Journal of CO₂ Utilization 33 (2019) 488–499

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Journal of CO2 Utilization

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

Bubble behaviors and CO2 absorption characteristics in nanoabsorbents T

⁎
Lirong Li, Yong Tae Kang
School of Mechanical Engineering, Korea University, 145 Anam-ro, Seongbuk-gu, Seoul, 02841, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: The objectives of this study are to present a comprehensive analysis of the CO2 bubble population dynamics and
Bubble wake to investigate their effects on the CO2 absorption characteristics in nanoabsorbents (methanol with various
Critical distance concentrations of Al2O3 nanoparticles) with a rectangular bubble column. The population balance model (PBM)
Coalescence and breakup as a well-established method based on the Euler-Euler model is employed to compute the size distribution of
Eulerian-Eulerian method
bubbles and to account for the bubbles coalescence and breakage in multiphase flow. The coupled volume-of-
Mass transfer coefficient
PBM
fluid (VOF) method is selected to clearly capture the coalescence and breakup processes of successively rising
bubbles. The results show that there is a significant influence of the leading bubble on the following one, in-
cluding the increment of the velocity, the deformation of the bubble shape and the flow instability. It is also
found that the critical distance at which the influences can be exerted is related to the bubble wake trailed by the
leading bubble. Accordingly, five types of bubble wakes and their effects on the bubble behaviors such as the
coalescence and breakup are categorized. Finally, by further analyzing the bubble behaviors in methanol with
different volume fraction of Al2O3, it is found that the coalescence and breakup of bubbles are dominated by the
bubble wake and enhanced by the eddy in local liquid. It is concluded that the higher concentration of nano-
particles is favorable to the bubble coalescence and breakup, which enhance the mass transfer performance by
increasing the interfacial area.

1. Introduction characteristics is quite important in multiphase systems.

The global climate change assessment report released by
Intergovernmental Panel on Climate Change (IPCC) clearly points out
that the greenhouse gas (mainly CO2) released by human activities is
the most important reason of the global warming [1]. Among which,
more than half of the CO2 emissions comes from the power industry
that burns a large amount of fossil fuels. Thus the development of CO2
capture technology becomes inevitable and necessary. Using the or-
ganic liquid to absorb the gas is considered to be a popular method with
simple process and high decarbonization efficiency, that is, the multi-
phase absorption system. Bubble columns as the multiphase contactors
are utilized intensively, where the gas is generally dispersed as bubbles
to obtain large interfacial areas available for mass, momentum and
energy transfer processes of the contacting phases. Especially the extent
of bubble-bubble interactions such as the coalescence and breakup of
bubbles in bubble column can significantly alter the interfacial area
between each phase by governing the bubble-size distribution. Such
alteration can profoundly influence the performance of heat and mass
transfer processes at the interfaces [2]. Therefore, the study on the gas
bubble behavior dynamics as well as their effects on the mass transfer
For better understanding of the details of peculiar flow physics as
well as the interactions between bubbles in complex multiphase flow,
the computational investigations have been increasingly employed to
provide practical solutions. The population balance concept was firstly
presented by Hulburt and Katz [3] in 1964 to solve the size variation
due to nucleation, growth and agglomeration processes of solid parti-
cles. A series of the concepts were thereafter developed until the
treatment of population balance equations (PBE) was successfully
generalized in 1985 [4] and its practical solution was fully exposed by
Ramkrishna in 2000 [5]. Over many decades, the population balance
model (PBM) finally became a well-established method to predict the
size distribution of the discrete species with their coalescence and
breakup in multiphase flow systems.
Several models for the bubble coalescence and breakage have been
proposed to reasonably predict the bubble size distribution. Liao and
Lucas [6,7] have given an objective review of these models. We briefly
introduce them here to clear the selection in our research work. The
models proposed by Prince and Blanch [8] considered the bubble
coalescence to be driven by turbulence, buoyancy and laminar shear
with an assumption of isotropic flow at the length scale of the bubble.

⁎
Corresponding author.
E-mail address: ytkang@korea.ac.kr (Y.T. Kang).

https://doi.org/10.1016/j.jcou.2019.07.037
Received 19 April 2019; Received in revised form 6 July 2019; Accepted 30 July 2019
Available online 05 August 2019
2212-9820/ © 2019 Published by Elsevier Ltd.
L. Li and Y.T. Kang
Nomenclature
Fk momentum equation source term, N⋅m−3
FD drag force, N⋅ m−3
CD icient, dimension, dimensionless
Re Reynolds number, dimensioner, dimensionle
EO Eötvös number, dimensioner, dimensionle
FL lift force, N⋅m−3
EO′ modified Eötvös number, dimensionber, dimensionl
db bubble diameter, calculateercalculated by 2 A/4π , m
dh long axis of the deformable bubble, m
FW wall lubrication force, N⋅m−3
CW wall lubrication coefficient, dimensiont, dimensionle
FTD turbulence dispersion force, N⋅ m−3
CTD user-defined constant
BB the “birth” due to breakup of bubbles, m−3⋅s−1
BC the “birth” due to coalescence of bubbles, m−3⋅s−1
DB the “death” due to breakup of bubbles, m−3⋅s-1
DC the “birth” due to coalescence of bubbles, m−3⋅s−1
ṁgl mass transfer rate of CO2 gas into the liquid solvent,
kg⋅s−1
A interfacial area between gas and liquid, m2
Vcell cell volume, m3
They reported that the breakup of bubbles was caused by the collisions
of turbulent eddies with sizes equal to or smaller than the bubble. They
proposed a critical value of 0.2d as a lower limit of the effective tur-
bulent eddies, which means the eddies smaller than 0.2 times of the
bubble size can hardly influence the overall breakup rate. Luo and
Svendsen [9] modeled the bubble coalescence by only considering
turbulence, in which they used the similar method to Prince and Blanch
[8] on the calculation of the bubble collision frequency. They proposed
a new bubble breakage model by giving the breakup rate of mother
bubbles and the daughter bubble sizes distribution simultaneously.
Afterward, Lehr et al. [10] modeled the bubble coalescence with ac-
counting for the turbulence and different rising velocity driven, by
which they gave the calculation formula of the total collision rate. As
for the bubble breakup model, they followed the method of Luo and
Svendsen [9] by adding the capillary constraint with the assumption
that the interfacial force and the inertial force were balanced each
other. Wang et.al [11]. compared these three models in their work to
conclude that Prince’s and Luo’s models did not well predict the bubble
size distribution but Lehr’s model could give reasonable results at
medium-to-high gas velocities. Therefore, we employed the models of
Lehr et al. [10] in the present study.
In the past decade, much research work has been done using the
PBM to predict the bubble population dynamics in gas-liquid systems,
including the bubble size distribution and gas holdup as well as the
coalescence and breakage effects of the gas bubbles. Chen and
Duduković [12] investigated the bubble size distribution in laboratory-
scale bubble columns with different diameters at various superficial gas
velocities. It was found that the bubble size distribution always re-
mained a single modal but became wider and moved toward a larger
bubble as the gas velocity increased. Díaz et al. [13] studied the in-
fluences of physical model selections on the gas holdup and plume
oscillation period when using the PBM. They concluded that the virtual
mass force term had no significant influence on the calculated results at
any of superficial gas velocity considered (0.24–2.30 cm/s) while the
lift force gave a remarkable negative effect at the highest superficial gas
velocity, which provided a basic reference for modeling selection for
the PBM. Ekambara et al. [14] analyzed the flow patterns in a bubble
column using the PBM coupled with the Reynolds stress model (RSM).
It was found that the model predictions with population balance were
good agreement with the experimental data. Acher et al. [15] carried
489
Journal of CO₂ Utilization 33 (2019) 488–499
C∞ CO2 concentration in the absorbent, kmol⋅ m−3
Csat saturation concentration, kmol⋅ m−3
Dl diffusion coefficient, m2⋅s−1
Δx discretization length, m
k mass transfer coefficient, m⋅s−1
l the critical distance, m
lb the maximum bubble dimensions of the deformed bubble,
m
lw the vertical length of the bubble wake, m
Greek letter
a volume fraction
μ viscosity, Pa⋅s
ρ liquid density, kg⋅m−3
Subscripts
l liquid
g gas
b bubble
m mixture
out simulations using the quadrature method of moments in PBM (PBM-
QMOM) to predict the flow field and local bubble size distribution in a
bubble column. They confirmed the capability of the model for the
prediction of gas-liquid multiphase flows by the validation of their si-
mulation results against the experimental and numerical data of Hansen
[16]. Upon that, Guo et al. [17] implemented the simulations using the
PBM in a bubble column with organic liquids under industrial condi-
tions. They quantitatively described the effect of liquid properties on
the bubble size, interphase forces and turbulence parameters with ac-
counting for the bubble breakup and coalescence behaviors. The results
showed that the liquid viscosity and surface tension played a key role in
changing the hydrodynamics of gas-liquid systems. Shi et al. [18]
modeled the influence of bubble shape variations on the bubble
breakage due to the eddy collision in bubble column. By comparing
their modeling results with the experimental data, they confirmed the
prediction capability of the PBM on the bubble breakage events. Also,
they proposed that the breakage behavior of bubbles had a significant
effect on the calculation of mass transfer rate.
In addition to a number of computational fluid dynamics (CFD)
studies, several experimental works were reported on the dynamics of
flow field and bubbles in gas-liquid systems, including the measurement
of bubble rise velocity, local average bubble size and interfacial area
concentration [19,20] as well as the time-averaged properties of gas-
liquid flows in bubble columns [21]. However, due to the complexity of
multiphase flows, many details of peculiar phase physics were un-
revealed by experiments on CO2 bubble behavior in ionic liquid [22]
and air bubble behavior in nanofluids [23]
The present work is focus on the studies of the successively rising
bubble behavior dynamics as well as their effects on the mass transfer
coefficient for CO2 absorption in nanofluids (methanol with various
concentration of Al2O3 nanoparticles). We gave the details of the
bubble-bubble interactions such as the coalescence and breakup pro-
cesses, and predicted the mass transfer enhancement by the coalescence
and breakup of bubbles.
2. Computational models
2.1. The Eulerian multiphase model
The Eulerian-Eulerian approach with the selection of multi-fluid
L. Li and Y.T. Kang Journal of CO₂ Utilization 33 (2019) 488–499

VOF model is employed to simulate the dynamics of both phases in the where EO' is a modified Eötvös number related to the long axis of the
gas-liquid-nanoparticles system. Here, it should be stated that the na- deformable bubble, dh :
noparticles were injected and tracked by the discrete particle model
g (ρl − ρg ) dh2
(DPM). The interchange terms such as drag force are added to the EO′ =
momentum equation to account for the coupling interaction between σ (9)
the dispersed phase (nanoparticle) and the continuous phases (gas and dh = db (1 + 0.163Eo 0.757)1/3 (10)
liquid). The details will be discussed in the following Section 2.4.
The governing equations in the Eulerian modeling framework are f (EO′ ) = 0.00105EO′ 3 − 0.0159EO′ 2 − 0.0204EO′ + 0.474 (11)
implemented by ensemble-averaged mass and momentum transport
equations for each phase, in which the interactions between phases are The wall lubrication force in liquid-gas bubbly flows is defined as a
made by the exchange terms that included in the momentum equations. force acting on the secondary phase (bubbles) that tends to push the
Many research efforts have contributed to the derivation of this model, bubbles away from the walls:
and the representative works were done by Kashiwa et al. [24] and →
FW = CW ρl αg |(→
ul − →
ug )II |2 →
nw (12)
Drew et al. [25]. The mass and momentum balance equations are given
by: → →
where ( ul − ug )II is the phase relative velocity component tangential to
∂ (ρk αk ) the wall surface. → n w is the unit normal pointing away from the wall.
+ ∇∙ (ρk αk →
uk ) = 0 And CW is the wall lubrication coefficient that calculated by the Antal
∂t (1)
et al. model [26]:
∂ (ρk αk →
uk ) →
+ ∇∙ (ρk αk →
uk →
uk ) = −αk ∇p + ∇∙τk + αk ρk g + Fk C C
∂t (2) CW = max ⎛⎜0, w1 + w2 ⎞⎟
⎝ db yw ⎠ (13)
→
where, ρ , α u and τ are the density, volume fraction, velocity vector
k k k k
and viscos stress tensor of the liquid phase (k = l) and gas phase (k = where Cw1 = 0.01 and Cw2 = 0.05 are non-dimensional coefficients, and
→ yw is the distance to the nearest wall.
g), respectively. Fk represents the sum of the interfacial forces for the
As for the turbulence dispersion force, the model of Lopez de
interaction between phases. In this work, the interfacial forces that
Bertodano [29] is selected to approximate the turbulent diffusion of the
include the drag force, lift force, wall lubrication force and turbulent
bubbles due to the liquid eddies. It is formulated b：
dispersion force as well as the force acting on the liquid phase from the
nanoparticles are considered. Each of the force component is described →
FTD = −CTD ρl k∇αl (14)
below.
The drag force caused by the resistance due to a relative velocity of where, k is the turbulent kinetic energy, and ∇αl is the gradient of the
two phases is calculated by: liquid volume fraction, and CTD is a user-modifiable constant. According
to the research work by Ekambara et al. [14], CTD = 0.5 is re-
→ C R
FD = D e commended with good results.
24 (3)

where, 2.2. Turbulence equations

ρl |→
ug − →
ul | db
Re= In this work, the bubble-induced turbulence and the shear turbu-
μl (4) lence are considered. The bubble-induced turbulence is mainly caused
by the vortex shedding from the rising bubbles and thereafter decays
In Eqs. (3) and (4), CD is the drag force coefficient that obtained
quickly due to the viscos dissipation. Given the features of this turbu-
from the model of Tomiyama et al. [26], and db is the equivalent dia-
lence, the standard k ˜ ε turbulence model is selected in the present
meter of the gas bubble. The model is well suited to the gas-liquid flows
simulations. And the Sato turbulence interaction model [30] is im-
in which the bubbles have a variation of shapes like spherical, spherical
plemented to present the turbulent interaction between the bubbles and
cap and oblate ellipsoidal. The drag coefficient is defined as:
the carrier phase. The turbulent kinetic energy k and dissipation rate ε
24 72 ⎞ 8 Eo ⎞ equations are expressed as:
CD = max ⎜⎛min ⎛ (1 + 0.15R e 0.687),
⎜ ⎟, ⎟

⎝ ⎝ Re R e ⎠ 3 Eo + 4 ⎠ (5) μt , m
∂ (ρm k )
+ ∇∙ (ρm →
um k ) = ∇∙ ⎡ ⎛μm + ⎜
⎞ ∇k⎤ + Gk, m − ρ ε
⎟
m
where, Eo is the Eötvös number defined by the ratio of the gravitational ∂t ⎢ σk ⎠ ⎥ (15)
⎣⎝ ⎦
force to the surface tension force, expressed as:
∂ (ρm ε ) μt , m
+ ∇ (ρm →
um ε ) = ∇∙ ⎡ ⎛μm + ⎞ ∇ε⎤ + ε (C1ε Gk, m − C2ε ρ ε )
g (ρl − ρg ) db2 ⎢⎝
⎜ ⎟
m
Eo = ∂t ⎣ σε ⎠ ⎥ ⎦ k
σ (6)
(16)
The lift force acting on the secondary phase bubbles is caused →
where, ρ , μ and u are the mixture density, viscosity and velocity,
m m m
mainly by the velocity gradients in the primary phase flow field. The
respectively. They are computed by:
Tomiyama lift force model [27] is supposed to be applicable to the lift
N
force acting on large-scale deformable bubbles in spherical cap and
ellipsoidal regimes. Frank et al. [28] thereafter in 2004 slightly mod-
ρm = ∑ αi ρi
i=1 (17)
ified the model. The equation of the lift force is given by:
N
→
FL = CL ρl αg (→
ug − →
ul ) × (∇ × →
ul ) (7) μm = ∑ α i μi
i=1 (18)
In this equation, CL is the lift force coefficient that is defined as:
N N
→
′ ′
⎧ min [0.288tanh(0.21R e ), f (EO )] EO ≤ 4
um = ∑ αi ρi →
ui / ∑ αi ρi
⎪ i=1 i=1 (19)
CL = f (EO′ ) 4 < EO′ ≤ 10 →
⎨ where αi , ρi , μi and ui are the volume fraction, density, viscosity and
⎪ −0.27 EO′ > 10 (8)
⎩ velocity of the ith phase, respectively.

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L. Li and Y.T. Kang Journal of CO₂ Utilization 33 (2019) 488–499

The mixture turbulent viscosity, μt , m is formulated as:

k2
μt , m = ρm Cμ + ρm Cμ, BIT αg db |→
ug − →
ul|
ε (20)

and Gk, m is the production of turbulence kinetic energy, which is given

by：

Gk, m = μt , m (∇→
um + (→
um )T ): ∇→
um (21)

Among these equations, Cμ, BIT = 0.6 is the Sato coefficient, and the
standard k ˜ ε model constant used here are Cμ = 0.09, C1ε = 1.44 ,
C2ε = 1.92 , σk = 1.0 , σε = 1.3.

2.3. Population balance model

In bubble columns, the size of the gas bubbles plays a key role in
their dynamic performance, including the bubble rising velocity and the
gas residence time, which in turn governs the gas holdup and interfacial
area as well as the species (mass, momentum, energy) transfer en-
countered through the interfaces. To obtain a thorough understanding
of the evaluation of the bubble size distribution and its involved in-
terfacial species transfer behaviors, the population balance approach
should be employed. It is a well-established method to describe the size
distribution of the dispersed phase in bubbly flow by considering the
effects of breakup and coalescence in a swarm of bubbles. The general
form of the population balance equation is given by:
∂f
+ ∇ (f→
ug ) = BB + BC − DB − DC
∂t (22)

where, → ug is the gas velocity and f is the number density of the size
group. And the “birth” and “death” due to the bubbles breakage (B) and Fig. 1. Simulated bubble column for gas-liquid-nanoparticles flow system.
coalescence (C) are included in the population balance equation, which
are BB , BC , DB and DC , respectively. The four source terms are obtained Table 1
from the models of bubble breakup and coalescence proposed by Lehr The details of each phase.
et al. [10] in this work. Collisions between the bubbles that arise from Al2O3 nanoparticle
their random motions due to the turbulence and different rising velo-
cities are also considered in this model. Diameter 50 nm
The breakup rate of bubbles is calculated as: Density 3890 kg/m3
Shape Sphere
d σ (λ + d )2 2σ Concentration 0.001 vol%, 0.01 vol%, 0.1 vol%
b(d ) = ∫d 0.8413 2 × exp ⎜⎛ ⎞
⎟ dλ Methanol
1 ρ1 ε 2/3d14 λ3/13 ⎝ ρ1 ε 2/3d λ2/3
1 ⎠ (23) Density 792 kg/m3
Viscosity 0.57 mPa s
where d1 is the diameter of the daughter bubble and λ is the size of Surface tension 0.0228 N/m
eddy. Diffusivity 4.75 × 10−9 m2/s
And the total coalescence rate of bubbles is formulated as:
2 N
π ⎡ αg, max 1/3 ⎤
c(d ) = (di + dj )2min (u′, ucrit )exp ⎢−⎛⎜ − 1⎞⎟ ⎥ DB = ∑ b (di ) fi
4 ⎝ αg 1/3 ⎠ (24) i=1 (28)
⎣ ⎦
N
u' = max ( 2 ε1/3 di2/3 + dj2/3 ), |ui − uj| (25) DC = ∑ c (d) fi f j
j=1 (29)
where ucrit = 0.08 is a model parameter and αg, max is the maximum
possible gas fraction, which is set to 0.6.
Therefore, the birth rates of bubbles in group i due to the breakage 2.4. Interaction forces between nanoparticles and continuous phases
of larger bubbles and coalescence of other two groups k and l can be
expressed as Eqs. (26) and (27) : The nanoparticles injected by the DPM are treated as Langrangian
N
discrete phases and their motions in the flow field are governed by the
BB = ∑ b (dj : di ) f j Newton’s second law. Thus, the governing equation for a single particle
j=i+1 (26) without collision can be written as:
dvp →+→ →
1
N N
mp = mp→
g + Vp ρg Ffp + Fbp
BC = ∑ ∑ c (d)i,kl fi f j dt (30)
2 k=1 l=1 (27)
where x p and Vp represent the position and volume of the nanoparticles,
The death rates of bubble in group i due to breakage of larger respectively. The four terms in the right-hand side of Eq. (30) stand for
bubble to smaller one and the coalescence with other bubbles are given the gravity force, buoyancy force, liquid interaction force and gas-
by: bubble interaction force, respectively. It should be noticed that the

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L. Li and Y.T. Kang Journal of CO₂ Utilization 33 (2019) 488–499

Fig. 2. The motion of the successive CO2 bubbles in methanol with Al2O3.

particle rotational acceleration or deceleration is neglected during the → → →

motion since the particle size (50 nm) is much smaller than the grid
size.
The force acting on a particle from the bubble is determined by
considering the surface tension force. When the particles move around
the gas-liquid interface, they will contact the surface tension from the
liquid film. Once the particle overcome this force, it would penetrate
the bubble surface. Thus, the force acting on the particles from the gas
bubble is expressed as:
→
Fbp = VP σk (→
x , t ) ∇F (→
x , t) (31)
The force acting on a particle from the liquid is defined as the dif-
ference of the drag force and the additional force:
Ffp = FD − FAM (32)
More details of the nanoparticles injection and the definitions of the
forces can be found in our research effort [31]. The particle-liquid in-
teractions and the particle-bubble interactions are achieved by the two-
way coupling method in the DPM.
2.5. Mass transfer equations
As the aforementioned dynamics of bubble population in bubble
column, the variation of the gas bubbles due to the coalescence and
breakup dominates the bubble rising velocity and the gas residence
time, which in turn determines the interfacial area and subsequently
the mass transfer characteristics between the phases. Therefore, the
mass transfer source between species gas and liquid is considered in this

492
L. Li and Y.T. Kang
Fig. 3. The presentation of the path fluctuation of the bubbles.
work by adding a source term (S= m˙ gl ) in the right-hand side of the
mass conservation equation (Eq. (1)):
∂ (ρk αk )
+ ∇ (ρk αk →
uk ) = S
∂t
The source term (S) is implemented by compiling the user-defined
function (UDF) code, which is given by:
m˙ gl = −∇CDl A
where,
A= (∂αg / ∂x )2 + (∂αg / ∂y )2 + (∂αg / ∂z )2 Vcell
∇ C= (Csat − C∞)/Δx
In the above equations, A is the interfacial area calculated for each
cell by multiplying the mesh cell volume and the magnitude of the void
fraction gradient. ∇C is the concentration gradient, and Δx is the dis-
cretization length. Dl is the CO2 diffusion coefficient that has been
measured by our published works [32,33]. Then the mass transfer
coefficient defined as the diffusion rate can be calculated by:
m˙ gl
k=
A(Csat − C∞ )
3. Boundary conditions and simulation methods
The simulations are performed in a rectangular bubble column
using the commercial software ANSYS 19.0. Fig. 1 shows the simulated
bubble column with 200 mm width ×200 mm height ×5 mm depth.
The squared gas inlet channel with 3.5 mm width ×3 mm height
×5 mm depth is concentric with the bubble column and modeled as a
mass-flow-rate inlet. The CO2 bubbles enter the bubble column con-
tinuously with a diameter of 4.6 mm as in the experiments [34]. No-slip
boundary conditions are used at all the column walls and the degassing-
outlet boundary condition is chosen. The computational domain is
meshed by uniformed cubes with three levels of refinement, the details
of which can be found in the literature [34]. Since the VOF method is
quite sensitive to the mesh size, we investigated the effects of mesh size
on the bubble diameter and mass transfer in our previous work [34]. By
comparing the results with mesh size ranged from 0.5 mm to 0.125 mm
at the bubble rising area, it was found that the bubble diameter and the
mass transfer coefficient tend to keep stable once the mesh scale less
than 0.25 mm. Thus, the grid size of 0.125 mm is employed in present
simulations. The related details of the grid-independent check will not
be given in this paper again.
All simulations start from a static initial condition where the column
Journal of CO₂ Utilization 33 (2019) 488–499
is filled with only methanol liquid or methanol liquid with suspended
Al2O3 nanoparticles. The details of each phase are listed in Table 1. The
time step size is set to 0.0001 s, which can keep the convergence of the
simulations based on the Courant-Friedrichs- Lewy (CFL) criterion [35].
A pressure-based time-dependent solver is used to solve the governing
equations for the balance of mass and momentum of each phase. The
pressure-velocity coupling is handled by the SIMPLE procedure. The
second-order schemes are implemented to discretize the turbulence
related equations and CO2 mass fraction equations. Finally, the post-
processing of the simulation data is dealt with CFD-Post 19.0.
4. Results and discussion
4.1. The behaviors of the following bubble related to the leading bubble
It is observed that when the adjacent two bubbles approach closely
enough, the behaviors of the following bubble appear to be changed,
which is the influences exerted by the leading bubble. By tracking the
motion of the successively rising CO2 gas bubbles in methanol with
Al2O3 nanoparticles, it is found that the changes can be classified into
three categories; that are, the increment of the bubble rising velocity,
the deformation of the bubble shape and the flow instability of the
bubble motion.
Fig. 2 shows the motions and velocities of three successively rising
(33)
bubbles. It shows that the following bubble can be significantly ac-
celerated at a certain distance away from the leading bubble. The ac-
celerated bubble may be collided with the leading bubble and there-
(34) after slow down to a stable terminal velocity. As we can see, if the
leading bubble and the following one are in a vertical line before they
coalesce (coalescence Ⅰ in Fig. 2(a)), the former firstly loses its topology
and attains a cap shape to be available for the latter to getting into its
(35) back. Meanwhile, the latter is deformed to be a bullet shape and rush to
(36) the former until they collide and coalesce. However, if the two bubbles
are not aligned vertically (coalescence Ⅱ in Fig. 2(a)), the following
bubble has no noticeable deformation before they coalescence. It is
supposed to be determined by the directions of the wake formed by the
leading bubble, which will be discussed in the next section.
In addition, the observed path of the third bubble shows strong
instability after the breakup of the leading bubble. The flow path of the
third bubble drifts to the left from the central axis at t = 0.45 s and
eventually coalesce with the leading daughter bubble at t = 0.48 s. It
means the motion of the leading daughter bubbles exerts an effect on
(37)
the path of the following bubble. To further confirm that, we track
another two bubbles that follow the daughter bubbles and their hor-
izontal positions over time are shown in Fig. 3. The results show that
the leading daughter bubble with a relative larger volume has a no-
ticeable influence on the flow path of the following bubble. Generally,
the leading parent bubble breaks into two daughter bubbles with dif-
ferent volumes. These daughter bubbles move toward the opposite di-
rection initially due to the inertial force. And the following bubble often
follows the daughter bubble with a larger volume, which is due to the
vortex shedding from the leading bubble. As the bubbles rise in a spiral
or zigzag path in the liquid, various bubble wakes with vortexes related
to the bubble sizes and shapes are generated. The following bubble can
be entrained when it comes into the wake and then follows the path of
the leading bubble.
4.2. The wakes of the successively rising bubbles
According to the above discussion in the Section 4.1, the influence
of the leading bubble on the following one necessarily leads to the
bubble-bubble interactions for the successively rising bubbles in liquid.
The local flow structures as well as the species transport across the
interface are supposed to be changed by the interaction between bub-
bles, especially due to their coalescence and breakup. Therefore, it is
necessary and significant to understand the interaction dynamics and
493
L. Li and Y.T. Kang
Fig. 4. The presentation of bubble wakes formed by the leading bubbles and their position relationship with the following bubbles in different conditions.
trigger mechanisms in multiphase flow. In this work, we investigate the
behaviors of the successively rising CO2 bubbles in methanol with dif-
ferent volume fraction of Al2O3 nanoparticles to confirm the fact that
the wake with vortex formed by the leading bubble has a dominant
effect on the occurrence of coalescence and breakup.
As a common physics, a trailed wake can be found when a bubble
rises through the liquid. Early in 1974, Narayanan et al. [36] experi-
mentally tested the wakes of air bubbles rising in water with glycerin
under different Reynolds numbers. Several patterns of wakes formed by
the bubble with different shapes are captured in their experiments,
including thin trailing wake, thin trailing wake with a cusp, wake with
stable vortex and turbulent wake, in which the wake with stable vortex
was considered to be an important factor in the acceleration of the
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Journal of CO₂ Utilization 33 (2019) 488–499
following bubble. However, due to the preset low Re (< 300) in their
experimental model, only the wake with toroidal vortex were visua-
lized. In the present work, we capture the wakes with various vortex
during the successively bubbles rising in quiescent liquid and give de-
tailed discussions about them.
Fig. 4 schematically presents the observations of five typical bubble
wakes and their position relationships with the following bubbles in
different conditions. The first two types of wakes are mainly formed by
the parent bubbles, and the last three ones are often found in the back
of daughter bubbles. Here, the term “parent bubble” is used to describe
that a kind of bubbles directly formed by the releasing gas, to distin-
guish it from “daughter bubble” that is birthed by the coalescence or
breakup process. It can be easily seen that the bubble wakes formed in
L. Li and Y.T. Kang
Fig. 5. The presentation of the relation between the bubble wake region and the longest axis of the bubble.
Fig. 6. The linear relations of the critical distance with the equivalent diameter
of the bubble.
all types are of various forms and directions.
The wake with good symmetry presented in type Ⅰ is often formed
by the bubble with a shape of oblate spherical cap, which is more likely
to entrain the following bubble. Once the following bubble comes into
the wake region, it will obtain a 30% additional upward velocity from
the leading bubble and another 15% upward velocity from the local
liquid [36]. That is the reason why the following bubble can be ac-
celerated when it moves closely enough to the leading bubble. This kind
of wake plays a significant role in leading to the coalescence of such two
bubbles.
The wake with two axisymmetric toroidal vortexes shown in type Ⅱ
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Journal of CO₂ Utilization 33 (2019) 488–499
mainly appears in the back of stretched bubble with a bone shape. A
stretched bubble is formed with two bulbous ends, each sides trails a
toroidal vortex. The following bubble that aligned vertically with the
stretched bubble can hardly get into each of the toroidal vortex of it. As
a result, when the following bubble approaches this kind of bubble, its
deduced upward flow will accelerate the breakup of the bubble rather
than the speed up to collide with it. Most of the symmetrical breakup
process is related to this kind of bubble wake.
The wakes trailed by bubble di1 and di2 shown in type Ⅲ are always
found in the back of daughter bubbles that birthed by the near-sym-
metrical breakup process of a parent bubble. Due to the different size
and shapes of the two daughter bubbles, variant vortex can be formed.
When the following bubble dj moves closely to these vortexes, a relative
larger vortex is more likely to entrain it. In this way, the flow path of
the following bubble will be changed as aforementioned in Fig. 3.
The wakes of the bubble dk and dj shown in type Ⅳ is a result of the
wakes combination. For two bubbles which are not in a vertical line, if
their wakes intersect in a certain direction, they are expected to com-
bine together as shown with the bold line. In this case, the following
bubble can be entrained even if it does not come into the wake region of
the leading bubble. This merged vortex is more favorable to bubble
coalescence.
Type Ⅴ is a special case existing in nanofluids. The bold lines stand
for the eddies in local liquid caused by the motion of nanoparticles. If
the size of the eddy lager than the bubble wake, it will encompass the
wake and dominate the bubble behaviors. Not only the occurrence of
bubble coalescence can be increased, but also the coalescence time can
be significantly shorten in such case. However, it is difficult to quantify
this case due to its randomness.
According to the above discussions, the size of the wake region
determines the critical distance at which the wake begin to influence on
the following bubble. By the quantitative analysis, it is found that the
L. Li and Y.T. Kang
Fig. 7. The results of observation for bubble coalescence processes.
Fig. 8. The bubble coalescence frequency in methanol with different volume
fraction of Al2O3 nanoparticles.
length of the wake region l w is almost equal to the longest axis of the
leading bubble lb , and the direction of the wake is coincide with the
bubble long axis for all cases, as shown in Fig. 5. Therefore, the length
of the longest axis of the leading bubble, lb can be defined as the critical
distance. It means as long as the vertical distance away from the leading
bubble less than the critical distance, the following bubble will be en-
trained (type I and Ⅲ) or inversely accelerate the breakup of the
leading bubble (type Ⅱ). For the special case in type Ⅳ, an analogy of
two tangent circles can be used, in which the two vortexes are likened
496
Journal of CO₂ Utilization 33 (2019) 488–499
to circles and the critical distance is the sum of their radius. In order to
intuitively describe the critical distance, we plotted the relations be-
tween the length of the longest axis and the equivalent diameter of
bubbles in Fig. 6. It is clearly found that the length of the bubble longest
axis lb is proportional to the equivalent bubble diameter db for the
bubbles in similar shape, and the linear relations are given in the Table
in Fig. 6.
4.3. The coalescence and breakup in a swarm of bubbles
The interaction between bubbles lead to the coalescence or breakup,
in which not only the bubble wake plays a dominate role, but also the
eddies in local liquid enhance their occurrence. To understand the
coalescence and breakup processes in nanofluids, a series of simulations
are performed in methanol with Al2O3 nanoparticles of various volume
fractions (concentrations).
Fig. 7 shows the results for the observation of CO2 bubble coales-
cence in liquid with different nanoparticle volume fractions. It can be
easily seen that more forms of bubble coalescence appear in the pre-
sence of nanoparticles. Without the nanoparticles, the coalescence of
two bubbles mainly caused by the wake entrainment, especially for the
larger bubble entrains the small one. Also, the following bubble often
undergoes significant deformation as it approaches the leading one, as a
consequence, the two bubbles to be coalesced show different shapes.
However, the coalescence of two bubbles with same shape can be found
in nanofluids due to the eddies involved. As aforementioned before, the
larger eddy can encompass the wake and dominate the bubble beha-
vior. If two bubbles are sucked into the same eddy, they will be brought
together very quickly and get into coalescence before they are de-
formed. With increasing the nanoparticle concentration, the size of the
L. Li and Y.T. Kang
Fig. 9. The results of observations for bubble breakup processes.
Fig. 10. The bubble breakup frequency in methanol with different volume
fractions of Al2O3 nanoparticles.
eddy formed in local liquid becomes larger and larger [31], leading to
more coalescence caused by the eddy entrainment. It can be clearly
seen from the coalescence frequency shown in Fig. 8. The higher con-
centration of nanoparticles is not only favorable to the bubble coales-
cence, but also enhance its occurrence. It is also found that the coa-
lescence frequency near the gas inlet is considerably increased with
increasing the concentration of nanoparticles.
Fig. 9 shows the results for the observation of bubble breakup
processes in methanol with variable concentrations of nanoparticles.
Without the nanoparticles, the breakup process is mainly caused by the
bubble stretch. The bubble stretches and forms two bulbous ends that
497
Journal of CO₂ Utilization 33 (2019) 488–499
Fig. 11. The average mass transfer coefficient in methanol with different vo-
lume fraction of nanoparticles.
are connected with a ligament in the middle. The ligament is con-
tinuously stretched due to the momentum until the two bulbous ends
are pinched off, resulting in the breakup of bubble. This kind of breakup
is always symmetrical or near symmetrical, unlike that caused by the
eddy collision. In the cases of nanofluids, except for the breakup caused
by bubble stretching, the turbulence eddy of which size equal to or
smaller than the bubble size collide the bubble, leading to asymmetrical
breakup or satellite breakup. Therefore, the breakup frequency in na-
nofluids is always higher than that in pure methanol as shown in
Fig. 10. Since the collision of the eddy whose size larger than the bubble
L. Li and Y.T. Kang
Fig. 12. The mass transfer coefficient of a single bubble during the whole rising
process in pure methanol.
cannot cause the breakup, the bubble breakup frequency in nanofluids
shows a noticeable decrease at the position far away from the gas inlet
where the bubble size is relatively smaller. Especially for methanol with
0.1 vol% Al2O3, the reduction rate of breakup frequency is significantly
larger (similar to the frequency of pure methanol) due to its larger size
of eddy formed in local liquid [31].
4.4. Mass transfer enhancement by the coalescence/breakup of bubbles
The coalescence and breakup can generate the polydisperse bubble
swarms, in which the variation interfacial areas of bubbles will de-
termine the mass transfer between phases. But little is known about
whether the coalescence and breakup processes effect the mass transfer
or not. In the present study, the mass transfer enhancement by the
coalescence/breakup of CO2 bubbles is considered. Fig. 11 shows the
relationship between the average mass transfer coefficient and the
column height for CO2 absorption in methanol with different con-
centrations of Al2O3 nanoparticles. Somewhat decrease and thereafter
increase trends of the mass transfer coefficient are found in all of the
presented cases at the column height between 40 mm and 80 mm. To
compare with the bubble coalescence frequency and breakup frequency
shown in Figs. 8 and 10, it is easy to find that this position range is a
focus area for the occurrence of coalescence and breakup. It means that
the coalescence and breakup of bubbles more or less dominate the mass
transfer across the interface. In order to further understand this trend,
we select the base case of which bubbles rise in pure methanol. Fig. 12
shows the mass transfer coefficient of an individual bubble in pure
methanol during its whole rising process with coalescence and breakup.
It is found that the mass transfer coefficient for a rising bubble sharply
decreases at the moment of breakup or coalescence, and then sig-
nificantly increase until the daughter bubble reaches a stable state.
During the coalesced process, at the time when a bridge is formed be-
tween two bubbles, gas inside each bubble preferentially move towards
the opposite bubble due to the momentum, leading to a decrease of the
momentum transport as well as mass transfer across the interface. With
the ligament being continuously stretched, the total interfacial area is
expanded, resulting in a new increase of the mass transfer coefficient.
While similar explanation can be applied for the breakup process, the
difference is that the momentum of the gas phase supplies the surface
energy requirement for breakup event at the time when the bubbles
breakup [9,37], resulting a temporary decrease of the mass transfer
across the interface. But by comparing with the bubble on equal con-
ditions, it is found that the total average mass transfer coefficient for
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Journal of CO₂ Utilization 33 (2019) 488–499
the bubbles experiencing coalescence and breakup is greater than that
without experiencing the coalescence or breakup. It is therefore con-
cluded that the coalescence and breakup processes enhance the mass
transfer performance between phases during the CO2 absorption pro-
cess. The average mass transfer coefficient of 4.08 × 10−4 m/s (black
dash in Fig. 12) is in good agreement with the experimental value of
4.46 × 10−4 m/s (black solid line in Fig. 12) measured in the literature
[32].
5. Conclusions
The behaviors of successively rising CO2 gas bubbles in methanol
with Al2O3 nanoparticles as well as their effects on the mass transfer
coefficient are studied in this work. The PBM based on Euler-Euler
model is employed to account for the effects of bubbles coalescence and
breakup on the mass transfer, and the coupled VOF method is used to
capture the behaviors in multiphase flow. From the results, the fol-
lowing conclusions are drawn:
1 The behaviors of the following bubble is significantly influenced by
the leading bubble. When the following bubble moves close to the
leading one, the flow characteristics will be changed, including the
increment of velocity, the deformation of the bubble shape and the
instability of the flow path.
2 The wake with vortex formed by the leading bubble has a dominant
effect on the occurrence of coalescence and breakup. And the eddy
in the local liquid can enhance the coalescence and breakup pro-
cesses. The critical distance at which the wake begin to influence on
the following bubble is equal to the length of the bubble longest
axis. The linear relations between the length of bubble longest axis
and the diameter of bubble in various shape are presented in this
work.
3 By analyzing the frequency of bubble coalescence and breakup in
nanofluids, it is found that a higher concentration of nanoparticles is
favorable to the bubble coalescence and breakup. The frequency of
coalescence and breakup both considerably increased with in-
creasing the concentration of nanoparticles.
4 It is concluded that the coalescence and breakup processes enhance
the mass transfer performance between each phase by increasing the
interfacial area.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgement
This work was supported by the National Research Foundation of
Korea (NRF) grant funded by the Korea government (MSIP) (No. NRF-
2019R1A2B5B03069991).
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