See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/285535915

Modeling and simulation of an ultrafiltration process for the removal of

suspended solids and colloids from wastewater

Article  in  Environmental Engineering and Management Journal · March 2010

DOI: 10.30638/eemj.2010.050

CITATIONS READS

4 1,423

2 authors:

George Barjoveanu Carmen Teodosiu

Gheorghe Asachi Technical University of Iasi Gheorghe Asachi Technical University of Iasi
39 PUBLICATIONS   593 CITATIONS    195 PUBLICATIONS   2,767 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Special Issue "Integrated Approaches of the Water Use Cycle: Technical and Environmental Challenges for Sustainability" - Call for Papers, WATER MDPI View project

Sustainability Special Issue "The Sustainability Management of Waste Electrical and Electronic Equipment " View project

All content following this page was uploaded by Carmen Teodosiu on 07 February 2018.

The user has requested enhancement of the downloaded file.

Environmental Engineering and Management Journal March 2010, Vol. 9, No.3, 361-371
http://omicron.ch.tuiasi.ro/EEMJ/

“Gheorghe Asachi” Technical University of Iasi, Romania

______________________________________________________________________________________________

MODELING AND SIMULATION OF AN ULTRAFILTRATION PROCESS

FOR THE REMOVAL OF SUSPENDED SOLIDS AND COLLOIDS
FROM WASTEWATER

George Barjoveanu ∗, Carmen Teodosiu

“Gheorghe Asachi” Technical University of Iasi, Faculty of Chemical Engineering and Environmental Protection, Department of
Environmental Engineering and Management, 73 Prof. Dr.docent Dimitrie Mangeron Str., 700050 Iasi, Romania

Abstract

Mathematical modeling of the ultrafiltration (UF) process is motivated by the complexity of retention phenomena that occur
during the UF in conjunction with the complexity of wastewater matrices submitted to ultrafiltration, as well as by the need to
predict the process behavior in extreme conditions, such as high pollution loads for UF-membrane cleaning cycles optimization or
for automated control of the process. Thus, series of laboratory-scale ultrafiltration experiments were performed with synthetic
wastewaters containing suspended solids and colloids onto two tubular polymeric membranes: one made of polysulfone (MWCO
20 kDa), the other made of modified polyethersulfone (MWCO 6 kDa). The experimental results have shown good removal
efficiencies for suspended solids and colloids for both the membranes (over 95% for the polysulfone membrane and 100% for the
other), as well as completely different hydrodynamic behaviors. The polysulfone membrane had produced high initial permeate
fluxes but was readily fouled by the suspended solids and colloids, while the polyethersulfone membrane had significantly lower
fluxes, but has shown a very good resistance to fouling. The mathematical model used for the verification of the experimental
results was based on the resistance-in-series model and considered, beside the intrinsic membrane resistance, the filtration
resistance due to superficial accumulation of the suspended solids and colloids. The model uses an exponential term for cake
filtration resistance growth and the experimental data verification was possible by calculating a statistical coefficient through non-
linear regression. The mathematical modeling was performed in two ways: for every experiment, as well as by using multiple data
sets. The results show that in both cases this model describes very well the UF process for the removal of suspended solids and
colloids from wastewaters, although the two membranes present different characteristics and filtration behaviors. The correlation
coefficients R were over 0.87, while the determination coefficients R2 had values of over 0.77. The good modeling results have
enabled the use of the model for the simulation of permeate fluxes in extreme conditions which usually are not replicable at
laboratory scale. The simulations were performed for very long UF times as well as for very high UF pressures.

Key words: colloids, modeling, resistances-in-series, simulation, suspended solids, ultrafiltration

1. Introduction membrane processes have some clear advantages over

Recent progresses in the fields of material
science, especially polymeric and composite
materials, in nanotechnologies, separation science and
process engineering have enabled the use of
membrane processes as the most feasible and versatile
processes for wastewater recycling (Asano et al.,
2007; Koltuniewicz and Drioli, 2008; Witgens et al.,
2005). Although the classification of advanced
wastewater treatment processes has to be based on
extensive technical and economical assessments,
other treatment processes (Barjoveanu and Teodosiu,
2006; Cheryan, 1998; Teodosiu et al., 2007; Zhou and
Smith, 2002): versatility and adaptability, reliability,
and energetic and economic efficiency.
The design of an ultrafiltration system for
wastewater recycling with high technical and
economical performance has to be carried out based
on extensive and laboratory and pilot scale testing,
because ultrafiltration membrane behavior depends on
the operational parameters in conjunction with the
characteristics of the treated wastewaters (Barjoveanu

∗
Author to whom all correspondence should be addressed: email: gb@ch.tuiasi.ro
 Barjoveanu and Teodosiu/Environmental Engineering and Management Journal 9 (2010), 3, 361-371
and Teodosiu 2006; Barjoveanu, 2009). Furthermore,
predicting ultrafiltration membranes behavior in
treating wastewaters is usually difficult because of the
complexity of phenomena that occur during this
process, given the inherent process characteristics of
flux decline over time in ultrafiltration, as well as the
inconsistency and variation of wastewater matrix
characteristics in real-scale operations.
In principle, the maximization of ultrafiltration
process performances refers to the determination of
optimal process parameters (feed flow,
transmembrane pressure, pollutants load,
ultrafiltration-membrane cleaning cycle duration) so
as to obtain the highest volumes of high quality
effluents to meet the discharging or recycling
requirements at the lowest costs. This is limited by
the permeate flux decline which occurs in
ultrafiltration because of the membrane fouling,
which consequently conducts to the need for cleaning
membranes which decreases the systems productivity
and can lead to secondary pollution due to the use of
chemical reagents (Barjoveanu and Teodosiu, 2009).
Modeling of the ultrafiltration processes is
usually difficult because the phenomena that occur
during the separation and membrane cleaning cycles
and the complex interactions between the membrane
and the wastewater lead to problems in finding
mathematical equations that accurately describe this
process.
Mathematical modeling of wastewater
ultrafiltration is particularly justified by the
following:
• Most industrial wastewaters, even with
appropriate pre-treatment, contain a large
number of pollutants (organic and inorganic
compounds, suspended solids, colloids or
microorganisms) in diverse concentrations that
can lead to a very rapid pore blocking at the
membrane surface or to membrane degradation
(Nuortila-Jokinen et al., 2003; Pizzichini et al.,
2005; Teodosiu et al., 1999);
• Ultrafiltration is a feasible wastewater treatment
option from the technical and economical points
of view as long as the productivity of the UF
step justifies the investment and operational
costs and in this respect mathematical modeling
of the UF process is an essential tool to support
the optimal operation and control of the process.
There are two major approaches for modeling
mass transport phenomena in ultrafiltration (Judd and
Jefferson, 2003). The most common approach starts
from Darcy’s law for mass transport through porous
media according to which the permeate flux depends
on the driving force of the process as well as on a
phenomenological coefficient which describes
membrane permeability (Strathmann et al., 2006).
In this approach, flux decline is described by
adding to the intrinsic membrane resistance different
hydraulic resistance coefficients to quantify the
effects of filtration phenomena in order to generate a
relation between the permeat flux and pressure
(Toyomoto and Higuchi, 1992), which is extensively
362
described in literature as the resistances in series
model (Ahmad et al., 2006; Baker, 2004; Cheryan,
1998; Katsikaris et al., 2005; Fane, 1998; Jacob and
Jaffrin 2000; Jones et al., 1993; Strathmann et al.,
2006). The approach is based on a boundary layer
theory which considers phenomena like:
solubilization – diffusion, sorption, pore and film
flow, electrical charging, to contribute to flux decline
in ultrafiltration.
The most common expression of this thin film
theory in mass transport through membranes is the
concentration-polarization model, which also is
extensively presented in literature (Beicha et al.,
2009; Judd and Jefferson 2003; Jonsson et al., 2006;
Kwon et al., 2008; Lee and Clark, 1998).
In a previous paper (Barjoveanu et al., 2006), a
resistances in series – derived model was developed
and successfully used to test experimental data
obtained onto two polymeric membranes used for the
ultrafiltration of petrochemical wastewaters as was
described by Teodosiu et al. (2000).
The objective of this paper is to present the
results of testing of the same mathematical model of
the ultrafiltration process onto experimental data
coming from two other polymeric membranes tested
with synthetic wastewaters containing suspended
solids and colloids. The modeling and simulation are
also motivated by the need to predict the process
behavior in extreme conditions: for very long UF
times as well as for very high UF pressures.
2. Model development
The model used in this paper is based on the
resistance in series model described by Eq. 1, and
considers, beside the intrinsic membrane resistance
RM, the resistance given by the fouling layer (cake)
developed at the membrane surface – RC, as well as
the resistance generated by the surface pore blocking
- RB.
∆P (1)
J (t ) =
η ⋅ (R M + ∆ R M (t ) + RC (t ) + R B )
where: ∆P – transmembrane pressure, (Pa/m); ∆RM(t)
– increase of resistance due to irreversible fouling of
the membrane pores (m-1); RC(t) – resistance due to
the cake deposition on membrane surface (m-1); RB –
resistance due to pore blocking (m-1);
To verify the model against experimental data,
an expression proposed by Bhatacharyya et al. (1979)
for the cake development in time was used.
According to this, the cake resistance exponentially
grows to a maximum Rcmax, as expressed in Eq. 2.
For using this model, the maximum cake
resistance was calculated for the lowest permeate
fluxes, being impossible to determine it for zero flux,
as this would have raised high risks of irreversible
membrane fouling and possible membrane
destruction.
 Modeling and simulation of an ultrafiltration process for the removal of suspended solids and colloids from wastewater

(
Rc = Rc max 1 − e − k ⋅t ) (2) of suspended solids and colloids in real wastewaters.
The presence of suspended solids and colloids in the
wastewater was measured with a turbidity analyzer
where: Rcmax - maximum cake resistance, (m-1), k –
(Hanna Instruments, model 93703-11). The particle
statistically determined coefficient, t – ultrafiltration
size distribution of the bentonite used to produce
time, (s).
synthetic wastewater was determined on a Shimadzu
In these conditions, the resistance in series
Laser Diffraction Particle Size Analyzer, SALD –
model used for the modeling of experimental data is
7001 model and it is presented in Fig. 1.
described by Eq. 3:

∆P (3) Particle size distribution

J (t ) =
(
η ⋅ RM + Rc max (1 − e − k ⋅t ) ) 100

In Eq. 3, RM represents the intrinsic hydraulic

58,864
membrane resistance and it also includes the
resistance due to internal membrane fouling (∆RM(t) % 50

in Eq. 1). The intrinsic hydraulic membrane resistance

17,556
was determined from the clean water fluxes (CWF), 12,949
6,759 3,766
which were experimentally determined at the 0
0,102

beginning of each ultrafiltration test. >100 50 -100 10 - 50 5 - 10 1-5 <1

The mathematical modeling of the Dimension, micrometers
ultrafiltration experimental results consists in
comparing the experimentally determined permeate
fluxes against calculated fluxes with the help of the Fig. 1. Bentonite particle size distribution
model presented in Eq. 3. The quality of the
approximations of the two data sets was analyzed 3.2. Membranes characteristics
with the help of the following statistical indicators:
dispersion, correlation coefficient and the The experiments were carried out on a
determination coefficient. laboratory scale setup (Fig. 2) which enabled all the
operational modes needed for rigorous UF testing:
3. Experimental dead-end, cross-flow, forward flushing and
backwashing.
3.1. Wastewater characteristics The most important element within the UF
system is the membrane module which houses the UF
All the wastewaters used for these studies were membranes. The experiments were performed onto
prepared in the laboratory using a bentonite to two tubular modules housing two different polymeric
replicate the presence of suspended solids and membranes whose characteristics are presented in
colloids in the wastewaters. Bentonite was used as Table 1.
reference material because it is a chemically inert
compound and presents a similar behaviour as the Table 1. UF membranes and modules characteristics
suspended solids that are present in industrial
Parameter (Units) PS 20000 EM006
wastewaters prior to recycling. By using an inert
Membrane Material Polysulfone Modified
compound, only membrane fouling was insured, and
Polyethersulfone
other membrane – pollutant interactions were Molecular weight cut-off, 20000 6000
prevented and also the risk of irreversible membrane MWCO (Dalton)
fouling was minimized. Membrane surface area (m2) 0.04 0.024
Synthetic wastewaters were preferred over real CWF Clean water flux (L/m2⋅h) 100
at 100 kPa
ones because they allow a stricter control of the
Maximum transmembrane 10 30
pollutant loads, which in turn ensures reliable UF pressure (bar)
results, as well as the possibility to study the process pH range 2 – 12 1.5 – 12
parameters influence over the UF process Maximum temperature (°C) 70 80
performance in an independent manner. Furthermore, Module length (mm) 1277 300
this study is part of a much broader experimental External Diameter (mm) 52 63.5
Membrane inner diameter (mm) 11.5 12.5
program to study and compare different advanced
treatment processes for wastewater recycling which
3.3. Ultrafiltration tests
calls for coherent and unified experimental protocols
which include fixed pollutant loads.
The ultrafiltration experiments were performed
The ultrafiltration tests were performed at
on the system presented above, using the dead-end
different suspended solids concentrations ranging
mode of operation at pressures between 1.4 and 2.5
from 40 to approximately 200 mg/L, which
bar onto the two membranes.
corresponds to 10 – 115 FTU turbidity grades, a
concentration range very similar to the concentrations

363
 Barjoveanu and Teodosiu/Environmental Engineering and Management Journal 9 (2010), 3, 361-371

Fig. 2. Laboratory scale UF system

The experimental results have shown very
good removal efficiencies for the suspended solids
and colloids: over 95% for the polysulfone membrane
and 100% for the modified poly-ether-sulfone
membrane. Furthermore, the two membranes have
presented completely different hydrodynamic
behaviours. While the polysulfone membrane
(PS20000) has produced high initial permeate fluxes
and it was readily fouled by the suspended solids and
colloids (Figs. 3 – 10), the polyetersulfone membrane
(EM006) had produced significantly lower fluxes, but
it has presented a very good resistance to surface
fouling (Figs. 11 – 22) (Barjoveanu et al., 2008).
Between the tests, the polysulfone membrane
(PS2000) was cleaned by backwashing with permeate
at 2.5 bar for 5 minutes, while the poly-ether-sulfone
membrane (EM006) was cleaned by forward flushing
also with permeate, as backwashing would have
damaged the membrane.
modifies at each iteration the parameters vector of the
result function (eq.3) so as the sum of the squared
differences between the experimental and the
generated values to be minimal (Kelley, 1999). The
result of this process was analyzed by calculating
specific dispersion analysis parameters like the χ2
reduced test, the correlation coefficient (R), the
determination coefficient (R2) and the dispersion (σ).
4. Results and discussions
4.1. Modeling of the PS2000 membrane fluxes
Some modeling results of the experimental
data obtained onto the polysulfone ultrafiltration
membrane are presented in the Figs. (3-10).
R = 0,942; R2 = 0,889
3

2.5
3.4. Modeling procedure
F lu x , m 3 /m 2 s , 1 0 -5

1.5
Mathematical modeling consists in comparing
the experimentally determined fluxes with the 1

calculated fluxes using the model in Eq. 3. 0.5

Confronting the experimental data obtained during 0
the ultrafiltration tests with the model in Eq. 3 was 0 100 200 300 400 500 600 700
performed using a software program which enabled Time, s
the calculation of the k coefficient in Eq. 3 so as the
Experimental Calculated
differences between the experimental and calculated
values of the permeate flux to be minimal. Compared
to the previous approach (Barjoveanu et al., 2006), Fig.3. Experimental and calculated flux values for the
when the resistances in series model was tested using T20-4 UF test, p=2 bar, dead-end
a method based on the Gauss-Newton approximation
method, in this case, it was used a method based on To facilitate the presentation of the results,
the Leevenberg – Marquardt algorithm. Both methods only the permeate fluxes are presented; given the very
involve an iterative approximation process, but the high removal efficiency for suspended solids and
Levenberg – Marquardt manages to produce an colloids. Also, in the figures above, as well as in the
acceptable solution even when the initial values of the discussions below the UF tests are codified using the
result function parameters are very different from the letter T, which stands for turbidity, then its value and
experimental points. Like the Gauss-Newton at the end the number of the test.
algorithm, the Levenberg – Marquardt process

364
 Modeling and simulation of an ultrafiltration process for the removal of suspended solids and colloids from wastewater

From Figs. 3 – 10, it is evident that the 2

10 R = 0,903; R = 0,816
resistances in series model presented in Eq. 3
9
describes well the decline of permeate flux during 8
these ultrafiltration tests. For this data series the

F lu x , m 3 /m 2 s , 10-5
7
correlation coefficients R had values between 0.786 6

and 0.977, and the determination coefficients between 5

4
0.618 and 0.955. The complete results of the 3
dispersion analysis for the modeling of these 2
experimental results are presented in Table 2. 1
0
0 100 200 300 400 500 600 700 800 900 1000
2
R = 0,936; R = 0,877 Time, s
2.5
Experimental Calculated
2
F lu x , m 3 /m 2 s , 1 0 - 5

1.5 Fig.7. Experimental and calculated flux values for the T40-
1 test , p=2 bar, dead-end
1

0.5
R = 0,960; R2 = 0,923
0 8

0 100 200 300 400 500 600 700 7

Time, s 6

F lu x, m 3 /m 2 s , 1 0 -5
Experimental Calculated 5
4

Fig. 4. Experimental and calculated flux values for the T20- 3

5, test p=2 bar, dead-end 2

2 0
10 R = 0,938; R = 0,880 0 200 400 Time, s 600 800 1000
9
8
Experimental Calculated
F lu x, m 3 /m 2 s, 10-5

7
6
5
4 Fig.8. Experimental and calculated flux values for the T40-
3 2 test , p=2 bar, dead-end
2
1
0 2
10 R = 0,896; R = 0,804
0 100 200 300 400 500 600
Time, s 9
8
Experimental Calculated
F lu x , m 3 /m 2 s , 1 0 -5

7
6
Fig. 5.Experimental and calculated flux values for the T30- 5
4 test, p=2 bar, dead-end 4
3
2
R = 0,954; R = 0,912
2 1
10
9 0
8 0 100 200 300 400 500
Flux, m 3 /m 2 s, 10-5

7 Time, s
6
Experimental Calculated
5
4
3
2
Fig. 9. Experimental and calculated flux values for the T50-
1 3 test, p=2 bar, dead-end
0
0 100 200 300 400 500 600 700 800 900 1000
By analyzing the data presented in Figs. 3 - 10
Time, s
and in Table 2, one may observe that the accuracy of
Experimental Calculated the model decreases from the tests performed with
synthetic wastewaters of 20FTU (R between 0.843
Fig.6. Experimental and calculated flux values for the T30- and 0.977), to the tests performed at 50 FTU (R
5 test , p=2 bar, dead-end between 0.845 to 0.934).

365
 Barjoveanu and Teodosiu/Environmental Engineering and Management Journal 9 (2010), 3, 361-371

2
R = 0,934 R = 0,872
This supports the idea that at the beginning of
10
9
the ultrafiltration tests, along with the cake filtration
8
retention mechanism, other phenomena occur
7 (especially pore blocking) leading to the dramatic flux
-5
Flux, m /m s, 10

6 decline. Unfortunately, verifying this hypothesis by

2

5
confronting the data with pore-blocking filtration
3

4
3
models (Chang et al., 2002; Hermia 1982) has not
2 produced reliable results.
1 The calculated k coefficient presented values
0
0 100 200 300 400 500 600 700
situated between 0.0004 and 0.00201, with an average
Time, s of 0.001, along with a slight tendency of rising
Experimental Calculated together with the bentonite concentration in the
synthetic wastewater. Comparing these results with
Fig. 10. Experimental and calculated flux values for the the ones in the previous paper (Barjoveanu et al.,
T50-6 test, p=2 bar, dead-end 2006), in which k had an average value of 0.0005, we
may advance the hypothesis that this coefficient
Also, it is important to notice that the represents a measure of the influence on the flux
differences between the calculated fluxes and the ones decline of the characteristics and concentrations of the
of experimental data occur mostly in the first period pollutants that are present in the wastewaters.
of the ultrafiltration tests; in each case, the real flux
decline being faster than the one calculated with
model in Eq. 3.

Table 2. Modeling results and quality of the PS20000 experimental data

Test code Experimental k Reduced χ2 σ R R2 No. of exp. points

conditions
P=1.4 bar,
T20-2 T=20FTU 0.00040 8.69E-12 5.35E-09 0.786 0.618 617
P=2 bar,
T20-3 T=20FTU 0.00111 4.82E-13 5.35E-11 0.977 0.955 112
T20-4 P=2.2 bar, T=20FTU 0.00101 8.06E-13 1.02E-10 0.943 0.889 127
T20-5 0.00076 1.26E-12 1.54E-10 0.937 0.877 123
T20-6 0.00086 1.10E-11 3.25E-09 0.961 0.924 297
P = 2 bar,
T20-7 T = 20 FTU 0.00083 9.83E-13 1.03E-10 0.843 0.711 106
T20-8 0.00035 5.39E-12 1.25E-09 0.965 0.931 234
T20-9 0.00044 2.48E-12 7.14E-10 0.977 0.955 289
T30-1 0.00135 1.55E-11 1.36E-09 0.944 0.891 89
T30-2 0.00088 1.11E-11 1.51E-09 0.943 0.889 137
P = 2 bar,
T30-3 T= 30 FTU 0.00155 8.06E-11 5.97E-09 0.901 0.812 75
T30-4 0.00066 6.24E-11 5.68E-09 0.938 0.880 92
T30-5 0.00201 2.59E-11 4.66E-09 0.955 0.912 181
T40-1 0.00089 1.11E-10 2.00E-08 0.904 0.817 182
T40-2 P = 2 bar, 0.00105 1.47E-11 2.70E-09 0.961 0.923 184
T= 40 FTU
T40-3 0.00094 7.77E-11 1.40E-08 0.916 0.840 181
T40-4 0.00115 1.55E-10 1.74E-08 0.869 0.755 113
T50-1 0.00112 2.36E-10 1.94E-08 0.845 0.715 83
T50-2 0.00104 1.82E-10 2.43E-08 0.867 0.751 135
T50-3 P =2 bar, 0.00128 1.19E-10 1.01E-08 0.897 0.804 86
T = 50 FTU
T50-4 0.00097 2.04E-10 2.55E-08 0.860 0.739 126
T50-5 0.00135 2.38E-10 2.14E-08 0.845 0.714 91
T50-6 0.00071 5.41E-11 7.41E-09 0.934 0.873 138

Table 3. Modeling results of the PS20000 flux values based on multiple data sets

Test series k Error, 10-4 Reduced χ2, 10-11 σ, 10-8 R R2 No. of exp. points
T20 0.00087 0.232 84.5 1.09 0.935 0.874 1288
T30 0.00181 1.10 3.49 2.00 0.940 0.883 574
T40 0.00109 0.671 7.90 5.17 0.912 0.831 659
T50 0.00128 1.03 0.168 0.117 0.878 0.770 658

366
 Modeling and simulation of an ultrafiltration process for the removal of suspended solids and colloids from wastewater

For the tests performed with wastewaters 2

T10 - 2.3 k = 0.00256, R =0,736951, R = 0,542
coming from the petrochemical industry (Teodosiu, 6

1998; Teodosiu et al., 1999), the suspended solids and 5

colloids in the wastewaters generated a turbidity of 12

Flux, m 3 /m 2 s, 10-6
4
– 14 FTU with dimensions varying between 7-8 µm,
3
and the values of k ranged between 0.0002 and
0.0008, while in this situation the major fraction 2

(70%) of the bentonite particles dimensions (Fig. 1) 1

ranged between 10 and 60 µm and k had presented
0
higher values averaging around 0.001. 0 10 20 30 40 50 60 70
Time, min
This tendency had lead to performing
Experimental Calculated
another round of modeling, in this case the
comparison of the experimental results with the
Fig. 12. Experimental and calculated flux values for the
model in Eq. 3 was done considering simultaneously
T10-2.3 test , EM006, P = 2.3 bar
sets of data rather than individual tests. In this way, a
single k value was generated for every experimental
2
data set (at the same bentonite concentration), the 6
T20 - 2.0, k = 0,000826, R =0,648, R = 0,420

results being more relevant because a much larger 5

number of data points and tests were considered. The

Flu x, m 3 /m 2 s, 10-6
“global” values of k are presented in table 3, where a 4

very good correlation between the experimental and 3

calculated flux values can also be observed (R being 2

above 0.87).
1

4.2. Modeling of the EM006 membrane fluxes 0

0 10 20 30 40 50 60 70
Time, min

The same resistances in series model was Experimental Calculated

tested onto the experimental data obtained during the

tests with synthetic wastewaters on the EM006 poly- Fig. 13. Experimental and calculated flux values for the
ether-sulfone tubular ultrafiltration membrane, even T20-2.0 test, EM006, P = 2 bar
though the hydrodynamic behavior of this membrane
was completely different from the PS20000 2
T20 - 2.3, k = 0,00328, R =0,841, R = 0,708
7
polysulfone membrane.
In this case the permeate fluxes were lower by 6

an order, but the flux decline was not as drastic 5

Flux, m 3 /m 2 s, 10-6

during one ultrafiltration test. Some examples of 4

results of the comparisons of the modeled and 3

experimental permeate flux values are presented in 2
the figures below (Figs. 11 to 22).
1

0
2 0 5 10 15Time, min 20 25 30 35
5
T10 - 2.0 k=0.0024, R =0,951, R = 0,905
4.5 Experimental Calculated

Fig. 14. Experimental and calculated flux values for the

F l u x , m 3 / m 2 s , 1 0 -6

3.5
3 T20-2.6 test, EM006, P = 2.6 bar
2.5
2
2
T40 - 2.6, k = 0,00312, R =0,881, R = 0,777
1.5 7
1 6
0.5
Flux, m 3 /m 2 s, 10 -6

5
0
0 10 20 30 40 50 60 70 4
Time, min
3
Experimental Calculated
2

1
Fig. 11. Experimental and calculated flux values for the 0
T10-2.0 test, EM006, P = 2 bar 0 5 10 15 20 25 30 35
Time, min
Experimental Calculated
By studying Figs. 11 to 22 and the Table 4
given below, it is clear that the resistances in series
Fig. 15. Experimental and calculated flux values for the
model describes fairly well the experimental data. T40-2.6 test , EM006, P = 2.6 bar

367
 Barjoveanu and Teodosiu/Environmental Engineering and Management Journal 9 (2010), 3, 361-371

2 2
T40 - 2.0, k = 0,00193, R =0,624, R = 0,389 T75-2.2, k = 0,00426, R =0,742, R = 0,551
6 6

5 5

F lu x, m 3 /m 2 s, 1 0 -6
F lu x, m 3 /m 2 s , 10 -6

4
4
3
3
2
2
1
1
0
0 0 5 10 15 20 25 30 35
Time, min
0 5 10 15 20 25 30 35
Time, min
Experimental Calculated
Experimental Calculated

Fig. 19. Experimental and calculated flux values for the

Fig. 16. Experimental and calculated flux values for the T75-2.2, EM006 test, P = 2.2 bar
T40-2.0 test, EM006, P = 2 bar
2
5 T75-2.0, k = 0,00103, R =0,903, R = 0,816
2
T50 - 2.0, k = 0,00246, R =0,758, R = 0,575 4.5
5
4
4.5

F lu x, m 3 /m 2 s, 10 -6
3.5
4
3
F lu x , m 3 /m 2 s , 1 0 -6

3.5
2.5
3 2
2.5 1.5
2 1
1.5 0.5
1 0
0.5 0 5 10 15 20 25 30 35
Time, min
0
Experimental Calculated
0 5 10 15 20 25 30 35
Time, min
Experimental Calculated Fig. 20. Experimental and calculated flux values for the
T75-2.0 test, EM006, P = 2.0 bar
Fig. 17. Experimental and calculated flux values for the
T50-2.0 test, EM006, P = 2 bar 2
T115-2.2, k = 0,00263, R =0,924, R = 0,854
5
4.5
2 4
T50 - 2.2, k = 0,00214, R =0,857, R = 0,735
F lu x, m 3 /m 2 s, 10 -6

6 3.5
3
5 2.5
2
F lu x , m 3 /m 2 s , 1 0 -6

4 1.5
1
3 0.5
0
2
0 5 10 15 20 25 30 35
Time, min
1
Experimental Calculated

0
0 5 10 15 20 25 30 35 Fig. 21. Experimental and calculated flux values for the
Time, min

Experimental Calculated
T115-2.2 test, EM006, P = 2.2 bar

2
T115-2.4, k = 0,00226, R =0,905, R = 0,815
Fig. 18. Experimental and calculated flux values for the 6
T50-2.2 test, EM006, P = 2.2 bar
5
F lu x , m 3 /m 2 s , 1 0 -6

One may observe that the calculated values of 4

k present the same order as for the PS20000 3

membrane, but in this case the variation of k between 2
the UF tests is roughly large, being impossible to
correctly explain the tendency of this variation. 1

For the EM006 data, from the table above, 0

one may notice that the correlation (R) and 0 5 10 15
Time, min
20 25 30 35

determination (R2) coefficients present rather high Experimental Calculated

variations even for the same tests series, while the
dispersion (σ) and reduced χ2 present improved values Fig. 22. Experimental and calculated flux values for the
compared to the results obtained onto the PS20000 T115-2.4 test, EM006, P = 2.2 bar
data.

368
 Modeling and simulation of an ultrafiltration process for the removal of suspended solids and colloids from wastewater

Another aspect that has to be mentioned is that
the correlation and determination coefficients are
affected by the number of experimental points
considered for the approximation, and in the case of
the EM006 tests the number of experimental points
obtained during one ultrafiltration test was
significantly lower than for the PS20000 membrane.
For these reasons, just as for the PS20000 data
another modeling round was performed considering
simultaneously multiple data sets. The results
presented in Table 5. evidence that conducting the
modeling onto multiple data sets has lead to an
improvement of the correlation and determination
coefficients, their values being of over 0,89 for the
correlation coefficient and of over 0.807 for the
determination coefficient respectively. The values
calculated for k are consistent with the individual test
modeling, but still no correlation with the bentonite
concentration can be drawn.
4.3. Simulations for different operating conditions
Because the experimental data generated in
completely different conditions (onto two membranes
with different material and operational characteristics,
at different pressures and initial pollutant
concentrations) were described fairly well by the
resistances in series model, it was possible to use this
model and the values of k presented in Tables 3 and 5
to conduct simulations of flux decline for the two
membranes in extreme conditions that would not be
possible in the laboratory: for very high operational
pressures, and for very long UF tests durations,
In general, ultrafiltration tests on the
polysulfone membrane lasted for 9 to 20 minutes,
given the acute tendency of rapid fouling of this
membrane, while the tests performed on the EM006
membrane lasted for 30 or 60 minutes. Simulating
very long ultrafiltration times can be helpful for
optimizing real-scale applications. In Figs. 23 and 24
are presented two of these simulations performed for
the two membranes respectively.
Simulating pressure conditions different from
the ones realizable on the laboratory scale setup is
very important because it allows the study of the
membranes behavior during real-scale applications. In
Figs. 25 and 26 are presented simulations of flux
decline over time at different pressures.
It has to be mentioned that these simulations
can be performed only for the pressure range for
which the clean water fluxes variation is linear, so as
to exist a linear dependence between the permeate
flux and the intrinsic membranes resistance.

Table 4. Modeling results and quality of the EM006 experimental data

Test code k Error, Reduced χ2, σ R R2 No. of exp. points

T10-2.0 0.00240 7.68E-05 0.329E-21 9.55E-20 0.952 0.905 30
T10-2.3 0.00256 1.30E-04 1.26E-20 3.39E-19 0.736 0.542 28
T10-2.5 0.00204 7.92E-05 6.20E-21 1.80E-19 0.909 0.826 30
T20-2.0 0.00083 7.36E-05 3.77E-21 1.05E-19 0.649 0.421 29
T20-2.3 0.00328 6.34E-04 1.03E-20 1.34E-19 0.842 0.708 15
T20-2.6 0.00286 3.70E-04 4.39E-21 5.70E-20 0.918 0.843 15
T40-1.8 0.00178 2.47E-04 4.40E-21 6.16E-20 0.689 0.475 15
T40-2.3 0.00517 6.92E-04 1.02E-20 1.33E-19 0.924 0.853 15
T40-2.6 0.00312 5.03E-04 7.77E-21 1.01E-19 0.881 0.777 15
T40-2.0 0.00193 0.09012 9.79E-21 1.17E-19 0.624 0.390 15
T50-2.0 0.00246 6.23E-04 7.21E-21 9.37E-20 0.759 0.576 15
T50-2.4 0.00214 3.79E-04 3.19E-21 4.14E-20 0.857 0.735 15
T50-2.3 0.00094 9.95E-05 1.32E-21 1.46E-20 0.820 0.673 12
T75-2.2 0.00426 4.41E-04 4.84E-21 3.87E-20 0.743 0.552 9
T75-2.0 0.00103 1.88E-04 2.52E-22 1.77E-21 0.904 0.817 9
T115-2.2 0.00263 1.78E-04 2.76E-21 3.87E-20 0.925 0.855 15
T115-2.4 0.00226 1.12E-04 1.33E-21 1.87E-20 0.905 0.819 15
T115-2.5 0.00242 5.21E-04 7.05E-21 9.17E-20 0.809 0.654 15

Table 5. Modeling results considering multiple data sets from the EM006 membrane

Test series k Error, 10-4 Reduced χ2, 10-21 σ R R2 No. of exp.

points
T10 0.00189 1.02 5.52 4.41 0.990 0.981 84
T20 0.0016 2.21 9.69 5.43 0.987 0.973 60
T40 0.0043 2.36 0.21 0.125 0.977 0.955 60
T50 0.00195 2.41 3.88 1.59 0.982 0.963 45
T75 0.00304 4.37 8.37 1.76 0.898 0.807 23
T115 0.00246 1.64 3.70 1.55 0.982 0.964 45

369
 Barjoveanu and Teodosiu/Environmental Engineering and Management Journal 9 (2010), 3, 361-371

5. Conclusions
T20-6, PS20000
8
The mathematical modeling of the
7
ultrafiltration process is a very useful instrument that
6
allows the identification and verification of the
Flux, m 3/m 2 s, 10-5

5
complex phenomena that cause permeate flux decline
4

3
during ultrafiltration. Finding and using a reliable
2
mathematical model to accurately describe the
1
complex phenomena that occur at membranes level
0
during ultrafiltration offer the possibility of
0 0.5 1 1.5 2 2.5 conducting simulations of the process that can be
Time, hours
subsequently used to test the process in extreme
Experimental Simulated conditions and to determine optimal process
parameters without the risk of permanently damaging
Fig. 23. 2.3 hour s UF test on the PS20000 membrane at p = the membranes.
2 bar For this study, the experimental data were
obtained by testing 2 polymeric tubular ultrafiltration
T20-2.0, EM006 membranes with very different material and
5 hydrodynamic characteristics. A semi-empirical
4.5 model of the flux decline during ultrafiltration was
4
tested for the evaluation of data obtained during
Flux, m 3 /m 2 s,10-9

3.5
3 ultrafiltration experiments with synthetic wastewaters
2.5
2 containing suspended solids and colloids. The model
1.5 is based on the well-known resistances in series
1
0.5 model and considers as main phenomenon
0 responsible for flux decline the cake formation at the
0 2 4 6 8 10 12 14
Time, hours
membrane surface, together with the cake filtration
Experimental Simulated
mechanism. The model describes the flux decline as a
cause of exponential growth of the cake resistance
subdued by the depositing of solid material at the
Fig. 24. 12 hours UF test on the EM006 membrane at p = 2
bar
membrane surface.
The verification of the experimental data was
performed using a non-linear algorithm by calculating
PS20000, T50
45.00
statistically a coefficient (k), which confers the
40.00
35.00
empiric characteristic of the model. Mathematical
modeling has lead to good results in terms of
F lux, m 3 /m 2 s, 10-5

30.00
25.00 approximation quality, given the completely different
20.00 experimental conditions: membranes characteristics
15.00
10.00
(fouling tendencies and intrinsic membrane
5.00 resistance), synthetic wastewater loadings, and
0.00 operational parameters (pressure).
0 100 200 300 400 500 600 700
The good modeling results have enabled the
Time, s
use of the model for the simulation of permeate fluxes
2 bar 4 bar 6 bar 10 bar in extreme conditions which usually are not replicable
at laboratory scale. The simulations were performed
Fig.25. UF tests simulations on the PS20000 membrane at p for very long UF times as well as for high UF
= 2, 4, 6 and 10 bar pressures.
This study is part of a complex research in
25.00 EM006, T50 which a comparison between several processes for
20.00
advanced wastewater treatment (such as membrane
processes, wet hydrogen peroxide oxidations,
Flux, m 3 /m 2 s, 10-6

15.00
adsorption on surfactant modified zeolites) is
10.00 performed based on a unitary experimental approach
5.00
and similar wastewater matrices.

0.00 Acknowledgement
0 5 10 15 20 25 30 35
Time, s
This paper was elaborated with the support of IDEI
project (code 368, contract no. 739/2009): Combined
2 bar 4 bar 6 bar 10 bar
advanced wastewater treatment processes for persistent
organic pollutant removal and enhancement of wastewater
Fig. 26. UF tests simulations on the EM006 membrane at p biodegradability, financed by the National Council of
= 2, 4, 6 and 10 bar Scientific Research (CNCSIS), Romania.

370
 Modeling and simulation of an ultrafiltration process for the removal of suspended solids and colloids from wastewater
References
Asano T., Burton F. L. Leverenz H. Tsuchihashi R.,
Tchobanoglous G., (2007), Water Reuse: Issues,
Technologies, and Applications, McGraw-Hill, New
York.
Ahmad A.L., Chong M.F., Bhatia S., (2006), Ultrafiltration
modeling of multiple solutes system for continuous
cross-flow process, Chemical Engineering Science, 61,
5057-5069.
Baker R.W., (2004), Membrane Technology and
Applications, 2nd Edition, Wiley and Sons, Chichester,
England.
Barjoveanu G., (2009), Studies on advanced wastewater
treatment by ultrafiltration for recycling in industry (in
Romanian), PhD Thesis, Gheorghe Asachi Technical
University of Iaşi, Romania.
Barjoveanu G., Teodosiu C., (2009), Priority organic
pollutants removal by ultrafitration for wasteswater
recycling, Environmental Engineering and
Management Journal, 8, 277-287.
Barjoveanu G., Teodosiu C., Volf. I, (2008), Study of
Membrane Performances for Wastewater Treatment by
Ultrafiltration, Conference Excellence Research – A
way to innovation, Section Environment and Health,
Technical Press, Bucharest, Romania.
Barjoveanu G., Teodosiu C., (2006), Advanced treatment
for pulp and paper wastewater recycling by membrane
processes, Environmental Engineering and
Management Journal, 5, 145-167.
Bhatacharyya D., Jumawan A.B., Gri Harris L.R., (1979),
Ultrafiltration characteristics of oil-detergent-water
systems: membrane fouling mechanisms, Separation
Science and Technology, 14, 529 – 249.
Beicha A., Zaamouche R., Sulaiman N.M., (2009),
Dynamic ultrafiltration model based on concentration
polarization–cake layer interplay, Desalination, 242,
138–148.
Chang I.S., Le Clech P., Jefferson B., Judd S., (2002),
Membrane fouling in membrane bioreactors for
wastewater treatment, Journal of Environmental
Engineering ASCE, 128, 1018–1029.
Cheryan, M., (1998), Ultrafiltration and Microfiltration
Handbook, Technomic, Lancaster, PA, USA.
Fane A.G., (1998), Ultrafiltration: Factors influencing Flux
and Rejection, in Progress in filtration and separation,
Elsevier, The Netherlands.
Hermia J., (1982), Constant pressure blocking filtration
laws: application to power-law non-Newtonian fluids,
Transactions of Institutions Chemical Engineering,
60,183-187.
Jacob S., Jaffrin M.Y., (2000), Purification of brown cane
sugar solutions by ultrafiltration with ceramic
membranes: Investigation of membrane fouling,
Separation Science and Technology, 35, 989 – 1010.
Jones K.L., Odderstol E.S., Wetterau G.E., Clark M.M.,
(1993), Using a hydraulic model to predict hollow-
fiber UF performance, Journal AWWA, Research and
Technology, 85, 87-97.
Jönsson A.-S., Jönsson B., Byhlin H., (2006), A
concentration polarization model for the ultrafiltration
View publication stats
of nonionic surfactants, Journal of Colloid and
Interface Science, 304, 191-199.
Judd S., Jefferson B., (2003), Membranes for Industrial
Wastewater Recovery and Re-use, Elsevier,
Kidlington, Oxford.
Katsikaris K., Boukouvalas C., Magoulas K., (2005),
Simulation of ultrafiltration process and application to
pilot tests, Desalination, 171, 1-11.
Kelley C. T., (1999), Iterative methods for optimization,
SIAM Frontiers in Applied Mathematics, 18, Society
for Industrial and Applied Mathematics, On line at:
http://www.siam.org/books/textbooks/fr18_book.pdf.
Koltuniewicz A., Drioli E., (2008), Membranes in Clean
Technologies. Theory and Practice, Wiley-VCH,
Weinheim.
Kwon B., Molek J., Zydney A.L., (2008), Ultrafiltration of
PEGylated proteins: Fouling and concentration
polarization effects, Journal of Membrane Science,
319, 206-213.
Lee Y., Clark M.M., (1998), Modeling of flux decline
during cross-flow ultrafiltration of colloidal
suspension, Journal of Membrane Science, 149, 181-
202.
Nuortila-Jokinen J., Huuhilo T., Nystrom M., (2003),
Closing pulp and paper mill water circuits with
membrane filtration, Annals of the New York Academy
of Sciences, 984, 39-52.
Pizzichini M., Russo, C., Di Meo, C., (2005), Purification
of pulp and paper wastewater, with membrane
technology, for water reuse in a closed loop,
Desalination, 178, 351 – 359.
Strathmann H., Giorno L., Drioli E., (2006), An
Introduction to membrane science and technology,
Consiglio Nazionale Delle Richerche, Roma.
Teodosiu C., (1998), Optimization of an advanced
wastewater treatment process for the removal of non-
biodegradable organic matter and suspended solids
removal, Ph.D thesis (In Romanian), Gheorghe Asachi
Technical University of Iasi.
Teodosiu C., Kennedy M., Van Straten H., Schippers J.,
(1999), Evaluation of secondary refinery effluent
treatment using ultrafiltration membranes, Water
Research, 33, 2171 – 2180.
Teodosiu C., Pastravanu O., Macoveanu M., (2000), Neural
network models for ultrafiltration and backwashing,
Water Research, 34, 4371-4380.
Teodosiu C., Barjoveanu G., Lupu L., Volf I., (2007),
Evaluation of process technologies for advanced
treatment and recycling of industrial effluents,
Conference Excellence Research – A way to ERA,
Section Environment and Health, Tehnical Press,
Romania.
Toyomoto K., Higuchi A., (1992), Microfiltration and
ultrafiltration, In: Membrane Science and Technology,
Osada I.Y., Nakagawa T. (Eds.), Marcel Dekker Inc.,
New York, 8.
Wintgens, T., Melin, T., Schiller, A., Khan, S., Muston, M.,
Bixio D., Thoeye C. (2005), The role of membrane
processes in municipal wastewater reclamation and
reuse, Desalination, 178, 1-11.
Zhou H., Smith D.W., (2002), Advanced technologies in
water and wastewater treatment, Journal of
Environmental Science, 1, 247 – 264.
371