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Chemical Engineering Science 62 (2007) 7305 7311

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Dynamic modeling and simulation of absorption of carbon dioxide


into seawater
Masahiro Tokumura, Mayumi Baba, Yoshinori Kawase
Department of Applied Chemistry, Toyo University, Kawagoe, Saitama 350-8585, Japan
Received 19 April 2007; received in revised form 18 June 2007; accepted 13 August 2007
Available online 30 August 2007

Abstract
In order to elucidate the dynamic performance of the CO2 ocean disposal process, effects of operating parameters, such as gas ow rate,
salinity and temperature, on the absorption of CO2 into seawater were examined. The rate-based model consisting of the rates of chemical
reaction and gasliquid mass transfer was developed for simulating dynamic process of CO2 ocean disposal. In modeling, non-ideal mixing
characteristics in the gas and liquid phases are described using a tanks-in-series model with backow. Experiments were performed to verify
dynamic CO2 absorption prediction capability of the proposed model in a cylindrical bubble column. The operation was batch and continuous
with respect to liquid phase and gas phase, respectively. Experimental results indicate that the CO2 gas injection rate increased the absorption
rate but the increase in salinity concentration caused inhibition of the absorption of CO2 . The proposed model could describe the present
experimental results for the dynamic changes and the steady-state values of dissolved CO2 concentration and hydrogen ion concentration. The
proposed model might effectively handle the prediction of the absorption of CO2 into seawater in the CO2 ocean disposal.
2007 Elsevier Ltd. All rights reserved.
Keywords: CO2 absorption; Seawater; Dynamic simulation model; CO2 ocean disposal

1. Introduction
There is an environmental concern for a reduction of greenhouse gas emitted from industrial sources to alleviate the
global warming problem. Although the ability to dispose
of large quantities of CO2 is highly uncertain, the CO2 gas
injection into the seawater is one of possible options (e.g.,
Kajishima et al., 1997; Kheshgi, 2004). A gas-lift advanced
dissolution system consisting of an inverse-J shape air-lift pipe
has been proposed as one of promising technologies for CO2
ocean disposal (Kajishima et al., 1997; Niwa et al., 2005)
(Fig. 1). From the viewpoint of low-cost and low-energy consumption, CO2 gas emitted from the emission sources such
as power plants and steel industries is concentrated before
it is compressed by compressor and injected into the airlift
pipe. Therefore, this system was rst proposed for highefciency sequestration of pure CO2 into the ocean (e.g.,
Kajishima et al., 1995, 1997). Later the system was extended
to low-purity CO2 gas system (CO2 purity of 0.6 0.9)
Corresponding author. Tel.: +81 492391377; fax: +81 4921311031.

E-mail address: bckawase@mail.eng.toyo.ac.jp (Y. Kawase).


0009-2509/$ - see front matter 2007 Elsevier Ltd. All rights reserved.
doi:10.1016/j.ces.2007.08.074

(Niwa et al., 2005). Bubbles of CO2 -rich gas mixture compressed by compressor are injected into the shorter pipe (riser)
being about 200 400 m depth. In the riser, bubbles lift up seawater and simultaneously CO2 gas dissolves into accompanied
seawater. The resulting CO2 -enriched seawater, the density of
which is heavier than that of the ambient seawater, ows down
in the longer pipe (downcomer) and is released into sea at a
depth of 1000 3000 m. In order to elucidate dynamic process
of CO2 ocean disposal, an understanding of CO2 absorption
into seawater associated with chemical reactions is essential
and certain fundamental data are required. An important design
feature is the transfer of CO2 from the gas phase to the liquid
solvent. Although few studies are available on the process of
CO2 absorption into seawater (i.e., Tsuchiya et al., 1997; Saito
et al., 2004), no mechanistic investigation appears to model
the dynamic process of CO2 absorption into seawater in which
the rates of chemical reaction and mass transfer are precisely
considered besides the equilibria. A dynamic model can provide valuable information for startup and shutdown operations,
optimal design and operability studies besides a steady-state
performance (i.e., Schulzke et al., 1998; Kanai et al., 2000).

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M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

Fig. 1. Schematic representing a gas-lift advanced dissolution system


(Kajishima et al., 1995).

In this work, we develop a model utilized to simulate and assess ocean disposal of CO2 . The model developed in this study
is based on reaction kinetics in the liquid phase and gasliquid
mass transfer combined with the tanks-in-series model for nonideal mixing in the gas and liquid phases. Effects of CO2 injection rate, salinity and temperature on the CO2 absorption
into seawater have been measured in a bubble column and the
present data have been compared with a proposed rate-based
simulation model.
2. Experimental
All experiments were carried out in a cylindrical bubble
column of 0.098 m diameter and 1.52 m height. Its working
volume was 5 L. The operation was batch and continuous with
respect to liquid phase and gas phase, respectively. Almost pure
gas CO2 (97%) was injected through the porous glass lter
sparger as well as the studies for elucidating the fundamental
phenomena in the gas lift advanced dissolution system of Saito
et al. (1999), Tsuchiya et al. (1997) and Niwa et al. (2005).
Incidentally, the CO2 purity range in the gas lift advanced dissolution system for low-purity CO2 gas system was from 0.6
to 0.9 (Niwa et al., 2005). The volumetric inlet ow rate of
CO2 gas was varied from 1 to 4 L min1 . In order to discuss
effects of salinity on absorption of CO2 , seawater and tap water were used as a liquid phase. Liquid samples were withdrawn intermittently from the top of the bubble column for the
determination of DIC (dissolved inorganic carbon) concentration. The combustion-infrared TOC (total organic carbon) meter

Fig. 2. The tanks-in-series model with backow for a semi-batch bubble


column.

(TOC-VE, Shimadzu, Co.) was used to measure DIC in the solutions. The pH or [H+ ] and temperature of the solution were
measured using a pH meter (HM-20P, Toa Denpa, Co.), which
was immersed near the top of the reactor. Salinity was measured using a refract meter (ATC-S, ATAGO).
3. Rate-based simulation model
In our previous work (Tokumura et al., 2006), a tanks-inseries concept was used to describe the dynamic behaviors of
CO2 removal from seawater by air stripping in the neutralization process of the acidied seawater efuent. It was assumed,
however, that the liquid phase is completely mixed and the ow
rate of air injected to remove CO2 is not changed due to transport of CO2 . We extended our previous model for CO2 removal
from seawater to the CO2 absorption into seawater in the CO2
ocean disposal. The tanks-in-series model with backow owing through a series of equal sized, well-mixed stirred tanks,
has been applied to represent performance of reactors under a
wide range of operating conditions (Fig. 2). We assumed that
the mixing in the gas phase is described by NG = 10 in this
simulation. The backow rate indicates the degree of mixing
in the reactor as well as the number of hypothetical tanks. In
other words, the incomplete liquid mixing can be described by
both the number of hypothetical tanks and backow rate. In
this study, the number of tanks for the liquid phase was xed as
NL = 10 and the change in liquid phase mixing with gas injection rate was taken into account by the backow rate through
the hypothetical tanks. In general the mixing in the liquid phase

M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

is more well-mixed as compared with that in the gas phase,


i.e., NL NG . Incidentally, NG must be equal to NL or even
number times of NL . The numbers of tanks for the gas and liquid phases in this work were chosen since they provided satisfactory prediction results in comparison with the experimental
data. Although we chose NL = NG = 10 in this study, the backow in the liquid phase is responsible for the more mixing in
the liquid phase as compared with the gas phase. The backow
rate was evaluated on the basis of the liquid velocity prole in
a bubble column. For batch operation with respect to the liquid phase, in the center region of the column the liquid rises
with the bubbles while in the outer annular region liquid ows
downward. As shown in Fig. 2, the rates of liquid up ow and
the liquid down ow corresponding to backow in the proposed
tanks-in-series model are equal to each other.
In seawater, carbon dioxide exists in four different inorganic forms: as free carbon dioxide (CO2 ), bicarbonate
2
ion (HCO
3 ), carbonate ion (CO3 ) and true carbonic acid
(H2 CO3 ) (Tokumura et al., 2006).
The concentration of CO2 dissolved in seawater is given by
Henrys law:
[CO2 ] = He YCO2 .

kf 1

+
CO2 + H2 O  (H2 CO3 )HCO
3 +H ,
kb1

(2)

kf 2

2
+
HCO
3  CO3 + H ,
kb2

kb3

2
+ QLi1 /(VL /NL ) ([CO2
3 ]i1 [CO3 ]i )
2
+ QLi /(VL /NL ) ([CO2
3 ]i+1 [CO3 ]i ).
(7)

The rate of change in dissolved carbon dioxide for ith tank


(i = 1, . . . , NL ) may be written as

[CO2 ]i )
d[CO2 ]i /dt = (KL aL )CO2 i (CCO
2i

+ (kb1 [H+ ]i + kb4 )[HCO


3 ]i
(kf 1 + kf 4 [OH ]i )[CO2 ]i
+ QLi1 /(VL /NL ) ([CO2 ]i1 [CO2 ]i )
+ QLi /(VL /NL ) ([CO2 ]i+1 [CO2 ]i ), (8)

where

CCO
= 1/R
2i

iR


He YCO2 j

(9)

j =(i1)R+1

and
(KL aL )CO2 i = 1/R

iR


(KL aL )CO2 j .

(10)

j =(i1)R+1

Since, as shown in Fig. 2, the rate of the upow from ith tank
must be equal to that of the downow from (i + 1)th tank, the
terms for QLi+1 are not included in Eqs. (5)(8).
The concentration of true carbonic acid (H2 CO3 ) is given by
the following equation obtained from Eq. (2):

[H2 CO3 ] = [H+ ][HCO


3 ]/KH2 CO3 .

(4)

The sum of the dissolved forms for the carbonate system, CO2 ,
2
HCO
3 and CO3 , is called total DIC which was experimentally
measured using the TOC meter.

At low pH, the hydration of CO2 (Eq. (2)) is predominant. The


reaction of Eq. (3) is considered to be instantaneous. At high
pH value, the controlling mechanism of CO2 absorption is a
reaction of CO2 with a hydroxyl ion giving a bicarbonate ion
(Eq. (4)).
The change in concentration of hydroxyl ion in seawater for
ith tank (i = 1, . . . , NL ) is written as

d[H+ ]i /dt = kf 1 [CO2 ]i kb1 [H+ ]i [HCO


3 ]i +kf 2 [HCO3 ]i
+
kb2 [CO2
3 ]i [H ]i
+QLi1 /(VL /NL ) ([H+ ]i1 [H+ ]i )
+ QLi /(VL /NL ) ([H+ ]i+1 [H+ ]i ).

2
+
d[CO2
3 ]i /dt = kf 2 [HCO3 ]i kb2 [CO3 ]i [H ]i

(3)

kf 3

CO2 + OH  HCO
3.

and

(1)

Since the hydration of CO2 leads to the formation of H2 CO3


but it may also yield hydrogen ion, H+ , and bicarbonate
ion, HCO
3 , the reaction of dissolved CO2 in seawater is described as

7307

(5)

2
For the material balances of [HCO
3 ] and [CO3 ] for ith tank
(i = 1, . . . , NL ), we have
2

+
d[HCO
3 ]i /dt = (kf 1 +kf 4 [OH ]i )[CO2 ]i +kb2 [CO3 ]i [H ]i

2
DIC = [CO2 ] + [HCO
3 ] + [CO3 ].

(11)

(12)

The decrease in gas ow rate due to the absorption into the


liquid phase and the gas-phase carbon dioxide concentration,
YCO2 j , for jth tank (j = 1, . . . , NG ) under continuous gas-ow
conditions can be represented by the following equations:
dQGj /dt = Ac dUGj /dVGj /dVGj /dt

= Ac {(QGj 1 QGj ) (KL aL )CO2 j (CCO


2j
[CO2 ]i )(Rg T /P )(VL /NL )} dUGj /dVGj (13)
and
YCO2 j = (QGCO2 j /QGj )P ,

(14)

respectively. Here, i is the largest integer in [1 + (j 1)/R].


The term of dUGj /dVGj in Eq. (13) is given as

(kb4 + kf 2 + kb1 [H+ ]i )[HCO


3 ]i

dUGj /dVGj = 1/d{gj /(1 gj ) VL /NL }/dUGj ].

[HCO
3 ]i ) + QLi /(VL /NL )

As presented below, the gas hold-up, gj , is a function of supercial gas velocity, UGj . It should be noted that the liquid ow
rates at the column bottom and the column top, QL0 and QLN L ,

+ QLi1 /(VL /NL ) ([HCO


3 ]i1

([HCO
3 ]i+1 [HCO3 ]i )

(6)

(15)

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M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

are zero because the liquid is batchwise. The correlations for


Henrys constant, the equilibrium constants and the reaction
rate constants in Eq. (1)(9) and (11), which are functions of
salinity and temperature, are summarized in our previous work
for neutralization of the acidied seawater efuent from the
ue gas desulfurization process (Tokumura et al., 2006).
In our previous work (Tokumura et al., 2006), the volumetric mass transfer coefcients and gas hold-ups for O2 transfer
into seawater and tap water were measured and the following correlations for CO2 transfer into seawater at 25 C were
obtained:
(KL aL )CO2 j = (DCO2 /DO2 )

0.5

region is
uri /u0i = 2.35{(r/R)2 1} 2.55 ln(r/R),
where the liquid velocity in the plume, u0 , is given as
2
u0i = (3.34/D){(Ugi D/)(Ugi
/Dg)0.25 }0.92 ,

j =(i1)R+1

The ow rate between the tanks in the liquid phase, QLi (i =


1, . . . , NL1 ), is evaluated by the following integration:
 2  R
QLi = 2
uri r dr d.
(21)

(16)

and

1.15
gj = 13.5Ugj
,

0.5R

By numerically solving the ve simultaneous ordinary differential equations (Eqs. (5)(8) and (13)), we can estimate the axial distributions of DIC (Eq. (12)), solution pH(= log[H+ ]),
concentrations of dissolved CO2 species and concentration and
ow rate distribution of CO2 in the gas phase as a function
of aeration time. A fourth-order Runge-Kutta technique was
applied to solve the differential equations.

(17)

respectively. Incidentally, the KL aL values in seawater were


about 50% higher than those in tap water but the gas hold-ups
in seawater were only slightly higher than those in tap water.
The values of KL aL and g at different temperatures were estimated using the widely used correlation (e.g., Eckenfelder,
2000). It should be emphasized that the changes in KL aL and
g with the gas ow rate along the column axis changed due
to dissolution of CO2 into the liquid are considered in the simulation. The ow rate between the tanks in the liquid phase,
QLi (i = 1, . . . , NL1 ), is evaluated using the central plume
model for the laminar liquid ow in semi-batch bubble columns
(Ulbrecht et al., 1985). In a semi-batch bubble column, liquid
ows downward in the outer annular region (0.5R < r < R)
while the liquid rises with the bubbles in the center of the column (0 < r < 0.5R) in the low Reynolds number region. The
resulting equation for the velocity prole in the outer annular

4. Results and discussions


The experiments were carried out to validate the proposed
dynamic simulation model for CO2 absorption. Fig. 3 depicts the experimental results for CO2 absorption processes
into seawater and tap water having salinity of 40 and 5 g/(kgsolution), respectively. After the start of CO2 gas injection,
the rather sharp increase in dissolved CO2 concentration, DIC,
with time was found and was followed by a plateau to steadystate value. The steady-state CO2 concentrations in seawater,

0.04

0.04
QG 0=1 L/min

QG0=2 L/min

QG 0=3 L/min

QG0=4 L/min

0.03
(DIC) at i=NL [M]

0.03

0.02
3
kDIC [min-1]

(DIC) at i=NL [M]

(19)

where Ugi is the supercial gas ow velocity dened as



iR

Ugi = 1
R
Ugj .
(20)

(KL aL )O2 j

0.44
= (DCO2 /DO2 )0.5 (0.190 Ugj
)

(18)

0.01

2
1

0.02

0.01

seawater (S=40 [g/L])


tap water (S=5 [g/L])

0
0
0.002 0.004 0.006 0.008 0.01
superficial inlet gas velocity, Ug (at j=0) [ms-1]

QG 0=1 L/min

QG 0=2 L/min

QG 0=3 L/min

QG 0=4 L/min

0
0

4
time [min]

4
time [min]

Fig. 3. Effect of CO2 gas injection ow rate on CO2 absorption (at 24 C); (a) seawater (S = 40 g L1 ), (b) tap water (S = 5 g L1 ) (Solid lines represent
the model predictions).

M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

0.03
3

0.02

0.01

10

time [min]
Fig. 4. Effects of salting-out and solvent on CO2 absorption process (seawater,
QG0 = 4 L min1 , T = 24 C).

i.e., the equilibrium dissolved CO2 concentrations, were lower


than those in tap water. Later this result is examined in detail. The absorption process was enhanced by the increase in
gas ow rate. The increase in gas ow rate enhanced the liquid phase mixing and as a result increased the specic surface
area causing an increase of the gasliquid mass transfer rate
and as a result improved the absorption rate of CO2 . At the beginning of CO2 absorption, the CO2 concentration in the outlet gas phase is almost zero due to the quick absorption into
the liquid phase. Therefore, the CO2 gas is not reached at the
column top. As a result, the lag time of DIC was observed
at lower gas injection rates as shown in the gure. In addition to the rigorous rate model, the data for CO2 absorption
was analyzed with the common pseudo-rst-order assumption.
This approach is useful to understand the CO2 absorption rate.
The changes in DIC at the initial stage of the absorption process could be described by the pseudo-rst-order kinetics with
respect to DIC
d(DIC)/dt = kDIC (DIC).

(DIC)

0.03
-1
[CO2(aq)]

0.025

log[HCO3-]

0.02
0.015

log[H2CO3]

0.01

log[CO32-]

(22)

The pseudo-rst-order kinetic constants for changes in DIC at


the initial stage of the absorption process, kDIC , were determined from the semi-logarithmic plots of DIC as a function
of time. It is clear from the gure for kDIC given in Fig. 3 (a)
that the rates of CO2 absorption are enhanced with increasing
CO2 gas injection rate and those into seawater and tap water
are similar to each other.
In the seawater with higher salinity the equilibrium values of
DIC were lower than tap water. The major difference between
seawater and tap water is the total concentration and the relative
proportion of ions dissolved in the solution. Seawater contains
more salt causing a solvent effect as compared with tap water
(Zeebe and Wolf-Gladrow, 2001). On the other hand, the higher
concentration of salinity decreases Henrys constant, He , due to
salting-out effect (Zeebe and Wolf-Gladrow, 2001). In Fig. 4,

-3
-5
-7

+
pH(=-log[H ])

0.005

-9
0

0
2

pH data

1 with salting-out and solvent effects


2 without salting-out effect
3 without solvent effect
0

DIC data

4
time [min]

14
12
10
pH

[CO2 (aq)] and (DIC) at i=NL [M]

(DIC) at i=NL [M]

0.035

log[HCO3-], log[CO32-] and


log[H2CO3] concentrations [M]

0.04

7309

8
6
4

2
Fig. 5. Changes in DIC, pH (or [H+ ]), [HCO
3 ], [CO3 ] and [H2 CO3 ]
at the bubble column top during CO2 absorption process (seawater,
QG0 = 4 L min1 , T = 24 C).

the computed effects of salting-out and solvent on dynamic CO2


absorption into seawater using the correlations in the literature
(Zeebe and Wolf-Gladrow, 2001, Tokumura et al., 2006) are
illustrated. Higher salinity led the lower DIC at equilibrium
and did not signicantly affect the absorption rate or the slope
of the DIC curves at the beginning of CO2 absorption process,
kDIC . It can be seen in Fig. 4 that the salting-out effect rather
signicantly depresses CO2 absorption while the solvent effect
enhancing CO2 absorption is very weak. The results suggest
that the salting-out effect overcame the solvent effect and as
a result caused the decrease in DIC at equilibrium. It can be
seen in Fig. 3 that the model predictions given as solid lines
reasonably t the experimental data of DIC at the column top
(i = NL ) for both seawater and tap water.
Computed concentration changes of DIC, CO2 (aq), bicar2
bonate (HCO
3 ), carbonate ion (CO3 ), carbonic acid (H2 CO3 )
+
and pH or proton (H ) in seawater during the absorption process at gas ow rate of 4 L min1 and T =24 C are depicted in
Fig. 5. The sharp increase in DIC is accompanied with the sharp
+
decreases in [CO2
3 ] and pH or increase in [H ] and the sharp

increase in [H2 CO3 ] while [HCO3 ] increases very slightly. Incidentally, when pH is higher than 5, [HCO
3 ] is the dominating
dissolved carbon dioxide species. For pH < 5, CO2 (aq) is the
dominant species. As shown in Fig. 4, the directly measured
data for DIC and pH or [H+ ] given as plots agree reasonably
well with the model predictions given as lines.
In this study, almost pure CO2 gas (97% purity) was used
as the gas phase. Therefore, almost injected gas was dissolved
into liquid phase while the liquid phase was unsaturated. As
a result, gas ow rate was decreased along the reactor height.
Fig. 6 shows model predictions of changing gas ow rate with
time at the inlet gas ow rate of 4 L min1 in seawater. As seen
from this gure, the outlet gas ow rate is signicantly low at
the beginning of CO2 absorption and increases with time or
degree of liquid phase saturation. Corresponding to this change
of QGN G , the rate of the liquid bulkow between the tanks
and CO2 partial pressure in the outlet gas ow increase with
time. The drastic increase in pCO2 in the outlet gas at the initial

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M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

12

QLNL-1 (Q G0=4 L/min)

QGNG and QLNL-1 [L/min]

10

120
pCO2 ( j=NG) (QG0=4 L/min)

pCO2 ( j=NG) (QG0=1 L/min)

80
QLNL-1 (QG0=1 L/min)

4
QGNG (QG0=4 L/min)

40

partial pressure , pCO2 at j=NG [kPa]

160

QGNG (QG0=1 L/min)

0
0

4
6
time [min]

10

Fig. 6. Computed changes of outlet gas ow rate, partial pressure of CO2 in


the outlet gas and liquid backow rate at the bubble column top (seawater,
QG0 = 4 L min1 , T = 24 C).

0.05

T=12.6[C]

T=15.2[C]

T=19.9[C]

T=23.7[C]

0.03
1
0.9

0.02

ln kDIC

(DIC) at i=NL [M]

0.04

0.8

18.5 103
RgT

0.5
0.00335 0.0034 0.00345 0.0035 0.00355
1/T [1/K]

0
0

5. Conclusions
We developed the rate-based model taking into account temperature and salinity of the solvents to simulate the dynamic
process of CO2 absorption into seawater. We also measured
changes in the concentration of DIC or dissolved CO2 concentration and solution pH or concentration of H+ in a bubble column during the absorption of CO2 into seawater and tap water.
It was experimentally found that the CO2 injection ow rate
enhanced the CO2 absorption rate and the salinity and temperature decreased the DIC at equilibrium. The proposed model,
which is based on the chemical reaction rates, the gasliquid
mass-transfer rate, and the nonideal mixing in both gas and
liquid phases, was validated by comparing its predictions with
the present experimental data for absorption of CO2 into seawater and tap water. The proposed model veried using the
almost pure CO2 gas system (97%) may be also applicable to
low-purity CO2 systems by taking account of mass transfer resistance in the gas phase. One of our future research subjects
is the study for the applicability of the model using the data in
full-scale plants, in which effects of pressure on CO2 absorption rate might be signicant.

0.7
0.6 kDIC = 4755.7 exp

0.01

temperature on the equilibrium constants and Henrys constant


in the above correlations (Tokumura et al., 2006). As shown in
the Arrhenius expression of the pseudo-rst-order rate constant,
with decreasing T or increasing the sea depth kDIC decreased.
The reduction in gas solubility with increasing the temperature
was overcome by the increase in sorption kinetics. It is seen
in Fig. 7 that on the whole the model predictions presented as
solid lines reasonably predict the experimental results at four
different temperatures.

10

time [min]
Fig. 7. Effect of temperature on CO2 absorption (seawater at QG0 =
4 L min1 ).

stage of CO2 absorption is due to almost purity of CO2 in the


inlet gas.
The seawater temperature is dependent of the sea depth. The
temperature distribution in the mid-latitude zone is rather large
along the range of depth between 50 and 700 m (Yanagi, 1988).
Fig. 7 presents the experimental data for effect of liquid temperature on the rate of CO2 absorption in seawater measured at
four different temperatures of 24, 20, 15 and 12.6 C, respectively. The temperatures of 24 and 20 C are corresponding to
the temperature near the sea surface in a mid-latitude zone.
The temperatures of 15 and 12.6 C are those at 215 and 275 m
depth, respectively (Yanagi, 1988). The DIC at equilibrium in
this experimental range of temperature decreased with increasing T. This result can be predicted by considering the effect of

Notation
AC
CCO2
D
DCO2
DO2
DIC
g
He
kb1
kb2
kb3
kf 1
kf 2
kf 3

Cross-sectional area of a bubble column, m2


dissolved carbon dioxide concentration at the
gasliquid interface, M
column diameter, m
diffusion coefcient of CO2 , m2 s1
diffusion coefcient of O2 , m2 s1
dissolved inorganic carbon, M
gravitational acceleration, m s2
Henrys constant, M Pa1
backward rate constant of carbonate system in seawater in Eq. (2), M1 s1
backward rate constant of carbonate system in seawater in Eq. (3), s1
backward rate constant of carbonate system in seawater in Eq. (4), s1
forward rate constant of carbonate system in seawater in Eq. (2), s1
forward rate constant of carbonate system in seawater in Eq. (3), s1
forward rate constant of carbonate system in seawater in Eq. (4), M1 s1

M. Tokumura et al. / Chemical Engineering Science 62 (2007) 7305 7311

kDIC
K L aL
KH 2 CO3
NG
NL
pCO2
P
QGCO2
QG
QL
r
R
Rg
S
t
T
ur
u0
Ug
VG
VL
YCO2

pseudo-rst-order reaction rate constant, min1


volumetric mass transfer coefcient, s1
Dissociation constant of true carbonic acid, M
the number of tanks for the gas phase
the number of tanks for the liquid phase
partial pressure of CO2 , Pa
pressure, Pa
volumetric gas ow rate of CO2 , m3 s1
volumetric gas ow rate, m3 s1
volumetric liquid ow rate, m3 s1
radial coordinate, m
ratio of the number of tanks for the gas phase to
that for the liquid phase(=NG /NL )
gas constant, J mol1 K 1
Salinity, gL1
time, s
temperature, K
radial liquid velocity distribution, m s1
liquid velocity at the center of a bubble column,
m s1
supercial gas velocity, m s1
gas volume, m3
liquid volume, m3
carbon dioxide concentration in the gas phase, Pa

Greek letters
g




gas hold-up
angular coordinate, rad
liquid viscosity, Pa s
liquid density, kg m3

Subscripts
i, j
0

ith and j th tank


inlet

7311

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