Environmental Technology & Innovation 10 (2018) 71–77

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Environmental Technology & Innovation

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

Municipal waste water treatment by natural coagulant

assisted electrochemical technique—Parametric effects
Rajamohan Natarajan a, *, Fatma Al Fazari a , Amal Al Saadi b
a
Chemical Engineering section, Faculty of Engineering, Sohar University, Sohar, Oman
b
Diwan of Royal Court, Sohar Municipality, Sohar, Oman

highlights

• A novel natural coagulant was synthesized from Pisum sativum.

• Municipal waste water was characterized.
• Optimal conditions were identified: pH 5.0, coagulant dose-4.0 g/L,voltage 20 V and current 1.5 A.
• An empirical relationship between COD removal efficiency and coagulant dose was proposed.

article info a b s t r a c t
Article history: Municipal waste water treatment was investigated in an electrocoagulation reactor em-
Received 30 September 2017 ploying a novel natural coagulant synthesized from Pisum sativum. The influence of
Received in revised form 22 January 2018 operating variables, namely, type of electrode (copper, steel and aluminum), effluent
Accepted 26 January 2018
pH (3.0–9.0), initial COD of the effluent (190–760 mg/L) ,coagulant dosage (1.0–6.0 g/L),
Available online 2 February 2018
voltage (10–30 V) and current (1.0–2.0 A) on the COD removal efficiency was investigated.
Aluminum electrode proved to be an effective choice for this application and resulted in
Keywords:
Dye enhanced flocs formation though aluminum hydroxides. The optimal conditions for better
Effluent COD removal efficiency were identified as pH 5.0, coagulant dose-4.0 g/L, voltage 20 V and
Modeling current 1.5 A. An empirical relationship between COD removal efficiency and coagulant
Kinetics dose was proposed (R2 = 0.966). This research study proved the feasibility of parallel plate
electrocoagulation reactor with a natural coagulant as a sustainable method for treating
municipal waste water.
© 2018 Elsevier B.V. All rights reserved.

1. Introduction

Due to rapid industrialization and economic growth, population migration in developing countries has resulted in un-
foreseen water requirement in urban areas. The volumes of water used and waste water produced in domestic communities
has increased significantly in the last few decades and a need for effective municipal waste water treatment is required to
ensure the environmental compliance and resource reuse. Domestic waste water quantity and quality varies with respect
to the population density and life style. Oman, located on the southeastern coast of Arabian Peninsula, has an approximate
land area of 310,000 sq km. The collection of domestic sewage was practiced through septic tankers in most of the places
and sewer systems in certain localities. The waste water treatment units use physical, chemical and biological techniques in
their multistage treatment and the treated effluents have been used for landscape irrigation and recharging ground water

* Corresponding author.
E-mail address: rnatarajan@soharuni.edu.om (R. Natarajan).

https://doi.org/10.1016/j.eti.2018.01.011
2352-1864/© 2018 Elsevier B.V. All rights reserved.
72 R. Natarajan et al. / Environmental Technology & Innovation 10 (2018) 71–77

Table 1
Characteristics of Municipal waste water.
Variable Value
pH 7.10
Total Solids (TS) mg/L 1350
Total Suspended Solids (TSS) mg/L 505
Total Dissolved Solids (TDS) mg/L 845
Chemical Oxygen Demand (COD) mg/L 760

to resist salt water intrusion in coastal areas (Baawain et al., 2011; Jaffar Abdul Khaliq et al., 2017). Municipal waste water
has unique properties compared to industrial waste water due to their diversified contents which are natural and chemical
in origin. Research investigations on the use of modified photo-Fenton treatment to degrade micro pollutants in municipal
wastewater have been carried out at neutral pH conditions (Klamerth et al., 2012). A sustainable way of treating municipal
waste water through biological nutrient removal and reduction of carbon foot print has been discussed (Hu et al., 2012).
In the midst of conventional waste water treatment methods like adsorption, flocculation, filtration, froth floatation and
aerobic biodegradation, electro coagulation is identified as an effective technique to treat medium strength waste water as
it combines the principles of electrochemical oxidation and coagulation for the removal of pollutants. Electrocoagulation is a
simple method which involves the generation of a flocculating agent from oxidation of an electrode. Conventional chemical
coagulation involves the addition of chemicals like aluminum sulfate or ferric chloride as a coagulant. In electrocoagulation,
electrodes perform the role of chemical coagulants and they tend to agglomerate the particulates as flocs (Butler et al.,
2011; Ahangarnokolaei et al., 2017; Song et al., 2015). Several studies on application of electrocoagulation for textile dye
waste water treatment (Hossain et al., 2013; Ubale and Salkar, 2017), removal of dyes (Ghalwa et al., 2016; Adeogun and
Balakrishnan, 2017; Nandi and Patel, 2017), dairy waste water treatment (Bazrafshan et al., 2013), hospital waste water
treatment (Veli et al., 2016) and treatment of tissue paper waste water (Un et al., 2016) were reported. With this background,
the objectives of this study are to demonstrate the application of an electrocoagulation process utilizing a novel natural
coagulant for the treatment of municipal waste water and optimize the operating variables, namely, type of electrode,
effluent pH, initial effluent concentration, coagulant dosage, voltage and current. The coagulant characterization was done
using Fourier Transform InfraRed Spectroscopy (FTIR).

2. Materials and methods

2.1. Physico-chemical characterization of Municipal waste water

The Municipal waste water was collected from the waste water treatment plant located nearby and the essential physico-
chemical characteristics were evaluated using standard methods (APHA, 2005) and presented in Table 1.

2.2. Synthesis of a natural coagulant

Pisum sativum, the common pea, is an herbaceous member in the Fabaceae (formerly Leguminosae) family and selected
as a biomass for the production of coagulant. The peas were sundried for 72 h and crushed into fine powder in a blender and
the particle size of 600 µm was selected. The powdered form of the natural biomass was used as a natural coagulant. The
powdered coagulant was characterized for surface functional groups.

2.3. Experiments

The electrocoagulation process was carried out in a single compartment reactor equipped with a magnetic stirrer operated
at 200 rpm throughout the experiments. The reactor was made of glass with a total volume of 5.0 L and working volume
of 2.0 L. The reactor was equipped with a DC power supply and two monopolar plate type electrodes, one cathode and the
other anode. The dimensions of both the electrodes were identical (12 cm × 10 cm × 2 mm). The total effective electrode
area was 120 cm2 per electrode and the distance between electrodes was 2 cm. The electrocoagulation experiments were
conducted under batch conditions at room temperature of 298 K. In the first set of experiments, the effect of type of electrode
on electrocoagulation performance was studied by choosing three different materials namely copper, steel and aluminum
and the operating variables such as initial pH, coagulant dose, current and voltage were fixed. All the experiments were
conducted with the actual undiluted effluent for an equilibrium time of 90 min at optimal pH unless or otherwise specified.
The second sets of experiments were aimed to identify the optimal pH suitable for better COD removal efficiency. The effects
of contact time and effluent concentration were investigated by varying the effluent concentrations in the range of COD
values 190–760 mg/L. The time versus COD data was recorded at periodic intervals of time. In the second set of experiments,
the influence of coagulant dose was studied in the range of 1.0–6.0 g/L with an initial COD value of 760 mg/L at optimal pH
and room temperature. The influence of voltage on the COD removal efficiency was studied in the range of 10–30 V and the
studies on effect of current was conducted in the range of 1.0 −2.0 A . The treated effluent samples were filtered and then
 R. Natarajan et al. / Environmental Technology & Innovation 10 (2018) 71–77 73

Fig. 1. Effect of type of electrode on the PCR using copper, aluminum and steel (pH = 5.0, voltage = 20 V, current = 1.5 A, w = 4 g/L).

the filtrates were collected and analyzed for remaining COD. The % COD removal was defined in Eq. (1).
( )
C0 − Ce
% COD removal (PCR) = × 100 (1)
C0
where Ce and Co (mg /L) are the initial and equilibrium COD values, respectively.

3. Results and discussion

3.1. Effect of type of electrodes

Electrocoagulation mechanism is dependent on the existence of metal ions in dispersion which is dependent on the type
of electrode employed. The nature of electrode material is one of the operating variables in all the waste water treatment
applications using electrocoagulation process. In this set of experiments, three different electrodes made of Aluminum,
copper and steel were used for the treatment of municipal waste water at an equilibrium electrolysis time of 90 min,
maximum current of 1.5 A, maximum voltage of 30 V and pH 5.0 Fig. 1 presents the variation of percentage of COD
removal with time using three types of electrode. It can be observed that the aluminum electrodes produced maximum
COD removal efficiency of 94.6% while copper and steel electrodes produced 84.6 and 77.2% respectively. The reason for
the better performance of aluminum electrode could be related to the hydroxides formed during electrochemical reactions
and the subsequent coagulation of the pollutants present in municipal waste water. Studies on treatment of chromium
contaminated water have reported superior performance of aluminum electrodes compared to stainless steel (Mahmad
et al., 2016).

3.2. Effect of pH

In all water treatment methods involving dissolved ionic impurities, pH is considered as significant parameter influencing
the solubility of ions. The effect of pH on electrocoagulation process was studied by varying the effluent pH in the range of
3.0–9.0 and presented in Fig. 2. The best electrode chosen from the previous set of experiments, aluminum, was employed
in this study. Better COD removal efficiencies were observed in the acidic pH range. The COD removal efficiencies decreased
in the alkaline pH (9.0) with the maximum COD removal efficiency attained as 70.4% which could be due to the alteration of
pollutant properties in the municipal waste water. The aluminum electrode upon oxidation produces hydroxides [Al (OH)2 or
Al(OH)3 ] which in turn coagulates the pollutants. At low pH values, the H+ ion scavenges the hydroxyl radicals and inhibited
the production of hydroxyl ions. This reason was reported as the controlling mechanism for better COD removal at low pH
values. The reaction occurring was given below in Eq. (2) (Yazdanbakhsh et al., 2015).

∗OH + H+ + e− → H2 O. (2)
Removal of chromium and nitrate using aluminum electrodes in the electrocoagulation reactor reported decrease in removal
efficiency with increase in pH (Rezaee et al., 2011).

3.3. Effect of coagulant dose

To enhance the rate of coagulation, a novel natural coagulant synthesized from Pisum sativum was added to the
electrocoagulation reactor. The effect of coagulant dose was studied in the range of 1.0–6.0 g/L while the other operating
parameters were fixed as pH 5.0, voltage 20 V and current 1.5 A. The COD removal efficiency increased in the dose range of
74 R. Natarajan et al. / Environmental Technology & Innovation 10 (2018) 71–77

Fig. 2. Effect of pH on the PCR (voltage = 20 V, current = 1.5 A, w = 4 g/L).

Fig. 3. Effect of coagulant dose on PCR (pH = 5.0, voltage = 20 V, current = 1.5 A, w = 4 g/L).

1.0–4.0 g/L as shown in Fig. 3. Better surface interaction of the coagulant molecules with the pollutants present in municipal
waste water could be the reason for this observation. The optimal coagulant dose was identified as 4.0 g/L. The empirical
relationship between coagulant dose (w ) and the COD removal efficiency was found to be exponential (R2 = 0.966) and
given by Eq. (3). Similar application of a natural coagulant, Moringa Oleifera Seeds, for waste water treatment was reported
(Sanchez-Martin et al., 2012).

w = 34.623 PCR0.629 . (3)

3.4. Effect of effluent concentration and contact time

The municipal waste water concentration can vary depending on the nature of impurities released in the domestic
household. The effect of effluent concentration was studied by using various concentrations of the effluent (25, 50, 75
and 100% effluent) with the COD varying in the range of 190–760 mg/L. As shown in Fig. 4, it was concluded that the COD
removal efficiency decreased with the increase of initial COD values. Even though the equilibrium removal efficiencies were
relatively similar at different effluent concentrations, the time taken to attain the maximum efficiency was different in each
of these experiments. With lower effluent concentrations (25 and 50%) having COD values in the range of 190–380 mg/L,
the time required to attain the maximum removal efficiency was less. Contrarily, the rates of COD removal were lower at
higher effluent concentrations. The ratio between the coagulating species and pollutant molecules was high during the initial
phase of contact which led to higher removal rates of COD during the initial contact period. Reduced availability of hydroxide
complex (flocs) at higher COD effluent resulted in the reduction of equilibrium COD removal efficiency. Studies on treatment
of tannery waste water using a physical process reported reduction in removal efficiency at higher COD values (Rajamohan
and Rajasimman, 2017).

3.5. Effect of voltage

Input voltage is reported as the most important parameter for controlling electrocoagulation rate and COD removal
efficiency (Butler et al., 2011). In order to determine the effect of voltage in on the treatment efficiency, electrocoagulation
process was carried out using different applied voltages at optimal pH for a contact time of 90 min. When the voltage was
 R. Natarajan et al. / Environmental Technology & Innovation 10 (2018) 71–77 75

Fig. 4. Effect of effluent concentration on PCR (pH = 5.0, voltage = 20 V, current = 1.5 A, w = 4 g/L).

Fig. 5. Effect of voltage on the PCR (pH = 5.0, current = 1.5 A, w = 4 g/L).

Fig. 6. Effect of current on the PCR (pH = 5.0, voltage = 20 V, w = 4.0 g/L).

increased from 10 V to 30 V, the COD removal percentage increased from 70.6% to 96.0%. The increase in equilibrium COD
removal was significantly higher when the voltage increased from 10 V to 20 V as shown in Fig. 5. The optimal voltage was
identified as 20 V as there was no appreciable change in COD removal efficiency when the voltage was increased to 30 V.
Studies on treatment performance of textile wastewater using electrocoagulation process reported similar observation (Naje
et al., 2015).

3.6. Effect of current

The current density, an important operating variable, is directly proportional to the current applied. The effect of current
on the electrocoagulation process was studied by applying current in the range of 0.5–1.5 A. From Fig. 6, it was inferred
that the COD removal efficiency increased with increase in current. The efficiency increased from 76.5 to 98.5% when the
current was increased from 0.5 to 1.5 A. During the increase in current, the extent of aluminum dissociation was high along
with the number of metal hydroxide flocs. This factor has contributed for the better removal of COD (Yazdanbakhsh et al.,
2015). The change in efficiency was comparatively higher during the current increase from 0.5 to 1.0 A. Form these results,
76 R. Natarajan et al. / Environmental Technology & Innovation 10 (2018) 71–77

the saturation current required to remove the COD of the municipal waste water was found to be 1.0A and any further
increase in current above this threshold value has not yielded proportional increase in removal performance. Degradation
of phenol using electrochemical oxidation reported increase in COD removal efficiency with current (Babuponnusami and
Muthukumar, 2012).

3.7. FTIR characterization of the coagulant

The different chemical functional groups present in the coagulant were identified using Fourier Transform Infrared
Spectroscopy (FTIR). The analysis was carried out in the spectral range varying from 3800 to 600 cm−1 using KBr pellets
(PerkinElmer Spectrum BX-FTIR, UK). The predominant surface functional groups were identified at peaks at 1003 cm−1
(=C–H bending of alkane or alkene), 1540 cm−1 (N–O asymmetric stretch of nitro compounds), 1641 cm−1 (C=C of aromatic
ring) and 3281 cm−1 (O–H stretching, H-bonded) (shown in supplementary data).

4. Conclusion

The present investigation revealed the potential application of natural coagulant, Pisum sativum, for treating the municipal
waste water in an electrocoagulation reactor with parallel plate electrodes. The COD removal efficiency was examined by
electrocoagulation using steel, aluminum and copper. Electrocoagulation studies were performed to evaluate the influence of
various experimental parameters such as type of electrode, pH, coagulant dose, effluent concentration, voltage and current.
With low COD waste water, the COD removal rates were comparatively higher than high COD waste water. The maximum
COD removal efficiency was 94.6% at an optimal pH 5.0, coagulant dose — 4 g/L, voltage — 20 V and current — 1.5 A.
The removal efficiency increased with increase in current and voltage. FTIR characterization of the coagulant revealed the
functional groups present.

Appendix A. Supplementary data

Supplementary material related to this article can be found online at https://doi.org/10.1016/j.eti.2018.01.011.

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