Article

pubs.acs.org/IECR

A Combined Coagulation/Flocculation and Membrane Filtration

Process for the Treatment of Paint Industry Wastewaters
Dimitris P. Zagklis, Petros G. Koutsoukos, and Christakis A. Paraskeva*
Institute of Chemical Engineering Sciences, Foundation for Research and Technology, Hellas (FORTH/ICE-HT), Stadiou Street,
Platani, Patras, GR 26504, Greece, and Department of Chemical Engineering, University of Patras, GR 26504, Rion, Patras, Greece

ABSTRACT: Coagulation/flocculation process is considered as a nonexpensive and effective method to reduce organic and
inorganic content of industrial wastewaters. In the present study series of polyelectrolytes were tested to optimize the existing
procedure with new chemical reagents that resulted in removal percentages up to 93%. Organic load expressed in terms of
chemical oxygen demand, particle size distribution, pH, and ζ potential of suspended particles were among the parameters that
were investigated for the best coagulation/flocculation of particles suspended in paint industrial wastewaters. The target was to
find the optimum concentration values of polyelectrolytes that neutralize the ζ potential and shrink the particle size distribution.
The remaining organic compounds were further treated with a combined ultrafiltration/reverse osmosis system that almost
eliminated the organic content, and the final permeate stream is suitable for reuse in the premises of the industry.

1. INTRODUCTION Table 1. Treatment Efficiency for Different Wastewaters

Industrial wastewaters can cause serious environmental damage with Coagulation/Flocculation
if disposed untreated to water banks, a fact that makes their coagulant/ dosage COD % cost
effective treatment imperative. This kind of waste contains a wastewater flocculant mg/L reduction €/m3 ref
large variety of compounds, with adverse effects to the tannery alum 418 53.3 0.14 7
environment and to human health, some well-known and alum−(C-496) 100−5 36.2 0.05
others still under investigation.1 If the wastewater produced by alum−(A-100) 160−5 48.3 0.06
a factory has great variation from sanitary wastewaters then it paint Fe 650 82.55 0.45 4
must be pretreated before it is disposed to the sewage system.2 Fe−PO 650−160 88.46 0.88
As large quantities of water are needed in most of the industrial Fe−SU 650−2.4 88.37 0.46
processes, the most viable solution for the occurring wastes is Fe−PR 650−5 84.42 1.70
their recycling,3 which can be achieved through several Fe−PO−SU 650−80−1.2 90.35 0.67
treatment processes. Paint industry produces wastewaters Fe−PO−PR 650−80−2.5 90.80 1.29
with significant organic content, unfit for direct disposal. The paint sodium 100 33 0.04 6
occurring waste consists mostly of washing waters from bentonite
polymerization and mixing tanks,4 containing the final products alum 100 52 0.04
diluted. A possible treatment method is coagulation/floccu- FeCl3 50 40 0.03
lation with the use of polyelectrolytes, which is widely used for FeSO4 100 53 0.04
the treatment of industrial wastewaters.4−6 Different applica- brine Volclay KWK 49 8
tions of coagulation/flocculation for the treatment of industrial Pangel C 150 56
wastewaters are summarized in Table 1, accompanied by their paint FeSO4 2000 30−80 5
treatment efficiency and cost. As it is shown, coagulation/ Al2(SO4)3 2500 70−95
flocculation combines moderate to high treatment efficiency PACl 4000 98
and relatively low treatment cost.
By administering the appropriate dosage of coagulants and
polyelectrolytes in the right conditions (pH) the contained
chemical oxygen demand (COD) and total solids (TS) can be been successfully implemented in the industry,3,9−13 enabling
reduced significantly. Aboulhassan et al.4 have achieved a COD the reuse of large quantities of water, minimizing the expenses
reduction of 91% with the use of FeCl3 combined with high of wastewater disposal, and it has also been used by the authors
molecular weight polyelectrolytes (flocculants). Other coagu- for the treatment of olive mill waste waters with significant
lants like FeSO4, Al2(SO)4, and poly(aluminum) chloride have results.14,15 Lau et al.11 in their review paper present a large
been used in combination with high molecular weight number of papers referring to the successful use of nano-
polymers, yielding a COD reduction of 96%.5 Eremektar et filtration membranes in the textile industry, where they
al.6 have also used FeCl3 and FeSO4 as well as sodium
bentonite and alum, leading to 52% of COD removal. After Received: August 4, 2012
coagulation/flocculation has removed most of the contained Revised: November 4, 2012
COD and TS, any remaining organic content can be removed Accepted: November 8, 2012
with the use of membrane filtration. Membrane filtration has Published: November 8, 2012

© 2012 American Chemical Society 15456 dx.doi.org/10.1021/ie302086j | Ind. Eng. Chem. Res. 2012, 51, 15456−15462
Industrial & Engineering Chemistry Research
represent one of the best solutions for the large quantities of
wastewaters produced.
The combination of coagulation and membrane filtration for
water based paint effluents has been examined by Into et al.,10
leading to 92% COD reduction. Moreover, membrane filtration
also leads to the removal of microorganisms from the
wastewater. As bacteria can thrive in water based paint effluents
and cause severe defects in the final product of paint industry,
they have to be removed if the water obtained from the
treatment is to be reused.9
In the present work the final effluents from the production
process of a paint industry were first characterized for their
organic (in terms of COD) and solid content (in terms of
particle distribution, ζ size potential, and TS concentration).
The first treatment step was the implementation of different
polyelectrolytes for the coagulation of the wastewater and the
definition of the optimum treatment conditions. The super-
natant phase, although with reduced COD, was not fit for
recycling or disposal to the environment. The second step of
the treatment was the use of membrane filtration, which
diminished the organic content of the waste.
2. MATERIALS AND METHODS
2.1. Analytical Techniques. Total COD was measured
with reagents by LaMotte according to standard methods 5220
D16 and TS according to method 2540 B.16 The ζ potential and
particle size were measured with Malvern Zetasizer Nano ZS.
2.2. Waste Composition. The treated waste is mainly the
washing waters of the polymerization tanks and contains the
products of the industry diluted, which are polyvinyl acetate
and poly(acrylic esters). For the conducted experiments, two
samples (sample 1 and sample 2) of wastewater were used from
the equalization tank of the industry. A third sample was also
used, taken after the existing physicochemical treatment
(sample 3). All three samples were analyzed, and their
characteristics are presented in Table 2. The first two samples
Table 2. Characteristics of Wastewater Samples
parameter 1st sample 2nd sample 3rd sample
COD (mg/L) 16 710 ± 280 19 887 ± 70 960 ± 212
TS (g/L) 11.55 ± 0.01 10.21 ± 0.61 5.64 ± 0.08
ζ potential (mV) −1.02 −30.7 −2.52
mean values
particle size (nm) 3797 (82%) 285 187 (100%) 83 (100%)
mean values (18%)
were treated with the coagulation/flocculation process, while
the third one was tested in a membrane system. In all cases pH,
particle size, and ζ potential values of the raw materials were
measured before the decision of the appropriate treatment with
polyelectrolytes and electrolytes. It is apparent that continuous
monitoring is required for the optimization of the process, as
there is variation in the characteristics of the wastewater,
depending on the daily products of the industry.
2.3. Polyelectrolytes. The first polyelectrolytes that were
used were poly(aluminum chloride) and anionic poly-
(acrylamide) that were supplied by the physicochemical
treatment routinely applied at the industrial plant. The new
polyelectrolytes that were used were poly(ethylenimine) (PEI)
average Mw 800 by light scattering, average Mn 600 by gel
permeation chromatography, CAS 25987−06−8, supplied by
Sigma Aldrich; poly(allylamine) Mw 15 000, 15 wt % in H2O,
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CAS 30551−89−4, supplied by Polysciences, Inc.; poly-
(diallyldimethylammonium chloride) (PDADMAC) average
Mw <100 000, 35 wt % in H2O, CAS 26062−79−3, supplied by
Sigma Aldrich.
2.4. Experimental Procedure. 2.4.1. Coagulation/Floc-
culation. The coagulation/flocculation experiments were
carried out in a jar test apparatus, with six beakers of 1 L in
volume (Figure 1). Initially a sample of waste was placed in
Figure 1. Coagulation/flocculation with the use of poly-
(diallyldimethylammonium chloride) (experiment nos. 30−35).
each beaker, and their pH was adjusted with solutions of NaOH
and HCl. The initial pH was near 5.5 and was increased to 12
for most of the coagulation experiments, except for the group of
experiments for the optimization of pH, where it was set from 2
to 12. The next step was the addition of coagulant and rapid
mixing for 3 min for the homogenization of the waste and the
neutralization of the suspended particles. Then the flocculant
was added, followed by slow mixing for 10 min, for the
agglomeration of the formed flocs. In the experiments that no
flocculant was used, the step of slow mixing was preserved. The
waste was finally left for its sedimentation and after two hours,
samples were collected from the supernatant phase for further
analysis.
2.4.2. Membrane Filtration. In the membrane filtration
experiments, the waste was initially treated with a pilot
ultrafiltration unit. Cross-flow filtration was implemented; the
module was ceramic (zirconia) with pore diameter 100 nm,
with 19 channels of 1020 mm length and 4 mm diameter and
an active area of 0.24 m2. The supplier was Hydro Air Research
SpA, Milan, Italy. The ultrafiltration filtrate was then fed to a
reverse osmosis pilot unit. Again the filtration mode was cross-
flow; the module was polymeric, composite noncellulosic, with
99% rejection of sodium chloride. The module type was Spiral
wound, 2.5 in in diameter, with a length of 40 in and an active
area of 2.5 m2. The supplier was, again, Hydro Air Research
SpA, Milan, Italy.
3. RESULTS AND DISCUSSION
3.1. Optimization of the Existing Process. In the
existing physicochemical treatment process, the coagulant used
is poly(aluminum chloride) (PAC), and anionic poly-
(acrylamide) is used as flocculant, at pH 12. The first step of
the present work was the optimization of the existing process,
in terms of coagulant/flocculant dosage and pH.
3.1.1. Polyelectrolyte Concentration. All the experiments
conducted are presented in Table 3. The first set of
experiments (nos. 1−6) was performed under constant pH
12 and flocculant dosage 22 mg/L (pH and flocculant
concentration as suggested by the industrial unit). Figure 2
shows the variation of ζ potential, COD, and TS with
polyelectrolyte (PAC) concentration. In Figure 2 it is apparent
that ζ potential is near zero at a coagulant dosage of 423 mg/L
(no. 3), and at the same area high reduction of COD and TS is
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Industrial & Engineering Chemistry Research Article

Table 3. Preparation Conditions of the Samples

coagulant no. sample flocculant dosage (mg/L) coagulant dosage (mg/L) pH
PAC 1 1 22 1 12
2 1 22 192 12
3 1 22 384 12
4 1 22 575 12
5 1 22 766 12
6 1 22 956 12
7 1 10 1 12
8 1 10 192 12
9 1 10 384 12
10 1 10 766 12
11 1 10 956 12
12 1 10 425 2
13 1 10 425 4
14 1 10 425 6
15 1 10 425 8
16 1 10 425 10
17 1 10 425 12
poly(ethylenimine) 18 2 200 12
19 2 400 12
20 2 500 12
21 2 600 12
22 2 800 12
23 2 1000 12
poly(Allylamine) 24 2 200 12
25 2 400 12
26 2 500 12
27 2 600 12
28 2 800 12
29 2 1000 12
poly(diallyldimethylammonium chloride) 30 2 200 12
31 2 400 12
32 2 500 12
33 2 600 12
34 2 800 12
35 2 1000 12

reduced at high concentration of tested polyelectrolyte and the

Figure 2. ζ potential, COD, and TS reduction of supernatant phase in
coagulation/flocculation experiments with different concentration of
PAC, 22 mg/L anionic poly(acrylamide), and pH = 12 (exp. nos.1−6).
exhibited. Moreover, as the coagulant dosage is increased, ζ
potential turns into positive values, restabilizing the suspended
particles and preventing sedimentation. COD and TS values
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reduction percentage is less than the reduction obtained at 1
mg/L of polyectrolytes. As a result, dosages of coagulant above
the optimum can deteriorate the efficiency of the process.
To examine the effect of flocculant dosage on the process, a
second set of experiments was carried out (nos. 7−11), which is
presented in Figure 3. The same concentrations of coagulant
were used, and the pH was 12 again; the only difference was the
concentration of the flocculant, which was 10 mg/L. The same
overall behavior was observed for ζ potential (coagulant dosage
of 427 mg/L), TS, and COD reduction, leading us to the
conclusion that the neutralization of the ζ potential is mainly
achieved by the coagulant (PAC), whereas the flocculant
(poly(acrylamide)) only increased the size of the flocs formed
after neutralization. The most important differences on the
effect of the concentration of the flocculant (comparison of
Figures 2 and 3) were observed only for concentration of
coagulant larger than 750 mg/L. It seems that use of high
dosages of coagulants and flocculants reversed the phenomen-
on of destabilization of the colloidal suspension (than enhance
the precipitation). It was therefore evident that increase of
concentrations of the coagulant and the flocculant past a certain
limit was detrimental to the treatment process aiming at
increasing flocculation and hence solids removal efficiency.
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Industrial & Engineering Chemistry Research
Figure 3. ζ potential, COD, and TS reduction of supernatant phase in
coagulation/flocculation experiments with different concentration of
PAC, 10 mg/L anionic poly(acrylamide), and pH = 12 (exp. nos. 7−
11).
Reversible stabilization of colloidal suspensions has been
reported in the literature in the case of membrane fouling.17
The interactions between the coagulant and the flocculant
are an important issue that needs further consideration. Since
the thickening of the flocs depends on the interactions of the
polymer with the particles, on which it is adsorbed, higher
coagulant concentrations are expected to affect the conforma-
tion of the polymer thus resulting in the restabilization of the
suspension.18
3.1.2. Effect of pH. As pH plays an important role in
coagulation,19 it is reasonable to examine the optimum pH
value for the coagulation of tested wastewaters. The initial pH
of the waste was near 5.5. The third set of experiments (nos.
12−17) was carried out for this purpose. The coagulant dosage
was constant and equal to the optimum concentration found in
the previous experiments, and the flocculant dosage was 10
mg/L. The results are presented in Figure 4. It is immediately
Figure 4. ζ potential, COD, and TS reduction of supernatant phase in
coagulation/flocculation experiments with 425 mg/L PAC, 10 mg/L
anionic poly(acrylamide) and different pH values (exp. nos. 12−17).
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apparent that only in pH 12 is coagulation possible. Also at pH
equal to 12 the COD and TS reduction percentages were
increased from ca. 45% to ca. 70%. From that point, all the
experiments were conducted in pH 12. It should be mentioned,
that depending on the final use of the treated wastewater
(recycling or disposal) the need of pH neutralization after the
treatment, should be examined. If the final effluent is used again
for rinsing of the polymerization tanks, the pH neutralization
might not be required, as the waste will be again treated with
the same process at high pH values.
3.2. New Proposed Polyelectrolytes. After the opti-
mization of the existing treatment process, three new
polyelectrolytes were examined. The purpose was the
replacement of PAC and anionic poly(acrylamide) with one
polyelectrolyte that plays the role of both coagulant and
flocculant at the same time. Also the possibility of higher COD
and TS reduction was examined. All the experiments with new
polyelectrolytes (nos. 18−35) were carried out with sample 2.
3.2.1. Poly(ethylenimine). The first polyelectrolyte that was
tested was poly(ethylenimine) (nos. 18−23), but at the
examined concentrations (200−1000 mg/L) the neutralization
of ζ potential was not possible. As a result no supernatant phase
was formed, and no COD or TS reduction took place. Despite
the fact the PEI is a cationic polyelectrolyte, it seems that at
such high pH values (pH 12) the degree of protonation of
some specific groups of PEI is very small. In our system, PEI is
diluted at high pH values as suggested by the protocol of the
experiments. The activity of PEI depends on the positive
charged aminogroups which interact with the negatively
charged suspended particles. However, these interactions are
highly dependent on the solution pH. The level of charge of the
PEI is expressed through the apparent dissociation constant
(pKapp) or the degree of dissociation (α). The effect of
polyelectrolyte on the precipitation of suspended particles
depends strongly on the degree of protonation (PEI).
Protonation/deprotonation is very important for the electric
charge and the structure of the PEI at the substrate/solution
interface. According to our earlier reports20,21 the optimal
condition for the protonation of PEI is at pH values lower than
5. Thus one cannot suggest arbitrarily any cationic polyelec-
trolyte to precipitate suspended particles before examining the
environment in which it can play the effective role of
coagulant/flocculant.
3.2.2. Poly(allylamine). The second polyelectrolyte that was
examined was poly(allylamine) (nos. 24−29). The results are
presented at Figure 5. The supernatant phase that was formed
was very thin and was more easily observed at experiments 28
and 29, where the ζ potential is closer to zero. Some
abnormality in measurements may have been caused because
of the difficulty in acquiring sample from the experiments with
the thin supernatant phase.
3.2.3. Poly(diallyldimethylammonium Chloride). The third
and last polyelectrolyte that was used was poly-
(diallyldimethylammonium chloride) (nos. 30−35); the results
are presented in Figure 6. The best results occurred in
experiment no. 32 with concentration of 500 mg/L of
polyelectrolyte, very near zero ζ potential. More over the
reduction of COD achieved reaches 93% and TS reduction
85%, whereas with the use of the existing process (poly-
(aluminum chloride) and anionic poly(acrylamide)) we could
only reach 81% COD reduction and 58% TS reduction.
Moreover, the coagulation and flocculation of the waste was
achieved with the use of a single compound. In Table 4 the
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Industrial & Engineering Chemistry Research
Figure 5. ζ potential, COD, and TS reduction of supernatant phase in
coagulation/flocculation experiments with different concentration of
poly(allylamine) (exp. nos. 24−29).
Figure 6. ζ potential, COD, and TS reduction of supernatant phase in
coagulation/flocculation experiments with different concentration of
poly(diallyldimethylammonium chloride) (exp. nos. 30−35).
removal efficiency (COD and TS) of the different polyelec-
trolytes used is presented.
3.3. Membrane Filtration. Although the proposed method
reduces significantly the organic content of the waste, the final
product is not suited for recycling or disposal to water banks as
the COD is still higher than the approved concentrations (960
mg/L). For its further treatment membrane filtration was
examined.
3.3.1. Ultrafiltration. Initially the waste (sample 3), which is
the final effluent of the existing physicochemical treatment
process of the industry with the use of poly(aluminum
Table 4. Comparison of the Treatment Efficiency for Different Polyelectrolytes
polyelectrolyte dosage mg/L flocculant dosage mg/L
PAC 384
poly(ethylenimine)
poly(allylamine) 1000
poly(diallyldimethylammonium chloride) 500
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chloride) and anionic poly(acrylamide), was treated with an
ultrafiltration unit, in different transmembrane pressures
(TMP). Concentration of total solids was about 5 mg/L, and
the mean particle size was close to 80 nm thanks to the efficient
coagulation/flocculation process that was preceded. UF was
implemented only to play an auxiliary role before the use of a
more effective membrane (NF or RO). Because the mean size
of suspended particles was 80 nm, and the mean pore of UF
membrane modulus was 100 nm, TS reduction was practically
zero (Figure 7), and only particles with size larger than 100 nm
Figure 7. COD and TS reduction achieved with Ultrafiltration
membrane.
were removed. However, UF led to the removal of 20% of the
organic matter. An unpleasant result was that the flux that was
acquired was low for an ultrafiltration process, which might
have been caused by clogging of membrane pores by the
suspended polymers. A high flux rate was recovered after a
thorough cleaning of the membranes with a NaOH solution for
half an hour (85% of the initial flux rate).
3.3.2. Reverse Osmosis. The permeate stream of Ultra-
filtration was fed to a reverse osmosis unit. The results were
very encouraging with COD and TS reduction being around
90−100% (Figure 8a). Initial COD values at 960 mg/L were
reduced to 16 mg/L after treatment with the RO process. TS
was reduced dramatically and their value in permeate stream do
not exceeded the value of 0.5 mg/L. On the other hand,
irreversible fouling phenomena were observed (Figure 8b), as
the flux of clear water was not the same before and after the
treatment of the waste, even after chemical cleaning of the
membrane module. Implementation of membranes shall take
place after a complete evaluation of all operational parameter
values and of the problems related to their performance (flux
decline, cleaning procedure, long-term behavior, etc).
pH COD % reduction TS % reduction
10 12 76.9 ± 1.0 56.8 ± 0.6
12 46.1 ± 0.2 4.5 ± 6.3
12 93.2 ± 0.1 84.3 ± 1.9
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Industrial & Engineering Chemistry Research
Figure 8. (a) COD and TS reduction and (b) flux achieved with
reverse osmosis membrane before and after cleaning procedure.
4. CONCLUSIONS
Through a parametric study, the optimization of the existing
physicochemical treatment process of a paint industry was
possible, in terms of coagulant concentration and pH. In the
first set of experiments, the coagulants and flocculants
implemented were the ones that are currently in use in the
wastewater treatment unit of the factory. It was found that
higher removal efficiency could be achieved if lower
concentration, compared to the one used by the industry, of
polyelectrolytes was used (400 mg/L instead of 1000 mg/L).
By working at higher concentrations of positive polyelectrolytes
the negative ζ potential value of suspended particles was
inverted to positive, stabilizing again the solution and the
particles remained under suspension. It was proved that the
coagulant, if used in excess, can have negative effects on the
separation. Moreover, a new polyelectrolyte that can cause the
coagulation and flocculation of the suspended solids was
proposed, which leads to higher COD and TS reduction than
the reductions possible with the existing process. An extra step
was taken for the treatment of the waste with the
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implementation of membrane technology. Ultrafiltration did
not alter significantly the waste but removed all the larger
suspended solids, preparing it for the step of reverse osmosis.
With the use of a reverse osmosis membrane, the organic
content of the waste was dramatically reduced to a value of
around 30 mg/L, and the final effluent was suitable for
recycling, irrigation, or disposal to water banks. Fouling
phenomena were apparent, but further experiments must take
place in order to find the experimental conditions that
minimize such problems.
■ AUTHOR INFORMATION
Corresponding Author
*Tel.: +30 2610 997252. Fax: +30 2610 997574. E-mail:
takisp@chemeng.upatras.gr; takisp@iceht.forth.gr.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
The present project was funded by the project SYNERGA-
SIA_MEKKA, code number 09SYN-42-620 supported by the
operational program “Competitiveness and Entrepreneurship,
EPAN II” (General Secretariat of Research and Technology,
Ministry of Development, Greece).
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