Separation and Purification Technology 251 (2020) 117396

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Separation and Purification Technology

journal homepage: www.elsevier.com/locate/seppur

Development of fractal-like Clark model in a fixed-bed column T

a,⁎ b c a
Qili Hu , Hengyuan Liu , Zhenya Zhang , Xiangjun Pei
a
College of Ecology and Environment, Chengdu University of Technology, Chengdu 610059, China
b
College of Chemistry and Life Sciences, Chifeng University, Chifeng 024000, China
c
Graduate School of Life and Environmental Sciences, University of Tsukuba, Tsukuba 305-8572, Japan

A R T I C LE I N FO A B S T R A C T

Keywords: The Clark model was used to describe a fixed-bed adsorption system based on the combination of the mass-
Adsorption transfer concept and the Freundlich isotherm. The previous study revealed a time-dependent mass-transfer
Fractal-like Clark model coefficient for the heterogeneous diffusion-limited process. Herein, this work proposed the fractal-like Clark
Mass-transfer coefficient model and its reliability was validated by the adsorption of norfloxacin on granular activated carbon. Moreover,
Fixed bed
the effects of the model parameters on the breakthrough curves and rate profiles were also investigated. The
results indicated that the fractal-like Clark model had a high adjusted coefficient of determination (Adj.
R2 > 0.977) and a small Akaike information criterion (AIC < −107.2) in all cases, providing more accurate
estimation of the model parameters than the Clark model. As a three-parameter model, the Clark model could
provide higher fitting accuracy (Adj. R2 = 0.997) for the adsorption of Cu(II) on Cystoseira crinitophylla biomass.
The breakthrough curve became more asymmetric when the parameters n and h deviated from 2 and 0, re-
spectively. The fractal-like Clark model may help readers to better understand the mass-transfer process in a
fixed-bed column.

1. Introduction limitation of the Clark model is related to the assumption of a constant

A fixed-bed column is preferred in the practical operation of full-
scale adsorption processes [1]. It is superior to a batch reactor because a
high driving force appears over the whole process and an adsorbate is
totally removed until the breakthrough occurs [2]. In such a system, the
adsorption of an adsorbate is a time- and distance-dependent process.
As a result, the design and optimization of a fixed-bed column are
difficult to be conducted a priori without a quantitative modeling ap-
proach describing the dynamic adsorption behaviors [3]. The modeling
of adsorption processes may cover simple analytical expressions or
complex partial differential equations when the mass and heat balance
are considered. It is desirable that an adsorption model can provide a
reliable estimation of the process performance without the use of the
extensive experimental data, and it should possess the suitable mathe-
matical complexity and acceptable accuracy in the evaluation of ad-
sorption performance under different operating conditions [4]. The
development of the Clark model is based on the use of a mass-transfer
concept in combination with the Freundlich isotherm, describing the
plug-flow behavior in a fixed-bed column [5]. It has been widely used
to analyze the breakthrough curves due to its explicit mathematical
expression and good fitting quality, reflecting a compromise between
the mathematical complexity and high accuracy. However, the main
mass-transfer coefficient, which is not suitable for describing the het-
erogeneous diffusion-limited process [6].
The classical reaction kinetics assumes that the rate constant is in-
dependent of time, which is found to be unsatisfactory when the re-
actants are spatially constrained by either walls, phase boundaries or
force fields on the microscopic level [7]. In practice, the interaction of
energetic and geometric heterogeneity can result in the fractal-like ki-
netics [8]. It represents a new insight into the adsorption behaviors at
the solid/solution interface. The adsorbent heterogeneity can be caused
by its physical structure and surface chemical nature [9]: The presence
of a distributed network of pores with different sizes and shapes creates
the physical heterogeneity and that of different functional groups on
the adsorbent surfaces produces the chemical heterogeneity (different
adsorption sites). Moreover, the rate of adsorption for the porous ad-
sorbents is related not only to the reaction rate on the active sites, but
also to the external mass transfer and intraparticle diffusion [10]. The
reaction rate on different types of the adsorption sites and mass transfer
in pores with different sizes and shapes may be more accurately de-
scribed by the fractal-like concept or a time-dependent mass-transfer
coefficient [6,11]. It is worthwhile to note that the fractal-like concept
has not been discussed in the Clark model. Therefore, the objective of
this study is to introduce the fractal-like concept or a time-dependent

⁎
Corresponding author at: College of Ecology and Environment, Chengdu University of Technology, Chengdu 610059, China.
E-mail address: huqili@cdut.edu.cn (Q. Hu).

https://doi.org/10.1016/j.seppur.2020.117396
Received 27 January 2020; Received in revised form 9 July 2020; Accepted 14 July 2020
Available online 17 July 2020
1383-5866/ © 2020 Elsevier B.V. All rights reserved.
Q. Hu, et al. Separation and Purification Technology 251 (2020) 117396

Nomenclature KT,0 fractal-like mass-transfer rate constant (minh−1)

La mass velocity of adsorbent to keep mass-transfer zone
A Clark constant (dimensionless) stationary (g min−1 cm−2)
A0 fractal-like Clark constant (dimensionless) m adsorbent mass packed in a fixed-bed column (g)
Adj. R2 adjusted coefficient of determination n Freundlich constant (dimensionless)
Cb concentration of adsorbate in the outlet at breakthrough r Clark or fractal-like Clark constant (min−1)
time tb (mg L−1) T temperature (°C)
Ce concentration of adsorbate at equilibrium (mg L−1) V linear flow velocity (cm min−1)
Ct concentration of adsorbate at time t (mg L−1) v flow rate (mL min−1)
Gs linear flow velocity (cm min−1) X amount of adsorbate uptake per unit mass of adsorbent
h fractal-like exponent (dimensionless) (mg g−1)
kF Freundlich constant ((mg g−1) (L mg−1)1/n) Z bed height (cm)
KT mass-transfer coefficient (min−1)

mass-transfer coefficient into the Clark model. Integration of Eq. (12) at the boundary conditions of Ct = Cb, t = tb
and Ct = Ct, t = t leads to
2. Theoretical analysis Ct dCt t
∫C b Ct − KCt n
= ∫t b
Rt−hdt
(13)
According to the derivation process of the Clark model [5], the
development of the fractal-like Clark model is based on a time-depen- or
dent mass-transfer coefficient. In a fixed-bed column, the concentration
Ct n−1 (1−KCbn−1) (n− 1) R 1−h
difference is regarded as a driving force for the mass-transfer process of ln = (tb − t 1−h)
Cbn−1 (1−KCt n−1) 1− h (14)
a contaminant to be removed and follows the Fick’s law.
dCt Let r = (n − 1)R then
KT (Ct − Ce) = Gs
dZ (1) 1/ K
Ct n−1 =
The heterogeneous diffusion-limited process can be described by a
time-dependent mass-transfer coefficient that is given by
1+ ( 1
KC bn−1 ) ⎣
r
−1 ∙exp ⎡ 1−h (tb1−h − t 1−h) ⎤
⎦ (15)

As t → ∞, Ct n−1
→ Ci n−1
(1/K = Ci n−1
). Eq. (15) is rewritten as
KT = KT,0 t −h    (0 ≤ h≤ 1) (2)
Ci
Substitution of Eq. (2) into Eq. (1) leads to Ct = 1

KT,0 t −h (Ct − Ce) = Gs

dCt
(3)
{ (
1+⎡
⎣
1
KC bn−1
−1 )∙exp ⎡⎣ r
t 1−h⎤ ⎤ ∙exp
1−h b ⎦ ⎦
(− r 1−h
1−h
t )}
n−1

(16)
dZ
Let
After separation of variables, Eq. (3) is rewritten as
1 r
dCt KT,0 t −hdZ A0 = ⎛ ⎜
n−1
−1⎞∙exp ⎡ ⎟tb1−h⎤
= ⎝ KCb ⎠ ⎣ 1− h ⎦ (17)
Ct − Ce Gs (4)
then the fractal-like Clark model is expressed as
If all of the adsorbates are removed at the outlet, an ideal mass
balance over the entire column is Ct 1
= 1
Ci
Gs Ct = La X (5)
⎣ (
⎡1+A0 ∙exp − 1−h t 1−h ⎤
⎦
r
) n−1
(18)
The Freundlich isotherm is expressed as
Eq. (18) is converted to the Clark model when h = 0.
1
X = kF Ce n (6) Ct 1
= 1
Substitution of Eq. (5) and Eq. (6) into Eq. (4) leads to Ci [1+A∙exp(−rt )] n−1 (19)

dCt KT,0 t −hdZ

=
Ct − [(1/ kF )n (Gs/ La )n] Ct n Gs (7) 3. Results and discussion

The velocity of the adsorption zone can be expressed as

3.1. Determination of the model parameters
V = dZ /dt (8)
In general, the accurate estimation of the model parameters is a
Substitution of Eq. (8) into Eq. (7) leads to
precondition for understanding the dynamic adsorption behaviors of
dCt the adsorbate in a fixed-bed column. The use of the Clark model re-
= [(KT,0/ Gs ) V ] t −hdt
Ct − [(1/ kF )n (Gs/ La )n] Ct n (9) quires that an adsorption process should follow the Freundlich model.
Let In this work, the fitting quality of the Clark model was evaluated by the
adsorption of Cu(II) on Cystoseira crinitophylla biomass [12] using the
K = (1/ kF )n (Gs/ La )n (10) nonlinear regression method. In such a system, the Cu(II) adsorption
followed the Freundlich model (n = 2.63). In order to obtain the Clark
R= (KT,0/ Gs)V (11)
constants A and r, two methods were utilized: (i) A and r were obtained
then by the curve fitting combined with the Freundlich constant n; and (ii) A,
r and n were directly obtained by the nonlinear regression. As shown in
dCt
= Rt−hdt Fig. 1, the first method provides a relatively poor fit (Adj. R2 = 0.992)
Ct − KCt n (12)
compared with the second method (Adj. R2 = 0.997). The

2
Q. Hu, et al.
Fig. 1. Adsorption of Cu(II) on Cystoseira crinitophylla biomass.
corresponding model parameters are A = 660797.5, r = 0.99, n = 2.63
and A = 143.4, r = 0.58, n = 1.13, respectively. There are significant
differences in the model parameters (A and r) given by the two
methods. Although the batch adsorption system obeyed the Freundlich
model, the fitting quality of the first method was not satisfactory. In a
batch system, the mass-transfer driving force decreased during the ad-
sorption process due to the decrease in concentration, while a high
mass-transfer driving force always remained over the whole process in a
fixed-bed column [2]. This intrinsic difference made the batch fitting
results difficult to be applied to the corresponding fixed-bed system. To
ensure a high fitting accuracy, the second method may be a better se-
lection to calculate the Clark constants A and r when the Clark model
was regarded as a three-parameter model.
3.2. Curve properties
The fractal-like kinetics indicated that the mass-transfer coefficient
KT was a time-dependent rate coefficient. As shown in Fig. 2, the KT
values were reduced with time and the rapid decrease occurs with the
increase in the fractal-like exponent h. This behavior was recently ex-
plained by the following two aspects: (i) the progressive occupation of
the adsorption sites via slower pathways available for the adsorbate in
the case of homogeneous surfaces and (ii) the adsorption onto sites
characterized by greater activation energies for heterogeneous surfaces
[13,14].
To identify the effects of the model parameters on the breakthrough
curves, the fractal-like Clark model (n = 2 and h = 0) is rewritten as
Ct 1
=
Ci 1
(
1+exp ⎡r r lnA0 −t ⎤
⎣ ⎦ ) (20)
Let
k= r
1
τ= lnA0
r (22)
then
Ct 1
=
Ci 1+exp[k (τ −t )]
As a result, the fractal-like Clark model is a logistic function in
mathematical nature. k is a shape parameter that influences the degree
of curvature alone, while τ is a position parameter that only affects the
position of the curve. The rate equation of the fractal-like Clark model
can be obtained by the first-order derivative of Eq. (18).
Separation and Purification Technology 251 (2020) 117396
d(Ct / Ci ) A r 1 r 1−h −h
= 0 ∙ n ∙exp⎛− t ⎞∙t
dt n− 1 ⎝ 1− h ⎠
⎡1+A0 exp
⎣ ( r
− 1−h t 1−h )⎤⎦
n−1
(24)
It can be clearly seen from Fig. 3 that the parameters A0 and r do not
influence the symmetry of the breakthrough curves and rate profiles.
With the increase in A0, the breakthrough curves and rate profiles are
shifted to the right-hand side by a certain distance and the degree of
curvature remains unchanged. In contrast, the parameter r can influ-
ence both the degree of curvature and the position of the curve. The
breakthrough curves become steeper and are shifted to the left-hand
side by a slight distance with the increase in r. The rate profiles exhibit
the corresponding changes.
The effects of the parameters n and h on the breakthrough curves
and rate profiles are described in Fig. 4. It is observed that n and h can
simultaneously influence the degree of curvature, symmetry and posi-
tion of the breakthrough curves and rate profiles and that these curves
are symmetric only when n = 2 and h = 0. An asymmetric rate profile
appears with widened left- and right-hand sides respectively when
1 < n < 2 and n > 2, and the breakthrough curve becomes more
asymmetric when the parameter n deviates from 2. In contrast, an
asymmetric rate profile appears with a widened right-hand side when
h > 0, and the breakthrough curve becomes more asymmetric when
the parameter h deviates from 0. It was reported that the breakthrough
curve was usually asymmetric in the adsorption of water pollutants
even for the adsorption of an individual solute [15], which was ascribed
to the following facts that: (i) The breakthrough curve may correspond
to the two different adsorption mechanisms [16]; (ii) the intraparticle
diffusion was the rate-controlling step [2]; and (iii) the adsorbent
consisted of two or more constituents of unequal reactivity [17]. Thus,
the fractal-like Clark model could better describe the adsorption of
water pollutants in a fixed-bed column based on the time-dependent
mass-transfer coefficient. It contained four adjustable parameters,
making the curve fitting more flexible.
3.3. Model comparison
An efficient way to discriminate the models was to compare them
statistically. In this work, the Akaike information criterion was used to
analyze the fitting quality of norfloxacin adsorption on granular acti-
vated carbon [18] using the Clark and fractal-like Clark models. As il-
lustrated in Fig. 5, the fitting curves provided by the fractal-like Clark
model can better describe the experimental data with smaller
(21)
(23)
Fig. 2. Effect of the fractal-like exponent h on the time-dependent mass-transfer
coefficient.
3
Q. Hu, et al. Separation and Purification Technology 251 (2020) 117396

Fig. 3. Schematic diagram of the breakthrough curves and rate profiles for different A0 and r (A0,1 < A0,2 < A0,3 < A0,4 < A0,5 and r1 < r2 < r3 < r4 < r5).

Fig. 4. Schematic diagram of the breakthrough curves and rate profiles for different n and h.

4
Q. Hu, et al. Separation and Purification Technology 251 (2020) 117396

Fig. 5. Adsorption of norfloxacin on granular activated carbon in a fixed-bed column.

Table 1
Fitting results and error analyses from the Clark and fractal-like Clark models.
Experimental conditions Clark model Fractal-like Clark model

Ci (mg L−1) v (mL min−1) Z (cm) A r n Adj. R2 AIC A0 r n h Adj. R2 AIC

150 0.5 25 0.115 0.048 1.008 0.972 −105.5 2.313 0.796 1.0004 0.696 0.982 −111.0
150 1.0 25 0.082 0.049 1.009 0.980 −108.4 30.60 0.950 1.002 0.758 0.990 −118.8
150 1.5 25 0.064 0.046 1.010 0.976 −105.5 20.23 0.937 1.001 0.789 0.991 −121.1
150 1.5 15 0.026 0.049 1.006 0.979 −107.3 31,737 1.14 1.050 0.866 0.996 −135.5
150 1.5 20 0.049 0.049 1.009 0.975 −103.5 1.371 0.829 1.0004 0.765 0.991 −121.4
150 1.5 25 0.056 0.047 1.009 0.977 −105.7 45.06 0.954 1.002 0.794 0.991 −120.9
75 1.5 25 0.091 0.043 1.009 0.963 −100.7 9.476 0.689 1.005 0.691 0.977 −107.2
150 1.5 25 0.061 0.047 1.009 0.978 −106.4 162.4 1.010 1.004 0.807 0.992 −122.4
225 1.5 25 0.041 0.062 1.006 0.997 −142.1 8349 0.992 1.624 0.710 0.999 −155.4

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Q. Hu, et al. Separation and Purification Technology 251 (2020) 117396

deviations in comparison to the Clark model at different flow rates, bed
heights and initial norfloxacin concentrations. In general, the one with
larger Adj. R2 and smaller AIC values was suggested to be a better
model for the dataset. As shown in Table 1, the fractal-like Clark model
has larger Adj. R2 and smaller AIC values for all cases. Therefore, the
fractal-like Clark model provided more reliable estimation for nor-
floxacin adsorption.
3.4. Practical significance
The development of the Clark model was based on a time-in-
dependent mass-transfer coefficient. It was not applicable to the de-
scription of the diffusion-limited process on the heterogeneous surfaces.
On the other hand, the fractal-like Clark model overcame this difficulty
and had better fitting performance. It has been proved that the fractal-
like exponent h could influence the degree of curvature, position and
symmetry of the breakthrough curves. Thus, the introduction of the
fractal-like concept into the Clark model improved its fitting quality,
obtained more reliable model parameters and greatly extended its ap-
plication scope in the adsorption of water pollutants. The design of a
fixed-bed adsorption column usually required extensive experiments
and tended to be expensive and time-consuming [19]. For this reason, it
was important to develop a model that could describe the dynamic
adsorption behaviors of the adsorbate in a fixed-bed column. This study
experimentally validated the applicability of the fractal-like Clark
model and revealed the effects of the model parameters (A0, r, n and h)
on the breakthrough curves and rate profiles. It was expected that the
fractal-like Clark model provided more accurate information for the
adsorber design.
4. Conclusions
This work proposed the fractal-like Clark model based on a time-
dependent mass-transfer coefficient. It represented an asymptotic and
asymmetric sigmoidal curve (n ≠ 2 or h ≠ 0) and provided more re-
liable estimation for the modeling of norfloxacin adsorption on granular
activated carbon at different flow rates, bed heights and initial con-
centrations. The model parameters n and h could influence the degree
of curvature, symmetry and position of the breakthrough curves and
rate profiles, making the curve fitting more flexible. The Clark model
was regarded as a three-parameter model, providing better fitting
performance for Cu(II) adsorption on Cystoseira crinitophylla biomass.
The fractal-like Clark model can describe the diffusion-limited process
on the heterogeneous surfaces and may provide an alternative method
for the modeling of pollutants adsorption in a fixed-bed column.
CRediT authorship contribution statement
Qili Hu: Writing - original draft, Conceptualization, Methodology,
Validation. Hengyuan Liu: Writing - review & editing, Data curation.
Zhenya Zhang: Data curation. Xiangjun Pei: Funding acquisition,
Conceptualization, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors acknowledge the financial support from the Scientific
Research Foundation (No. 10912-KYQD2019-08165), the Natural
Science Foundation of Inner Mongolia (No. 2019BS02006), and the
Research Start-up Funds for the Chifeng University (No. QDJRCYJ022).

Appendix A

The fitting quality of the models is evaluated by the adjusted coefficient of determination (Adj. R2).
n− 1
Adj.R2 = 1− (1 − R2)∙
n− p (A.1)
The comparison of two models is conducted by the Akaike information criterion (AIC).

AIC =
⎧ N ∙ln( ) + 2K
RSS
N
N
K
>40
⎨ N ∙ln
⎩
( ) + 2K +
RSS
N
2K ∙ (K +1)
N − K −1
N
K
<40
(A.2)
where R is the multiple coefficient of determination (R = 1 − RSS/TSS, TSS is total sum of squares, RSS is residual sum of squares); N is the
2 2

number of the data points; p is the number of the model parameters; and K is the number of the model parameters plus 1.

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