Carbon 42 (2004) 30813085

www.elsevier.com/locate/carbon

Prediction of breakthrough curves for adsorption on activated

carbon bers in a xed bed
Tongbao Cheng

a,*

, Yi Jiang b, Yinping Zhang b, Shuanqiang Liu

School of Civil Engineering and Architecture, Beijing Jiaotong University, Beijing 100044, PR China
Department of Building Science, School of Architecture, Tsinghua University, Beijing 100084, PR China
Received 20 October 2002; accepted 5 July 2004
Available online 13 September 2004

Abstract
A new model is proposed to describe the removal of volatile organic compounds (VOC) from a gas stream passing through a bed
packed with activated carbon bers (ACFs). Toluene was used as the test compound. Both pore diusion and surface diusion are
considered in the model. The equilibrium behavior is shown to t the DubininRadushkevich isotherm with the values of parameters K and W0 of 1.101 10
9 and 57.73 kg/m3, respectively. The experimental results show that this model can predict VOC
breakthrough curve very well.
 2004 Elsevier Ltd. All rights reserved.
Keywords: A. Activated carbon, Carbon bers, C. Adsorption, Modeling

1. Introduction
The removal of volatile organic compounds (VOC) is
of signicant interest to air quality control. There are
several chemical engineering processes that are commonly used in industry to deal with VOC emissions such
as photocatalytic oxidation and adsorption [1]. Adsorption is a useful way in dealing with VOC pollutions and
many authors are studying the eects on adsorption. In
this paper, the focus is on the adsorption technique.
Activated carbon bers (ACFs) are new-type high-eciency adsorbents. They have many favorable characteristics such as high adsorption capacities, high mass
transfer rates for both adsorption and desorption, and
easier to handle than granular and powdered adsorbents. Therefore they have received increasing attention
in recent years as adsorbents for purifying air. Normal

Corresponding author. Tel.: +86 10 51688297; fax: +86 10

51840085.
E-mail address: chengtongbao2003@yahoo.com.cn (T. Cheng).
0008-6223/$ - see front matter  2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.07.021

ACF contactors are xed beds. To improve the design

of ACF absorbers and to nd the best operating conditions, the adsorption process needs to be modeled.
Numerous models have been published in recent years
to describe the process of xed bed adsorption of ACFs
[2]. Simplied models are often obtained by using appropriate approximations in order to get substantial savings
in computational time. However, every approximate
solution has its own restricted scope of validity which
should be accurately dened, otherwise wrong results
might be obtained owing to signicant deviations from
the exact solution [35]. For example, solid diusion
model is often used in literature, and it is worth indicating that this model neglects the intra-ACF gas phase diffusion. The consequence of the approximation is the
dissatisfaction of mass balance for ACF adsorbent.
The aim of the present study is to establish a new
model to predict breakthrough curves of VOC adsorption on ACFs in a xed bed. The model considers
not only pore diusion but also surface diusion
which could be used to describe the removal of VOC
from a gas stream passing through the ACF bed. The

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T. Cheng et al. / Carbon 42 (2004) 30813085

DubininRadushkevich (DR) isotherm is used to describe the adsorption equilibrium of VOC on ACF.
The accuracy of the predictions is assessed by comparing them with toluene experimental breakthrough
curves. The reason to choose toluene as the experimental
pollutant is that it is one of the major and most often reported indoor VOCs [6].

where Ca is gas phase concentration (kg/m3); t is time

(s); Dl is axial dispersion coecient (m2/s); x is axial distance from adorber bed entrance (m); u is interstitial
velocity (m/s); e is porosity of ACFs adsorber bed; Kf
is inter-phase mass transfer coecient (m/s), and Cs is
concentration at the surface of ACFs (kg/m3).
2.2. ACF column

2. Theoretical approach
The following assumptions are made:
(1)
(2)
(3)
(4)

(5)
(6)

(7)
(8)

The pressure drop of the xed bed is very small.

The system is isothermal for low concentrations.
VOC vapor is considered as an ideal gas.
Once VOC reaches ACF surface, adsorption occurs
instantaneously and equilibrium is assumed to be
established between the adsorbate in uid and that
on the surface.
The viscous ow and intra-ber forced convection
in ACF are neglected.
Pore diusion and surface diusion occurs simultaneously and equilibrium is assumed to be established at any location in one ber.
ACFs are a cylinder of innite length.
The bed is subjected to axial (longitudinal) dispersion, external mass transfer, and intra-ber diusion of adsorbing species.

The mathematical model of the isothermal, dynamic

adsorption breakthrough process in a xed bed is based
on transient material balance, gas phase and intra-ber
mass transfer, the adsorption equilibrium relationship,
boundary conditions, and initial conditions. Two basic
dierential equations of the model are the mass balances
for the adsorbate, both in the axial direction (x) and in
the radial direction (r) of ACFs. The uid phase mass
balance describes the spatial and temporal variations
of the adsorbate concentration in the main air-stream.
The ber column mass balance describes the removal
rate of adsorbate from the gas phase into the adsorbent
at a given axial location in the bed.
In xed beds, the main parameters of transport of
adsorbate are the axial dispersion coecient and the
uid-to-ACFs mass transfer coecient. The other
important parameter, the intra-ber diusion coecient
is independent of the type of adsorption contactors
[7].
The following are the mathematical descriptions derived from mass balances:

where ep is porosity of ACF bed; qi is adsorbed phase

concentration (kg/m3); Cai is intra-ber gas phase concentration (kg/m3); Dei is eective gas phase diusion
coecient in tortuous pores (m2/s); r is radial distance
from center of ACF (m), and Dsi is surface diusion
coecient (m2/s).
2.3. Adsorption isotherm
There are various isotherm equations ranging almost
fully empirical to largely theoretical in adsorption literature. Among them, the simplest isotherm is the Langmuir equation which applies to uniform surfaces. The
Freundlich isotherm is probably the most commonly
used isotherm when the surface is not energetically uniform. The DubininRadushkevich (DR) isotherm uses
an exponent of 2, which has been found appropriate for
microporous adsorbents [9]. In our present study, we
nd that DR isotherm ts experimental data better
than Langmuir and Freundlich equations, so we choose
DR isotherm as adsorption isotherm as follows:
"
#
2
A
W W 0 exp
k
3
b
A RT ln
C ai

2.1. Air-stream phase

oC a
o2 C a
oC a 21
e
K f C a
C s
Dl 2
u


Re
ot
ox
ox

Adsorption in activated carbon is usually controlled

by two diusion processes. One is the diusion of free
species through the pore space, and the other is the surface migration of the adsorbed molecules. The surface
diusion could not be ignored in the adsorption of gases
in activated carbon ber, because its surface area is very
large, of the order of 1000 m2/g [8]. Therefore the equation for ACF column is

2

oqi
oC ai
o C ai 1 oC ai
ep
ep Dei
1
ep

r or
ot
ot
or2

2

o qi 1 oqi

1
ep Dsi
2
or2 r or


Ps
P

M BP
RT

Pe
P eref

4
5
6

T. Cheng et al. / Carbon 42 (2004) 30813085

Pe

n2r
1M B
n2r 2q






kR2 T 2 2
P sM B
qi W 0 exp
ln
1000C ai RT
b2

where W is volume of micropore lled by adsorbate

(m3/kg); W0 is maximum mass lled in the void volume
(kg/m3); k is characteristic parameter of adsorbent
(mol2/J2); A is adsorption potential (J/mol); b is anity
coecient; R is ideal gas constant (8.314 J/Mol K); T is
temperature (K); Ps is saturated pressure of adsorbate
at the adsorption temperature T (Pa); P is pressure of
adsorbate vapor at a certain concentration (Pa); MB is
molecular weight of adsorbate (g/mol); Pe is electronic
polarization of adsorbate (cm3 /mol); Peref is electronic
polarization of referenced adsorbate (cm3/mol); nr is
refractive index of adsorbate, and q is density of adsorbate (kg/m3).
2.4. Initial conditions
The initial conditions are:
C a C a0
qi qi0

for x P 0 and t 0

for r P 0 and t 0

C ai C ai0

10

for r P 0 and t 0

11
3

3083

3. Experimental results
The accuracy of the predictions is assessed by comparing them with toluene experimental breakthrough
curves under the experimental conditions as shown in
Table 1. The adsorbent used was viscose-based ACF
provided by Anshan ACF plant, China. The properties
of adsorbent and toluene are summarized in Table 2.
3.1. Adsorption equilibrium experiment
An ACF adsorber was used to obtain adsorption
breakthrough curves, and it was placed in a room with
constant temperature. The ACF sample was kept at
120 C for 24 h and then cooled in a dry atmosphere before experiments. The mass of ACFs used ranged from
11 to 15 mg. The toluene concentration was obtained
by mixing toluene with air containing only nitrogen
and oxygen. The air-stream which has a pressure of
1.11 105 Pa passed through the adsorber, and on-line
VOC concentration detector Innova 1312 was used to
measure toluene concentration with time. The adsorbed
amount was calculated by mass balance equation. The
relationship of adsorption capacity and equilibrium
(i.e. inlet) concentration was characterized by DR
equation, as given in Eq. (3). The values of W0 and K
are 57.73 kg/m3 and 1.101 10
9 mol2/J2, respectively.

where Ca0 is initial gas concentration in uid (kg/m ); qi0

is initial adsorbed phase concentration (kg/m3), and Cai0
is initial intra-ber gas phase concentration (kg/m3).

3.2. Evaluation of model parameters

2.5. Boundary conditions

Dl

3.2.1. Mass axial diusion coecient (Dl) in air

1=2

10
3 T 1:75 1=M A 1=M B

1=3

1=3

P m V A V B 2

18

The boundary conditions are:

Dl

oC a

uC in
C a for x 0 and t > 0
ox

12
Table 1
Experimental parameters used in the new model for prediction of
toluene breakthrough curves

where Cin is gas phase inlet concentration (kg/m3).

oC a
0
ox
oqi
0
or
oC ai
0
or

for x L and t > 0

for r 0 and t > 0
for r 0 and t > 0

13
14

6 10
3
17
298
50
0.072

15
Table 2
Parameters of adsorbent and toluene used in test the correction of the
new model

oC ai
oq
1
ep Dsi i
or
or
for r Rf and t > 0

16

C ai C s

17

K f C a
C s ep Dei

for r Rf and t > 0

Bed diameter (m)

Interstitial velocity (m s
1)
Bed temperature (K)
Relative humidity of air (%)
Porosity of ACF adsorber

The above model equations are closed; therefore, the gas

concentration could be obtained using the nite-dierence method.

Radius of ACF (m)

Density of ACF (kg m
3)
Porosity of ACF
Molecular weight of toluene (kg mol
1)
Density of toluene (kg m
3)
Refractive index of toluene
Toluene anity coecient

13 10
6
87
0.072
92.14 10
3
0.8669
1.4961
1

T. Cheng et al. / Carbon 42 (2004) 30813085

3.2.2. Pore diusion coecient (Dei)

Pore diusion coecient (Dei) can be determined
according to the following equation:
ep
Dei 2 Dl
K

20.0

19

where K is tortuosity factor of the micropore, which varies from 2 to 6 [7]. Dierent ACF has dierent value of
K. In our work, the K was estimated by tting the model
predictions to the experimental result, and the K2 and
Dei obtained by this way are 3 and 2.05 10
8 m2/s,
respectively.

16.0
12.0
8.0
4.0
0.0
0

(a)

20.0
Outlet Concentration,mg m-3

where MA is molecular weight of air (g/mol); Pm is air

pressure with toluene (Pa); VA is molecular volume of
air (cm3/mol), and VB is molecular volume of adsorbate
(cm3/mol).
Each VOC diusion coecient in air can be obtained
using the above equation [10]. The value for toluene in
air is 8.4 10
6 m2/s.

Outlet Concentration,mg m-3

3084

100
Time, min

16.0
12.0
8.0
4.0
0.0

200
(b)

100
Time, min

200

Fig. 1. Breakthrough curves for 6 mm ACF adsorbent (a) and for

8 mm ACF adsorbent (b). Solid line: model calculation; data marks:
experimental measurements.

where the Sherwood number is Sh = (Kfdf)/Dei and the

Schmidt number is Sc = l/(qaiDv), and Renold number
is Ref = (dfqai u)/l. where l is dynamic viscosity of air
(Pa.s); qai is density of air (kg/m3).
In our experiment, diameter of ACF (df) is
2.6 10
5 m, and the interstitial velocity is 17 m/s; therefore Sc is 1.84; Ref, 13.2; and Sh, 2.634. The value of Kf
is then calculated as 4.5 10
3 m/s according to the
above equations.

the numerical accuracy of calculations depends strongly

on the number of designated discrete points of space and
time. For a specic situation, certain grid sizes of space
and time may exist, which could cause a lower relative
error than is permitted. For the prediction of the breakthrough curves, the adsorber is divided into N equal sections along the length. The calculated breakthrough
curves for ACF adsorber with 8 mm in length converge
when N is greater than 533, and the calculated breakthrough curves for ACF adsorber with 6 mm in length
converge when N is greater than 400. Therefore, we
use N of 533 and 400 for 8 mm and 6 mm ACF adsorbers
respectively to ensure that there is no error due to
numerical resolution of the system.
In our experiment, the inlet toluene concentration of
the bed is 17.36 mg/m3; the shape of the adsorber is cylinder which has the diameter of 1 mm and the length of
the cylinder changes from 6 mm to 8 mm. The outlet
concentration of experimental data and prediction data
for 6mm thick adosrober is shown in Fig. 1a.
In the prediction procedure, we rst estimated the
tortuosity factor of the micropore (K), the pore diusion
coecient (Dei) and the surface diusion coecient (Ds)
based on the method given in section 3.2. Then we keep
the three values unchanged, and predict the result of
8 mm adsorber. The outlet concentration of experimental data and prediction data for 8 mm thick adosrober
is shown in Fig. 1b. The prediction data agree well with
the experimental result. Therefore, it is possible to utilize
the proposed model to analyze the relationship of breakthrough curve with time and bed thickness.

3.3. Comparison between experimental and numerical

results

4. Conclusions

This equation group is closed; therefore, the gas concentration could be obtained using the nite-dierence
method. Each discrete point represents a certain region,
and its concentration is a measure of the average concentration of the region at a certain time. Therefore,

This paper presentes a new model which considers not

only pore diusion but also surface diusion. The model
can be used to describe the removal of VOC from a gas
stream passing through the ACF bed. The Dubinin
Radushkevich isotherm is used to describe the adsorp-

3.2.3. Surface diusion coecient (Dsi)

Despite various eorts to correlate the surface diusivity with physical parameters such as concentration
is still dicult [1114], similar to Dei we estimated the
Dsi also by curve tting, and the result is 2 10
8 m2/s.
3.2.4. Fluid-ACF mass transfer coecient (Kf)
Fluid-ACF mass transfer coecient Kf can be determined using analogy between heat and mass transfer.
For any xed geometry and for similar boundary conditions, an equation describing mass transfer can be obtained from heat transfer equation when the Nusselt
number is replaced by the Sherwood number and the
Prantdtl number by the Schmidt number as the following equations [15,16]:
Sh 0:75Sc0:37 R0:4
ef

20

T. Cheng et al. / Carbon 42 (2004) 30813085

tion equilibrium of VOC on ACF. The main advantage

of the approach developed in this work is that the parameters appearing in the model could easily be estimated
from correlations of Eqs. (3)(8) or determined from
experiments. In addition, this model does not require
much computing time. Toluene is used to verify the model prediction with measurement data, and the results
shows that the model ts the experimental data very well.
For dierent VOCs, the model could also be used to
determine the breakthrough curve with time as long as
the anity coecient is known according to its physical
parameter and that of the reference VOC (toluene).

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