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The State Key Laboratory of Chemical Engineering, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China
Cooperative Research Centre for Greenhouse Gas Technologies (CO2 CRC), Department of Chemical and Biomolecular Engineering, The University of Melbourne,
Victoria 3010, Australia
b
a r t i c l e
i n f o
Article history:
Received 31 January 2011
Received in revised form 6 July 2011
Accepted 7 July 2011
Available online 10 August 2011
Keywords:
Super Mini Rings (SMRs)
CO2 capture
Flue gas
K2 CO3 solution
Packed column
a b s t r a c t
CO2 capture and storage has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO2 with hot potassium carbonate (K2 CO3 ) solutions has been
used in the past, however potassium carbonate solutions have a low CO2 absorption efciency. Various
techniques can be used to improve the absorption efciency of this system with one option being the
addition of promoters to the solvent and another option being an improvement in the mass transfer
efciency of the equipment. This study has focused on improving the efciency of the packed column by
replacing traditional packings with newer types of packing which have been shown to have enhanced
mass transfer performance. Three different packings (Super Mini Rings (SMRs), Pall Rings and Mellapak)
have been studied under atmospheric conditions in a laboratory scale column for CO2 absorption using
a 30 wt% K2 CO3 solution. It was found that SMR packing resulted in a mass transfer coefcient approximately 20% and 30% higher than that of Mellapak and Pall Rings, respectively. Therefore, the height of
packed column with SMR packing would be substantially lower than with Pall Rings or Mellapak. Meanwhile, the pressure drop using SMR was comparable to other packings while the gas ooding velocity was
higher when the liquid load was above 25 kg m2 s1 . Correlations for predicting ooding gas velocities
and pressure drop were tted to the experimental data, allowing the relevant parameters to be estimated
for use in later design.
2011 Published by Elsevier Ltd.
1. Introduction
In the battle against global warming, CO2 capture and storage
has gained widespread attention as an option for reducing greenhouse gas emissions. Chemical absorption and stripping of CO2 with
aqueous solvents including alkanolamines and hot potassium carbonate (K2 CO3 ) solutions are well-known and effective processes
for removing CO2 from power plant ue gases (Jassim and Rochelle,
2006). Compared with alkanolamines, potassium carbonate is less
toxic, less prone to oxidative solvent degradation and has a low heat
of regeneration (Cullinane and Rochelle, 2004; Uyanga and Idem,
2007). The reaction of K2 CO3 with CO2 has been studied extensively
and occurs via the following overall chemical reaction (Savage et al.,
1980):
CO2 + K2 CO3 + H2 O 2KHCO3
(1)
Corresponding author. Tel.: +61 3 8344 6621; fax: +61 3 8344 8824.
E-mail address: gstevens@unimelb.edu.au (G.W. Stevens).
1750-5836/$ see front matter 2011 Published by Elsevier Ltd.
doi:10.1016/j.ijggc.2011.07.006
1164
Nomenclature
a
specic surface area of the packing (m2 m3 )
C
constant
d
diameter (m)
A, B
constants from Eq. (2)
C1 , CFl , CP,0 Billet and Schultes coefcients
dp
diameter (or nominal size) of packing (m)
gas or vapour capacity factor (kg1/2 m1/2 s1 )
Fv
g
gravitational acceleration (m s2 )
G
mass owrate of liquid
H
Henrys Law constant (kmol m2 m3 N)
hL
column holdup
K
wall factor
overall gas phase mass transfer coefcient
Ky
(kmol m3 h1 )
k
parameter in the Takehashi pressure drop correlation
ky
gas lm mass transfer coefcient (kmol m3 h1 )
liquid lm mass transfer coefcient (kmol m3 h1 )
kl
L
mass ow of liquid (kg m2 s1 )
LW
liquid load (m3 m2 h1 )
Mt
molecular weight of water (kg kmol1 )
P
pressure (kPa)
Re
Reynolds number (Re = Du/)
S
column cross sectional area (m2 )
Sc
Schmidt number (Sc = /D)
T
temperature (K)
u
supercial velocity (m s1 )
V
mass ow of gas (kg m2 h1 )
x
equilibrium CO2 concentration in solution
(kmol m3 )
X
mass fraction of K2 CO3 in solution
Y
CO2 mol% in gas
y*
CO2 mol% in gas at equilibrium
Z
column height (m)
Greek letters
enhancement factor
Table 1
Geometric characteristics of SMR, Pall Ring and Mellapak packings.
Type of packing
Voidage, (m3 m3 )
13 mm SMR
13 mm Pall Ring
Mellapak 700Y
419
360
700
0.980
0.928
0.936
0.0130
0.0130
0.0036
1165
Fig. 1. Different packings used in this study: (a) 13 mm SMR; (b) 13 mm Pall Ring; and (c) Mellapak 700Y.
Fig. 2. Experimental set-up and ow scheme (1, solvent pump; 2, oil bath; 3, rotameter; 4, absorber; 5, liquid sample point; 6, cooling water; 7, condenser coil; 8, rich
solvent tank; 9, lean solvent tank).
rate, mass transfer coefcients were determined using a higher concentration of 85 mol% CO2 and 15 mol% N2 in order to enhance the
absorption performance.
The geometric characteristics of 13 mm SMR, 13 mm Pall
Ring and Mellapak 700Y are listed in Table 1. The equivalent
diameter of Mellapak 700Y was estimated using the calculation
procedures presented by Haan et al. (McCabe, 1967). The height of
each Mellapak 700Y packing element was 10 cm and 9 elements
were used in the packed section of the column.
The physical properties of the experimental system are shown
in Table 2. Gas viscosity was calculated using the method presented
in Perrys Chemical Engineers Handbook (Perry, 1984) and liquid
In a packed column, the gas and liquid rates are limited by the
tendency of the column to ood. As either liquid or gas velocity is
increased, the liquid holdup in the packing increases, the free area
for gas ow decreases, and the pressure drop through the column
increases. A point is nally reached when the gas bubbles violently
through the liquid, the pressure drop rises extremely sharply with
the slightest increase in gas velocity, and liquid is raised to the top of
the column via the upowing gas. This point is called the ooding
point and is determined by both gas and liquid rates. Although the
best operating conditions are determined by an economic balance, a
knowledge of ooding velocities is extremely useful in rstly determining the limiting gas and liquid rates above which operation is
not possible, and secondly in estimating the optimum liquid and gas
rates where there are not enough data to make an exact economic
balance of operating and xed cost (Sherwood et al., 1938).
As shown in Fig. 3, the gas ooding velocity of 13 mm SMR is
about 10% higher than that of the other packings at higher liquid
loads (>25 kg m2 s1 ). Higher liquid loads are preferred for this
application in order to improve CO2 absorption, as K2 CO3 solutions
have relatively low absorption efciency for CO2 capture. Under
these conditions, a higher gas velocity can also be utilized with
13 mm SMR. These characteristics suggest that SMR packing would
be benecial for the high throughputs required for CO2 capture
from coal red power stations.
Bain and Hougens equation (Bain and Hougen, 1944) can be
used to predict the ooding gas velocity of the different packings
discussed in this study (refer to Table 4). In the present case, the
Table 2
Physical properties of the gas and liquid phases.
System type
Temperature, T (K)
Density, (kg m3 )
343
343
343
1300
1.074
1.477
987.27
1.905
1.678
1166
0.7
0.6
Author
0.5
uv.Fl =
Billet and Schultes
(1999)
0.4
Fl
2g(hL,Fl )3 hL,Fl L
V
Fl a
0.2 2nFl
L
v
L
C2
Fl
L
L
0.4,
v
L
0.3
when
0.2
CFl = 0.6244CFl
L 0.1028
V
to conditions when
u2
0.0
0
V
SMR 13mm
Mellapak 700Y
Pall 13 mm
0.1
1/2
10
15
20
25
30
35
log
v,Fl a V
g 3 L
L
V
0.16
v
L
0.4.
L 1/4 v 1/8
= b 1.75
L
experimental data can be reasonably tted to this expression. However, the value of the constant b, is signicantly different from the
range suggested by these authors (0.0220.26) with an average
value across the three packings of 0.96 0.04. This constant is different to that proposed by Bain and Hougen most likely due to the
fact that this correlation was developed using only three types of
random packing materials and for a limited range of operating conditions. Alternatively, the expressions of Billet and Schultes (1999)
can be used to determine the ooding velocity, in combination with
the ooding holdup (see Tables 3 and 4). Again, the t to this expression is reasonable, but the values of the adjustable ooding constant
(CFl ) differ from that suggested by these authors (Table 5).
3.2. Liquid holdup
In a packed column, the liquid holdup refers to the liquid
retained in the packed bed including liquid lms or droplets on the
surface of the packing or the liquid trapped in the interstitial space
between the packing. There is a need to study the liquid holdup
because it has a direct inuence on liquid-phase mass transfer,
loading behaviour, gas-phase pressure gradients and mass transfer
(Skrbic and Cvejanov, 1994). It can be seen from Fig. 4 that 13 mm
Table 3
Pressure drop models for packed columns used in this study.
Author
Table 5
Values of the Billet and Schultes (1999) ooding constant (CFl ) in comparison to the
literature values.
SMR 13 mm
Pall Ring 13 mm
Mellapak 700Y
a
This study
1.48
1.41
1.89
2.92a
SMR and Mellapak 700Y generally have a higher liquid holdup than
the 13 mm Pall Ring.
3.3. Pressure drop
Pressure drop determines the operating reliability and cost of
the packed column. A comparison of the experimental pressure
drop in 13 mm SMR, 13 mm Pall Ring and Mellapak 700Y has
been shown in Fig. 5. From these results it can be seen that all three
packings have comparable pressure drops under the conditions
studied.
Several models for predicting the pressure drop in a packed column have been presented in the literature and the details of two
such correlations are shown in Table 3. Nonlinear regression of
the experimental data was used to evaluate the model parameters for the different packings (Table 6 and Fig. 6). The constant
developed for Pall Ring packing using the Billet and Schultes correlation is completely consistent with the values suggested in this
paper, and the parameters for the other two packings are well
within the range of values presented for all packings in this paper
(0.191.3). The Takehashi correlation was less successful but the
Fv2 1
a
(hl )3 2 K
where:
L =
64
Rev
CP.0
1.8
Re0.08
v
hl
1.5 h 0.3
L
hL,s
exp(C1
0.16
FrL )
u2 a
FrL =
1
= 1 + 23 1
Fv = uv v
1
K
hL =
0.18
13,300
3/2
C1 =
dp =
0.20
Holdup hL
P
Z
6(1)
a
12 L
g L
dp
ds
uL a2
P
Z
h=
= 2f
0.10
0.06
1/3
V
dp
SMR
MellaPak
Pall
0.04
where uv uv,s
0.02
0.742
; ReG 200, f = 6.85 ReG 0.216
ReG < 200,
f = 114
ReG
u2
0.12
0.08
0.14
u 2
3
+ kh
0.75
L
W
dp1.20
0.00
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Fig. 4. Comparison of liquid holdup for CO2 (14 mol%) absorption into K2 CO3 solution at 70 C using 3 packings: 13 mm SMR, 13 mm Pall Ring and Mellapak 700Y
at a liquid phase owrate of 14 kg m2 s1 .
1167
200
180
160
140
120
100
SMR
Mellapak
Pall
80
60
40
20
0
0.0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
Fig. 5. Comparison of pressure drop for CO2 (14 mol%) absorption into K2 CO3 solution at 70 C using 3 packings: 13 mm SMR, 13 mm Pall Ring and Mellapak 700Y
at a liquid phase owrate of 14 kg m2 s1 .
Table 6
Values of the Billet and Schultes (1999) pressure drop constant (CP,0 ) and the
Takahashi et al. (1979) pressure drop parameter (k) in comparison to the literature
values.
SMR 13 mm
Pall Ring 13 mm
Mellapak 700Y
a
Takehashi k parameter
This study
This study
0.84
1.00
0.56
Billet and
Schultes (1999)
0.96a
8.33 105
3.65 105
Takahashi et al.
(1979)
1
1
H
=
+
Ky a
ky a
kl a
5.22 104
(3)
(4)
Ky a(yCO2 yCO
)=
2
L dxCO2
G dYCO2
=
S dZ
S dZ
(5)
dYCO2
dxCO2
L
G
1
1
=
S (yCO2 yCO
S (yCO2 yCO
) dZ
) dZ
2
(6)
Eq. (6) is universally used in the literature to determine the overall mass transfer coefcient (Aroonwilas and Tontiwachwuthikul,
1997a,b, 1998; Aroonwilas and Veawab, 2004; Aroonwilas et al.,
200
(2)
where H and stand for the Henry constant and the enhancement
factor for the chemical reaction, respectively.
Ideally the overall mass transfer coefcient Ky a would be
directly determined from Eq. (2). However, this approach is not
extensively used because experimental determinations of the individual mass transfer coefcients ky and kl involve the use of
extremely difcult techniques. A more practical approach for calculating the overall mass transfer coefcient is to perform absorption
experiments where the concentration prole of absorbed component in the gas phase is measured along the tested column length
(Aroonwilas and Veawab, 2004). In this case the ux of CO2 is calculated and characterized by the overall gas-phase mass transfer
coefcient (Ky ):
NA adZ =
To examine the mass transfer performance of the different packings, the overall mass transfer coefcient per unit volume (Ky a) was
determined. Higher Ky a values indicate better mass transfer performance. The overall mass transfer coefcient can be determined
from the following Eq. (2) (Lin et al., 2003):
250
160
140
120
100
Pall
Mellapak
SMR
80
60
40
180
200
150
Pall
SMR
100
50
20
0
0
0
50
100
150
200
50
100
150
200
250
Fig. 6. Comparison of pressure drop (wet) as calculated from (a) the Billet and Schultes (1999) correlation and (b) the Takahashi et al. (1979) correlation versus the experimental
data for the three packings. No appropriate t could be provided for the Takehashi correlation and Mellapak700Y.
1168
4.5
4.0
kya, kmol/m3h
3.5
3.0
2.5
2.0
1.5
4. Conclusions
1.0
SMR
MellaPak
Pall
Acknowledgments
0.5
0.0
0
10
15
20
25
1999). In an ideal case, the CO2 concentration in the gas phase along
the column is measured and interpreted in terms of mole ratio and
subsequently plotted as a function of column height. Due to equipment limitations it was not possible to obtain this prole in the
current study, so Eq. (6) was further simplied. This was done by
substituting yCO2 and y in Eq. (6) by the equations for the operating and equilibrium curves. The resulting equation was solved
numerically between the liquid inlet and outlet concentrations.
The data of Tosh et al. (1959) was used to determine the equilibrium equation for CO2 absorption at 70 C using 30 wt% K2 CO3 :
y = 0.00568 exCO2 /0.00767
(7)
(8)
(9)
xCO2 +
(10)
xCO2 +
References
where
=
L
;
G
Yin + L xin
;
G
=+1
(11)
Replacing yCO2 and y in Eq. (6) by Eqs. (7) and (10) gives:
Ky a =
dYCO2
G
1
S (yCO2 yCO
) dZ
L
=
SZ
1
dxCO2
(xCO2 )/(xCO2 )0.00433 exCO2 /0.00795
(26)
1169