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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.
(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).
7306
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
(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
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)
[CO2 ]i )
d[CO2 ]i /dt = (KL aL )CO2 i (CCO
2i
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):
(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.
2
+
d[CO2
3 ]i /dt = kf 2 [HCO3 ]i kb2 [CO3 ]i [H ]i
(3)
kf 3
CO2 + OH HCO
3.
and
(1)
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)
(14)
[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 ,
([HCO
3 ]i+1 [HCO3 ]i )
(6)
(15)
7308
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
(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)
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]
(19)
(KL aL )O2 j
0.44
= (DCO2 /DO2 )0.5 (0.190 Ugj
)
(18)
0.01
2
1
0.02
0.01
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).
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).
(DIC)
0.03
-1
[CO2(aq)]
0.025
log[HCO3-]
0.02
0.015
log[H2CO3]
0.01
log[CO32-]
(22)
-3
-5
-7
+
pH(=-log[H ])
0.005
-9
0
0
2
pH data
DIC data
4
time [min]
14
12
10
pH
0.035
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).
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
7310
12
10
120
pCO2 ( j=NG) (QG0=4 L/min)
80
QLNL-1 (QG0=1 L/min)
4
QGNG (QG0=4 L/min)
40
160
0
0
4
6
time [min]
10
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
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
10
time [min]
Fig. 7. Effect of temperature on CO2 absorption (seawater at QG0 =
4 L min1 ).
Notation
AC
CCO2
D
DCO2
DO2
DIC
g
He
kb1
kb2
kb3
kf 1
kf 2
kf 3
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
Greek letters
g
gas hold-up
angular coordinate, rad
liquid viscosity, Pa s
liquid density, kg m3
Subscripts
i, j
0
7311
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