International Journal of Heat and Mass Transfer 67 (2013) 696–703

Contents lists available at ScienceDirect

International Journal of Heat and Mass Transfer

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

Research on mass transfer of CO2 absorption using ammonia solution in

spray tower
Shuangchen Ma ⇑, Bin Zang 1, Huihui Song 2, Gongda Chen 1, Jiehong Yang 2
School of Environment, North China Electric Power University, Baoding 071003, PR China

a r t i c l e i n f o a b s t r a c t

Article history: Research on mass transfer of carbon capture process plays an important role in the design of absorbing
Received 11 March 2013 device. The effects of ammonia concentration, L/G, gas flow rate, gas temperature, CO2 partial pressure
Received in revised form 21 June 2013 and other factors on the volumetric overall mass transfer coefficient (KGaV), the gas phase mass transfer
Accepted 22 August 2013
coefficient (kG) and the effective mass transfer cross-sectional area (aV) were investigated with ammonia
Available online 18 September 2013
solution as the absorbent in homemade spray tower. Experimental results show that KGaV has upward trend
with the increasing ammonia concentration, L/G and gas flow rate, and first increases and then decreases
Keywords:
with the rises of CO2 partial pressure and gas temperature; kG increases with the increasing L/G, gas flow
Spray tower
Ammonia
rate and CO2 partial pressure; aV increases with the increasing ammonia solution and gas flow rates; CO2
CO2 partial pressure has less impact on KGaV, kG and aV. Under the experimental conditions, maximums of KGaV,
Mass transfer kG and aV are 0.17 kmol m3 h1 kPa1; 0.0022 kmol kPa m2 h1 and 99.25 m2 m3 respectively.
Research Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction
Global warming caused by greenhouse gas emissions, particu-
larly by a large amount of CO2 released into the atmosphere by
burning fossil fuel continues to receive worldwide attentions
[1–4] . The absorption method for CO2 capture based on chemical
solution is the optimized method at present. Using absorption
method to capture CO2 has been broadly applied in some chemical
industries such as ammonia synthesis and urea industries while it
is rarely used in flue gas of power plant for carbon capture. This is
because the flue gas of power plant has high flow rate(1.2  106 -
m3 h1 for traditional 300 MW unit), high gas velocity, high tem-
perature (almost 130 °C after electrostatic precipitator), relatively
low CO2 volume fraction (12%  15%), complex flue gas co-existing
components (particles, SO2, NOX and HCl etc.) and low pressure of
flue gas (about 1 atm) etc., the traditional absorption process faced
with these characteristics have many difficulties and presents
some problems, such as a huge system volume, high invest and
operation cost etc. [5–7]. However, compared with other post-
combustion carbon capture methods, chemical absorption method
has some advantages, such as high removal efficiency and selectiv-
ity, relative lower energy consumption and invests etc. Although
this method cannot meet the demand of power plant in scale
⇑ Corresponding author. Tel./fax: +86 312 7522714.
E-mail addresses: msc1225@163.com (S. Ma), 154537723@qq.com (B. Zang),
494881150@qq.com (H. Song), majestychen@vip.qq.com (G. Chen),
578056770@qq.com (J. Yang).
1
Tel.: +86 312 7522714; fax: +86 312 7522343.
2
Tel./fax: +86 312 7522243.
and technology, from the prospect of this method, it will be one
of the most likely technologies for large-scale power plants in
post-combustion carbon capture [8–10].
At present, the main commercial of carbon capture technology
applied in the world is Monoethanolamine (MEA) based on the
chemical absorption method [11]. MEA has a strong ability to
absorb acid gas, and it has the most advantage to capture the
low level CO2 in the flue gas usually with 90% carbon removal
efficiency [12]. But research about CO2 absorption from NETL
pointed out that traditional MEA process represents some prob-
lems, such as decomposition, corrosion, and high energy consump-
tion for regeneration. Additionally, because of oxidation, thermal
decomposition, irreversible reaction happening and evaporation,
MEA has mass loss in the process. Furthermore, MEA technology
has a rigid demand of SO2 level in the flue gas (under 10 ppm),
but the existing flue gas desulfurizaiont (FGD) process cannot meet
the too low level of SO2 in the flue gas [13,14]. The shortcomings
mentioned above lead to slightly higher investment and operating
cost. Thus, it is urgent to do further basic researches on carbon cap-
ture and what is expected to get is to keep carbon capture from the
flue gas at an acceptable cost. The research directions can be put on
areas such as the development of new-style absorbent, improving
absorption devices, products recycling after carbon absorbed and
CO2 desorption with lower energy. As for the characteristics of
the flue gas of power plants, the new-style absorbent is expected
not only as high removal efficiency but also low absorbent cost
and low consumption of regeneration energy [15–17].
Spray tower is one of the important equipment for CO2 absorp-
tion process, gas–liquid mass transfer coefficients, such as the vol-

0017-9310/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.ijheatmasstransfer.2013.08.090
 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703 697

Nomenclature

aV the effective mass transfer cross-sectional area, m2 m3 kL mass transfer coefficient of liquid phase under no chem-
CM absorbent concentration at the interface of gas–liquid, ical reaction, kmol (m2 h (kmol m3))1
kmol m3 k1 reaction rate constant of absorption of CO2 using ammo-
dY the molar ratio of CO2 to N2 at an infinitesimal height of nia solution, m3/kmol h
dh p total gas pressure, kPa
dh an infinitesimal height in spray tower, m PA CO2 partial pressure in gas-phase, kPa
DNH
CO2
3
the diffusion coefficient of CO2 in an aqueous ammonia pA CO2 equilibrium partial pressure corresponding with li-
solution, m3/h quid CO2 concentration, kPa
H Henry’s coefficient, kPa m3 kmol1 Vr reactor volume, m3
HT the effective height of spray tower, m Y1, Y2 the molar ratio of CO2 to N2 at the inlet and outlet of
G1 N2 flow rate, kmol m2 h1 tower respectively
KG total mass transfer coefficient, kmol (m2 h (kPa))1 b enhancement factor of chemical reaction
KGaV volumetric overall mass transfer coefficient, kmol m2 - X cross-sectional area of spray tower, m2
h1 kPa1
kG mass transfer coefficient of gas phase, kmol (m2 -
h (kPa))1

umetric overall mass transfer coefficient (KGaV), the gas phase mass
transfer coefficient (kG) and the effective mass cross-sectional area
(aV) are important parameters of absorption performance and de-
sign of tower body size, which has an important significance on
the study of chemical absorption process. Table 1 lists the related
study of the gas–liquid mass transfer area and mass transfer kinet-
ics relational equations.
As can be seen, most mass transfer studies were carried out in
packed tower, less of spray tower, and all of the relational equa-
tions were restricted by the relevant conditions, many parameters
were selected and had differences greatly. Therefore, selection of
existing relational equation of CO2 mass transfer parameters for
calculating spray tower is not fit.
In this work, based on experimental data, the volumetric overall
mass transfer coefficient (KGaV), the gas phase mass transfer coef-
ficient (kG) and the effective mass cross-sectional area (aV) of CO2
absorption using ammonia solution in spray tower were studied
with the aid of two-film theory, and calculated by the differential
method and linear fitting mathematical approach etc. The effects
of concentration of ammonia solution, L/G, gas flow rate, gas tem-
perature, CO2 partial pressure and other factors on the mass trans-
fer coefficient were investigated by experiments. The experimental
results provide a valuable reference for CO2 removal system design
using ammonia solution.
tion in the gas mixture, the mixed gas flowed into the bottom of
the column after CO2 concentration kept stable, and discharged
from the tower top while countercurrent contacting with absorb-
ing liquid, CO2 concentration in exhaust gas was measured by
CO2 analyzer after exhaust gas was pickled for removal of ammo-
nia and dried for removal of water. The absorption liquid was
pumped through ammonia pump to the tower top, and then dis-
charged from the bottom into the waste tank. Temperature control
and regulation systems were installed in mixed gas cylinder.
2.2. Experimental methods
Before the experiment, different concentrations of aqueous
ammonia solution were prepared in the liquid storage tank. At
the same time, simulated flue gas flowed through a bypass of
three-way valve into the CO2 analyzer. When CO2 concentration
reached a steady state, the gas path was switched, and simulated
flue gas entered into the bottom of absorber, ammonia pump
was opened simultaneously. At this moment, the CO2 analyzer be-
gan to record monitoring data online. The experimental data ob-
tained by changing the concentration of ammonia solution, L/G,
gas flow rate, the gas temperature, CO2 partial pressure and other
conditions, was used to calculate the mass transfer parameters.
The parameters of the spray tower used in the present experiment
and experimental conditions are shown in Table 2.

2. Experimental 2.3. Calculation methods for different parameters

2.1. Experimental device
The experimental apparatus is shown in Fig. 1; the main equip-
ment used is the spray tower. N2 and CO2 from gas cylinders en-
tered into the mixed gas cylinder after depressurization by
reducing valve, CO2 analyzer was used to measure CO2 concentra-
2.3.1. The calculation for volumetric overall mass transfer coefficient
(KGaV)
Based on the two-film theory and material balance, an
infinitesimal height of dh is taken in any location of spray tower,
volumetric overall mass transfer coefficient for the absorption of
CO2 using ammonia solution can be expressed as:

Table 1
The related gas–liquid mass transfer area and mass transfer kinetics relational equations.

Correlation equations Reactor Content Ref.

 0:11L0:022 Packed column Random packing [18]
808Gn
a ¼ 40:11 q0:5 L0:14
g
0.0657
a = 522.6G Packed column Stainless steel wire mesh ring [19]
m  17 mg dp 0:3 qg Dg 2=3 Packed column Random saddle types [20]
kg ¼ 5:23 Mg gpS at dp slg lg
 1=3  2=3  
1=2  0:4 Packed column Randomly ring or saddle types [21]
kL gqlLL ¼ 0:0051 apLl Scg ap dp
L
0:462HM
K G ¼ 3:3Hþ0:14M Stirring kettle Absorption for O2, SO2, NH3, HCI [22]
KGa = 2.119(L)0.5[(a⁄  a)C/P  0.0193] Packed tower Structured packing absorption for CO2 [23]
698 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703

2.3.2. The calculations for the gas phase mass transfer coefficient (kG)
and the effective mass transfer area (aV)
According to two-film theory, the mass transfer resistance of
the gas–liquid reaction can be expressed as,
1 1 H
¼ þ ð4Þ
K G kG bkL
where K1G represents total mass transfer resistance; k1G represents
mass transfer resistance of gas phase; kL represents mass transfer
coefficient of liquid phase under no chemical reaction; H represents
Henry’s coefficient; b represents enhancement factor of chemical
reaction.
The unit volume absorption rate of U is defined to characterize
the reaction rate, which is defined in the following formula [25].
U ¼ K G aV ðPA  PA Þ ð5Þ
where U is the unit volume absorption rate; KGaV is the volumetric
overall mass transfer coefficient.
U can also be calculated by the following formula [26],
Fig. 1. Experimental system diagram. 1 – N2; 2 – CO2; 3 – reducing valve; 4 – flow G1 XðY 1  Y 2 Þ
meter; 5 – check valve; 6 – mixed gas cylinder; 7 – three-way valve; 8 – absorber; 9 U¼ ð6Þ
Vr
– liquid storage tank; 10 – ammonia pump; 11 – waste tank; 12 – pickling bottle;
13 – dry tower; 14 – CO2 analyzer; 15 – data treatment system. where G1 represents nitrogen flow rate with the unit of kmol m2 -
h1; X represents cross-sectional area of spray tower with the unit
of m2; Vr is reactor volume with the unit of m3.
Table 2
Parameters of spray column and test conditions. Eq. (7) can be obtained from the Eq. (4) and Eq. (5),

Parameters Conditions PA 1 1 1 H
¼ þ ð7Þ
Height of tower/cm 35 U aV kG aV bkL
External diameter of tower/cm 7
Inner diameter of tower/cm 5.5
Edward’s analogy research showed that the absorption of CO2 using
Pressure/mPa 0.1 ammonia solution is a rapid pseudo-first-order reversible reaction
Gas flow rate/(m3 h1) 0.2–0.4 process, the enhancement factor can be calculated as follows [27],
Volume fraction of CO2/% 10–20 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
Ammonia flow rate/(L min1) 1.5–3 k1 DNH CO2 C M
3

Ammonia concentration/% 1–7 b¼ ð8Þ

Temperature/°C 20–50 kL
where k1 is reaction rate constant of absorption of CO2 using ammo-
G1 dY nia solution; DNH
CO2 indicates that the diffusion coefficient of CO2 in
3

K G aV ¼ ð1Þ an aqueous ammonia solution; CM is absorbent concentration at

pðPA  PA Þdh
the interface of gas–liquid, and is approximately equal to the con-
where dY represents the molar ratio of CO2 to N2 at an infinitesimal centration of the liquid phase under rapid pseudo-first-order
height of dh; G1 represents N2 flow rate, the unit is kmol m2 h1; p reversible reaction process.
represents total gas pressure, the unit is kPa; PA represents CO2 The following Eq. (9) can be obtained by the substitution of Eq.
Y
partial pressure in gas-phase, the unit is kPa; P A ¼ 1þY ;Y represents (8) into Eq. (7),

the molar ratio of CO2 to N2; PA represents CO2 equilibrium partial PA 1 H 1 1
pressure corresponding with liquid CO2 concentration, the unit is ¼ qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi þ ð9Þ
U aV k DNH3 C aV kG
kPa; dh represents an infinitesimal height in spray tower, the unit 1 CO2 M

is m.
CO2 absorption using ammonia solution belongs to a rapid In a certain gas flow rate and liquid flow rate, the experiments
chemical reaction, and the experimental study in this paper was were carried out by changing the concentration of ammonia
conducted in a high absorption rate and high partial pressure of solution, the figure of PUA versus pffiffiffiffiffiffiffiffiffiffi
H
will be plotted, and the
k1 DC M
CO2 (PA), CO2 equilibrium partial pressure (PA ) at interface of the resulting slope is a1V , the intercept is kG1aV , and other parameters, such
gas–liquid was low, therefore, PA  PA can be approximated equal
as aV, kG can be obtained through calculation.
to PA[24,25]
1þY 
G1 Y
dY 3. Experimental results and discussions
K G aV ¼ ð2Þ
pdh
3.1. The volumetric overall mass transfer coefficient for the absorption
Eq. (2) was integrated from the bottom of the column to the top of of CO2 using ammonia solution (KGaV)
the column, so

G1 Y1
K G aV ¼ In þ ðY 1  Y 2 Þ ð3Þ 3.1.1. The effect of ammonia concentration on KGaV
pHT Y2
To investigate the influence of ammonia concentration on KGaV,
where Y1 and Y2 present the molar ratio of CO2 to N2 at the inlet and following experimental conditions were used, inlet gas flow rate of
outlet of tower respectively; HT represents the effective height of 0.4m3 h1, ammonia flow rate of 3 L min1, CO2 partial pressure of
spray tower, m. 15 kPa, gas temperature of 20 °C, ammonia concentrations of 1%,
 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703 699

2%, 3%, 4%, 5%, 6% and 7% (mass fraction), the relationship between
KGaV and ammonia concentration in the CO2 absorption process is
shown in Fig. 2. The CO2 concentrations at inlet/outlet under differ-
ent ammonia concentrations is shown in Table 3.
As can be seen from Fig. 2, as ammonia concentration increases,
KGaV presents linearly rising trend basically, KGaV has an increase of
77.49% when ammonia concentration increases from 1% to 7%, This
is because as ammonia concentration increases, ammonia mole-
cules at the interface between gas and liquid phases increase, thus
the chemical reaction enhancement factor improves, the mass
transfer resistance of liquid phase reduces, so KGaV increases, but
ammonia concentration is constrained by the ammonia volatility.

3.1.2. The effect of L/G on KGaV

To investigate the influence of L/G on KGaV, following experi-
mental conditions were used, inlet gas flow rate of 0.4m3 h1, Fig. 3. Effect of L/G on KGaV.

CO2 partial pressure of 15 kPa, gas temperature of 20 °C, ammonia

concentrations of 3% and 5% (mass fraction), the relationship be- Table 4
tween KGaV and L/G in the CO2 absorption process is shown in CO2 concentrations at inlet/outlet under different L/G.

Fig. 3. The CO2 concentrations at inlet/outlet under different L/G L/G/m3 m3 CO2 concentration (inlet)/% CO2 concentration (outlet)/%
are shown in Table 4. 3%NH3 5%NH3 3%NH3 5%NH3
It can be seen from Fig. 3, under different ammonia concentra-
0.2250 15.0 15.0 9.5 8.9
tions conditions, KGaV rises as the L/G increases, and keeps the 0.2625 15.0 15.0 9.4 8.8
same upward trend. When L/G changes from 0.225 m3 m3 to 0.3000 15.0 15.0 9.3 8.6
0.45 m3 m3, KGaV companying with ammonia concentrations of 0.3375 15.0 15.0 9.2 8.4
3% and 5% has an increase of 13.39% and 21.20% respectively. With 0.3750 15.0 15.0 9.1 8.3
0.4125 15.0 15.0 9.0 8.1
the increase of L/G, the turbulence degree at the two-phase inter-
0.4500 15.0 15.0 8.9 7.9
face of gas–liquid increases [28], the effective mass transfer cross-
sectional area, the gas phase mass transfer coefficient, liquid phase
mass transfer coefficient increase all, so KGaV enlarges apparently. 3.1.3. The effect of gas flow rate on KGaV
To investigate the influence of gas flow rate on KGaV, following
experimental conditions were used respectively, ammonia flow
rate of 3 L min1, CO2 partial pressure of 15 kPa and gas tempera-
ture of 20 °C, ammonia concentrations of 3% and 5%, the relation-
ship between KGaV and the gas flow rate in the CO2 absorption
process is shown in Fig. 4. The CO2 concentrations at inlet/outlet
under different gas flow rates are shown in Table 5.
As can be seen from Fig. 4, under different the ammonia concen-
trations, as the gas flow rate increases, the value of KGaV increases,
and the upward trend is consistent. When the gas flow rate rises
from 0.2 m3 h1 to 0.4 m3 h1, KGaV companying with ammonia
concentrations of 3% and 5% has an increase of 40.59% and
41.42% respectively. This is because with the increasing of flow
rate, the gas phase transfer coefficient (kG) increases and the mass
transfer between the gas–liquid two-phase improves, and thereby
the value of KGaV increases. However, increasing gas flow rate will
shorten the residence time of the gas in the spray tower, so the re-
moval rate will reduce; therefore the gas flow rate should be kept
suitable value.

Fig. 2. Effect of the ammonia concentration on KGaV.

Table 3
CO2 concentrations at inlet/outlet under different ammonia concentrations.
Ammonia CO2 concentration
concentration/% (inlet)/%
1 15.0
2 15.0
3 15.0
4 15.0
5 15.0
6 15.0
7 15.0
3.1.4. The effect of CO2 partial pressure on KGaV
To investigate the influence of CO2 partial pressure on KGaV, fol-
lowing experimental conditions were used, ammonia flow rate of
3 L min1, gas flow rate of 0.4 m3 h1, gas temperature of 20 °C,
ammonia concentrations of 3% and 5%, the relationship between
CO2 concentration
(outlet)/%
KGaV and CO2 partial pressure in the CO2 absorption process is
shown in Fig. 5. The CO2 concentrations at inlet/outlet under differ-
10.0
9.6
ent CO2 partial pressures is shown in Table 6.
8.9 As can be seen from Fig. 5, under different ammonia concentra-
8.4 tions, as the CO2 partial pressure increases, the value of KGaV first
7.9 increases and further reduces, the maximum value appears in
7.6
15 kPa. When CO2 partial pressure increases from 10 kPa to
7.1
15 kPa, KGaV rises from 1.98% to 9.66% corresponding ammonia
700 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703

Table 6
CO2 concentrations at inlet/outlet under different CO2 partial pressures.

CO2 concentration (inlet)/% CO2 concentration (outlet)/%

3%NH3 5%NH3 3%NH3 5%NH3
10.0 10.0 5.9 5.5
12.0 12.0 7.5 6.5
14.0 14.0 8.3 7.4
15.0 15.0 8.9 7.9
16.0 16.0 9.6 8.5
18.0 18.0 11.2 9.8
20.0 20.0 12.8 11.1

cantly, causing a chemical reaction enhancement factor declines,

thereby the liquid phase mass transfer coefficient reduces, which
hinders mass transfer between gas and liquid. The combined effect
of these two influencing factors lead to KGaV a slight increase firstly
and decrease later on. It also illustrates KGaV is affected by the com-
bined actions of gas and liquid mass transfer coefficients.
Fig. 4. Effect of the gas flow rate on KGaV.

3.1.5. The effect of gas temperature on KGaV

concentrations of 3% and 5%; but when CO2 partial pressure rises To investigate the influence of gas temperature on KGaV, follow-
from 15 kPa to 20 kPa, KGaV decreases by 10.71% and 5.03% corre- ing experimental conditions were used, ammonia flow rate of
sponding ammonia concentrations of 3% and 5% respectively. 3 L min1, gas flow rate of 0.4 m3 h1, CO2 partial pressure of
According to two-film theory, with the increase of CO2 partial pres- 15 kPa, ammonia concentrations of 3% and 5%, the relationship be-
sure in gas phase, gas phase transfer coefficient increases, which is tween KGaV and gas temperature in the CO2 absorption process is
in favor of KGaV .But with too high CO2 partial pressure in the gas shown in Fig. 6. The CO2 concentrations at inlet/outlet under differ-
phase, liquid phase absorbent concentration decreases signifi- ent gas temperatures is shown in Table 7.
It can be seen from Fig. 6, with the rise of gas temperature under
different ammonia concentrations, the value of KGaV first increases
Table 5
and then reduces, maximum KGaV occurs at 40 °C when 3% ammo-
CO2 concentrations at inlet/outlet under different gas flow rates.
nia concentration was used; maximum KGaV appears at 35 °C when
Gas flow rate/m3 h1 CO2 concentration CO2 concentration 5% ammonia concentration was used. This is because when tem-
(inlet)/% (outlet)/%
perature rises, the diffusion coefficients of gas and liquid phase will
3%NH3 5%NH3 3%NH3 5%NH3 be promoted, and is conducive to the improvement of KGaV. But as
0.200 15.0 15.0 7.0 5.9 temperature increases, the solubility of CO2 in the solution will
0.225 15.0 15.0 7.5 6.4 reduce, especially when temperature reaches more than 40 °C,
0.250 15.0 15.0 7.9 6.8 the reverse reaction of ammonium bicarbonate may occurred dur-
0.275 15.0 15.0 8.1 7.0
0.300 15.0 15.0 8.4 7.3
ing CO2 absorption process [29], resulting in lower KGaV in the pro-
0.325 15.0 15.0 8.5 7.4 cess of CO2 absorption.
0.350 15.0 15.0 8.5 7.5
0.375 15.0 15.0 8.7 7.8
3.2. The calculations for the gas phase mass transfer coefficient (kG)
0.400 15.0 15.0 8.9 7.9
and the effective mass transfer cross-sectional area (aV)

The inlet gas flow rate, gas temperature and CO2 partial pres-
sure were kept constant, the volume percentages of CO2 at the out-

Fig. 5. Effect of CO2 partial pressure on KGaV. Fig. 6. Effect of gas temperature on KGaV.
 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703 701

Table 7
CO2 concentrations at inlet/outlet under different gas temperatures.

Gas temperature/°C CO2 concentration CO2 concentration

(inlet)/% (outlet)/%
3%NH3 5%NH3 3%NH3 5%NH3
20 15.0 15.0 8.9 7.8
25 15.0 15.0 8.4 7.1
30 15.0 15.0 7.9 6.6
35 15.0 15.0 7.6 6.4
40 15.0 15.0 7.4 6.5
45 15.0 15.0 7.8 6.9
50 15.0 15.0 8.8 7.9

let of the tower were obtained after CO2 absorption using ammonia
concentrations of 2%, 3%, 4%, 5% respectively. According to Eq. (9),
the different ammonia concentrations corresponds to different H/
(DAkCM)0.5 and Pa/U, a linear correlation can be achieved through
plotting Pa/U versus H/(DAkCM)0.5 (correlation coefficient of
0.997), as shown in Fig. 7, the experiments were carried out under
following conditions, ammonia flow rate of 3 L min1, inlet gas
flow rate of 0.4 m3 h1, CO2 partial pressure of 15 kPa, gas temper-
ature of 20 °C. According to Eq. (9), a1v ¼ 0:010; kG1av ¼ 4:60 can be
obtained, then aV = 98.33 m2/m3, kG = 0.0022 kmol kPa m2 h1 can
be calculated.
3.2.1. Effects of L/G on kG and aV
To investigate the influences of L/G on kG and aV, following
experimental conditions were used, gas flow rate of 0.4 m3 h1,
CO2 partial pressure of 15 kPa, gas temperature of 20 °C, ammonia
concentrations of 2%, 3%, 4% and 5%, the relationships of kG and aV
with L/G in the CO2 absorption process are shown in Fig. 8.
As can be seen from Fig. 8, KG and aV all increase with the in-
crease of the L/G, and rising trend of aV is even more obvious. kG
and aV increase by 10.05% and 20.11% respectively when the L/G
changes from 0.225 m3 m3 to 0.45 m3 m3. This is because of
the increasing L/G will exacerbate the turbulence degree at the
interface of the gas–liquid two-phase, so that the mass transfer
resistance at the interface of gas–liquid reduces, thereby the mass
transfer coefficient of gas phase at the interface will increase; on
the other hand, the increase of L/G will increase the number of
the droplets of aqueous ammonia, thereby increasing the effective
Fig. 8. Effects of L/G on kG and aV.
mass transfer across-sectional area will happen between the gas
and liquid phases.
3.2.2. Effects of gas flow rate on kG and aV
To investigate the influences of the gas flow rate on kG and aV,
the experiments were carried out with following conditions, the
ammonia flow rate of 3 L min1, CO2 partial pressure of 15 kPa,
gas temperature of 20 °C, aqueous ammonia concentrations of
2%, 3%, 4%, 5%, the effects of different gas flow rate on kG and aV
in the CO2 absorption process were investigated, and the experi-
mental results are shown in Fig. 9.
As can be seen from Fig. 9, kG and aV values increase with
increasing gas flow rate, and the upward trend of kG is more obvi-
ous. When the gas flow rate changes from 0.2 m3 h1 to 0.4 m3 h1,
kG and aV increase by 21.43% and 7.22% respectively. This is
because with the increase of the gas flow rate, gas speed acceler-
ates, the turbulence between ammonia atomized particles and
gas increases greatly, so that the mass transfer resistance at the
gas–liquid interface reduces, so as to effectively increase the mass
transfer partial coefficient of gas phase; on the other hand, CO2 ab-
sorbed by ammonia at the gas–liquid interface increases quickly
companying with the increasing gas flow rate, higher CO2 distribu-
tion amount is maintained, thereby aV at the gas–liquid interface is
enhanced. But increasing the gas flow rate will reduce the ratio of
liquid to gas, resulting in lower CO2 removal rate. Therefore, for the
consideration of practical application, operator can try to increase
the gas flow rate to improve the mass transfer performance in CO2

Fig. 7. Calculation curve of Pa/U versus H/(DAkCM)0.5. Fig. 9. Effects of gas flow rate on kG and aV.
702 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703

As can be seen from Fig. 10, with the rising of partial pressure of
CO2, kG values increase slightly, aV values un-change essentially.
When CO2 partial pressure rises from 10 kPa to 20 kPa, kG rises
7.18%; the changing amount of aV keeps at ±1.04%. This is because
higher CO2 concentration in the gas phase, higher the partial pres-
sure of the gas phase, the mass impetus of gas phase enhances,
which makes kG value increase. According to two-film theory, aV
is unchanged under constant gas flow rate, the absorbent flow rate
and the absorbent concentration [30], the experimental calculation
data matches the theoretical results, thus the accuracy of the rele-
vant experimental methods and data processing methods are
proved.

3.3. Summary of main mass transfer parameters

Table 8 shows the comparison of the CO2 mass transfer param-

Fig. 10. Effects of CO2 partial pressure on kG and aV.
absorption process under the precondition of ensuring CO2
removal efficiency.
3.2.3. Effects of CO2 partial pressure on kG and aV
To investigate the influences of CO2 partial pressure on kG and
aV, the experiments were carried out with following conditions,
the ammonia flow rate of 3 L/min, the gas flow rate of
0.4 m3 h1, gas temperature of 20 °C, aqueous ammonia concentra-
tions of 2%, 3%, 4%, 5%, the effects of different CO2 partial pressure
on kG and aV in the CO2 absorption process were investigated, and
the experimental results are shown in Fig. 10.
eters between the calculated results in this experiment and other
results gotten from similar experimental conditions in packed
tower. Through the comparison in Table 8 we can see that the mass
transfer parameters calculated in this experiment is less than those
in packed tower under similar conditions. This shows that gas–li-
quid mass transfer performance of packed tower is better than that
of spray tower. This is because the filler can effectively increase gas
liquid contact area in the absorption tower.
4. Conclusions
The experimental study of CO2 absorption using ammonia solu-
tion was carried out in the spray tower, some important factors re-
lated to the design of absorbing device, such as volumetric overall

Table 8
Main mass transfer parameters summary.

KGaV/ a V/ kG/ Reactor size Filler type Experimental conditions References

kmol m3 h1 kPa1 m2 m3 kmol kPa1 m2 h1
0.33–1.17 – – Tower diameter: 50 mm Glass spring Pressure: 3 kPa [31]
Absorbent: 1.5%–5% ammonia
CO2 concentration: 8%–16%
Gas flow rate: 0.6 m3 h1
Liquid flow rate: 0.03–0.13 L min1
0.13–0.22 – – Tower height: 2.4 m 350Y(structured Pressure : 0.1 MPa [32]
packing)
Packing layer height: Temperature: 300 K
2.0 m
Tower diameter: 0.15 m Absorbent: 0.36–0.72 mol L1
ammonia
CO2 concentration: 2.8%–8%
Gas flow rate: 7.9–12.7 m3 h1
Liquid flow rate: 1.83–3.67 L min1
– 128.2– – Packing layer height : Raschig ring: Pressure : 0.1 MPa [33]
170.9 70 cm 4  4  1 mm
Temperature: 25 °C
Tower diameter: 35 mm Absorbent: 0.5MNa2CO3–
0.5MNaHCO3,
Absorbent concentration: 0.005–
0.02 mol L1
Liquid flow rate: 1.6–5.6 kg m2 s1
0.09–0.20 115.5– 0.00065–0.0076 Packing layer height : Raschig ring: u8 Pressure : 0.1 MPa [34]
135.9 400 mm
Temperature: 20 °C
Tower diameter: 100 mm Absorbent: 2%–8% mol L1 ammonia
CO2 concentration: 15%
Gas flow rate: 0.96–1.68 m3 h1
Liquid flow rate: 0.27 L min1
0.08–0.17 81.87– 0.0018–0.0022 Tower diameter: 5.5 cm Pressure : 0.1 MPa In this
99.25 experiment
Temperature: 20 °C
Absorbent: 1%–7% mol L1
ammonia:
CO2 concentration: 10%–20%
Gas flow rate: 0.2–0.4 m3 h1
Liquid flow rate: 0.15–0.3 L min1
 S. Ma et al. / International Journal of Heat and Mass Transfer 67 (2013) 696–703
mass transfer coefficient, the gas phase mass transfer coefficient
and effective cross-sectional area are measured in the paper, main
conclusions list in the following:
(1) KGaV increases as the increasing ammonia concentration, L/G
and gas flow rate; KGaV increases at first and then decreases
with the increasing CO2 partial pressure and gas tempera-
ture, the highest KGaV value appears under CO2 partial pres-
sure of 15 kPa and gas temperature of 30–40 °C.
(2) kG rises with the increasing L/G, gas flow rate, CO2 partial
pressure; aV increases as the L/G and gas flow rate increase.
The effects of L/G on aV and gas flow rate on kG are more
apparent.
(3) The impact of CO2 partial pressure on KGaV, kG and aV is not
obvious, mass transfer process of CO2 absorption using
ammonia solution is mainly affected by the gas and liquid
flow rate.
Acknowledgements
The authors are highly thankful for the financial supports of Na-
tional Natural Science Foundation of China (21176064?and Natural
Science Foundation of Hebei province( B2013502263).
References
[1] J.D. Figueroa, T. Fout, S. Plasynski, H. McIlvried, R.D. Srivastava, Advances in
CO2 capture technology, the US department of energy’s carbon sequestration
program, Int. J. Greenhouse Gas Control 2 (2008) 9–20.
[2] F. Karadas, M. Atilhan, S. Aparicio, Review on the use of ionic liquids (ILs) as
alternative fluids for CO2 capture and natural gas sweetening, Energy Fuels 24
(2010) 5817–5828.
[3] P.H.M. Feron, Exploring the potential for improvement of the energy
performance of coal fired power plants with post-combustion capture of
carbon dioxide, Greenhouse Gas Control 4 (2010) 152–160.
[4] G. Puxty, R. Rowland, A. Allport, Q. Yang, M. Bown, R. Burns, M. Maeder, M.
Attalla, Carbon dioxide post combustion capture: a novel screening study of
the carbon dioxide absorption performance of 76 amines, Environ. Sci. Technol.
43 (2009) 6427–6433.
[5] J.Z. Liu, S.J. Wang, B. Zhao, H.L. Tong, C.H. Chen, Absorption of carbon dioxide in
aqueous ammonia, Energy Procedia 1 (2009) 933–940.
[6] R. Wang, D.F. Li, D.T. Liang, Modeling of CO2 capture by three typical amine
solutions in hollow fiber membrane contactors, Chem. Eng. Process. 43 (2004)
849–856.
[7] J.T. Yeh, K.P. Resnik, K. Rygle, H.W. Pennline, Semi-batch absorption and
regeneration studies for CO2 capture by aqueous ammonia, Fuel Process.
Technol. 86 (2005) 1533–1546.
[8] J. Wolf, M. Anheden, J. Yan, Comparison of nickel-and iron-based oxygen
carriers in chemical looping combustion for CO2 capture in power generation,
Fuel 84 (8) (2005) 993–1006.
[9] M. Wang, L.Q. Zhang, L.X. Gao, K.W. Pi, J.Y. Zhang, C.G. Zheng,
Improvement of the CO2 absorption performance using ionic liquid
[NH2emim][BF4] and [emim][BF4]/[bmim][BF4] mixtures, Energy Fuels 27
(2013) 461–466.
[10] N. Liu, D.P. Liu, Y.M. Xie, Experimental study on CO2 storage by hydrate
crystallization, Proc. CSEE 29 (14) (2009) 36–40.
703
[11] R. Idem, M. Wilson, P. Tontiwachiwuthikul, A. Chakma, A. Veawab, A.
Aroonwilas, D. Gelowitz, Pilot plant studies of the CO2 capture performance
of aqueous MEA and mixed MEA/MDEA solvents at the university of Regina
CO2 capture technology development plant and the boundary dam CO2
capture demonstration plant, Ind. Eng. Chem. Res. 45 (2006) 2414–2420.
[12] S.C. Ma, M.X. Wang, Y.W. Sun, J.W. Cui, W.Z. Chen, Comparing experimental
research on capture of CO2 from flue gas by ammonia solution and MEA, J.
Power Eng. (1) (2012) 52–58.
[13] Z.Q. Niu, Y.C. Guo, W.Y. Lin, Comparison of capture efficiencies of carbon
dioxide by fine spray of aqueous ammonia and MEA solution, J. Chem. Chin.
Univ. 21 (3) (2010) 514–517.
[14] K.P. Resnik, J.T. Yeh, H.W. Pennline, Aqua ammonia process for simultaneous
removal of CO2, SO2 and NOx, Int. J. Environ. Technol. Manage. 4 (1/2) (2004)
89–104.
[15] G. Pellegrini, R. Strube, G. Manfrida, Comparative study of chemical absorbents
in post combustion CO2 capture, Energy 35 (2) (2010) 851–857.
[16] J.Y. Kim, K. Han, H.D. Chun, CO2 absorption with low concentration ammonia
liquor, Energy Procedia (1) (2009) 757–762.
[17] X.N. Li, E. Hagagaman, C. Tsouris, J.W. Lee, Removal of carbon dioxide from flue
gas by ammonia carbonation in the gas phase, Energy Fuels 17 (1) (2003) 67–
74.
[18] R.E. Tteybal, Mass-transfer Operation, 3rd ed., McGraw Hill, New York, 1985.
[19] P.C. Luo, Z.B. Zhang, Z. Jiao, Z.X. Wang, Investigation in the design of a CO2
cleaner system by using aqueous solutions of monoethanolamine and
diethanolamine, Ind. Eng. Chem. Res. 42 (2003) 4861–4866.
[20] K. Onda, E. Sada, H. Takeuchi, Gas absorption with chemical reaction in packed
columns, Chem. Eng. Jpn. 1 (1968) 62.
[21] K. Onda, H. Takeuchl, Y.J. Okumoto, Gas absorption in packed column, Chem.
Eng. Jpn. 1 (1966) 56.
[22] W.G. Whitman, D.S. Davis, Comparative absorption rates for various gases, Ind.
Eng. Chem. 16 (12) (1924) 1233–1237.
[23] A. Adisom, T. Paitoon, Mass transfer coefficients and correlation for CO2
absorption into 2-amino-2-methyl-1-propanol(AMP) using structured
packing, Eng. Chem. Res. 37 (1998) 569–575.
[24] D. Montigny, P. Tontiwachwuthikul, A. Chakma, Comparing the absorption
performance of packed columns and membrane contactors, Ind. Eng. Chem.
Res. (44) (2005) 5726–5732.
[25] Q. Zeng, Y.C. Guo, Z.Q. Niu, W.Y. Lin, Volumetric overall mass transfer
coefficients of CO2 absorption into aqueous ammonia of fine spray, Proc. CSEE
31 (2) (2011) 45–50.
[26] S. Maaleja, B. Benaddab, M. Otterbeinb, Interfacial area and volumetric mass
transfer coefficient in a bubble reactor at elevated pressures, Chem. Eng. Sci.
58 (2003) 2365–2376.
[27] B.W. Wang, C.F. Zhang, S.J. Qin, Study on CO2 absorption kinetics of MDEA
solution, CIESC J. (4) (1991) 466–474.
[28] Q. Zeng, Y.C. Guo, Z.Q. Niu, W.Y. Lin, The absorption rates of CO2 by aqueous
ammonia solution in a spray column, Acta Sci. Circumstantine 31 (2) (2011)
381–387.
[29] H. Bai, A.C. Yeh, Removal of CO2 greenhouse gas by ammonia scrubbing, Am.
Chem. Soc. 36 (6) (1997) 2490–2493.
[30] H. Boseh, G.F. Verseteg, W.P.M. Swaaij, Gas-liquid mass transfer with parallel
reversible reactions – III. Absorption of CO2 into solutions of blends of amines,
Chem. Eng. Sci. 44 (10) (1989) 2745–2750.
[31] Z.Z. Qiu, S.L. Gong, C.R. Zeng, L. Zhang, H. Li, P. Li, Q.M. Li, Simultaneous
absorption of SO2 and CO2 by aqueous ammonia in a packed column, J. Chin.
Soc. Power Eng. 31 (9) (2011) 700–704.
[32] Z.L. Tang, J.X. Zhao, B.T. Liu, C.J. Liu, T. Chen, X.G. Yuan, Volumetric overall mass
transfer coefficients of CO2 absorption into aqua ammonia in structured
packed column, CIESC J. 63 (2012) 1102–1107.
[33] G.W. Xu, C.F. Zhang, S.J. Qin, B.C. Zhu, Study of gas liquid mass transfer
parameters in packed tower (I)-effective mass transfer area and the volumetric
mass transfer coefficient, Chem. Eng. 24 (1) (1996) 15–18.
[34] Q. Zeng, Y.C. Guo, Z.Q. Niu, W.Y. Lin, Mass transfer performance of CO2
absorption into aqueous ammonia in a packed column, CIESC J. 62 (2011) 146–
150.