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' = (4)
In our model, we use
1
m
/
n
k k q
' = and obtain the rate
expression as
( )
e
d
d
n
t t
m
q q q
k
t t
= (5)
where q
m
, q
e
and q
t
are the adsorption capacity at
maximum, at equilibrium and at time t, respectively,
and k is the rate constant. The boundary conditions for
Eq. (5) are: when t = 0, q
t
= 0; when t = t, q
t
= q
t
. The
integrated form of Eq. (5) is the adsorption kinetic
model
e 1
e
lg lg lg lg ( 1)
2.303
t
q k
n t n
q q
( | | | |
= + =
|
( |
\ .
\ .
(6)
( )
(1 )
1 1
e
e
1 1 1
( 1)
1
m
n
n n
t
n
k t n
m q
q q
= + =
(7)
Equation (6) is the Bangham model, which is a special
case for 1 n = and can describe SO
2
adsorption by
ZL50 activated carbon with different water vapor
concentrations [2] and different SO
2
inlet concentra-
tions [4]. When 1 n = , Eq. (7) is in a non-logarithmic
form, which is the form used in this work to investi-
gate SO
2
adsorption.
With rearrangement, Eq. (7) can be expressed as
1/( 1)
e
1
1
e
1
( 1)
( 1) 1
1
n
t
m n
n
q q n
k n
t
m q
(
= =
(
+ (
(
(8)
When 2 n = , it is the second order kinetic model
2 1
2 e
1
2 e
(1 )
m
t
m
k q t
q
m k q t
=
+
(9)
which can be rearranged as a linearized form, the
second order linear adsorption kinetic model I,
1
21
e e
1 1 1
1
m
t
k t
q q m q
= +
(10)
Another linearized form is the second order linear ad-
sorption kinetic model II
1
1
2
e 2II e
1 1
m
m
t
t m
t
q q k q
= + (11)
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 225
Adsorption rate equations can be obtained by
differentiating Eqs. (8) and (9),
/(1 )
1
1
e
( 1) 1
1
d
( 1)
d
n n
m n
n
n
t
m
k n
k t
m q q
n
t t
(
+
(
= = (12)
2 2
2 e
2
1
2 e
d (1 )
d
(1 )
t
m m
q k q m
t
t m k q t
=
(
+
(13)
Equation (5) is a general form of the adsorption
kinetic model. The adsorption kinetic models used
previously are its special cases:
when 1 n = , Eq. (5) reduces to the Bangham ad-
sorption kinetic model [24, 7, 8];
when m= 0 (t>0) and 1 n = , Eq. (5) reduces to
the pseudo-first order adsorption kinetic model of
Lagergren [3, 4, 10, 11, 15, 16];
when m = 0 (t>0) and 2 n = , Eq. (5) is the
pseudo-second order adsorption kinetic model of Ho
[3, 4, 10, 15, 16];
when m= 0 (t>0), Eq. (5) is the pseudo-nth order
adsorption kinetic model [10, 17].
The proposed kinetic model describes the SO
2
adsorption by carbon materials, with which the adsorp-
tion capacity and adsorption rate at time t can be calcu-
lated, and the chemisorption mechanism and rate de-
termining step can also be deduced. Following the pro-
posal of Boyd et al. [12], we assume that if the rate con-
trolling step is surface reaction or surface adsorption
(gas-solid systems), the rate constant k is independent
of particle diameter and space velocity and will depend
only on the adsorbate in the gas phase and temperature.
If the intraparticle or pore diffusion is the rate control-
ling step, the fitted line with equation q
t
= k
i
t
1/2
passes
through the origin [10, 32, 33]. Moreover, Lagergrens
model and Boyds model can be used to determine
whether the film diffusion is the rate-controlling step.
Using these characteristics, it is possible to determine
the rate controlling step being surface reaction, film
diffusion or intraparticle diffusion, for the adsorption
of SO
2
in flue gas by carbon adsorbents.
3 RESULTS AND DISCUSSION
3.1 Modeling results
Figure 1 shows the modeling results of the pro-
posed adsorption kinetic models at different water va-
por and sulfur dioxide concentrations. The model gives
a good fitting and is in agreement with the experimental
results. The abscissa shows the functions of adsorption
time, and the ordinate shows the functions of adsorp-
tion capacity of SO
2
by ZL50 activated carbon. The
two functions and their relationship change with the
increase of water vapor and sulfur dioxide concentra-
tions, indicating that the changes in adsorption capac-
ity are due to the transition from physisorption to
chemisorption. It also suggests that the adsorption
capacity of SO
2
by ZL50 activated carbon is directly
proportional to the nth driving force (q
e
q
t
)
n
and the
second order driving force (q
e
q
t
)
2
separately, and
inversely proportional to t
m
.
The more appropriate model and mechanism can
be determined from the modeling results. In Figs. 1 (a)
and 1 (d), on the plot of
( )
2 2
1
e,SO ,SO
1/
n
t
q q
against
1
( 1) /(1 )
m
n t m
against
1 m
t
deviate from
experimental data to a larger extent. Thus the nth or-
der adsorption kinetic model and the second order
linear adsorption kinetic model I well fit the data but
the second order linear adsorption kinetic model II
shows some deviations. It indicates that the concentra-
tions of water vapor and SO
2
result in some variations
in the adsorption. A particular point to note is the
drastic changes in Figs. 1 (b) and 1 (c) with or without
water vapor in the flue gas, which may be due to the
transition from physisorption to chemisorption. As
discussed earlier, it can be inferred that the surface
catalytic reaction is the rate controlling step in the
early adsorption stage by observing how the rate con-
stant varies with the increase of water vapor concen-
tration and SO
2
inlet concentration.
The two parameters, m and n, used in the pro-
posed model are affected by the concentrations of wa-
ter vapor and sulfur dioxide. We assume that the pa-
rameters m and n are related to the magnitude of the
time compensation and adsorption driving force, re-
spectively. For the nth kinetic model, Table 1 shows
that the values of n first decreases and then increases
with the increase of water vapor concentration. The
adsorption driving force increases with water vapor
concentration in the range of 4%20% as shown by
the variation of n, while the effects of adsorption
driving force and time compensation become complex
because the adsorption changes from physisorption to
chemisorption in the range of 04%, which is re-
flected by the variations of n and m that represent the
driving force effect and time compensation effect, re-
spectively. However, as shown by Table 2, the value
of n increases with sulfur dioxide concentration in the
range of (5004000)10
6
, which indicates that the
adsorption driving force increases with sulfur dioxide
concentration and the value of n increases correspond-
ingly because of the relationship with the adsorption
driving force.
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 226
(a) By nth order kinetic model with different water
vapor concentrations
(b) By second order linear kinetic model I with
different water vapor concentrations
(c) By second order linear kinetic model II with
different water vapor concentrations
(d) By nth order kinetic model with different
sulfur dioxide concentrations
(e) By second order linear kinetic model I with
different sulfur dioxide concentrations
(f) By second order linear kinetic model II with
different sulfur dioxide concentrations
Figure 1 Modeling results by the proposed adsorption kinetic models for flue gas
Lines: fitting results by the proposed kinetic models
Symbols: experimental data; water vapor concentrations/%: 0; 4; . 7; 10; 15; . 20;
sulfur dioxide concentrations: M 50010
6
; & 100010
6
; A 200010
6
; * 300010
6
; 4 400010
6
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 227
Table 1 Modeling results at different water vapor concentrations
nth order linear kinetic model Second order linear kinetic model I Second order linear kinetic model II
Water vapor
concentration
(
2
H O,in
)/%
k
n
10
4
/mg
1n
g
n1
min
m1
2
e,SO
q
/mgg
1
m n R
2
k
2,I
10
5
/gmg
1
min
m1
2
e,SO
q
/mgg
1
m R
2
k
2,II
10
5
/gmg
1
min
m1
2
e,SO
q
/mgg
1
m R
2
0 772.2 16.26 0.3969 0.6055 0.9999 38 33.15 0.3684 0.9999 41 32.29 0.3684 0.9941
4 1530 25.66 0.2279 0.2828 1.0000 6 80.35 0.1857 0.9999 6 77.85 0.1857 0.9812
7 368.4 38.34 0.1800 0.6639 1.0000 7 76.44 0.1496 1.0000 7 75.03 0.1496 0.9945
10 4.1 72.71 0.1479 1.655 1.0000 7 82.92 0.1425 1.0000 7 82.51 0.1425 0.9992
15 2.8 73.20 0.1057 1.749 1.0000 8 79.91 0.1004 1.0000 8 79.75 0.1004 0.9998
20 4.8 66.39 0.0595 1.649 1.0000 9 74.57 0.04875 1.0000 9 74.31 0.04875 0.9998
Table 2 Modeling results at different feeding SO
2
concentration
nth order linear kinetic model Second order linear kinetic model I Second order linear kinetic model II
Inlet SO
2
concentration
(
2
SO ,in
)
k
n
10
4
/mg
1n
g
n1
min
m1
2
e,SO
q
/mgg
1
m n R
2
k
2,I
10
5
/gmg
1
min
m1
2
e,SO
q
/mgg
1
m R
2
k
2,II
10
5
/gmg
1
min
m1
2
e,SO
q
/mgg
1
m R
2
50010
6
346.7 34.33 0.09987 0.3881 0.9999 3 62.03 0.0139 0.9999 4 54.69 0.0139 0.9631
100010
6
40.8 51.07 0.1074 1.066 1.0000 4 80.48 0.09533 1.0000 4 80.16 0.09533 0.9995
200010
6
4.1 72.71 0.1479 1.655 1.0000 7 82.92 0.1425 1.0000 7 82.51 0.1425 0.9992
300010
6
2.1 76.58 0.1756 1.875 1.0000 11 79.86 0.1731 1.0000 11 79.43 0.1731 0.9997
400010
6
2 87.31 0.1763 1.881 1.0000 11 90.75 0.1736 1.0000 11 90.45 0.1736 0.9995
(a) nth order kinetic model with different water
vapor concentrations
(b) Second order linear kinetic model I with
different water vapor concentrations
(c) nth order kinetic model with different sulfur
dioxide concentrations
(d) Second order linear kinetic model I with
different sulfur dioxide concentrations
Figure 2 Comparison of calculated results by the proposed kinetic models with experimental data
Lines: calculation; == adsorption capacity of sulfur dioxide; adsorption rate of sulfur dioxide
Symbols: experimental data; water vapor concentrations/%: 0; 4; . 7; 10; 15; . 20;
sulfur dioxide concentrations: M 50010
6
; & 100010
6
; A 200010
6
; * 300010
6
; 4 400010
6
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 228
3.2 Model validation
The calculated values of SO
2
adsorption capacity
and adsorption rate are compared with experimental
data [2, 4] to validate the proposed adsorption kinetic
models, as shown in Fig. 2. The calculated values by
the proposed adsorption kinetic models are in good
agreement with the experimental data under different
adsorption conditions. Figs. 2 (a) and 2 (c) show that
the nth order kinetic model is in good agreement with
experimental data. Figs. 2 (b) and 2 (d) also indicate
that the second order linear kinetic model I is appro-
priate, though with some slight deviations. It can be
inferred that the surface catalytic reaction is the rate
controlling step in the early adsorption stage.
3.3 Uncertainty analysis
The accuracy of the proposed adsorption kinetic
models is analyzed by the sum of square errors
(SSE) [10] and the average absolute percentage devia-
tion (Desv.):
( )
2
,exp , theo
2
,exp
SSE
t t
t
q q
q
(
(
=
(
(14)
,exp ,theo
1 ,exp
1
Desv. 100%
N
t t
i t
q q
N q
=
(15)
The results are listed in Tables 3 and 4. The values of
SSE are less than 1.0 under the conditions studied ex-
cept for the case without water vapor with the nth or-
der kinetic model, which is 1.012 in Table 3. However,
the values of Desv. range from 0.5 to 3.2, higher than
those of SSE. The nth order adsorption kinetic model
and the second order adsorption kinetic model (linear
form I and nonlinear form) describe well the phy-
sisorption and chemisorption of SO
2
in flue gas by
ZL50 activated carbon and similar carbon adsorbents,
as shown by the small SSE and Desv. values, high R
2
values, and good fitting in Fig. 1. The accuracy of the
three adsorption kinetic models is: nth order adsorp-
tion kinetic model>second order linear adsorption ki-
netic model I>second order linear adsorption kinetic
model II.
3.4 Model comparison
The Bangham kinetic model ( 1 n = ) [24], the
Elovich kinetic model [35], Lagergrens pseudo-first
order kinetic model [3, 4] and Hos second order ki-
netic model [3, 4] have been applied to describe the
SO
2
dynamic adsorption processes in flue gas by car-
bonaceous adsorbent-catalysts. Tables 5 and 6 give the
SSE and Desv. analysis for these kinetic models based
on the previous modeling results [24]. The compari-
son shows that the modeling by the nth kinetic model
and the second order linear adsorption kinetic model I
is as good as that by the Bangham kinetic model and
Elovich kinetic model, and better than that of Lager-
grens pseudo-first order kinetic model and Hos
pseudo-second order kinetic model.
In this study, the effects of temperature, O
2
con-
centration and space velocity are not considered, so
that the application of the proposed model is limited.
Moreover, the values of rate constant k and parameter
n in the nth order kinetic model fluctuate from 0 to
Table 3 Uncertainty of calculated values with different water vapor concentrations
nth order linear kinetic model Second order linear model I Second order linear model II
Water vapor
concentrations
(
2
H O,in
)/% SSE Desv./% SSE Desv./% SSE Desv./%
0 1.012 1.342 0.7314 1.604 0.8184 1.458
4 0.08581 0.7463 0.4152 4.594 0.1987 1.999
7 0.04944 0.5130 0.07914 1.725 0.1503 2.302
10 0.1579 0.6222 0.1556 1.838 0.2067 2.657
15 0.1458 0.9743 0.1448 1.309 0.1282 0.9562
20 0.02221 0.6973 0.2802 3.777 0.2000 3.164
Table 4 Uncertainty of calculated values with different SO
2
concentrations
nth order linear kinetic model Second order linear model I Second order linear model II
SO
2
concentrations
(
2
SO ,in
)
SSE Desv./ % SSE Desv./ % SSE Desv./ %
50010
6
0.3185 1.326 0.1479 2.558 0.2067 3.083
100010
6
0.2727 0.7461 0.2244 2.592 0.2748 3.230
200010
6
0.1579 0.6222 0.1556 1.838 0.2067 2.657
300010
6
0.1737 0.9558 0.1426 1.148 0.1703 1.996
400010
6
0.1382 1.885 0.2195 2.804 0.1637 2.227
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 229
20% as water vapor concentration increases. This
problem may be solved with further studies to cover
more variables.
4 CONCLUSIONS
A semi-empirical adsorption kinetic model was
proposed to describe the dynamic adsorption of SO
2
in
flue gas by ZL50 activated carbon in the presence of
water vapor and oxygen. Values of SSE were less than
1.0 and values of Desv ranged from 0.5 to 3.2 under
most of the conditions studied.
The nth order adsorption kinetic model and the
second order linear adsorption kinetic model I well
describe the adsorption of SO
2
in flue gas by ZL50
activated carbon, while the second order linear ad-
sorption kinetic model II shows more deviations. Sur-
face adsorption and catalytic reaction are the rate de-
termining steps in the early adsorption stage.
The parameters m and n in the nth order adsorp-
tion kinetic model are related to the magnitudes of the
time compensation and adsorption driving force, re-
spectively. The variation of n with water vapor concen-
trations indicates that the adsorption driving force in-
creases with the water vapor concentration in the range
of 4%20%, while the effects of adsorption driving
force and time compensation become complex due to
the change from physisorption to chemisorption in the
range of 04%. The increase of n with sulfur dioxide
concentrations in the range of (5004000)10
6
indi-
cates an increase in adsorption driving force.
The calculated results from the proposed models
have an accuracy similar to that of the Bangham ki-
netic model and Elovich kinetic model, and are better
than that of Lagergrens pseudo-first order kinetic
model and Hos second order kinetic model.
NOMENCLATURE
dq
t
/dt adsorption rate at time t, mgg
1
h
1
k
n
rate constant of the nth order adsorption kinetic model,
mg
1n
g
n1
min
m1
k
2,I
rate constant of the second order linear adsorption kinetic
model I, gmg
1
min
m1
k
2,II
rate constant of the second order linear adsorption kinetic
model II, gmg
1
min
m1
m model parameter
n model parameter
q
e
adsorption capacity at equilibrium, mgg
1
q
m
maximum adsorption capacity, mgg
1
q
t
adsorption capacity at time t, mgg
1
2
H O
water vapor concentration (volume fraction), %
2
SO
SO
2
concentration (volume fraction)
Subscripts
e adsorption equilibrium
exp experimental data
in inlet of adsorptive reactor
theo calculated data
ACKNOWLEDGEMENTS
The discussions with Dr. ZHANG Qiang and Dr.
LIU Malin are gratefully acknowledged.
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