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Abstract
In industrial applications CO2 is frequently removed from gas streams at elevated pressures by absorption and subsequent chemical
reaction in carbonate/bicarbonate solutions (e.g. Beneld process). The criterion that determines whether or not this reaction can be
regarded as pseudo-rst order is given by Danckwerts and Sharma (1966), but its derivation has never been published. In the present
study, a consistent set of equations and physico-chemical parameters is presented to describe the CO2 absorption/reaction process. It was
found that the criterion was justied, but should be somewhat conned to reduce possible errors. Furthermore, the model was validated
by experiments in a stirred cell reactor up to CO2 partial pressures of 16 bar.
2005 Elsevier Ltd. All rights reserved.
Keywords: Danckwerts-plot; CO2 absorption; Mass transfer; Stirred cell; Elevated pressure
1. Introduction
The Danckwerts-plot technique (Danckwerts et al., 1963)
is used in chemical engineering to simultaneously obtain
the mass transfer parameters, kL and a, from mass transfer
experiments. From the measurements of the gas absorption
rate, RA (mole s1 ), at different apparent rst order reaction
rate constants the values of kL and a can be determined
simultaneously using the Danckwerts surface renewal model
(Danckwerts, 1950) with a (pseudo) rst order reaction:
RA
m A c A VL
2
= (kL a)2 + k1,app DA a 2 .
(1)
When the left-hand side of Eq. (1) is plotted versus the apparent rst order rate constant times the diffusion coefcient of the gas into the liquid (k1,app DA ), the slope equals
the squared specic gas liquid interfacial area (a 2 ) and the
Corresponding author. Tel.: +31 53 489 3327; fax: +31 53 489 4774.
DCO 2 k1,app
1 +
1 1.
(2)
kL2
The reaction can be regarded as pseudo-rst order when the
concentrations of all the ions are uniform throughout the
mass transfer zone. Although this Danckwerts-criterion is
often referred to in literature, its derivation has never been
published. Moreover, it was found that although the left-hand
side of Eq. (2) is much smaller than 1, still large concentration gradients could exist, and thus considerable deviations
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k42 cH CO cH + ,
(12)
(13)
(14)
(15)
(16)
+ cCO 2 ,bulk ,
(17)
(18)
2. Reaction system
+ 2cCO 2 ,bulk .
CO 2 + OH H CO
3,
(3)
k12
k21
H CO
3 + OH CO 3 + H2 O,
(4)
k22
k31
OH + H + H2 O,
(5)
k32
k41
+
CO 2 + H2 O H CO
3 +H .
(6)
k42
(19)
The concentration proles of all species in the mass transfer zone can be calculated as a function of time using the
following equation:
jcA (x, t)
j2 cA (x, t)
F j((x, t)cA (x, t))
= DA
z A DA
jt
jx 2
RT
jx
(20)
+ rA (x, t).
The electrostatic potential gradient () can be calculated by
the use of the NernstEinstein equation (Newman, 1973)
assuming dynamic electroneutrality:
NC
jcq (x,t)
RT
q=1 zq Dq
jx
(x, t) =
.
NC 2
F
q=1 zq Dq cq (x, t)
(21)
cH + cH CO
3
cCO 2 (L)
cCO 2
3
cH CO cOH
(7)
(8)
KW = cH + cOH .
(9)
t = 0,
t > 0,
t > 0,
x = 0:
jcion (x, t)
F
zion Dion
(x, t)cion (x, t) = 0,
jx
RT
Dion
x = : cA (x, t) = cA,bulk .
(22)
(10)
(11)
The ux of CO2 through the gasliquid interface is calculated using the Higbie penetration model (Higbie, 1935). The
complete system of equations was solved using the method
of lines.
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3. Physical parameters
The solubility and diffusivity of CO2 in the 0.5 M/0.5 M
potassium carbonate/potassium bicarbonate solution are
given elsewhere (Cents et al., 2001). All physical parameters
at 24 C are given in Table 1.
The ionic diffusion coefcients have been estimated using
the Nernst equation (Horvath, 1985):
=
DA
A
RT
.
zA F 2
(23)
= 8.916
log k11
2383
.
T
Parameter
k11 ,
k12 ,
k21 ,
m3 mol1 s1
s1
m3 mol1 s1
k22 , s1
k31 ,
k32 ,
k41 ,
k42 ,
m3 mol1 s1
mol m3 s1
s1
m3 mol1 s1
Value
Parameter
Value
1.41 101
3.11 104
6.00 106
DCO 2 , m2 s1
DOH , m2 s1
DH CO , m2 s1
1.59 109
5.17 109
1.18 109
1.22 106
1.40 108
1.29 100
0.24 101
5.71 101
DH + , m2 s1
DK + , m2 s1
mCO 2 , W , kg m3
CO 2
3
, m2 s1
9.20 1010
9.21 109
1.95 109
5.24 101
9.97 102
4. Chemical parameters
k11
log = 0.11 103 cK + + 0.17 103 cCO 2 .
3
k11
Table 1
Used physical and chemical parameters at 297 K for the absorption of
CO2 in a 0.5 M KHCO3 /0.5 M K2 CO3 solution
(25)
log(K2 ) =
1568.9
2.5866 6.737 103 T.
T
(28)
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x 10-4
1.5
water
buffer solution
model
kL * EA (m/s)
0.8
-
HCO3
0.6
1
2-
CO3
0.4
OH0.5
0.2
CO2
0
0
4
x 10-4
JCO2
1.1
pfo
JCO2
1
variation of pCO2
0.9
0.8
variation of kL
0.7
0.6
0.5
0
0.2
0.4
0.6
0.8
1.2
1.4
0
0
10
15
20
pressure (bar)
K2
1.01 cK + /1000
log =
+ 6.1 105 cK + . (30)
K2
1 + 1.49 cK + /1000
Not taking this ionic effect on K2 into account, was supported by two other measurements:
Measurement of the CO2 bulk concentration was performed by leading a small nitrogen stream through an
intensely stirred buffer solution. It was veried that the
outlet gas stream was saturated with CO2 by variation of
the ow rate. At 21 C the nitrogen stream was saturated
with 0.21% CO2 , which could be calculated back to a liquid concentration of 0.053 mol/m3 . With: K2 = K1 /KW
2
[CO 2 ][CO 2
3 ]/[H CO 3 ] this leads to K2 = 5.8 (K2 innite dilution = 5.8, K2 ionic effect = 19.6).
The hydroxyl concentration was measured using a PHmeter. At 21.2 C a pH of 10.38 was measured. This can
be reworked to a hydroxyl concentration of 0.18 mol/m3 .
Using K2 =[CO 2
3 ]/([H CO 3 ][OH ]) this leads to K2 =
5.6. (K2 innite dilution = 5.8, K2 ionic effect = 19.5).
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Table 2
Detailed experimental and modelling results
Experimental
Model
Pressure
(bar)
Temperature
( C)
RA
(106 mol/s)
JA a
103 mol/(m2 s)
kL E A
105 m/s
kL E A
105 m/s
0.52
1.34
2.02
3.60
5.95
7.54
10.59
15.17
24.0
24.5
24.1
24.0
24.2
24.2
24.2
23.9
2.26
5.34
7.60
12.07
18.04
22.11
27.34
36.07
0.69
1.62
2.31
3.67
5.49
6.73
8.32
10.98
6.19
5.74
5.38
4.80
4.35
4.21
3.70
3.41
6.38
6.04
5.55
5.00
4.50
4.23
3.85
3.43
Relative diff.
%
3.07
5.29
3.12
4.14
3.49
0.55
3.85
0.77
OH
int /OHbulk
b (-)
0.79
0.58
0.48
0.34
0.22
0.17
0.12
0.07
aA
2
cell = 32.9 cm .
bAt the end of a penetration time.
DA
EA
F
k1,app
kL
i
m
6. Conclusions
The results of this study show that the presented equations and physico-chemical parameters form a consistent
set to describe CO2 absorption in (0.5 M/0.5 M) carbonate/bicarbonate solutions. The Danckwerts criterion as presented in Eq. (2) is justied and could be conned to:
1
2
mCO 2 cCO 2 (G)
+
cCO 2
cH CO
3
3
k
D
CO 2 1,app
1 +
1 < 0.1
kL2
to reduce the possible error in the ux calculation to less
than 3% when a pseudo-rst order reaction is assumed.
Furthermore, experimental validation of the used model
was performed in a stirred cell reactor up to CO2 partial
pressures of 16 bar. The criterion becomes more important
at these high CO2 partial pressures, which emphasizes its
signicance for industrially applied CO2 removal units operating at elevated pressure.
Notation
Acell
cA
rA
R
RA
t
T
x
z
Greek letters
W
density of water, kg m3
electrostatic potential gradient, J C1 m1
All other equilibrium and kinetic rate constants are dened
in the text.
Subscript and superscript
bulk
int
References
Benson, H.E., Field, J.H., Jimeson, R.M., 1954. CO2 absorption employing
hot carbonate solutions. Chemical Engineering Progress 50, 356363.
Cents, A.H.G., Brilman, D.W.F., Versteeg, G.F., 2001. Gas absorption in
an agitated gasliquidliquid system. Chemical Engineering Science
56, 10751083.
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