Journal of CO₂ Utilization 20 (2017) 318–327

Contents lists available at ScienceDirect

Journal of CO2 Utilization

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

Process intensification and environmental consideration of sodium MARK

bicarbonate production in an industrial soda ash bubble column reactor by
CO2 recycling
D. Ghanbari Maharlooa, Ali Darvishia, Razieh Davanda, Majid Saidib,
⁎
Mohammad Reza Rahimpoura,
a
Department of Chemical Engineering, Shiraz University, Shiraz 71345, Iran
b
Faculty of Engineering, Shahrekord University, Shahrekord, Iran

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

Keywords: In the present study, a mathematical model is developed for a new configuration of sodium bicarbonate pro-
Bubble column reactor duction in an industrial bubble column reactor. In the conventional configuration, the CO2outlet stream from the
Sodium bicarbonate reactor is vented to the atmosphere while in the new configuration, a portion of the outlet CO2 stream is recycled
Mass transfer and mixed with the inlet CO2flow of the reactor in order to reduce the greenhouse gas emission and also achieve
CO2 emission
a high purity level of the desired product. A gas sparger is installed at the bottom of the bubble column to
CO2 recycling
provide a uniform gas flow distribution. A three−phase mass balance equation is considered. Liquid thermal
behavior, gas pressure profile, CO2 conversion and mole fractions in the gas phase which mainly affect the
production and size distribution of sodium bicarbonate crystals, are investigated. The results of the proposed
model are compared with the conventional bubble column reactor (without recycle stream). The results show
314 mol/m2.s CO2 saving and 50% increase in solid production as well as significantly reduction of air pollutants
are also achieved with the new configuration. The optimized operating temperature for sodium bicarbonate
production which was determined theoretically is reported to be 323 K.

1. Introduction CO2 + M2 CO3 + H2 O → 2MHCO3 (R−1)

Sodium bicarbonate as an environmentally friendly product has
numerous applications such as surface cleaning, neutralizer of acids in
exhaust flue gas of several industries, food additive, animal feeds, paper
sizing, plastic foams, soft water treatment, smoke scrubbing and fire
extinguisher powders [1]. Commonly, bubble column reactors are used
to produce sodium bicarbonate with high purity. A bubble column re-
actor is a cylindrical vessel with a gas sparger at the bottom of it which
distributes the gas bubbles into either a liquid phase or a liquid–solid
suspension [2]. The most important advantages of bubble columns are
appropriate heat and mass transfer, low operating and maintenance
cost, moderate operating condition, high catalyst durability, and no
moving parts leading to lower wearing and tearing [3,4]. The liquid
feed is introduced at the top of the bubble column and contacts coun-
ter−currently with the gas stream containing CO2 which distribute at
the bottom of column by gas sparger. The pure CO2 is transferred from
the gas bubbles to the brine liquid solution and the following reaction
will take place in the liquid phase:
To produce sodium bicarbonate crystal (NaHCO3), firstly, a super−-
saturated solution of NaHCO3 will be generated via above reaction and
consequently contact nucleation process will be occurred. Finally,
under adjusted operating condition, the solid NaHCO3 will be con-
tinuously precipitated [5]. Since there is no concentration gradient in
the gas phase, all mass transfer resistance is located in the liquid phase.
As a result, the chemical equilibrium is reached at the liquid−gas in-
terface. In this process, the molecular diffusion is the dominant mass
transfer mechanism [6].
Gas holdup is one of the hydrodynamic parameters in slurry bubble
column reactor which influences the gas−liquid contact area, mass
transfer rate and overall reaction rate. It is defined as the volume
fraction of gas phase occupied by the gas bubbles. It is well documented
that the gas holdup enhances with increasing the mass flow rates of gas
stream and operating pressure, whereas it reduces with increasing li-
quid viscosity and solid concentration [7–11]. Another important factor
which affects the gas holdup and many other parameters characterizing
bubble columns is gas sparger type. The most common gas sparger

⁎
Corresponding author.
E-mail address: rahimpor@shirazu.ac.ir (M.R. Rahimpour).

http://dx.doi.org/10.1016/j.jcou.2017.06.005
Received 25 October 2016; Received in revised form 13 May 2017; Accepted 7 June 2017
2212-9820/ © 2017 Elsevier Ltd. All rights reserved.
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Nomenclature Q Liquid flow rate (m3/s)

R Gases constant (J/g mol K)
Asparger Inlet cross sectional area of sparger (m2) S Molar velocity of solid (mol/m2s)
B Growth order (g) T Liquid temperature (K)
CCO2e Carbon dioxide concentration in liquid bulk (mol/m3) T Time (s)
CCO2i Carbon dioxide concentration in gas–liquid interface Ug Gas phase velocity (m/s)
(mol/m3) Ul Liquid phase velocity (m/s)
dB Average of bubbles diameter (m) V Volume of element (m3)
DCO2 Carbon dioxide molecular diffusion coefficient(m2/s) W Weight fraction of component in liquid phase
Dg Gas phase radial dispersion coefficient (m2/s) Δw Super saturation (g NaHCO3/kg solution)
Dl Liquid phase radial dispersion coefficient (m2/s) X Mole fraction of components in liquid phase
dR Column diameter (m) x*NaHCO3 Mole fraction of sodium bicarbonate at super saturation
E Enhancement factor Y Mole fraction of components in gas phase
G Gravity (m/s2) Z Height of column (m)
G Molar velocity of gas (mol/m2s)
G0 Growth rate (μm/s) Greek symbols
GFR Gas flow rate (m3/s)
H Column height (m) αg Gas–liquid interface (m2/m3)
H Henry constant (Kmol/atm.m3) αs Solid–liquid interface (m2/m3)
I Ionic content of solution (kg ion/m3) αsparger Porosity of the sparger
I0 Height of column that sodium bicarbonate reaches to sa- Δ Liquid surface tension (N/m)
turation concentration (m) εg Gas holdup
K Constant rate of first order reaction (1/s) εl Liquid holdup
Kl Liquid phase mass transfer coefficient (m/s) μl Liquid dynamic viscosity (N s/m2)
L Molar velocity of liquid (mol/m2s) ρH2O Water density (kg/m3)
LFR Liquid mass flow rate (kg/s) ρl Liquid density (kg/m3)
MT Magma density (g crystal/kg solution) νl Liquid kinematic viscosity (m2/s)
N Flux of mass transfer (mol/m2s)
nDis Flux of mass transfer by dispersion (mol/m2s) Subscripts
P0 Gas pressure at bottom of column (atm)
PCO2 Carbon dioxide partial pressure at gas phase (atm) I At inlet point position of element
PCO2e Carbon dioxide partial pressure at liquid bulk (atm) I0 At I0 point position
PCO2i Carbon dioxide partial pressure at gas–liquid interface In At inlet point position of column
(atm) O At outlet point position of element

types are perforated plate, porous plate, membrane, ring type dis- examined in a domestic petrochemical plant, a portion of outlet CO2
tributors and arm spargers [12]. Among these different types, appli- stream is recycled to the inlet CO2stream. This new configuration re-
cation of perforated plate distributor provides higher mass transfer sults CO2 saving, reducing air pollution and increasing production rate.
coefficient. The new configuration has been compared with a conventional bubble
Bubble column reactors are used extensively in the literatures. column reactor. For more investigation, a mathematical model based on
Rahimpour et al. [3] used a commercial size slurry bubble column re- three−phase mass balance is developed. Danckwerts theory is used to
actor for catalytic conversion of synthesis gas to methanol. In another predict the CO2 diffusion from the gas stream into the liquid phase and
work, Rahimpour et al. [4] proposed a novel configuration of a cascade CO2 absorption via mass transfer and chemical reaction are considered.
double membrane assisted slurry bubble column reactor for Fischer- Also, the effect of operating parameters such as temperature, pressure,
e−Tropsch process. Development of bubble column scale up criteria and mole fraction of CO2 in the gas phase are considered.
has been attempted by a number of researchers [13–15]. In a related
work, Mc.Clure et al. [16] developed a Computational Fluid Dynamics
2. Process description
(CFD) model of mixing in bubble column reactors. Also, Kuzmin and
Turek [17] developed a dynamic Euler−Euler model for gas−liquid
Providing CO2 is an important factor affecting the production cost
flows to investigate the mass transfer phenomena in the bubble column
and yield of soda production. An effective method to reduce the CO2
reactors. Haut et al. [18] represented a mathematical model for a
emission to the atmosphere and supply a portion of process feed is
specific bubble column for industrial production of sodium bicarbonate.
application of a recycle stream. In this technique, the off−gas flow
In an experimental study, Chen et al. [19] used a bubble column in
leaving the reactor returns to the main feed gas stream entering the
order to eliminate CO2purge gas under constant pH. Zhu et al. [20]
reactor which in turn causes to increase the soda production yield and
developed a super−saturation determination method to relate the
decrease the product cost. Fig. 1−a shows a schematic diagram of
density variation of the solution to the super−saturation of NaHCO3.
conventional reactor (Case I) in a domestic
Also, they studied kinetics of sodium bicarbonate crystallization in a
petrochemical plant. Also, the operating conditions are summarized
continuous stirred tank crystallizer.
in Table 1. As represented in this figure, the outlet CO2 from the reactor
The focus of this study is developing a novel configuration for an
is vented to the atmosphere. A novel schematic of bicarbonate pro-
industrial bubble column reactor located in a domestic petrochemical
duction reactor with CO2 recycle (Case II) is represented in Fig. 1−b.
plant to produce high purity sodium bicarbonate crystal with en-
The liquid solution containing water, sodium carbonate and sodium
vironmental consideration. In the conventional configuration which is
bicarbonate is injected to the reactor by means of a centrifugal pump.
used commonly in the industrial units, outlet CO2 stream vented to the
The liquid solution enters the column from the top of reactor. The gas
atmosphere. In the new proposed configuration which is applied and
mixture of CO2 and air is continuously entered to the compressor. In the

319
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Fig. 1. (a) Schematic diagram of conventional reactor (case

I), (b) Schematic diagram of new configuration with CO2
recycling (case II).

compressor, the stream is mixed with the gas stream recycling with Na2 CO3 ↔ 2Na+ + CO3− (R−4)
99% CO2 content. As a result, the concentration of the inlet stream to
the reactor with the new configuration is the same as the inlet stream to CO32 − + H2 O ↔ HCO3− + OH− (R−5)
the conventional reactor. With the purpose of having a uniform gas flow
distribution, a sparger is installed at the bottom of the bubble column.
Also, the absorption heat of CO2 is controlled using a water jacket Na+ + HCO3− ↔ NaHCO3 (R−6)
around the column such that the temperature of the operation is as-
In the process, when the concentration of produced sodium bicarbonate
sumed to be constant.
reaches to its solubility limit in the solution, (R−6) takes place and
During the sodium bicarbonate production process, the following
crystallization process begins [17]. The solubility of NaHCO3 in the
equilibrium reactions take place.
presence of Na2CO3 is expressed as [17]:
CO2(g ) ↔ CO2(aq) (R−2)
843.0681
log(x *) = 6.71535 − − 2.24336* log(T )
CO2(aq) + OH− ↔ HCO3− (R−3) T (1)

320
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Table 1 εL. DL d 2 (x i ) d (x i )
. L. + L. = β . NCO2. αg , i = Na2CO3 , NaHCO3 , H 2O
Operating condition. UL dz 2 dz
Parameters Value (7)
Where β = 1 for Na2CO3 and H2O and β = −2 for NaHCO3. Due to
Liquid temperature (K) 323
Gas pressure(atm) 2.5
presence of super–saturated liquid in the second zone, the amount of
Gas flow rate(Nm3/h) 200 precipitated sodium bicarbonate is equal to the amount of produced
Gas temperature (K) 298 sodium bicarbonate during the chemical reactions in each element. So
Column diameter (m) 1.2 the mole balance equation in the second zone is expressed as:
Column height (m) 22
Liquid composition (mole%) Na2CO3 2.72 dl
NaHCO3 2.99
= NNaHCO3. αs
dz (8)
H2O 94.28
Gas composition (mole%) CO2 56.08 For other components in the second zone, the mole balance equation is
Air 43.92 expressed as:
εL. DL d 2 (.x i L) d (x i L)
. + = β . NCO2. αg , i = Na2CO3 , NaHCO3 , H 2O
3. Model development UL dz 2 dz
(9)
A one−dimensional differential control volume is considered along
Where β = 1 for Na2CO3 and H2O, β = −2 for NaHCO3. In the above
the length of reactor as shown in Fig. 2 to develop governing mass
equation, x, εL, UL and DL are mole fraction, liquid hold up, liquid ve-
transfer equations. The column is divided into two zones. As re-
locity and liquid phase radial dispersion coefficient (m2/s), respec-
presented in Fig. 1−a, the first zone is started from top to a point at
tively.
which sodium bicarbonate reaches to saturation state (point I0), and the
It should be noted that the details of mole balance equations are
second zone is started from saturation point to the bottom of column.
given in Supporting information.
Additionally, due to rotational flow in the gas and liquid phases, a ra-
The liquid velocity can be calculated by:
dial dispersion model is used for the bubble column. The following
assumptions are considered during the model development: 4LFR
UL =
✓ Steady state condition π dR2 εL ρL (10)
✓ Isothermal condition due to the presence of cooling jacket.
✓ Equilibrium condition at the gas–liquid interface At the top of column, there is no solid production, so the solid phase
✓ Validation of Henry's law mole variation is zero. The produced sodium bicarbonate in the second
✓ Negligible end effects zone enters to the solid phase. Therefore, at the bottom zone of the
The governing equation of mole balance in the gas phase of bubble column, the corresponding variation is expressed as:
column can be written as Eq. (2): ds
= −2NCO2. αg
dz (11)
dG
= −Nco2. αg
dz (2) It is assumed that the crystals have the same velocity as the liquid ve-
locity. The boundary conditions used for the bubble column are as:
Where αg is gas–liquid interface. By considering spherical bubbles, the
specific gas–liquid interfacial area can be expressed based on the gas at z = 0:
d (xi)
= 0, yCO2 = yCO2 in
dz (12)
holdup (εg) and the mean bubble diameter (db):
6εg at z = I0 : x i = x i I0 , S = 0 (13)
αg =
db (3)
d
at z = h: x i = x iin , dz
(GyCO2 ) = 0 L = Lin (14)
The mole balance equation for CO2 can be determined as Eq. (4):
The initial CO2 velocity (gas velocity) is defined as:
d (G. yCO2 ) εg.Dg d 2 (G. yCO2 )
− . = −NCO2. αg G
dz Ug dz 2 (4) Vin =
Asp arg er . αsp arg er (15)
Where the gas velocity (Ug) can be calculated by Eq. (5):
The CO2 absorbance rate is defined by Danckwerts equation:
4GFR
Ug =
π dR2 εg (5)

In the above equation, the first and second terms are determined based
on the fluid bulk motion and dispersion in the gas phase, respectively.
Under industrial condition, since the inlet gas flow rate is constant and
by considering low enough consumption of CO2 in gas phase through
the length of the column, it is supposed that the gas velocity is constant
in the column. Also since sodium bicarbonate production is a prompt
reaction at high temperatures in the liquid phase, it would be con-
sidered that CO2 consumption and absorption rates are the same.
By applying the mole balance on the first zone of the column, the
overall mole balance equation of liquid phase is expressed as Eq. (6):
dl
=0
dz (6)

The governing equation for the sodium carbonate, sodium bi-

carbonate, and water in the first zone can be written as follows: Fig. 2. Differential control volume along the length of column.

321
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

NCO2 = E . KL. (CCO2, i − CCO2, e )
Where E is the enhancement factor which can be determined from the
following equation:
DCO2 . k
E= 1+
K12
Danckwerts obtained CO2 absorbance rate based on the mass transfer
and chemical reaction as the following equation:
NCO2 = E . H . KL. (PCO2, i − PCO2, e )
Due to high circulation of bubbles and gas mixing, Eq. (18) can be re-
written as:
NCO2 = E . H . KL. (PCO2 − PCO2, e )
Also CO2partial pressure can be ignored in the liquid bulk, because CO2
reacts rapidly with the sodium carbonate in the liquid phase [17]. It
should be noted that volumetric mass transfer coefficient, kL, enhances
with increasing the gas flow rate, gas density and pressure whereas it
reduces with increasing solid concentration and liquid viscosity
[21,22].
In nucleation process, one of the important parameters is magma.
Magma is a two phase mixture of solution and crystals with different
size which occupies the crystallizer. Magma can be calculated as fol-
lows:
S. MwNaHCO3
MT =
L. Mw H2 O
The equations listed in Table 2 provide the hydrodynamics and mass
transfer parameters in the bubble column [23–27].
Moreover, in order to define molar volume of gas phase compo-
nents, it is necessary to calculate pressure distribution over the length
of column. The macroscopic momentum equations are expressed as
[17]:
∂V
ρG ⎛ G + (VG. ∇) VG ⎞ = −ε∇p + ρG g
⎝ ∂t ⎠ (21)
∂V
ρL ⎛ L + (VL. ∇) VL ⎞ = −(1 − ε ) ∇p + ρL g + (μ [∇VL + (∇VL)T ])
⎝ ∂t ⎠ (22)
The momentum transfer due to gas dissolution is negligible. In Eq. (21),
since the density of the gas phase is less than the liquid phase, the in-
ertia and gravity terms in the gas phase momentum balance can be
omitted (∇p = 0) [17].
(16) For the liquid phase, the continuity equation is replaced by the
standard incompressibility constraint. So the standard Navier–Stokes
equations with an extra buoyancy term proportional to the gas holdup
will be recovered as [17]:
∇p = ρL g
(23)
(17)
Li and Prakash [7] reported that the static pressure drop along the
height of column can be expressed as:
∇p = (ρg εg + ρL εL + ρs εs ) gΔh (24)
(18)
4. Results and discussion
(19) The present developed model is composed of a set of ordinary dif-
ferential equations. These equations are solved by Gauss−Newton
method in MATLAB programming environment based on backward fi-
nite difference method. As summarized in Tables 3 and 4, the validity
and accuracy of the model was confirmed by comparing the modeling
results with plant data of the bicarbonate production unit of a domestic
petrochemical plant. In order to compare the model predictions with
the plant data, absolute percentage error (APE) is calculated based on
Eq. (25):
Exp . −Calc.
APE (%) =
Exp . (25)
The validation data for case I is reported in Table 3. The molar and mass
(20) fraction of components presented in this table for case I represent that
the maximum error is 4.6%. Also, the comparison of the industrial data
for the new configuration (case II) and modeling results indicates that
the maximum error is 9.63% (Table 4).
4.1. Process analysis and comparison of case I and case II
The solid production through the length of reactor is investigated in
Fig. 3. As represented in this figure, the solid production for case I and
case II is started at z = 11.0 m and z = 9.2 m, respectively. This
manner indicates that the application of new configuration improves
the solid production significantly and as a result, increases the process
income. Fig. 3 indicates that CO2 recycling causes to 50% increase in
solid production which is in good agreement with industrial data. Ac-
cording to plant data the annual production capacity in Case 1 and 2 are
20000 and 30041 ton/year, respectively. As a result, this 50% increase
in production of industrial plant confirms the modelling results.

Table 2
The hydrodynamics and mass transfer parameters in the bubble column.

Parameter Unit Equation Ref.

εg – 7 [28]
ρL σ 3 ⎞ 24
εg
(1 − εg )4
= 0.25 ( ) ⎛⎝
Ug μL
σ
⎜
4
gμL ⎠
⎟

Kl 0.5 gd 2 ρ 0.375 [23]

( ) m
s
Kl db
Dl
μ
= 0.5 ⎛ l ⎞ ⎛⎜ b l ⎞⎟
⎝ ρl Di ⎠ ⎝
σ
⎠
H [24]
( kmol
atm . m3 ) log ( H Hw ) = −Ks. I
HW log Hw = ( 1140 T ) − 5.30 [24]
( kmol
atm . m3 )
Dg 2 Ug [25]
⎛m ⎞ Dg = 5dR
εg
⎝ s ⎠
db (m) 4 [23]
σ ⎡ Vl ⎤
dB = 26
ρl g ⎢ Ug2 d5 g ⎥
⎣ R ⎦
DCO2 2 586.9729 [26]
⎛m ⎞ log DCO2 = −30.0188 −
T
− 0.04437
⎝ hr ⎠
Dl 2 Dl = 2.74dR1.4 (0.219U g0.77 + 0.122U g0.1) [27]
⎛m ⎞
⎝ s ⎠
K (1/s) [25]
k = ⎡2.2*107* exp −
⎣ ( 71500
RT ) ⎤⎦ − ⎡⎣3.2*10 −6ρ
H2 O * exp (− 13800
RT ) ⎤⎦

322
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Table 3
Comparison between model prediction and domestic petrochemical plant data for case I.

Gas pressure (atm) P = 2.40 P = 2.50

Plant Model ARD(%) Plant Model ARD(%)

0.20 0.22 10.00 0.30 0.34 13.33

G (Nm3/h) 105.00 109.34 4.13 105.00 109.34 4.13
WNa2CO3 2.43 2.51 3.29 2.45 2.5 2.04
WNaHCO3 3.78 3.77 0.26 3.78 3.81 0.79
WH2O 93.79 93.72 0.07 93.77 93.69 0.09
XCO2 28.00 27.31 2.42 27.00 26.48 1.92

Gas pressure (atm) P = 2.60 P = 2.70

Plant Model ARD(%) Plant Model ARD(%)

Gas pressure (atm) 0.40 0.43 7.50 0.50 0.52 4.00

G (Nm3/h) 105 109.34 4.13 105 109.34 4.13
WNa2CO3 2.41 2.50 3.73 2.39 2.50 4.60
WNaHCO3 3.83 3.85 0.52 3.91 3.89 0.51
WH2O 93.76 93.65 0.12 93.7 93.61 0.10
XCO2 26.00 25.76 0.92 25.00 25.18 0.72

Table 4
Comparison between model prediction and domestic petrochemical plant data for case II.

Gas pressure [atm] P = 2.40 P = 2.50

Plant Model ARD(%) Plant Model ARD(%)

0.10 0.11 10.00 0.20 0.21 5.00

G [Nm3/hr] 188.00 178.92 4.82 188.00 178.92 4.82
WNa2CO3 2.25 2.45 8.88 2.21 2.14 3.16
WNaHCO3 3.58 3.68 2.79 3.59 3.45 3.89
WH2O 94.19 93.87 0.33 94.21 94.41 0.21
XCO2 25.00 26.31 5.24 25.00 26.53 6.12

Gas pressure [atm] P = 2.60 P = 2.70

Plant Model ARD(%) Plant Model ARD(%)

0.30 0.32 6.67 0.40 0.42 5.00

G [Nm3/hr] 188.00 178.92 4.82 188.00 178.92 4.82
WNa2CO3 2.20 2.39 8.63 2.18 2.39 9.63
WNaHCO3 3.60 3.54 1.66 3.73 3.79 1.60
WH2O 94.04 94.07 0.03 93.99 93.82 0.18
XCO2 25.00 25.89 3.56 25.00 25.8 3.2

Fig. 4. Mole fraction of CO2 through the length of column.

Fig. 3. Solid production through the length of column.

323
D.G. Maharloo et al.
Plant data analysis and modeling results reveal that by recycling
CO2 in the new configuration, 314 mol/m−2 s−1CO2 is saved in each
loop. As shown in Fig. 4, the CO2 mole fraction in the gas phase thought
the column in case II is more than that of case I, It is obvious that higher
concentration of reactant in case II leads to higher reaction rate.
The mass fraction of NaHCO3 in the liquid phase through the length
of reactor is presented in Fig. 5. The liquid stream enters from the top of
column, so due to chemical reaction, the mass fraction of sodium bi-
carbonate increases continuously through the length of reactor to reach
a maximum value. But due to the solid precipitation, the mass fraction
of sodium bicarbonate decreases in the second zone. It is observed that
in the precipitation zone, the mass fraction of sodium bicarbonate for
case II is lower than that of case I, which means that more amount of
sodium carbonate is produced and crystallized.
As mentioned in above sections, the sodium bicarbonate super−-
saturation state in the liquid phase depends on the CO2 transfer flux
from the gas phase to the liquid phase and sodium bicarbonate transfer
flux from the liquid phase to the solid phase.
As demonstrated in Fig. 6, in comparison with case I, there are more
super–saturated liquid at the first zone of column in case II, but in the
second zone, due to solid formation, the super–saturated liquid in case
II is lower than case I.
It is obvious that the flux of CO2which decreases through the length
of column is a function of the inlet concentration of CO2 in the gas
phase. Also, the flux of sodium bicarbonate is a function of the nu-
cleation and growth of crystals, such that they depend on super−-
saturation and magma density. According to Fig. 7, before starting the
solid production, there is no magma production which is logical. Based
on reported data in Fig. 7and the solid production represented in Fig. 3,
it can be concluded that the magma formation is the starting point of
the solid phase formation. Also, it can be seen from this figure that the
density of magma in case II is more than case I.
Finally, comparison of different modes reveals that at the same
operational conditions, applying the new configuration by CO2 re-
cycling (Case II) not only decreases the greenhouse gas emission, but
also reduces the gas consumption, and especially CO2 consumption. A
summary of comparison between case I and case II is reported in
Table 5. The results indicate that by applying the new configuration,
the production of solid increases from 8.4 to 11.9 (mol/m2s−1) and the
magma density enhances from 0.48to 0.61 (Kg of crystal/kg of solu-
tion), which leads to more favorable product. In addition, the weight
fraction of sodium bicarbonate is dropped from 0.121 in case I to 0.119
in case II which in turn means the increase in solid production. Due to
increasing demand of soda consumption and need to high quantity
production of this strategic substance by petrochemical companies, the
new proposed configuration will result in higher production.
4.2. Investigation of the parameters affecting case II
In the following, the effect of different effective parameters on soda
production, solid molar rate and CO2 conversion will be considered.
The CO2 conversion is defined as follows:
G. yCO2, out − G. yCO2, in
ConvCO2 =
G. yCO2, in
The CO2 conversion and molar velocity of solid through the length of
column are presented in Fig. 8. As shown in this figure, the CO2 con-
version increases significantly in the precipitation zone due to solid
production by chemical reactions. But it can be seen that because of
decreasing the driving force for chemical reaction, the rate of CO2
consumption decreases through the length of column and finally the
CO2 conversion reaches to a constant value. As indicated in this figure,
the maximum molar velocity of the solid production happens at the
bottom of column, but it reduces through the length of column so that
from the height of 9.2 m to the top of the column, there is no solid
324
Journal of CO₂ Utilization 20 (2017) 318–327
production and the CO2consumption is very low.
The final molar flow rate of NaHCO3 and the mole fraction of the
CO2 in the gas phase are in good agreement with the plant production
rate, which is 20,000 ton/year of NaHCO3 crystals and the plant con-
version of CO2, which is 40%.
Fig. 9 shows the flow rates of gas, liquid and solid phases through
the length of reactor. As mentioned in the process description, the li-
quid enters from the top of column (z/z0 = 1) and since there is no
solid production in the first zone, the molar velocity of solid is zero and
also the changes in liquid flow rate can be ignored due to insignificant
dissolution of CO2 in liquid phase. As demonstrated in this figure, after
the solid production in the precipitation zone (second zone), the liquid
flow rate drops which is confirmed by industrial data.
Gas holdup (εg) and volumetric mass transfer coefficient (kL) en-
hance with increasing the inlet gas pressure. At higher gas pressure,
more CO2 diffuse into the liquid phase and therefore CO2 absorption
increases. As can be observed in Fig. 10, with the increase in the inlet
gas pressure, the efficiency of CO2 absorption and sodium bicarbonate
production increase due to increasing the density of gas and decreasing
the bubble size which in turn result in the increase in liquid−gas phase
interface.
According to Fig. 11, it can be seen that the increase in feed gas flow
rate leads to drop in CO2 absorption efficiency while sodium bicarbo-
nate production increases. Moreover, the increase in gas flow rate gives
rise to the increase in apparent velocity of the gas inside of column
which in turn it will move flow regime away from homogenous regime.
Increasing the apparent velocity of gas results in the increase in bubble
diameter in column and consequently, causes to the decrease in ga-
s−liquid interface. Consequently, absorption efficiency decreases;
however, because of the rise in feed gas flow rate to column, input
molar flow rate of CO2 increases which results in the increase in pro-
duction. In addition, increasing the apparent gas velocity causes to
increase in gas holdup (εg) and kg which in turn increases solid pro-
duction. On the other hands, as the apparent gas velocity increases the
residence time of CO2 in the reactor decreases which causes to decrease
in the conversion.
Sodium bicarbonate production reaction is considered as a rapid
reaction at high temperatures; however, sodium bicarbonate is a sub-
stance that decomposes and releases CO2 at high temperatures. Thus, an
optimum temperature should be determined. As can be seen in Fig. 12,
with the increase in temperature up to 323 K, absorption efficiency
increases and afterwards with more increase in temperature, because of
increasing the sodium bicarbonate decomposition rate and also de-
creasing Henry coefficient, absorption efficiency reduces rapidly. The
obtained optimum operational temperature is 323 K.
Fig. 5. Mass fraction of sodium bicarbonate through the length of column.
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Fig. 6. Sodium bicarbonate super−saturation state profile through the length of column. Fig. 8. CO2 conversion profile and solid molar flow rate through the length of column.

Fig. 7. Magma density profile through the length of column.

Table 5 Fig. 9. Flow rates of phases through the length of column.

Summary of comparison between case I and case II.

Case I Case II

2 −1
Solid production (mol/m s ) 8.400 11.900
Carbon dioxide molar fraction per pass 0.280 0.340
Mass fraction of sodium bicarbonate 0.121 0.119
Magma density (Kg of crystal/kg of solution) 0.480 0.610

Increasing the initial CO2 concentration increases the molar flow

rate of CO2 and thereby more moles of CO2 enter the column; therefore,
as can be seen in Fig. 13, by increasing the concentration of CO2,
production and absorption efficiency will be increased. By increasing
the inlet CO2 percentage, concentration difference between gas and
liquid phase becomes greater and consequently, more CO2 transfers
from the gas to liquid phase and leads to more sodium bicarbonate
production (Fig. 14) which justifies the rise in production and absorp-
tion efficiency.
Fig. 15a–c illustrates the effect of column diameter on solid pro-
duction and CO2 conversion. With increasing the column diameter
Fig. 10. CO2 conversion profile and solid production as a function of pressure.
more than 1 m, small amount of CO2 enter the liquid phase while the
large amount remain in the gas phase. Fig. 15−c shows that with in-
diameter (aspect ratio) is larger than 5, the influence of the column
creasing the column diameter, molar fraction of CO2 increases at the
height on gas holdup is insignificant [7–11]. It was reported that mass
end of reactor which means that less amount of CO2 enters the liquid
transfer coefficient is dependent upon column diameter and it increases
phase. It is well documented that if the ratio of the column height to the
as the column diameter decreased. Therefore, diffusion of CO2 from gas

325
D.G. Maharloo et al. Journal of CO₂ Utilization 20 (2017) 318–327

Fig. 14. Solid production as a function of input molar fraction of CO2.

Fig. 11. CO2 conversion and production profiles as a function of gas flow rate.

Fig. 12. CO2 conversion and production profiles as a function of column temperature.

Fig. 13. CO2 conversion as a function of input molar fraction of CO2.

to liquid phase increases with decreasing column diameter. There is an

optimum diameter for the column. In columns with diameters lower
Fig. 15. (a) Solid production, (b) CO2 conversion and (c) CO2 mole fraction in the gas.
than this optimum value (lower than 1 m), CO2 conversion and also
production decreases. This point is justified by entering the hetero-
configuration, the flow rate of injected CO2 was about 200 Nm3/hr, but
geneous flow as the apparent velocity of gas in column increases by
only 25–30 voltric percent of CO2 was absorbed and the rest of it was
decrease in column diameter.
released from the top of column to atmosphere. The present research
reveals that CO2 recycling is one of the effective techniques to optimize
5. Conclusion the raw materials consumption, absorption and production efficiency
and also to control the greenhouse gas emission. The obtained results
In this study, a new configuration of sodium bicarbonate production reveal that recycling the CO2 in the new configuration leads to a
in an industrial bubble column reactor is investigated. In the old

326
D.G. Maharloo et al.
significant enhancement in production capacity of soda. We inferred
that the absorption efficiency and production rate will be improved by
increasing the initial pressure of the feed gas stream. According to the
investigations made, the best range of pressure for getting the highest
absorption and production efficiency is between 2 and 3 atm. Increase
in the feed gas flow rate is accompanied by the drop in gas absorption
efficiency; however, it gives rise to the increase in production.
Increasing the CO2 concentration using recycle stream leads to 50%
increase in production and 314 mol/m2 s−1 decrease of CO2 con-
sumption. Also, it is observed that excessive increase in process tem-
perature, not only does not increase the reaction rate, but also increases
the sodium bicarbonate decomposition rate. Studies have shown that
the best operating temperature for sodium bicarbonate production is
323 K. Specific heat of gases are lower than liquids; therefore, only in
the gas inlet zone, the effect of gas temperature on liquid phase tem-
perature profile is considerable.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in the
online version, at http://dx.doi.org/10.1016/j.jcou.2017.06.005.
References
[1] A.S. Goharrizi, B. Abolpour, Estimation of sodium bicarbonate crystal size dis-
tributions in a steady-state bubble column reactor, Res. Chem. Intermed. 38 (2012)
1389–1401.
[2] N. Kantarci, F. Borak, K.O. Ulgen, Bubble column reactors, Process Biochem. 40
(2005) 2263–2283.
[3] K. Salehi, S. Jokar, J. Shariati, M. Bahmani, M. Sedghamiz, M. Rahimpour,
Enhancement of CO conversion in a novel slurry bubble column reactor for me-
thanol synthesis, J. Nat. Gas Sci. Eng. 21 (2014) 170–183.
[4] M. Bayat, M. Rahimpour, B. Moghtaderi, Genetic algorithm strategy (GA) for op-
timization of a novel dual-stage slurry bubble column membrane configuration for
Fischer–Tropsch synthesis in gas to liquid (GTL) technology, J. Nat. Gas Sci. Eng. 3
(2011) 555–570.
[5] Y. Zhu, M.-P. Delplancke-Ogletree, Etude expérimentale de la cristallisation du
bicarbonate de sodium, 2004.
[6] E. Harvey, W. Smith, The absorption of carbon dioxide by a quiescent liquid, Chem.
Eng. Sci. 10 (1959) 274–280.
[7] H. Li, A. Prakash, Influence of slurry concentrations on bubble population and their
rise velocities in a three-phase slurry bubble column, Powder Technol. 113 (2000)
158–167.
[8] L. Pino, R. Solari, S. Siquier, L. Antonio Estevez, M. Yepez, A. Saez, Effect of op-
erating conditions on gas holdup in slurry bubble columns with a foaming liquid,
Chem. Eng. Commun. 117 (1992) 367–382.
[9] A. Prakash, A. Margaritis, H. Li, M. Bergougnou, Hydrodynamics and local heat
327
Journal of CO₂ Utilization 20 (2017) 318–327
transfer measurements in a bubble column with suspension of yeast, Biochem. Eng.
J. 9 (2001) 155–163.
[10] M. Saidi, S. Heidarinejad, H.R. Rahimpour, M.R. Talaghat, M.R. Rahimpour,
Mathematical modeling of carbon dioxide removal using amine-promoted hot po-
tassium carbonate in a hollow fiber membrane contactor, J. Nat. Gas Sci. Eng. 18
(2014) 274–285.
[11] M.R. Rahimpour, M. Saidi, M. Baniadam, M. Parhoudeh, Investigation of natural
gas sweetening process in corrugated packed bed column using computational fluid
dynamics (CFD) model, J. Nat. Gas Sci. Eng. 15 (2013) 127–137.
[12] M. Bouaifi, G. Hebrard, D. Bastoul, M. Roustan, A comparative study of gas hold-up,
bubble size, interfacial area and mass transfer coefficients in stirred gas–liquid re-
actors and bubble columns, Chem. Eng. Process. Process Intensif. 40 (2001) 97–111.
[13] A.A. Youssef, M.E. Hamed, J.T. Grimes, M.H. Al-Dahhan, M.P. Dudukovic,
Hydrodynamics of pilot-scale bubble columns: effect of internals, Ind. Eng. Chem.
Res. 52 (2012) 43–55.
[14] A. Shaikh, Bubble and Slurry Bubble Column Reactors for Syngas to Liquid Fuel
Conversion: Mixing, Flow Regime Transition, and Scale-Up, Washington University
in St Louis, Saint Louis, MO, USA, 2007.
[15] A. Forret, J. Schweitzer, T. Gauthier, R. Krishna, D. Schweich, Scale up of slurry
bubble reactors, Oil Gas Sci. Technol.-Revue de l'IFP 61 (2006) 443–458.
[16] D.D. McClure, N. Aboudha, J.M. Kavanagh, D.F. Fletcher, G.W. Barton, Mixing in
bubble column reactors: experimental study and CFD modeling, Chem. Eng. J. 264
(2015) 291–301.
[17] D. Kuzmin, S. Turek, Efficient Numerical Techniques for Flow Simulation in Bubble
Column Reactors, Univ. Dortmund, Fachbereich Mathematik, 2000.
[18] B.t. Haut, V. Halloin, T. Cartage, A. Cockx, Production of sodium bicarbonate in
industrial bubble columns, Chem. Eng. Sci. 59 (2004) 5687–5694.
[19] P.-C. Chen, K. Kou, H. Tai, S. Jin, C. Lye, C. Lin, Removal of carbon dioxide by
reactive crystallization in a scrubber—kinetics of barium carbonate crystals, J.
Cryst. Growth 237 (2002) 2166–2171.
[20] Y. Zhu, P. Demilie, P. Davoine, M.-P. Delplancke-Ogletree, Application of density
meter in the supersaturation determination of the two-component equilibrium
systems, J. Cryst. Growth 263 (2004) 459–465.
[21] A. Verma, S. Rai, Studies on surface to bulk ionic mass transfer in bubble column,
Chem. Eng. J. 94 (2003) 67–72.
[22] R. Krishna, J. Van Baten, Mass transfer in bubble columns, Catal. Today 79 (2003)
67–75.
[23] K. Akita, F. Yoshida, Bubble size, interfacial area, and liquid-phase mass transfer
coefficient in bubble columns, Ind. Eng. Chem. Process Des. Dev. 13 (1974) 84–91.
[24] P.V. Danckwerts, M.M. Sharma, P.V. Danckwerts, P.V. Danckwerts, The Absorption
of Carbon Dioxide into Solutions of Alkalis and Amines:(with Some Notes on
Hydrogen Sulphide and Carbonyl Sulphide), Institution of Chemical Engineers,
1966.
[25] R.T. Pavlica, J.H. Olson, Unified design method for continuous-contact mass
transfer operations, Ind. Eng. Chem. 62 (1970) 45–58.
[26] A. Tamimi, E.B. Rinker, O.C. Sandall, Diffusion coefficients for hydrogen sulfide,
carbon dioxide, and nitrous oxide in water over the temperature range 293–368 K,
J. Chem. Eng. Data 39 (1994) 330–332.
[27] R. Wendt, A. Steiff, P.M. Weinspach, Flüssigphasenrückvermischung in blas-
ensäulenreaktoren, Chem. Ing. Technol. 55 (1983) 796–797.
[28] K. Akita, F. Yoshida, Gas holdup and volumetric mass transfer coefficient in bubble
columns. Effects of liquid properties, Ind. Eng. Chem. Process Des. Dev. 12 (1973)
76–80.