December 2010, Volume 1, No.

2
International Journal of Chemical and Environmental Engineering

Improvement of Coagulation-Flocculation Process

for Treatment of Detergent Wastewaters Using
Coagulant Aids
A. Ayguna, T. Yilmazb
a
Department of Environmental Engineering, Selcuk University, Konya, Turkey, ahmetaygun@selcuk.edu.tr
b
Kocaeli Provincial Department of Environment and Forestry, Kocaeli, Turkey, tuba.ertugrul@gmail.com

Abstract
In this study, coagulation-flocculation process was used to treat detergent wastewater with ferric chloride as coagulant. The
improvement of the process by using polyelectrolytes and clay minerals (montmorillonite and bentonite) as coagulant aids was also
investigated. The results of the wastewater characterization showed that the concentration of organic matter expressed as chemical
oxygen demand (COD) was as high as 24.3 g/L while the biochemical oxygen demand was low. Chemical treatment can be
considered as a suitable option for treatment of detergent wastewater due to the low ratio of BOD5/COD. Coagulation/flocculation and
precipitation studies were performed in a conventional jar-test apparatus. The coagulant dosage of ferric chloride ranged between 0.5
g/L and 3 g/L, whereas the concentrations of polyelectrolyte and clay minerals varied between 5-75 mg/L and 25-750 mg/L,
respectively. The optimal condition was obtained at the dosage 2 g/L ferric chloride at pH 11 with the COD removal efficiency of
71%. Addition of coagulant aids provided higher removal efficiencies. Using clay minerals at the dose of 500 mg/L with ferric
chloride provided 84% of COD removal and the removal efficiency of COD increased with using polyelectrolyte, resulting in an
efficiency of 87%. The maximum removal efficiency was obtained with the addition of polyelectrolyte and it was found that the ferric
chloride combination with coagulant aids, at certain pH and agitation speed, provided higher removal efficiencies compared to
coagulation with ferric chloride alone.

Key Words: coagulation-flocculation, detergent wastewater, ferric chloride, polyelectrolyte, clay minerals

1. Introduction
Detergent wastewater discharge can cause serious
environmental problems because detergent product and its
ingredients can be relatively toxic to aquatic life [1].
Anionic and nonionic surfactants are major components
of synthetic detergents. In order to protect the water
environment, an efficient treatment process must be
applied [2]. Due to its complexity, detergent wastewater
is very difficult to treat [3].
Methods for removal of surfactants involve
processes such as chemical and electrochemical
oxidation, membrane technology, chemical precipitation,
photocatalytic degradation, adsorption and various
biological methods. Each of them has limitation and some
drawback in application [4].
Treatment of surfactant wastewaters by biological
processes such as activated sludge is problematic due to
the low kinetics of degradation and foam production [5].
Hence, among the currently employed chemical unit
processes in wastewater treatment, coagulation-
flocculation has received considerable attention because
of high impurity removal efficiency.
Coagulation/flocculation is a commonly used
process in water and wastewater treatment in which
compounds such as ferric chloride and/or polymer are
added to wastewater in order to destabilize the colloidal
materials and cause the small particles to agglomerate
into larger settleable flocs [6]. FeCl3 is an important
coagulant in wastewater treatment and can be used for
color removal [7-8], organic matter removal in leachate
[9], solid removal from fisheries wastewaters [10],
treatment of municipal wastewater [11], surfactant
removal from microelectronic plant wastewater [4].
Abdulhassan et al, [4] found that coagulation-
flocculation process using FeCI3 can be used effectively
for removal of surfactants and COD from microelectronic
plant wastewater and the removal efficiencies of 99% and
88% were obtained, respectively. Also they found that the
rate of COD removal decreased if the pH was lower than
7 or higher than 9.
High operating costs due to the use of chemical
substances and high amount of sludge and its disposal
costs are shown as the important disadvantages of
chemical treatment [12]. Therefore, researchers have
focused on new alternative methods to reduce chemical
usage by improving discharge standard with adding low
cost natural substance.
Clay minerals are natural substances used in
wastewater treatment and have high ion exchange
 capacity, absorption, and catalysis properties as well as 2.1Experimental Procedure
natural and low-cost materials [13]. Some researchers
Coagulation-flocculation and precipitation studies were
reported that clay minerals can be preferable coagulant
performed in a six-place conventional jar-test apparatus,
aid for removal of toxic compounds, pesticide, herbicide,
equipped with 6 beakers of 500 mL volume. Before
heavy metals and color removal [14].
coagulation/flocculation process, wastewater sample was
It is clear that all treatment methods in use have
thoroughly shaken to avoid possibility of settling solids.
some drawbacks, and there is a need to look for other
The experimental process consisted of the initial rapid
alternative methods. In the literature, there is some
mixing stage that took place for 5 min at 150 rpm, the
evidence that clay minerals, when used in conjunction
following slow mixing stage for 30 min at 30 rpm and the
with coagulants result in improved COD removals, as
final settling step for 1 h. After 1 hour settling period,
compared to used alone [15]. However, there are no
samples were withdrawn from supernatant for analyses.
detailed studies in the literature about the comprehensive
Process performance was monitored by using COD
investigation of using clay minerals in coagulation
values.
process for treatment of detergent wastewater.
The aim of this study is treatment of detergent Table 2.Chemical analyses of the clay minerals used in this study
wastewater by coagulation-flocculation process using
Properties Unit By Mass
ferric chloride as coagulant. And also, improvement of
SiO2 (%) 52.69
process performance is investigated by using Al2O3 (%) 12.19
polyelectrolytes and clay minerals as coagulant aids in Fe2O3 (%) 8.63
flocculation step. CaO (%) 6.15
MgO (%) 4.15
TiO2 (%) 1.92
2.Materials and Methods K2O (%) 0.11
Na2O (%) 0.46
Wastewater sample was collected from outfall of a Loss on Ignition (%) 13.86
recycling plant located in Dilovası Organized Industrial
Specific Surface Area (m2/g) 538.72
Zone, Kocaeli city, Turkiye. In the recycling plant, IBC
tanks, used for storage and transport, are brought for >45 µm (%) 12.56
cleaning of detergent residues before they are used again. >10 µm (%) 28.82
Cleaning is carried out by using high pressurized water >2 µm (%) 48.67
and after cleaning, wastewater containing detergent has to
be treated before it is discharged to sewage system. The
.Experimental studies carried out in three steps. In
average flow rate of wastewater is about 25 m3/day.
the first step, optimum pH for the treatment was
Wastewater sample collected from the plant was placed in
determined. The study was carried out between the pH
plastic containers to be transported to the laboratory and
stored at 4 0C in a refrigerator. The composition of the values of 4-12. Desired pH values of wastewater were
detergent wastewater is presented in Table 1. adjusted by using 6N and 0.1 N H2SO4 and NaOH. In the
second step coagulation-flocculation was performed
Table 1.the composition of detergent wastewater between ferric chloride concentration of 0.5-3 g/L and
Parameter Value optimum concentration was investigated. In the last step
pH 12.31 polyelectrolyte and clay minerals were added as coagulant
Chemical oxygen demand (COD) (g/L) 24.3 aids for improving process performance and the most
Biochemical oxygen demand (BOD5) (g/L) 3.2
BOD5/COD 0.05 efficient coagulant aid was determined. The
concentrations used in this step were between 5-75 mg/L
for polyelectrolyte and 25-750 mg/L for clay minerals.
In this study, two kinds of coagulant aids were used.
One of them was polyelectrolyte (anionic 1858 S) 3.Results and discussion
whereas the other was clay minerals. The clay minerals
Coagulation-flocculation process was conducted for
used in this study were collected from an area in
the treatment of the detergent influent. Numerous jar tests
Ermenek, Konya City (Turkey). Chemical analyses of the
were carried out in order to establish a practical
clay minerals are illustrated in Table 2.
understanding of the coagulation performance and to find
pH, COD, BOD5 were analysed in the laboratory optimum pH, coagulant dosage and coagulant aid dosage.
according to the methods given in the Standard Methods.
pH measurements were done by using the WTW 3.1Effect of pH on Coagulation
Multiparameter 340i. Closed reflux colorimetric method
In the coagulation–flocculation process, pH is very
(Method 5220 C) was used for COD analysis and BOD5
important since the coagulation occurs within a specific
was analysed (Method 5210) as dictated by Standard
pH range for each coagulant. In this study, a wide range
Methods [16].
of pH between 4-12 was selected.

98
 The results of the study showing the effect of pH
on COD removal efficiencies and effluent COD
concentrations when FeCl3 was used as a coagulant are
presented in Figure 1. To determine optimum pH value,
FeCl3 dosage was constant at 1.5 g/L. When pH increased
from 4 to 11, COD removal efficiency increased from
34% to 57% and COD concentration of effluent was
10560 mg/L. At higher pH value, COD removal
efficiency decreased. It is clear that optimum pH was 11
for the coagulation-flocculation process at 1.5 g/L FeCl3
dosage.
pH is an important parameter for coagulation process
since it controls hydrolysis species. When a coagulant
such as aluminum or ferric salt is added to water, a series
of soluble hydrolysis species are formed. These
hydrolysis species have positive or negative charges
depending on the water pH. They are positively charged
at low pH (< 6) and negatively charged at high pH. The
positively charged hydrolysis species can absorb onto the
surface of colloidal particles and destabilize the stable
colloidal particles. This mechanism is called ‘charge
neutralization’. A precipitate of aluminum or ferric
hydroxide is formed at sufficiently high coagulant dosage.
These precipitates can physically sweep the colloidal
particles from the suspension. This mechanism is called
‘sweep-floc coagulation’ [17]. In this study, after FeCl3
addition as a coagulant, mechanism of coagulation
showed properties of sweep-floc coagulation due to the
high pH in operation.
Figure 1. COD removal efficiency and effluent COD concentrations
at different pH values
3.2 Determination of the optimal coagulant dosage
Effect of FeCl3 dosages on the COD removal
efficiency is shown in Figure 2. Coagulation-flocculation
was performed between ferric chloride concentrations of
0.5-3 g/L. At a concentration of 2 g/L, removal efficiency
was 71% that was accepted as the optimum dosage. COD
removal efficiency decreased by increasing FeCl3
concentration. At high coagulant doses, metal hydroxides
are produced and organic substances are removed by
incorporation into or sorption onto hydroxide flocs [18].
According to the study of Papadopoulos et al. [3]
use of 1.5 g/L lime in coagulation-flocculation process
provided COD removal efficiency of 29%, combination
with 1.5 g/L alum improved COD removal up to 18%,
99
leading to total COD removal of 47%. Mahvi et al. [2]
reported that when lime, alum and ferric chloride were
used as a coagulant, COD removal resulted in 21%, 37%
and 89%, respectively. This results shows that ferric
chloride can be noteworthy option and provide higher
removal efficiencies than lime, alum and their
combinations.
Figure 2. Effect of FeCl3 dosages on the effluent COD and COD
removal efficiency
3.3 Effect of Polyelectrolyte
Polyelectrolytes are commercial coagulant aids.
Synthetic polyelectrolytes are currently the most widely
used chemicals in the treatment of industrial wastewaters.
Generally, a little amount of polyelectrolyte dosage is
enough to reach high efficiency. Because of they have
some advantages including the possibility of structuration
in response to specific requirements, greater purity, higher
quality, stability and greater efficiency [19]. With
polyelectrolytes as coagulant aids, the metal coagulant
dosage can be reduced without cutting down the
performance [20]. Yu et al, [21] reported that the charge
density and molecular weight of polyelectrolyte play
important role in the coagulation.
Effluent COD and COD removal efficiencies versus
different polyelectrolyte dosages are given in Figure 3. At
the lowest concentration of polyelectrolyte, COD removal
efficiency was 74% and effluent COD concentration was
6.4 g/L . With increase in polyelectrolyte concentration,
removal efficiency increased up to 87%. At a higher
concentration than 50 mg/L, effluent COD decreased thus
50 mg/L polyelectrolyte dosage was accepted as optimum
dosage. Optimum concentration of polyelectrolyte forms
a bridge between particles and cause good flocculation.
However high concentration of polyelectrolyte forms an
envelope on the suspending particles and causes them to
remain in suspension thus removal efficiency decreases
[18]. Similar result was obtained from this study and
when the polyelectrolyte concentration was increased,
process performance was decreased.
Figure 3. Effect of polyelectrolyte dosages on the effluent COD and
COD removal efficiency
3.4 Effect of clay minerals on coagulation
Clay minerals may be used as coagulant aids in
flocculation step of binding already formed small flocs
into larger particles when aluminum or iron salts have
been used as the primary coagulant. Coagulation with
clay minerals followed by sedimentation can clean up
industrial effluent when the flocs formed are dense
enough [22].
Effect of clay minerals dosages on the effluent COD
and COD removal efficiency is illustrated in Figure 4.
When clay minerals used as a coagulant aids in the range
of 25-500 mg/L, effluent COD value decreased from 24.3
g/L to 6.08 at minimum clay concentration and to 3.84
g/L at maxium clay concentration Maximum removal
efficiency was 84% and obtained at the concentration of
500 mg/L which was accepted as the optimum dosage.
Although COD removal was slightly higher at 750 mg/L,
the difference was only 1% that can be accepted
insignificant. In addition to this, Dilek and Bese [15]
reported that the clay addition during alum coagulation
had a positive effect on the dewaterability of the sludge in
treating pulp-and-paper industry wastewaters. This
improvement was more pronounced in combinations with
higher clay dosages.
In this study, removal efficiencies of clay minerals
and polyelectrolyte were similar to each other. Clay
minerals are natural and local sources, so when clay
minerals and polyelectrolyte used as coagulant aids, if the
removal efficiency of each coagulant aid is close to each
other, the operation cost of treatment with clay minerals
may be lesser than polyelectrolyte. In the study of
Demirci et al. [18], the results were shown clearly and the
cost of the annual waste water treatment of 2.16x106 m3
using the common coagulant alum together with clay or
polyelectrolyte was calculated. The results indicated that
the cost in the treatment with clay was about 50 000
dollars whereas it was about 1 600 000 dollars in the
treatment with polyelectrolyte.
100
Figure 4. Effect of clay minerals dosages on the effluent COD and
COD removal efficiency
4. Conclusion
In treatment of detergent wastewater that contains
relatively high COD and low BOD, coagulation process
can be used as a pretreatment process. In this study, FeCl3
had the lowest COD removal efficiency when it was used
alone and it was determined that addition of
polyelectrolyte and clay minerals to FeCl3 as coagulant
aids, improved the COD removal efficiency. The highest
removal efficiency was obtained from the combination of
FeCl3 with clay minerals. Comparing all the results and
possibilities, using clay minerals as coagulant aid
accompanied with FeCl3 can be advisable and more
economical option for the treatment of detergent
wastewater since it has similar removal efficiency
compared with polyelectrolyte and more economic.
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