Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60

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Journal of the Taiwan Institute of Chemical Engineers

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

Influence of various operating conditions on cleaning efficiency in

sequencing batch reactor (SBR) activated sludge process. Part V:
Chemical cleaning model
Zhan Wang∗, Ximing Zhang, Zhongya Zhu, Yadong Kong, Kui Gao, Wei Yao
Beijing Key Laboratory for Green Catalysis and Separation, Department of Chemistry and Chemical Engineering, Beijing University of Technology, Beijing
100124, PR China

a r t i c l e i n f o a b s t r a c t

Article history: A flux recovery model of chemical cleaning of microfiltration membranes in membrane bioreactor (MBR)
Received 2 October 2015 was proposed based on Hom–Haas model. This model provides intuitive prediction of flux recovery as a
Revised 8 February 2016
function of cleaning time and cleaning solution concentration for PAN microfiltration membrane fouled
Accepted 14 March 2016
with activated sludge from membrane bioreactor (MBR). The quantitative effects of different chemical
Available online 9 April 2016
cleaning conditions (temperature, transmembrane pressure and agitation speed) on model parameters
Keywords: were calculated by means of Multiple Linear Regression. High accuracy of the proposed model is ap-
Membrane proved not only by chemical cleaning agent of NaOCl, but also by other cleaning agents such as NaOH
Chemical cleaning and SDS.
Flux recovery © 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
Model
Activated sludge

1. Introduction model was used to describe the unsteady-state hydraulic resistance

Chemical cleaning processes are carried out usually in effec-
tively recovering the permeate flux of fouled membrane [1]. Mass
researches have been performed to find out the best cleaning time
and concentration of chemical agent [2–4]. However, in order to
obtain fruitful solution, kinetic models are required to illustrate the
mechanisms of membrane cleaning.
Bird and Fryer [5] introduced an analytical model including two
differential equations for the cleaning of the membrane fouled
with whey proteins. Bartlett et al. [6] suggested a qualitative
model which describes different removal characteristics of de-
posited species. Cabero et al. [7] suggested a first-order rinsing
model with two time-dependent rates and the rinsing model used
to predict the decrease in the membrane resistance. Gan et al.
[8] successfully employed a first order decay kinetic model to ex-
plain the cleaning mechanism for the membrane fouled with beer
and beverages. After entering 21th century, more studies were fo-
cused on cleaning models associated with membrane application.
For inorganic membranes fouled with whey proteins, a first-order
model for rinsing and a second-order model for alkaline clean-
ing were introduced by Matzinos et al. [9]. Bird et al. [3] devel-
oped a mathematical model with a second-order decrease in the
cake resistance and a second-order in-pore deposit swelling. The
∗
Corresponding author. Tel.: +86 1067396186; fax: +86 10 67391983.
E-mail address: wangzhan3401@163.com, wangzh@bjut.edu.cn (Z. Wang).
http://dx.doi.org/10.1016/j.jtice.2016.03.022
1876-1070/© 2016 Taiwan Institute of Chemical Engineers. Published by Elsevier B.V. All rights reserved.
variation resulted from surface morphological changes and in-pore
foulant during alkali cleaning process of membrane fouled by whey
proteins. A simple first-order model for the cleaning of membranes
fouled by fermentation broth of glutamic acid was suggested by Li
et al. [10]. Zondervan et al. [11] proposed a simple cleaning model
which facilitates online adaptation of model parameters in terms
of macroscopic component balances. The model predicts the irre-
versible fouling decay with cleaning time and cleaning agent con-
centration. Considering chemicals and energy consumption, Zon-
dervan et al. [12] suggested a chemical cleaning sequence model
to minimize the overall operating costs. Koyuncu et al. [13] sug-
gested a kinetic model as a function of cleaning solution concen-
tration and cleaning time to evaluate the dissolution of deposit
on the membrane surface. For the ceramic membranes fouled by
whey proteins, Svetlana et al. [4] proposed a second-order kinetic
model with five parameters for alkali cleaning and a third-order ki-
netic model with six parameters for detergent cleaning. Although
these proposed cleaning models provide important insights into
the mechanisms of membrane cleaning, few studies were reported
about the mechanism of the chemical cleaning of microfiltration
membranes fouled by activated sludge suspensions from MBR.
The main objectives of the present study are to build an ef-
fective and intuitive model to predict the flux recovery of chem-
ical cleaning of PAN microfiltration membrane fouled by activate
sludge suspensions from MBR, and to determine model parameters
and evaluate the quantitative contributions of operating condition
to model parameters.
 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60 53

Nomenclature

C concentration of cleaning solution (wt%)

J permeate flux of the membrane (m3 /m2 /s)
J0 pure water flux of pre-rinsed membrane (m3 /m2 /s)
Jw pure water flux of virgin membrane (m3 /m2 /s)
Jr the percentage flux recovery (%)
R0 resistance of pre-rinsed membrane (m−1 )
Rc cake resistance (m−1 )
Rcp resistance due to concentration polarization (m−1 )
Rm intrinsic resistance of membrane (m−1 )
Rin resistance due to in-pore fouling (m−1 )
Rtf the total fouling resistance of membrane (m−1 )
Rtf (t) the total fouling resistance of membrane at certain
time t of chemical cleaning operation (m−1 )
T absolute temperature (K)
t time (s)
TMP trans-membrane pressure drop (Pa)

Greek symbol
ω agitation speed of magnetic stirrer (rpm)
μ liquid viscosity (Pa s)

2. Theory of kinetic model

The membrane flux can be expressed as follows:

T MP
J=
μRt f
where J is the permeate flux of the membrane, m3 /m2 /s; TMP
is the trans-membrane pressure, Pa; μ is permeate viscosity
(0.8360 × 10−3 at 28 °C), Pa s; Rtf is the total resistance of fouled
membrane, m−1 ; Rtf is expressed as follows:
Rt f = Rm + Rcp + Rin + Rc
where Rm is the intrinsic resistance of the membrane, Rcp is the
resistance due to concentration polarization, Rin is the resistance
due to in-pore fouling and Rc is the hydraulic resistance of deposit
at the membrane surface.
Since the fouled membrane was rinsed 10 min with DI-water
with agitation speed (ω) of 400 rpm before being exposed to
chemical cleaning, it can be assumed that weakly attached layer
due to concentration polarization would be swept away during
pre-rinsing [3]. So, Rcp in Eq. (2) could be neglected.
Flux recovery was evaluated by comparing the pure water flux
of a fouled membrane subjected to the cleaning procedures (Jcw )
with the pure water flux of a virgin membrane, Jw . Flux recovery
(Jr ) is expressed as follows:
Jcw
Jr = × 100%
Jw
As proposed by the Hom–Haas model [14,15]:
N
ln = −kC n t m
N0
where N/N0 is the survival ratio of organisms, k is a kinetic con-
stant, C and t are cleaning solution concentration and cleaning
time, respectively, and m and n are empirical constants.
By relating the organisms’ survival number to membrane re-
sistance, a kinetic model for chemical cleaning of microfiltration
membrane fouled by activated sludge suspension from MBR can
be developed as follows:
 
Rt f (t ) − Rm
ln = −kC n t m
Rt f (0 ) − Rm
(1)
(2)
Fig. 1. The theoretical analysis of the model. (a) Jr as function of cleaning time. (b)
Jr as function of cleaning solution concentration.
where Rtf (t) is the total fouling resistance of microfiltration mem-
brane at certain time t of chemical cleaning operation, C and t are
cleaning solution concentration and cleaning time, respectively.
By combining Eqs. (3) and (5), the flux recovery of the pre-
rinsed membrane after chemical cleaning can be deduced:
1
Jr = Jw −J0
(6)
1+ J0
exp (−kC n t m )
(3)
where J0 is the pure water flux of the membrane after pre-rinsed
operation.
In Eq. (6), Jw is greater than J0 , and if model parameters (k, m
(4) and n) are above zero, then Jr will increase with increasing clean-
ing time or cleaning solution concentration. This trend shown in
Fig. 1(a) and (b) is reasonable. When the cleaning time is zero,
Jr(t = 0 ) is J0 /Jw . And when the cleaning time tends to infinite,
Jr ( t→∞ ) will be 1 and the trend of flux recovery is showed in Fig.
1(a). Similarly, when the concentration of cleaning agent tends to
infinite, Jr ( c→∞ ) will be 1 too (Fig. 1(b)). This conclusion is obtained
at ideal conditions. Moreover, when the concentration of cleaning
agent is equal to zero, Jr ( c = 0) is J0 /Jw which is equal to Jr ( t = 0) .
Here, the pre-rinsing of 10 min is considered sufficient and increas-
ing the rinsing time will have no effect on cleaning efficiency any
(5)
more. And this assumption is also an ideal condition.
54 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60
Table 1
Operating parameters of bioreactor.
MLSS (g/L) T (°C) DO (mg/L) pH HRT (h)
2.7 20 4.0 7.5–8.0 18
3. Materials and methods
3.1. Experimental setup and membranes
The laboratory-scale experimental system is a dead-end mi-
crofiltration cell and it is described elsewhere in the literature
[16,17]. The 0.1 μm polyacrylonitrilerile (PAN) membrane was ob-
tained from Beijing Ande Membrane Separation Technology and
Engineering (Beijing) Co., Ltd., were used in this study. All flat-
sheet membranes were cut into pieces with 53.28 cm2 of active
membrane area. Prior to each experiment, the membranes were
soaked in deionized water for 12 h to remove glycerin (protectant)
at 4 °C.
Activate sludge suspension is taken from an intermittent mode
bioreactor system with an effective volume of 25 L [16]. The de-
tail operating parameters of the bioreactor system are shown in
Table 1. No sludge is discharged during the operation period. The
main parameters of feed suspension used in this experiment were
chemical oxygen demand (COD) (34.6–40.7 mg/L), NH3 –N (9.4–
11.22 mg/L) and total oxygen content (TOC) (31.5–37.8 mg/L).
3.2. Experimental procedure
Before conducting any experiments, the initial pure water flux
(Jw ) of the origin PAN membrane was measured using distilled wa-
ter (DI-water). This was acquired in situ at a trans-membrane pres-
sure (TMP) drop of 0.04 MPa and DI-water temperature of 25 °C.
The next procedure was filtration of feed suspension (activated
sludge suspension from membrane bioreactor or yeast suspension
freshly prepared) and the membrane flux was measured until a
pseudo-steady state flux approximately 3.75% of the initial flux
value achieved [3]. In all cases, experiments were performed with
fixed TMP of 0.04 MPa and agitation speed (ω) of 200 rpm at room
temperature (25 ± 1 °C). After the fouling step, the fouled mem-
brane was rinsed 10 min by DI-water with agitation speed (ω)
of 400 rpm to remove all loosely bounded fouling deposit from
the microfiltration membrane surface [18,19], then the water flux
was measured. The next step was the chemical cleaning process.
Sodium hypochlorite (0.5–5 wt%) was used as cleaning agents. All
these agents were analytical grade and were supplied by the Bei-
jing Chemical Engineering Factory. All chemical agents were dis-
solved in 1 L of DI-water and fresh cleaning solutions were pre-
pared daily and all the cleaning solutions were preheated to a pre-
determined cleaning temperature. The effects of agitation speed
(ω), trans-membrane pressure (TMP), cleaning solution concentra-
tion (C), cleaning temperature (T) and cleaning time (t) on flux
recovery (Jr ) were evaluated. When the chemical cleaning process
was finished, the pure water flux (Jcw ) was also measured.
4. Result and discussion
4.1. Determination of model parameters
A series of the experiments of NaOCl-cleaning at 28 °C (The ag-
itation speed was 200 rpm and TMP was 0 MPa) were carried out
with altering cleaning time and NaOCl concentration respectively.
Flux recovery after a 30-min cleaning procedure increased remark-
ably with NaOCl concentration increasing from 0 to 0.5 wt% (Fig.
2(a)). However, flux recovery increased rather slowly when the
Table 2
Model parameters for different cleaning agents (0 MPa,
400 rpm, 28 °C).
Cleaning agent R2 Parameter
k m n
NaOCl 0.921 0.380 0.429 0.339
NaOH 0.933 0.198 0.487 0.487
SDS 0.960 0.545 0.325 0.254
concentration of NaOCl was more than 0.5 wt%. This was in con-
sistent with reports that cleaning agents had an optimal concen-
tration to clean membranes [10,20,21]. The cleaning efficiency in-
creased until cleaning agent concentration got to its optimal value.
Similarly, the effect of cleaning time on flux recovery was much
more significant in the first 15 min than that in the subsequently
15 min at NaOCl concentration of 0.5 wt% (Fig. 2(b)). This phe-
nomenon might result from the removal of loose deposit within
the first 15 min while remaining deposit which was strongly ad-
sorbed on the membrane could not be significantly removed by
increasing the cleaning time [22].
The trend of flux recovery in Fig. 2 was in accordance with
that in Fig. 1. This phenomenon confirmed the validity of proposed
model to some extent. Powerful evidence to prove the validness
of the proposed model was obtained by fitting experimental data
with the model. Model parameters were estimated by processing
experimental data by the nonlinear regression using 1stopt soft-
ware (China) and the results were shown in Table 2. The values of
model parameters in Table 2 were obtained by fitting experimental
data with the model predictions at high R2 [23].
The variation of model predictions of flux recovery of chemical
cleaning for microfiltration membrane is clearly shown in Fig. 3(a)
and more information about the relationship between flux recov-
ery, cleaning time and concentration of cleaning solution is shown
in Fig. 3(b). From Fig. 3, effective flux recovery could be obtained at
optimal cleaning time and cleaning solution concentration, which
was of significance for the chemical cleaning processes. Take clean-
ing time of 20 min as example, flux recovery for 0.75 wt% NaOCl
solution reached the yellow area which was nearly 70%. As the
concentration increased to 1.25 wt%, flux recovery arrived at the
edge of saffron area which was nearly 76%. This means that flux re-
covery was lifted just 6% with concentration increasing by 0.5 wt%.
Moreover, flux recovery increased more slowly with concentration
increasing further. However, if the cleaning time is not limited, in-
creasing the cleaning time to 30 min for 0.75 wt% NaOCl solution,
flux recovery can be reached nearly 75%. As a result, an effective,
environmental and economy cleaning scheme can be obtained in
Fig. 3.
4.2. Effect of operating conditions on model parameters
Operating conditions are significant for the chemical cleaning
process [24]. In order to determinate the impacts of the clean-
ing conditions on model parameters, a series of experiments were
performed at several temperatures (28, 33, 39, 46 and 55 °C) and
transmembrane pressures (0.00, 0.02, 0.04, 0.06 and 0.08 MPa) and
agitation speeds (20 0, 30 0, 40 0, 50 0 and 60 0 rpm) with altering
cleaning time and NaOCl concentration. As shown in Fig. 4, the
general trends of flux recovery for all selected conditions are all
similar to those of the two ideal curves in Fig. 1, i.e. flux recovery
was increased sharply at the early stage and increased slowly at
the later stage.
The flux recovery was increased with increasing temperature
at fixed NaOCl concentration and the cleaning time (Fig. 4(a) and
(b)). This result was reasonable and it has been explained by many
 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60 55

Fig. 2. Flux recovery as function of concentration cleaning time of NaOCl solution (0 MPa; 400 rpm; 28 °C). (a) NaOCl concentration, (b) cleaning time of NaOCl solution.

Fig. 3. Model figure for NaOCl solution cleaning process (0 MPa; 400 rpm; 28 °C). (a) 3-d figure, (b) projection figure. (For interpretation of the references to color in this
figure, the reader is referred to the web version of this article.)

authors [25,22,26]. The equilibrium constant of the reaction and
the solubility of foulants were increased at higher temperature
[25]. Besides, higher temperature decreases the viscosity of the
chemical cleaning solution [3]. As a consequence, flux recovery in-
creased with increasing temperature. However, flux recovery ex-
ceeded 100% when NaOCl concentration was above 0.2 wt% in 46 °C
and 55 °C. This phenomenon may be caused by the damage of the
membrane resulting in large pores. In addition, the membrane sur-
face became more hydrophilic when the chemicals were used and
a high flux recovery is expected [20]. In conclusion, the limitations
of the membrane material prohibit consideration of very high tem-
perature [22].
As regarding to the effect of transmembrane pressure (TMP)
which is a detrimental factor for hydraulic cleaning efficiency
[18,27,28], experimental results of Jr for different TMPs (0–
0.08 MPa) are summarized in Fig. 4(c) and (d). Clearly, TMP had
a remarkable effect on flux recovery. In case of fouled membrane
cleaned by 0.5 wt% NaOCl solution for 30 min, a maximum value
of flux recovery was 73% in the absence of TMP and this value
reduced gradually with increasing TMP. As TMP was adjusted to
0.08 MPa, Jr decreased to 47%. The phenomenon was due to the
fact that the swollen and partially hydrolyzed foulant particles
were forced by the applied TMP into the membrane pores during
chemical cleaning operation [3]. In conclusion, the absence of TMP
is optimum during chemical cleaning procedure.
As a hydraulic parameter, agitation speed (ω) has an effect on
flux recovery [22]. Flux recovery may increase with increasing ag-
itation speed if the chemical reaction is favorable during cleaning
process [22]. Fig. 4(e) and (f) demonstrates the variety of flux re-
covery with increasing agitation speed at a fixed temperature. No
considerable difference between plots of flux recovery for different
agitation speeds with identical NaOCl concentration and cleaning
time. As ω increased from 200 rpm to 600 rpm at the cleaning
time of 30-min and NaOCl concentration of 0.5 wt%, the corre-
sponding flux recovery increased from 69.3% to 75.5%. The small
increase was due to the fact that an increase in shear rate result-
ing from increasing the applied agitation speed failed to enhance
the back mass transfer of foulant to the bulk solution [29,22,30].
Experimental data of flux recovery were compared with pre-
dictions of the proposed kinetic model. As shown in Table 3, all
the values of R2 were above 0.900 except for 46 °C and 55 °C,
which suggested that the proposed kinetic model was effective
in selected range of operating condition except for high temper-
ature. Therefore, parameter values obtained at high temperature
56 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60

Fig. 4. Impacts of different cleaning conditions on flux recovery as a function of concentration of NaOCl solution and cleaning time. (a, b) Different temperatures, (c, d)
different transmembrane pressures, (e, f) different agitation speeds.
 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60 57

Table 3
Model parameters for NaOCl solution cleaning in different operating conditions.

k m n
TMP T ω R2
Value Standard error Value Standard error Value Standard error

0.00 28 400 0.921 0.380 0.156 0.429 0.125 0.339 0.051

0.02 28 400 0.923 0.382 0.147 0.378 0.061 0.365 0.117
0.04 28 400 0.965 0.178 0.067 0.471 0.040 0.515 0.113
0.06 28 400 0.952 0.096 0.050 0.528 0.053 0.630 0.156
0.08 28 400 0.963 0.061 0.035 0.610 0.051 0.678 0.169
0.00 28 400 0.921 0.380 0.156 0.429 0.125 0.339 0.051
0.00 33 400 0.953 0.440 0.123 0.584 0.092 0.462 0.076
0.00 39 400 0.900 0.802 0.312 0.563 0.159 0.638 0.167
0.00 46 400 0.559 0.431 0.152 1.499 4.947 1.445 5.292
0.00 55 400 0.266 Failed Failed Failed Failed Failed Failed
0.00 28 200 0.904 0.320 0.156 0.454 0.144 0.425 0.074
0.00 28 300 0.914 0.387 0.151 0.420 0.128 0.428 0.072
0.00 28 400 0.921 0.380 0.168 0.429 0.125 0.339 0.0510
0.00 28 500 0.931 0.427 0.156 0.426 0.107 0.430 0.065
0.00 28 600 0.926 0.486 0.152 0.401 0.106 0.427 0.068

Table 4
Multiple Linear Regression results of relationships between operating conditions and model parameters (0–0.08 MPa, 28–55 °C, 20 0–60 0 rpm).

Cleaning solution Model parameters Contribution (%) Mathematical relationships

TMP T ω

NaOCl k 53.28 42.40 4.32 k = −5.11 · T MP + 0.014 · T + 0.01% · ω

m 48.12 51.87 0.00 m = 2.192 · T MP + 0.014 · T
n 70.09 28.85 1.07 n = 2.955 · T MP + 0.015 · T
NaOH k 51.20 41.52 7.28 k = −9.527 · T MP + 0.014 · T
m 2.50 54.53 42.97 m = 0.005 · T + 0.001 · ω
n 22.74 0.03 77.23 n = 4.671 · T MP + 0.001 · ω
SDS k 71.11 21.11 7.78 k = −6.634 · T MP + 0.006 · T
m 29.18 69.71 1.11 m = 4.202 · T MP + 0.011 · T
n 7.10 84.08 8.82 n = 0.012 · T

experiments (46 °C and 55 °C) were not used in the following sta-
tistical analysis.
Method of Multiple Linear Regression was used to evaluate the
effects of the operating conditions (temperature, agent concentra-
tion and agitation speed) on the values of model parameters (k,
m, n) for NaOCl agent and the contribution of each operating con-
dition to model parameters were calculated and summarized in
Table 4. By statistical analysis, the three selected operating con-
ditions for NaOCl agent were all influencing factors for kinetic
constant (k). Contributions of TMP, T and ω were 53.28%, 42.4%
and 4.32%, respectively. The statistical result showed that agitation
speed was not a significant factor for m and n. With a contribution
value of 70.09% to n, TMP was the dominant factor as compared to
28.85% to T. As regarding to m, however, the effect of T with 48.12%
was nearly equal to that of TMP with 51.87%. Coefficients of in-
fluencing factors for model parameters were obtained by Multiple
Linear Regression. And results in Table 4 for NaOCl agent showed
these quantitive relationships between model parameters and in-
fluencing factors.
To further verify the effectiveness of this model for NaOCl
agent, model predictions were compared with new experimental
observations (Fig. 5(a)). The new experimental points were very
close to the surface consisting of prediction values of the proposed
model. In Table 5, relative mean error between experimental data
and model predictions were almost less than 4% for NaOCl agent.
This indicated that this model could accurately predict the varia-
tion of flux recovery with the cleaning time and NaOCl concentra-
tion during chemical cleaning operation.
4.3. Validation and applicability of the kinetic model
In order to verify the applicability of proposed kinetic model,
NaOCl solution was replaced by NaOH and SDS solutions to clean
the fouled membrane. Similar cleaning experiments and statisti-
cal analysis described above were performed and the results were
summarized in Fig. 6 and Table. 6. Fig. 6 showed the 3-d and pro-
jection figure of the model for NaOH and SDS solutions at a cer-
tain cleaning condition (28 °C for temperature, 0 MPa for TMP and
400 rpm for ω). The flux recovery of NaOH or SDS solution was not
as good as that of NaOCl solution. When the cleaning time is fixed
as 20 min, flux recovery of 0.15 wt% NaOH and 0.15 wt% SDS solu-
tions reached about 48% and 53%, respectively and higher concen-
tration cannot increase flux recovery remarkably which is similar
to NaOCl solution. Moreover, increasing cleaning time can improve
the cleaning effect. In addition, by comparing the three model fig-
ures, a conclusion can be drawn that if flux recovery is expected
above 65%, NaOCl is the only suitable agent which can be used. In
contrast, flux recovery of NaOH or SDS is not likely above 65%.
A value of 93.3% for R2 indicated that the proposed model was
effective for NaOH cleaning operation. Better fitting result with
96.0% for R2 proved the applicability of the proposed model for
SDS solution. In addition, effect of operating condition on model
parameters was also studied by means of Multiple Linear Regres-
sion. As shown in Table 4, the kinetic constant (k) was affected by
TMP and T for NaOH agent. The contributions of TMP and T were
51.2% and 41.52%, respectively. As to m, both T and ω were sig-
nificant factors with contribution values of 54.53% and 42.97%, re-
spectively. ω was also an effect factor for n with contributing about
77.23% while TMP contributed 22.74% to n.
Similar to NaOH agent, TMP and T during SDS solution cleaning
operation affected k a lot and contributions of them were 71.11%
and 21.11%. In addition, they were also the affecting factors for m
and the contribution of TMP was 29.18% which was lower than that
of T. However, there was only T influence n in operating range and
it was the dominant factor with contributing 84.08% to n value.
The mathematical relationships between model parameters and
58 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60

Fig. 5. Comparison between experimental data and model predictions in terms of flux recovery vs. cleaning time and concentration for cleaning agent of (a) NaOCl (b) NaOH
and (c) SDS (0 MPa; 400 rpm; 28 °C).

Table 5
Relative mean error between experimental data and model predictions for chemical cleaning operation with NaOCl solution.

Cleaning time Concentration Relative mean error (%) Cleaning time Concentration Relative mean error (%)

0 1.20 0.0 30 0.85 1.2

5 1.20 9.5 30 1.40 1.8
10 1.20 2.2 30 2.00 0.0
15 1.20 1.6 0 2.00 0.0
20 1.20 0.7 5 2.00 2.5
25 1.20 2.5 10 2.00 1.9
30 1.20 0.9 15 2.00 3.6
30 0.15 0.9 20 2.00 1.8
30 0.35 1.8 25 2.00 2.4
30 0.65 0.4 30 2.00 0.0

operating conditions for NaOH and SDS solution were showed in
Table 4.
In order to test the applicability of the proposed model on
NaOH and SDS cleaning operation, new experimental data were
compared with the predictions of the kinetic model. Clearly, the
experimental points were almost on the nets consisting of predic-
tion values of the proposed model (Fig. 5(b) and (c)). For NaOH so-
lution, relative mean error (Table 6) were all less than 4%, showing
the good coherence between experimental data and model predic-
tions. And the relative mean errors (Table 6) for SDS solution were
all less than 2.2%, indicating the better agreement between exper-
imental data and model predictions. These results confirmed the
applicability of the proposed model for chemical cleaning opera-
tion.
 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60 59

Fig. 6. Model figure for NaOH ((a) 3-d figure, (b) projection figure) or SDS ((c) 3-d figure, (d) projection figure) agent cleaning process (0 MPa; 400 rpm; 28 °C).

Table 6
Relative mean error between experimental data and model predictions for agent of NaOH or SDS.

NaOH SDS

Cleaning time Concentration Relative mean error (%) Cleaning time Concentration Relative mean error (%)

0 0.25 0.0 0 0.25 0.0

5 0.25 0.3 5 0.25 2.2
10 0.25 2.3 10 0.25 1.7
15 0.25 3.2 15 0.25 1.4
20 0.25 1.9 20 0.25 0.0
25 0.25 3.9 25 0.25 0.8
30 0.25 3.1 30 0.25 0.3
30 0.05 2.2 30 0.05 0.7
30 0.15 1.7 30 0.15 0.8
30 0.35 1.4 30 0.35 0.1

5. Conclusion was effective for NaOCl cleaning in different operating conditions

In the present paper, a kinetic model was proposed to describe
the variation of flux recovery with cleaning time and cleaning solu-
tion concentration during the chemical cleaning processes. Theory
analysis approved reasonability of the proposed model. A system-
atic study of chemical cleaning of PAN microfiltration membrane
fouled by activated sludge suspension from membrane bioreactor
was thoroughly undertaken. And the results of fitting the proposed
model with experimental data showed that the proposed model
except for high temperature. Contributions of selected operating
conditions to model parameters were calculated by means of Mul-
tiple Linear Regression and the results showed that TMP and tem-
perature are the main influencing factors. In addition, to verify the
effectiveness of the model, model predictions were compared with
the new experimental data. Furthermore, applicability of the model
was verified through replacing NaOCl by NaOH and SDS and the
results indicated that the model was effective for NaOH and SDS
cleaning as well.
60 Z. Wang et al. / Journal of the Taiwan Institute of Chemical Engineers 63 (2016) 52–60
Acknowledgments
The authors acknowledge the financial support from the Na-
tional Natural Science Foundation of China (Project nos. 21176006
and 21476006).
References
[1] Blanpain-Avet P, Migdal JF, Bénézech T. Chemical cleaning of a tubular ce-
ramic microfiltration membrane fouled with a whey protein concentrate sus-
pension Characterization of hydraulic and chemical cleanliness. J Membr Sci
2009;337:153–74.
[2] Corbatón-Báguena MJ, Álvarez-Blanco S, Vincent-Vela MC. Salt cleaning of ul-
trafiltration membranes fouled by whey model solutions. Sep Purif Technol
2014;132:226–33.
[3] Bird MR, Bartlett M. Measuring and modeling flux recovery during the chemi-
cal cleaning of MF membranes for the processing of the whey protein concen-
trate. J Food Eng 2002;53:143–52.
[4] Popovic´ SS, Miodrag NT, Mirjana SD. Kinetic models for alkali and detergent
cleaning of ceramic tubular membrane fouled with whey proteins. J Food Eng
2009;94:307–15.
[5] Bird MR, Fryer PJ. An analytical model for the cleaning of food process plant.
IChemE Symp Ser 1992;126:325–30.
[6] Bartlett M, Bird MR, Howell JA. An experimental study for the development of
a qualitative membrane cleaning model. J Membr Sci 1995;105:147.
[7] Cabero ML, Riera FA, lvarez RAÂ. Rinsing of ultrafiltration ceramic mem-
branes fouled with whey proteins: effects on cleaning procedures. J Membr
Sci 1999;154:239–50.
[8] Gan Q, Howell JA, Field RW, England R, Bird MR, McKechinie MT. Synergetic
cleaning procedure for a ceramic membrane fouled by beer microfiltration. J
Membr Sci 1999;155:277–89.
[9] Madaeni SS, Mansourpanah Y. Chemical cleaning of reverse osmosis mem-
branes fouled by whey. Desalination 2004;161:13–24.
[10] Li X, Li J, Fu X, Wickramasinghe R, Chen J. Chemical cleaning of PS ultra-
filters fouled by the fermentation broth of glutamic acid. Sep Purif Technol
2005;42:181.
[11] Zondervan E, Betlem BHL, Roffel B. Development of a dynamic model for
cleaning ultrafiltration membranes fouled by surface water. J Membr Sci
2007;289:26–31.
[12] Zondervan E, Betlem BHL, Blankert B, Roffel B. Modeling and optimization of a
sequence of chemical cleaning cycles in dead-end ultrafiltration. J Membr Sci
2008;308:207–17.
[13] Koyuncu I, Luttge A, Wiesner RM. Interferometric observations and kinetic
modeling of the chemical cleaning of humic materials deposited on mem-
branes. J Membr Sci 2008;313:127–34.
[14] Hom LW. Chlorine disinfection of ponded ecosystems. Chim Ind Gen Chim
1972;105(15):33.
[15] Haas CN, Joffe J. Disinfection under dynamic conditions-modification of Hom
model for decay. Environ Sci Technol 1994;28(7):1367.
[16] Wang Z, Zhao S, Liu F, Yang L, Song Y, Wang X, Xi X. Influence of operat-
ing conditions on cleaning efficiency in Membrane bioreactor (MBR) activated
sludge process-water rinsing introduced membrane filtration process. Desali-
nation 2010;259:235–42.
[17] Wang Z, Cui Y. The convective model of flux prediction in a hollow–
fiber module for a steady-state cross-flow microfiltration system. Desalination
2009;238:192–209.
[18] Blanpain P, Migdal JF, Benezech T. The effect of multiple fouling and clean-
ing cycles on a tubular ceramic microfiltration membrane fouled with a whey
protein concentrate: membrane performance and cleaning efficiency. Trans
IChemE Part C: Food Bioprod Process 2004;82:231–43.
[19] Zhang Y, Tian J, Liang H, Nan J, Chen Z, Li G. Chemical cleaning of
fouled PVC membrane during ultrafiltration of algal-rich water. J Environ Sci
2011;23:529–36.
[20] Madaeni SS, Rostami E, Rahimpour A. Surfactant cleaning of ultrafiltration
membranes fouled by whey. Int J Dairy Technol 2010;63:273–83.
[21] Puspitasaria V, Granville A, Clech PL, Chen V. Cleaning and ageing effect of
sodium hypochlorite on polyvinylidene fluoride (PVDF) membrane. Sep Purif
Technol 2010(72):301–8.
[22] Madaeni SS, Samieirad S. Chemical cleaning of reverse osmosis membrane
fouled by wastewater. Desalination 2010;257:80–6.
[23] Basha S, Jha B. Estimation of isotherm parameters for biosorption of Cd(II)
and Pb(II) 420 onto brown seaweed, Lobophora ariegata. J Chem Eng
2008;53:449–55.
[24] Shi Xf, Tal G, Hankins NP, Gitis V. Fouling and cleaning of ultrafiltration mem-
branes: a review. J Water Pro Eng 2014;1:121–38.
[25] Ang WS, Lee S, Elimelech M. Chemical and physical aspects of clean-
ing of organic fouled reverse osmosis membranes. J Membr Sci
2006;272(1–2):198–210.
[26] Wilson YMJ, Bird DI. Fluid dynamic gauging of microfiltration membranes
fouled with sugar beet molasses. J Food Eng 2012;108:22–9.
[27] Liikanen R, Kuivila JY, Laukkanen R. Efficiency of various chemical cleanings
for nanofiltration membrane fouled by conventionally-treated surface water. J
Membr Sci 2002;195:265–76.
[28] Souza NM, Mawson AJ. Membrane cleaning in the dairy industry: a review.
Crit Rev Food Sci Nutrit 2005;45:125–34.
[29] Mohammadi T, Madaeni SS, Moghadam MK. Investigation of membrane foul-
ing. Desalination 2002;153(1–3):155–60.
[30] Kazemimoghadam M, Mohammadi T. Chemical cleaning of ultrafiltration
membranes in the milk industry. Desalination 2007;204:213–18.