𝐼 𝑑 ( ) = 𝐿𝐶𝐴𝑚𝑖𝑛𝑒 (𝑑𝛼𝐶𝑂2 ) (45)
𝑃𝑡𝑜𝑡𝑎𝑙 −𝑃𝐶𝑂2

where is the mole ratio of CO2 in the gas phase. The material balance equation can also
be rewritten as:

𝑑𝑃𝐶𝑂2 (𝑃𝑡𝑜𝑡𝑎𝑙 −𝑃𝐶𝑂2 )2 𝐿 𝑜

={ } (𝐺 ) 𝐶𝐴𝑚𝑖𝑛𝑒 (46)
𝑑𝛼𝐶𝑂2 𝑃𝑡𝑜𝑡𝑎𝑙 𝐼

with complete information on process parameters (including gas flow rate, liquid flow rate,
amine concentration, CO2 content in feed gas, and CO2 loading of lean amine solution), the
operating line for CO2 absorption column can be drawn as illustrated in Figure 4 for a CO2-
MEA system.

Figure 5. Equilibrium and operating lines of CO2 absorption column using 30wt% MEA solution
(PCO2,in = 15 kPa and PCO2,out = 1 kPa).

It should be noted that the CO2 absorption into the amine solution can be achieved only
when the operating line is located above the equilibrium line. From a thermodynamic
viewpoint, the greater the proximity between the operating and the equilibrium lines, the
higher the mass transfer driving force established within the absorption column. From Figure
5, a larger driving force can be achieved by using the lean amine solution with a lower CO2
loading (0.22 mol/mol in this case). Producing the lean amine solution, however, requires a
considerable amount of energy during solvent regeneration process, thus leading to more
operating cost for capturing CO2. The use of the relatively higher lean CO2 loading for the
 Mass Transfer in Amine-Based CO2 Absorption Process 83

absorption column is now considered as one of the operational strategies to reduce energy
consumption of the entire CO2 capture unit. Increasing the lean loading, however, must be
done within thermodynamic limits controlled by the equilibrium lines for individual amine
solutions. Table 3 shows the maximum levels of lean CO2 loading for selected amine
solutions according to their equilibrium data at 40oC.

Table 3. Maximum lean CO2 loading for amine solutions at 40oC

Amine solution Max. lean CO2 loading (mol/mol)

30 wt% MEA 0.46
25wt% DEA 0.33
2 kmol/m3 AMP 0.37
PZ 0.32
26 wt% MDEA Not applicable
1

HEAT OF REACTION BETWEEN CO2 AND AMINE

As mentioned in the previous section, the absorption of CO2 into aqueous amine solutions
is associated with a series of chemical reactions such as carbamate formation and bicarbonate
formation. These chemical reactions are exothermic, that release a certain amount of heat
energy to the surroundings, resulting in an increase in temperature of the medium in which
the reactions are taking place. In the typical operation, absorption reactions occur in a full-
length absorption column where the amine solution with a relatively low temperature is
introduced into the column top, absorbs CO2 from the gas stream while trickling down
through column internals, and finally reaches the column bottom. Because of the exothermic
nature of the CO2 absorption, the operation of industrial columns never takes place at a
constant and specific temperature, but is always subjected to significant dynamic variations in
temperature throughout the column length. Such exothermic effect can be observed from the
temperature bulk commonly developed near the bottom of the absorption column.
The system temperature is thus one of the most important process parameters controlling
all fundamental aspects of gas absorption including mass transfer (diffusion), kinetics, as well
as vapor-liquid equilibrium or thermodynamics. Knowing the magnitude of heat released due
to absorption reactions (commonly known as heat of reaction or enthalpy of solution) can
help us determine energy balance and temperature profiles around the absorption column. In
addition, the use of heat of reaction data is also necessary for the design and operation of
amine regeneration column as it helps us evaluate energy consumption (or heat duty) for the
entire CO2 absorption plant.
Because of the recent focus on the development of cost-effective and energy-efficient
carbon capture technologies, the heat of reaction between CO2 and amine has become one of
the most studied research topics in the last decade. To date, there are a number of research
studies reporting heat of reaction data for different amines including conventional amines
such as MEA, DEA, and MDEA, the sterically hindered amine such as AMP, and the
polyamine such as PZ. The reported values of heat of reaction were obtained either through
the estimation using vapor-liquid equilibrium (VLE) data, or through the direct measurement
using different types of calorimeters. The latter appears to be the common trend for more
84 Adisorn Aroonwilas and Amornvadee Veawab

recent studies. In general, each amine has its own range of heat of reaction that would not be
affected by amine concentration, but in most cases varies significantly with CO2 loading of
amine solution. For the effect of temperature, it was found to be inconclusive as some
researchers reported the increase in heat of reaction with temperature while some other
researchers demonstrated no temperature impact. A summary of heat of reaction data for well
recognized amines is given below.

Conventional Amine

MEA is the conventional amine that has been most referred to in many studies as the
baseline/benchmark solvent for the development of cost-effective carbon capture
technologies. The information on reaction heat for CO2 into MEA solution was reported as
early as 1974 by Lee [38] and has been published more intensively in recent years [39-42].
Most published data were presented in terms of differential heat of reaction (∆Hdiff)
representing heat release per mole of CO2 when a small amount of CO2 is absorbed by the
solution at a specific CO2 loading.
The effects of process parameters on heat of reaction have been studied to understand
synergistic behavior of energy requirement for plant operation. It was found that heat of
reaction for MEA typically remains unchanged at 85 kJ/mol of CO2 (approximately 1,930
kJ/kg CO2) with CO2 loading of solution. However, it decreases with an increase in CO2
loading when the CO2 loading is raised beyond its theoretical limit (0.50 mol CO2/mol amine)
[37]. For instance, the reaction heat value decreases to 70 and 50 kJ/mol of CO2 when the
CO2 loading is increased to 0.53 and 0.60 mol CO2/mol amine, respectively. Such CO2
loading effect on heat of the reaction was consistently confirmed by a number of studies [38,
41-42].
The effect of temperature was mentioned in the study by Kim [41] where the differential
heat of reaction of 30 wt% MEA solution was measured experimentally in a calorimeter at
40oC, 80oC, and 120oC. It was found that the heat of reaction increases with absorption
temperature. The similar temperature effect was also addressed in a work by Mathonat [39].
In contrast, other studies including Lee et al. and Arcis et al. [38, 42] found conflicting
findings in that the temperature has no effect on heat of reaction.
The effect of amine concentration was studied by Carson et al. [40] and by Arcis et al.
[42]. They found that amine concentration has no significant impact on heat of reaction for
the MEA solution with concentrations ranging from 10 to 30 wt%.
MDEA is another important conventional amine commonly referred to in many carbon
capture studies. Its relatively low heat of reaction with CO2 makes this tertiary amine popular
as one of the key ingredients in several amine blends such as MEA-MDEA, AMP-MDEA,
and PZ-MDEA. Similar to the CO2 loading effect found in MEA systems, the heat of reaction
for MDEA solution remains constant at 62 kJ/mole of CO2 (approximaterly 1,409 kJ/kg CO2)
for the CO2 loading up to 0.1 mol CO2/mol amine [37]. It, however, gradually decreases to
54.3 and 33.7 kJ/mol of CO2 as the CO2 loading increases to 0.5 and 1.0 mol CO2/mole
amine, respectively. Most studies [43-45] reported that heat of reaction for MDEA tends to
increase with temperature, except for the study by Kabadi suggesting no temperature effect
[46]. Increasing MDEA concentration was reported to cause heat of reaction to rise
[43, 45, 47].
 Mass Transfer in Amine-Based CO2 Absorption Process 85

DEA is the secondary amine that reacts with CO2 at a lower rate compared to MEA but a
much higher rate compared to MDEA. Similarly, the heat of reaction of DEA is also in
between those of these two amines. For a DEA solution (3.5-N), the differential heat of
reaction is at 76.3 kJ/mol of CO2 (approximately 1,734 kJ/kg CO2) for the CO2 loading of 0.2
mol CO2/mol amine. It can be reduced to 65.4 and 50.3 kJ/mol of CO2 as the CO2 loading
reaches 0.4 and 0.5 mol CO2/mol amine.

Hindered Amine and Polyamines

AMP is the most studied sterically hindered amine for CO2 absorption as it offers higher
CO2 absorption capacity (i.e., 1.0 mol CO2/mol amine) and lower heat of reaction compared
to MEA. According to Chowdhury et al. [48], the heat of reaction for AMP is about 76
kJ/mol of CO2 accounting for 12% lower than that of MEA. Despite the great attention
received, data on the heat of reaction for AMP is scarce. Arcis [49] reported the differential
heat of reaction measured experimentally for 15 and 30 wt% aqueous AMP at 49.35oC and
pressure up to 5 MPa.
PZ is a polyamine that has been studied extensively in recent years. This polyamine was
primarily used as a promoter with other amines to improve the overall CO2 absorption rate.
The concentrated aqueous PZ solution alone is recently considered as a potential candidate
for capturing CO2 from coal-fired power stations [50]. Heat of CO2 absorption with aqueous
PZ was measured by Hilliard and Liu using ChemiSens CPA-122 reaction calorimeter [51].

Figure 6. Heat of reaction for different amines. Data from references [37, 52-53].
86 Adisorn Aroonwilas and Amornvadee Veawab

In addition to PZ, heat of reaction of other polyamines including diethylenetriamine

(DETA), triethylenetetramine (TETA), tetraethylenepentamine (TEPA) and (MAPA) was
also measured in recent years. Based on the comparison study by Kim [52], the values of heat
of reaction are 87.00, 89.48, 84.91, and 85.87 kJ/mol of CO2 for MAPA, DETA, TETA, and
TEPA respectively. These are comparable to that of conventional MEA.
Also, several synthetic amines (recently developed by the Research Institute of
Innovative Technology for the Earth-RITE) were tested for their heat of reaction with CO2
[48]. It was found that the four synthetic amines referred to as IPEA, IPAP, IBAE, and SBAE
offer lower heat of reaction compared to the MEA, ranging from 61 to 69 kJ/mol of CO2. For
comparison purposes, values of the heat of reaction for different amines are summarized in
Figure 6.

SIMULATION OF ABSORPTION COLUMN

From a practical aspect, the CO2 absorption operation is commonly carried out in a gas-
liquid contactor where the gas stream containing CO2 is brought into a direct contact with the
amine solution. The typical contactor is the packed column fitted with packing materials that
could be categorized as random and structured packings. With its excellent performance and
advanced design, the structured packing has become the most studied column internal for CO2
capture application.
To design the CO2 absorption unit such that a desired capture target is met, mass transfer
performance of the full-length absorption column must be precisely known. Simulating the
column performance for CO2 absorption by amine is not an easy task due to the fact that all
mass-transfer and heat-transfer activities (including molecular diffusion, CO2-amine reaction,
vapor-liquid equilibrium, and heat generation by exothermic reaction) take place
simultaneously. The most common simulation strategy is based on the theoretical packed
column design procedure for adiabatic gas absorption with chemical reaction, which was first
described by Pandya [54]. The procedure accounts for heat of absorption, solvent evaporation
and condensation, chemical reaction in liquid phase, and heat-and mass-transfer resistance in
both gas and liquid phases. In addition, the hydrodynamic features of the packed column
revealing an interfacial gas-liquid contact area must also be included in the simulation
procedure.
The simulation of an absorption column is achieved by dividing the column height into a
series of sections with a differential height of dz as illustrated previously in Figure 2. Each of
these sections is treated as a non-equilibrium (or rate-based) discrete stage, which is governed
by material balance and energy balance equations. For material balance, the amount of CO2
removed from the gas phase is equivalent to the amount of CO2 absorbed into the amine
solution as shown below.

𝑑𝑌𝐶𝑂2 𝑜 𝑑𝛼𝐶𝑂2
𝐺𝐼 ( 𝑑𝑧
) = −𝐿𝐶𝐴𝑚𝑖𝑛𝑒 ( 𝑑𝑧
) (47)

where GI is the inert gas flow rate, YCO2 is the mole ratio of CO2 in gas phase, z is the column
length, L is the liquid flow rate, Coamine is the total amine concentration, and αCO2 is the CO2
loading in solution.
 Mass Transfer in Amine-Based CO2 Absorption Process 87

For the energy balance, the change in sensible heat of the amine solution (liquid phase) is
derived from three energy components including: i) sensible heat of the gas phase, ii)
condensation or evaporation of water vapor in the gas phase, and iii) heat of reaction between
CO2 and amine due to absorption activities. The energy balance equation can be written as:

𝑑𝑇𝐿 𝑑𝑇𝐺 𝑑𝑌𝑤𝑎𝑡𝑒𝑟 𝑑𝑌𝐶𝑂2

𝐿𝐶𝑝,𝐿 (
𝑑𝑧
) = 𝐺𝐼 (∑𝑗 𝑌𝑗 𝐶𝑝,𝑗 ) (
𝑑𝑧
) + 𝐺𝐼 𝜆𝑤𝑎𝑡𝑒𝑟 (
𝑑𝑧
) + 𝐺𝐼 𝐻𝑟𝑥 (
𝑑𝑧
) (48)

where TL and TG are the temperature of amine solution and gas stream, respectively, Cp,L and
Cp,j are the specific heat of the amine solution and gaseous component j, respectively, Yj is the
mole ratio of component j in gas phase, λwater is the heat of vaporization for water, and Hrx is
the heat of reaction between CO2 and amine. Besides the balance equations, the column
sections are also governed by mass-transfer and energy transfer equations. Mass transfer of
CO2 from gas to liquid phases can be written as:

𝑑𝑌𝐶𝑂2 𝑃𝑦𝐶𝑂2,𝑖
𝐺𝐼 ( ) = 𝑘𝐺,𝐶𝑂2 𝑃 𝑎𝑒 (𝑦𝐶𝑂2,𝐺 − 𝑦𝐶𝑂2,𝑖 ) = 𝐸𝑘𝐿𝑜 𝑎𝑒 ( − 𝐶𝐶𝑂2,𝐿 ) (49)
𝑑𝑧 𝐻𝐶𝑂2

where kG,CO2 is the gas-phase mass transfer coefficient for CO2, and ae is the effective mass-
transfer area provided by the column internals. A similar mass transfer equation can also be
written for water vapor in the gas phase.

𝑑𝑌𝑤𝑎𝑡𝑒𝑟
𝐺𝐼 ( 𝑑𝑧
) = 𝑘𝐺,𝑤𝑎𝑡𝑒𝑟 𝑃 𝑎𝑒 (𝑦𝑤𝑎𝑡𝑒𝑟,𝐺 − 𝑦𝑤𝑎𝑡𝑒𝑟,𝑖 ) (50)

The energy transfer rate between gas and liquid phases can be described below.

𝑑𝑇𝐺
𝐺𝐼 (∑𝑗 𝑌𝑗 𝐶𝑝,𝑗 ) ( ) = ℎ𝐺 𝑎𝑒 𝑇𝐺 − 𝑇𝐿 (51)
𝑑𝑧

where hG is the gas-phase heat transfer coefficient. It should be noted that the effective area ae
can be determined using equations developed specifically for certain column internals or
packings.
It is obvious from the above material and energy equations that the column simulation
requires not only the information on properties of amine used for CO2 capture, but also the
operational data and design specifications of the carbon capture process. Henry’s law constant
(HCO2) and vapor-liquid equilibrium data (or CO2 solubility data) are used for establishing the
driving-force in mass-transfer equation for CO2. Diffusivity of CO2 (DCO2) and rate constant
of CO2-amine reaction (k2 or kapp) are used to determine the enhancement factor (E) and
mass-transfer coefficient (koL) in the CO2 mass-transfer equation. Heat of reaction is the key
component in the energy balance equation defining the changes in fluid temperature along the
length of the absorption column (dTL/dz and dTG/dz). The operating conditions such as
operating pressure (P), gas flow rate (GI), liquid flow rate (L), and total amine concentration
(CoAmine) are used in both balance and transfer equations. The concentrations of CO2 in the
feed gas entering the column and in the treated gas leaving the column are design
specifications defining the boundaries or scope of the column simulation.
The simulation of the absorption column is an iterative procedure where the calculations
for individual non-equilibrium stages (based on above equations) are carried out repeatedly
88 Adisorn Aroonwilas and Amornvadee Veawab

until all boundary conditions of the column are satisfied. The following describes one
possible algorithm that starts (for a given iteration) the calculations for the first non-
equilibrium stage located at the bottom of the absorption column where the gas stream is
introduced. For this first stage, the calculations are based on operating conditions of feed gas
(i.e., composition, temperature and flow rate) as well as the assumed conditions of rich amine
solution (i.e., CO2 loading and temperature). The calculation results from the first non-
equilibrium stage serve as the input data for the calculations in the adjacent stage. The stage
calculations are carried out sequentially from the bottom to the top where the treated gas
stream leaves the absorption column. The calculation results from the top stage are then
compared to the design specification which could be either the height of the column or the
concentration of CO2 required in the treated gas. If the required specifications are satisfied,
the simulation calculations are terminated and the complete results are produced. Otherwise,
the sequential calculations will be repeated using new assumed conditions of the rich amine
solution leaving the bottom of the column. The followings are the general calculation steps
carried out for individual stages;

 Calculations of fluid physical properties such as density, viscosity, surface tension,

and specific heat.
 Calculations of effective mass-transfer area (ae).
 Calculations of fundamental data including diffusivity, Henry’s constant, rate
constant, enhancement factor, vapor-liquid equilibrium (or CO2 solubility), and heat
of reaction.
 Calculations of mass-transfer and heat-transfer coefficients.
 Calculations of changes in temperature and composition of gas- and liquid-phases
within the current non-equilibrium stage.
 Calculations of input conditions for the next non-equilibrium stage.

In general, the simulation results from the full-length absorption column are presented as
a gas-phase CO2 concentration profile, CO2 loading profile for the amine solution and
temperature profiles for both gas- and liquid-phases. The profiles are usually plotted against
the axial positions along the column. To validate the simulation accuracy, the profiles are
compared with the experimental results or measured data obtained from the CO2 capture
plants or pilot-plants.
Figure 7 shows examples of simulation results presented as the temperature profiles along
the absorption column. The temperature bulge near the bottom of the column is caused by the
heat transfer between the incoming gas stream with a relatively low temperature and the
warmer amine solution leaving the column after absorbing CO2. The figure also shows the
good agreement between the simulation data and the experimental results. It should be noted
that the experimental results were taken from the published pilot plant data [61] obtained
from the Technical University of Denmark. The pilot plant was equipped with 0.1m-diamter
absorption column packed with Mellapak 250Y structured packing. The packing height of the
column can be varied up to 8.2 m. The tested data were obtained for the CO2 absorption into
30 wt% MEA aqueous solution using the gas stream containing about 9.2-10.5% CO2. Figure
7-a and -b show the temperature profiles when a lean CO2 loading of 0.112 mol/mol was
used, while Figure 7-c shows the profiles for the lean CO2 loading of 0.271 mol/mol.
 Mass Transfer in Amine-Based CO2 Absorption Process 89

(a) (b)

(c)

Figure 7. Simulated temperature profiles of CO2 absorption column using MEA solution.

CONCLUSION
Mass transfer in CO2 absorption processes is a complex mechanism that depends heavily
on a series of fundamental attributes of liquid absorbents and gas-liquid contactors including
chemical reaction kinetics, vapor-liquid equilibrium, heat transfer and hydrodynamics.
Because of their interrelated nature, all of these attributes must be included in any
comprehensive column model to reveal the practicality of absorption system. In other words,
proper use of mass transfer knowledge in the column design serves as a powerful tool to
evaluate if the currently available or the newly developed solvents can practically be used
within the design limit of industrial equipments to achieve a required CO2 capture target.
90 Adisorn Aroonwilas and Amornvadee Veawab

This book chapter describes the application of mass transfer knowledge to the design of
CO2 absorption columns using amine as liquid absorbent, which is considered the most
mature technology for capturing CO2 from low-pressure gas stream. A wealth of data, such as
mass-transfer coefficient, Henry’s law constants, equilibrium solubility of CO2, reaction
kinetics, and physical properties are presently available for the conventional amines,
particularly MEA. With such data, it is apparent that capturing CO2 using aqueous amine
solutions is achievable by using absorption columns with reasonable sizes, and the amine-
based technology has a promise for future industrial use despite its shortcoming including
intensive energy consumption, generation of degradation products, and amine emission due to
volatility. Today, a series of newly developed solvents for CO2 absorption processes are being
studied at research stage. Examples of these are ionic-liquid and ionic-liquid based solvents.
They are known to have merits on being environmentally friendly and consuming less energy
for solvent regeneration, and demerits on low absorption performance compared to amines.
Thus, to compete with amines, mass transfer performance of these solvents must be improved
significantly. However, the mass transfer data for these newly developed solvents are limited.
There is still a vast research opportunity in this area.

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