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SEPARATION SCIENCE AND ENGINEERING

Chinese Journal of Chemical Engineering, 18(2) 223=230 (2010)


An Adsorption Kinetic Model for Sulfur Dioxide Adsorption by ZL50
Activated Carbon
GAO Jixian (), WANG Tiefeng (|), SHU Qing (,[), Zeeshan Nawaz (r),
WEN Qian (]), WANG Dezheng ()) and WANG Jinfu ()
*
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engi-
neering, Tsinghua University, Beijing 100084, China
Abstract A semi-empirical adsorption kinetic model was proposed with the time compensation method to de-
scribe the chemisorption of SO
2
in flue gas by carbon adsorbents for flue gas purification. The change in adsorption
capacity and adsorption rate with time at different water vapor concentrations and different SO
2
concentrations was
studied. The model was in good agreement with experimental data. The surface reaction was probably the rate con-
trolling step in the early stage for SO
2
adsorption by ZL50 activated carbon. The parameters m and n in the nth order
adsorption kinetic model were related to the magnitude of the time compensation and adsorption driving force, re-
spectively. The change of parameter n with water vapor concentrations and sulfur dioxide concentrations was stud-
ied and some physical implications were given. The sum of square errors was less than 1.0 and the average absolute
percentage deviations ranged from 0.5 to 3.2. The kinetic model was compared with other models in the literature.
Keywords adsorption kinetic model, time compensation method, flue gas purification, ZL50 activated carbon,
adsorption capacity, adsorption rate
1 INTRODUCTION
To prevent acid rain, flue gas desulphurization
and denitrification methods have been widely applied
for flue gas purification since the 1970 s. Among
various flue gas desulphurization methods, the removal
of SO
2
by carbon adsorbents has found wide application
in industries and has been investigated extensively [1].
The technique uses chemisorption with a catalytic reac-
tion to oxidize SO
2
to H
2
SO
4
in the presence of water
vapor and oxygen in flue gas [16], which is charac-
terized by the adsorption in the low temperature range
of 80160 C to remove SO
x
, NO
x
and other hazard-
ous materials and the desorption in the high tempera-
ture range of 350450 C, or washing by water or di-
luted acid, for regeneration of the carbon adsorbent.
Compared with other desulphurization techniques for
flue gas such as the limestone-gypsum method, the
carbon adsorbent method has the advantages of little
consumption of water, wide range of operating condi-
tions, and effective recovery of sulfur. It will have
broad applications in China in the near future.
For developing an industrial SO
2
removal proc-
ess by carbon adsorbents, the adsorption kinetic stud-
ies are needed. Both experimental and mathematical
studies on the adsorption kinetics of SO
2
with carbon
adsorbent-catalysts were reported [16]. Various ad-
sorption kinetic models, such as the Bangham model
[24, 7, 8], the Elovich model [35, 810], the pseudo-first
order kinetic model of Lagergren [3, 4, 1020], the
pseudo-second order kinetic model of Ho [3, 4, 10,
1416, 18, 2022], and Ritchies pseudo-nth order ki-
netic model [10, 17], were used to describe the adsorp-
tion processes quantitatively and to analyze and iden-
tify the adsorption mechanism [25, 810, 1216, 1833],
e.g., the rate controlling step was diffusion or surface
reaction. Among these adsorption kinetic models, the
pseudo-nth adsorption kinetic model [10, 17] has been
applied to chemisorption processes, in which the rate
is proportional to the nth power of the driving force
(q
e
q
t
)
n
, and deserves more attention.
Adsorption of SO
2
by activated carbon and acti-
vated coke is a chemisorption process that includes
catalytic oxidation reaction, adsorption and diffusion.
There exist some problems for describing quantita-
tively the adsorption of SO
2
in flue gas by carbon ad-
sorbents. First, not much work has been reported to
describe the dynamic adsorption processes except for
the reactive adsorption kinetic models [26]. Second,
the accuracy of the pseudo-first order adsorption ki-
netic model of Lagergren and the pseudo-second order
adsorption kinetic model of Ho need to be improved
for specific circumstances. Another important issue is
to determine the mechanism, e.g., the rate controlling
step is diffusion or surface reaction. Among the ad-
sorption models, although the Elovich model de-
scribes SO
2
adsorption well [35], it has some disad-
vantages, lacking of a parameter q
e
and unable to de-
termine the mechanism, compared with the driving
force models. However, the results from the driving
force kinetic models such as Lagergrens pseudo-first
order adsorption kinetic model and Hos pseudo-second
order adsorption kinetic model show some deviations
from experimental data under some circumstances. In
the Bangham model, the rate is directly proportional
to a first order driving force (q
e
q
t
) and inversely
proportional to the mth power of adsorption time t
m
.
Although the Bangham model is in good agreement
with experimental data [24], indicating a possibility
of improving the model by modifying Lagergrens

Received 2009-06-18, accepted 2010-01-07.
* To whom correspondence should be addressed. E-mail: wangjf@flotu.org
Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 224
model with a time compensation function t
m
[7], it
only involves the first order driving force (q
e
q
t
),
which is a special case of the nth order driving force
(q
e
q
t
)
n
with time compensation. Therefore, a more
general semi-empirical chemisorption kinetic model is
needed to describe the SO
2
adsorption capacity and
adsorption rate as functions of time, to improve the
accuracy and determine the mechanism.
In this study, we propose a semi-empirical adsorp-
tion kinetic model based on a driving force model and
time function compensation method, which includes
the nth and second order adsorption kinetic models.
The experimental data [2, 4] are used to support and
validate the kinetic model, in which the water vapor
concentration and SO
2
concentration are based on the
volume fraction in the presence of water vapor and
oxygen for the flue gas studied. The proposed model
is used to analyze the adsorption of SO
2
in flue gas by
ZL50 activated carbon under isothermal conditions.
2 EXPERIMENT AND MODELS
2.1 Materials and methods
The adsorbent ZL50 activated carbon for desul-
phurization and denitrification was from Shanxi Xinhua
Corporation. Its BET analysis data showed a surface
area of 104.5 m
2
g
1
, pore volume of 0.08596 mlg
1
,
mean pore diameter of 3.291 nm, and dominant pore
diameter of 0.8 nm.
The experiments [2, 4] were conducted at 140 C,
3000 h
1
, and manometer pressure (25)10
4
Pa. The
flue gas concentration was in volume fraction. For
investigating the variation of water vapor concentration
[2], the feed flue gas was: SO
2
= 200010
6
, O
2
= 7%,
CO
2
= 13.9%, with water vapor = 0, 4%, 7%, 10%,
15%, and 20% separately in N
2
. For investigating the
variation of SO
2
concentration [4], the feed flue gas
was: O
2
= 7%, CO
2
= 13.9%, water vapor = 10%, with
SO
2
= 50010
6
, 100010
6
, 200010
6
, 300010
6
,
400010
6
separately in N
2
.
2.2 Adsorption kinetic models
The semi-empirical adsorption kinetic model in-
cludes several kinetic steps, i.e., film diffusion, in-
traparticle diffusion and surface catalytic reaction.
Both physisorption and chemisorption are considered
in the proposed kinetic models. The adsorption rate
decreases as adsorption time increases and is deter-
mined by a surface coverage driving force f(u
e
u
t
).
The adsorption rate r
a
is a function of surface cover-
age u
e
, u
t
and t
( )
a e
d
, ,
d
t
t
r f t
t
u
u u = = (1)
It can be expressed as
( ) ( )
a e 1 e 2
d
, ( )
d
t
t t
r f t f f t
t
u
u u u u = = = (2)
In this model, the adsorption rate is directly propor-
tional to the driving force (u
e
u
t
)
n
and is inversely
proportional to t
m
, based on the observation that it
needs to compensate for and enhance the driving force
effect for the Bangham adsorption kinetic model. Thus
the semi-empirical adsorption rate is
( )
e
d
d
n
t t
m
k
t t
u u u
' = (3)
When u
t
= q
t
/q
m
, u
e
= q
e
/q
m
, it becomes
( )
e
1
m
d 1
d
n
t t
n m
q q q
k
t q t


' = (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

, the calculated values from the nth


order model are in good agreement with experimental
data, with slight deviations for a few cases. Similarly,
the values calculated by the second order linear ad-
sorption kinetic model I with
( )
2 2
e,SO ,SO
1/
t
q q
against
1
/(1 )
m
t m

are also in good agreement with


the experimental data as shown in Figs. 1 (b) and 1 (e).
However, the data from the second order linear ad-
sorption kinetic model II shown in Figs. 1 (c) and 1 (f)
by the plot of
2
1
,SO
/
m
t
t q

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.
REFERENCES
1 Gao, J.X., Wang, J.F., Wang, T.F., Wang, G.R., Progress of flue gas
purification and sulfur recovery using TSA technology by carbona-
ceous methods in moving beds, Chem. Ind. Eng. Prog., 28 (2),
325333 (2009). (in Chinese)
2 Gao, J.X., Wang, T.F., Wang, G.R., Wang, J.F., Effect of water va-
por concentration in flue gas on temperature swing adsorptive
desulphurization process using activated carbon, Chin. J. Proc.
Eng., 9 (1), 1822 (2009). (in Chinese)
3 Gao, J.X., Wang, T.F., Wang, G.R., Wang, J.F., Kinetics of SO
2
ad-
sorption by ZL50 activated carbon for various water vapor volume
fractions, J. TsingHua Univ. (Sci. Tech.), 50 (3), 434437 (2010).
(in Chinese)
4 Gao, J.X., Wang, T.F., Wang, J.F., Effect of SO
2
volume fraction in
flue gas on the adsorption behaviors adsorbed by ZL50 activated
carbon and kinetic analysis, Environ. Sci., 31 (5), 11521159 (2010).
(in Chinese)
5 Zhao, X.S., Cai, G.Y., Wang, Z.Z., Yang, Y.H., Sulfur dioxide re-
moval from flue gas by means of active carbon catalyst, Chin. J.
Environ. Sci., 13 (5), 6770/96 (1992). (in Chinese)
6 Gaur, V., Asthana, R., Verma, N., Removal of SO
2
by activated
carbon fibers in the presence of O
2
and H
2
O , Carbon, 44 (1),
4660 (2006).
7 Bangham, D.H., Sever, W., An experimental investigation of the
dynamical equation of the process of gas-sorption, Phil. Mag., 49
(6), 935944 (1925).
8 Low, M.J.D., Kinetics of chemisorption of gases on solids, Chem.
Rev., 60 (3), 267312 (1960).
9 Taylor, H.A., Thon N., Kinetics of chemisorption, J. Am. Chem.
Soc., 74 (16), 41694173 (1952).
10 Ho, Y.S., Ng, J.C., McKay, G., Kinetics of pollutant sorption by
Table 5 Desv. analysis for calculated values with other
kinetic models at different water vapor concentrations
Desv./% Water vapor
concentrations
(
2
H O,in
)/%
Bangham
model
Elovich
model
Pseudo-second
order model
Pseudo-first
order model
0 3.420 4.022 6.836 9.202
4 1.534 3.856 6.037 5.745
7 0.7179 2.980 5.069 5.059
10 1.924 2.134 3.638 4.509
15 2.066 1.122 2.264 3.512
20 1.315 0.6962 2.669 2.566
Table 6 Desv. analysis for calculated values with other
kinetic models at different SO
2
concentrations
Devs./%
SO
2
concentra-
tions (
2
SO ,in
)
Bangham
model
Elovich
model
Pseudo-second
order model
Pseudo-first
order model
50010
6
1.310 1.553 2.327 1.963
100010
6
2.142 1.536 2.395 2.871
200010
6
1.924 2.134 3.638 4.509
300010
6
1.890 2.095 3.994 5.358
400010
6
1.258 2.093 3.853 5.537

Chin. J. Chem. Eng., Vol. 18, No. 2, April 2010 230
biosorbents: Review, Sep. Purif. Methods, 29 (2), 189232 (2000).
11 Lagergren, S., Zur theorie der sogenannten adsorption gelster
stoffe, K. Sven Vetenskapsakad. Handl., 24 (4), 139 (1898).
12 Boyd, G.E., Adamson, A., Myers, L.S., The exchange adsorption of
ions from aqueous solutions by organic zeolites (II) Kinetics, J. Am.
Chem. Soc., 69 (11), 28362848 (1947).
13 Rudzinski, W., Plazinski, W., Studies of the kinetics of solute ad-
sorption at solid/solution interfaces: on the possibility of distin-
guishing between the diffusional and the surface reaction kinetic
models by studying the pseudo-first-order kinetics, J. Phys. Chem.
C, 111 (41), 1510015110 (2007).
14 Rudzinski, W., Plazinski, W., Kinetics of solute adsorption at
solid/solution interfaces: A theoretical development of the empirical
pseudo-first and pseudo-second order kinetic rate equations, based
on applying the statistical rate theory of interfacial transport, J.
Phys. Chem. B, 110 (33), 1651416525 (2006).
15 Ho, Y.S., Mckay, G., A comparison of chemisorption kinetic models
applied to pollutant removal on various Sorbents, Process Saf. En-
viron. Prot. (Trans. Ichem E, Part B), 76 (4), 332340 (1998).
16 Ho, Y.S., Mckay, G., Pseudo-second order model for sorption proc-
esses, Process Biochem., 34 (5), 451465 (1999).
17 Zhang, J., Jiang, B., Li, X.G., Sorption kinetic analysis for the re-
moval of copper (II) by using biofilm, Chin. J. Chem. Eng., 13 (1),
135139 (2005).
18 Rill, C., Kolar, Z.I., Kickelbick, G., Wolterbeek, H.T., Peters, J.A.,
Kinetics and thermodynamics of adsorption on hydroxyapatite of
the [160Tb] Terbium complexes of the bone-targeting ligands DOTP
and BPPED, Langmuir, 25 (4), 22942301 (2009).
19 Rudzinski, W., Plazinski, W., Kinetics of dyes adsorption at the
solid-solution interfaces: A theoretical description based on the
two-step kinetic model, Environ. Sci. Technol., 42 (7), 24702475
(2008).
20 Song, H.P., Li, X.G., Sun, J.S., Yin, X.H., Wang, Y.H., Wu, Z.H.,
Biosorption equilibrium and kinetics of Au(III) and Cu(II) on mag-
netotactic bacteria, Chin. J. Chem. Eng., 15 (6), 847854 (2007).
21 Tong, J.M., Wu, Z.S., Sun, X.F., Xu, X.L., Li, C., Adsorption ki-
netics of -carotene and chlorophyll onto acid-activated bentonite in
model oil, Chin. J. Chem. Eng., 16 (2), 270276 (2008).
22 Raven, K.P., Jain, A., Loeppert, R.H., Arsenite and arsenate adsorp-
tion on ferrihydrite: kinetics, equilibrium, and adsorption envelopes,
Environ. Sci. Technol., 32 (3), 344349 (1998).
23 Yang, X.Y., Al-Duri, B., Kinetic modeling of liquid-phase adsorp-
tion of reactive dyes on activated carbon, J. Colloid Interf. Sci., 287
(1), 2534 (2005).
24 Saxena, A., Srivastava, A.K., Singh, B., Kinetics of adsorption of
2-CEES and HD on impregnated silica nanoparticles under static
conditions, AIChE J., 55 (5), 12361245 (2009).
25 Acharya, J., Sahu, J.N., Mohanty, C.R., Meikap, B.C., Removal of
lead (II) from wastewater by activated carbon developed from tama-
rind wood by zinc chloride activation, Chem. Eng. J., 149 (1-3),
249262 (2009).
26 Wang, L.H., Lin, C.I., Adsorption of lead (II) ion from aqueous so-
lution using rice hull ash, Ind. Eng. Chem. Res., 47 (14),
48914897 (2008).
27 Basha, S., Murthy, Z.V.P., Jha, B., Removal of Cu (II) and Ni (II)
from industrial effluents by brown seaweed, cystoseira indica, Ind.
Eng. Chem. Res., 48 (2), 961975 (2009).
28 Rudzinski, W., Plazinski, W., Theoretical description of the kinetics
of solute adsorption at heterogeneous solid/solution interfaces on the
possibility of distinguishing between the diffusional and surface re-
action kinetics models, Appl. Surf. Sci., 253 (13), 58275840 (2007).
29 Xia, X.Y., Alnoncourt, R.N.D., Strunk, J., Litvinov, S., Muhler, M.,
Isothermal adsorption kinetics on heterogeneous surfaces, Appl.
Surf. Sci., 253 (13), 58515855 (2007).
30 Liu, Z.N., Zhou, A.N., Wang, G.R., Zhao, X.G., Adsorption behav-
ior of methyl orange onto modified ultrafine coal powder, Chin. J.
Chem. Eng., 17 (6), 942948 (2009).
31 Zhang, J.S., Stanforth, R., Slow adsorption reaction between arse-
nic species and goethite(-FeOOH): diffusion or heterogeneous sur-
face reaction control, Langmuir, 21 (7), 28952901 (2005).
32 Choy, K.K.H., Porter, J.F., Mckay, G., Intraparticle diffusion in sin-
gle and multicomponent acid dye adsorption from wastewater onto
carbon, Chem. Eng. J., 103 (1-3), 133145 (2004).
33 Baral, S.S., Das, S.N., Chaudhury, G.R., Swamy, Y.V., Rath, P.,
Adsorption of Cr(VI) using thermally activated weed salvinia cu-
cullata, Chem. Eng. J., 139 (2), 245255 (2008).