RESEARCH PAPERS

COD REMOVAL OF COAL GASIFIER EFFLUENT BY ELECTRO

COAGULATION AND OPTIMIZATION USING RESPONSE SURFACE
METHODOLOGY
By

B. UMA SHANKAR * M.V.V. CHANDANA LAKSHMI **

V. SRIDEVI *** L.NEELIMA CHANDRA LEKHA ****
*, **** M.Tech, Department of Chemical Engineering, A.U. College of Engineering, Andhra University,
India. **, *** Professor, Department of Chemical Engineering, A.U. College of Engineering, Andhra University,
India.

ABSTRACT
Coal Gasification is considered as an ace technology compared to other non renewable energy producing technologies
such as petroleum and natural gas. The effluent generated from coal gasification contains high amounts of organic and
toxic compounds. The present work is focused on removal of COD from the Coal Gasifier effluent by Electro-Coagulation
(EC) using Aluminium electrode. The purpose of this research is to reduce the pollution which is generally caused by Coal
Gasifier effluent. In the process of EC, metal cations are released into water through dissolving metal electrodes.
Simultaneously, beneficial side reactions can remove flocculated material from the water, which is an advanced
alternative for chemical coagulation and flocculation. The electrochemical reactor performance was analysed in batch
reactor of the effluent having constant inter-electrodes distance. The effect of process parameters such as Electrolysis
Time, pH, and Voltage on COD removal % was studied. During EC process the optimum values of process parameters
are found to be Electrolysis Time-60 min, pH-8 and Voltage-9 V. The parameters used in this experiment were optimized
by using Response Surface Methodology. It has been observed that the predicted values are in good agreement with
experimental values with a correlation coefficient of 0.998.
Keywords: Coal Gasifier Effluent, COD, Electro-Coagulation (EC), Aluminium Electrode, Optimization.

INTRODUCTION (BOD), Chemical Oxygen Demand (COD), Total

The industrialization and modification of manufacturing
process have resulted in an increase in the volume of
wastewater discharge into the environment which causes
water pollution (Manisankar, Vishwanathan, and Rani, 2003).
In India, the number of coal gasification industries increased
rapidly in recent years. These industries generate huge
amount of waste every day. These effluents can alter the
physical, chemical and biological nature of the receiving
water body. Pollution of water by organic and inorganic
chemicals is of serious environmental concern. Industrial
wastewater differs in characteristics from the domestic
wastewater. Industrial waste waters result from spills, leaks,
and product washing and water resulting from cooling
processes. The organic content of wastewater is traditionally
measured using lumped parameters such as Biological
Oxygen Demand
Suspended Solids (TSS) and Total Organic Carbon
(TOC). These parameters do not show any chemical
identity of organic matter. In recent years, increasing
awareness of the environmental impact of COD has
prompted a demand for the purification of industrial waste
waters prior to discharge into natural waters (Sachin
Madhavrao Kanawade 2016). Coal Gasification
Wastewater (CGW) generated in the process of coal gas
purification and coal chemical production which contains
high concentration of organic compounds, with COD high
to 50,000–60,000 mg/L. Only a limited number of
researches and experiments have been carried out for
treatment of Coal Gasifier effluent.
The electro coagulation is one of the advanced process,
potentially a powerful method of pollution control, offering
high removal efficiencies in compact reactors

8 i-manager’s Journal on Future Engineering & Technology, Vol. 12 ·No.2 ·November 2016 - January 2017
 RESEARCH PAPERS
with simple equipment's for control and operation(Guven,
Perendeci and Tanyolac, 2008).
1. Objective
The main objective of this present research is the removal
of COD from Coal Gasifier effluent using Electro-
Coagulation Treatment there by reducing the pollution
which is generally caused by Coal Gasifier effluent.
2. Review of Literature
Coagulation is a routine practice for the treatment of drinking
water, waste water and industrial effluents (Norulaini, 2001).
Treatment of water using electricity was first proposed in UK
in 1889. The application of electrolysis in
beneficiation was patented by Elmore in
(Kumarasinghe, Pettigrew and Nghiem, 2009). Electro-
Coagulation, precipitation of ions (heavy metals) and colloids
(organic and inorganic) using electricity has been known as
an ideal technology to upgrade water quality for a long time.
It is being successfully applied to a wide range of pollutants
in even wider range of reactor designs (V. Sridevi, et al.,
2016). Many processes have been developed to treat this
effluent such as electrochemical oxidation (Guven, Perendeci
and Tanyolac, 2009; Mancera, et al., 2010), Electro-
coagulation is the technique to create conglomerates of the
suspended, dissolved or emulsified particles in aqueous
medium using electrical current causing production of metal
ions at the expense of sacrificing electrodes and hydroxyl
ions as a result of water splitting. Metal hydroxides are p r o d
u c e d a s a r e s u l t o f E C a n d a c t s a s
coagulant/flocculent for the suspended solids to convert them
into flocs of enough density to be sediment under gravity.
The electrical current provides the electromotive force to
drive the chemical reactions to produce metal hydroxides
(Balasubramanian, and Madhavan, 2001). In this experiment,
Aluminium electrodes were used as electrodes in different
batch experiments. The metal (anode) based coagulants
were found enough efficient to reduce the Chemical Oxygen
Demand (COD) and turbidity of Coal Gasifier effluent. The
remarkable pollutants removal was also associated with the
hydrogen production as a revenue to contribute the
operational cost of wastewater treatment.
production was also found helpful to remove the lighter
suspended solids
i-manager’s Journal on Future Engineering & Technology, Vol. 12 ·No.2 ·November 2016 - January 2017
towards surface.
The parameters of this study was optimized statistically by
using Response Surface Methodology (RSM) RSM is a
designed regression analysis to predict the value of a
dependent variable based on the controlled values of the
independent variables. It leads to the need for an
experimental design, which can generate a lot of samples
for consumer evaluation in a short period of time, and
thus laboratory level tests are more efficient. (P.
Asaithambi, & Manickam, 2011). RSM was used to
optimize the experimental parameter for a different
mineral process, which includes an advanced oxidation process
1904 (Otto, 1999), electrochemical oxidation (Gurses, Yalcina &
Dogar, 2002) and adsorption (Montgomery, 2002). The
two most common designs used in RSM are the Central
Composite Design (CCD) and the Box–Behnken Design
(BBD). In the present study, CCD with RSM was used to
optimize the experimental parameters like various
operation parameters such as voltage, pH and
Electrolysis Time on the COD removal efficiency
3. Materials and Methods
3.1 Experimental Setup
A laboratory scale batch unit was assembled to conduct
the experiment in this present study. The unit consists of
four components: reactor, magnetic stirrer, electrodes and
DC power supply. The reactor made up of glass material
with 1 litre volume was used. The working volume of the
reactor is 800 ml. The space between the electrodes are
maintained constant as (20 mm). The dimensions of
electrodes also maintained constant as (8 cm x 3 cm x 1
mm) the DC (Direct Current) power supply was used for
maintain desired voltage. Stirrer speed kept
Hydrogen
Figure 1. Batch Mode Electro-Coagulation Experimental Setup
9
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500 rpm. Figure 1 is the pictorial representation of the
experimental setup.
3.2 Methodology
Experiments were carried out in a 1000 ml of batch
electrochemical reactor Aluminium electrodes of
dimensions 8x3x0.1 cm were used as anode and
cathode. The electrodes were connected with regulated
power supply to supply electrical energy to the system.
The experiments were carried out under potentially static
conditions covering wide range of operating conditions
and samples were collected and analysed periodically.
The anode was weighed before and after the experiment
for each experiment run to estimate the electrode
consumption. The electrodes were connected with
regulated power supply to supply electrical energy to the
system. During the electrochemical reaction, the organic
compound in the effluent was oxidized at the anode and
a reduction reaction occurred at the cathode.
3.3 COD Analysis
The organic matter present in sample gets oxidized
completely by Potassium dichromate (K2Cr2O7) in the
presence of Sulphuric acid (H2SO4), Silver sulphate (AgSO4)
and Mercury sulphate (HgSO4) to produce CO2 and H2O.
The sample is refluxed with a known amount of Potassium
dichromate (K2Cr2O7) in the Sulphuric acid medium and
the excess potassium dichromate (K2Cr2O7) is determined
by titration against ferrous ammonium sulphate, using
ferroin as an indicator. The dichromate consumed by the
sample is equivalent to the amount of O2 required to
oxidize the organic matter. (APHA, AWWA ,WEF, 1995, V.
Sridevi, et al., 2016).
3.3.1 Effect of Electrolysis Time
The Electrolysis Time has a significant effect on the
pollutant removal. The pollutant removal efficiency
increases with increase in the Electrolysis Time. But beyond
the optimum Electrolysis Time, the pollutant removal
efficiency becomes constant and does not increase with
an increase in the Electrolysis Time because the metal
hydroxide ions are formed by the dissolution of anode.
3.3.2 Effect of pH
The maximum pollutant removal efficiency was obtained
10 i-manager’s Journal on Future Engineering & Technology, Vol. 12 ·
at an optimum solution for a particular pollutant. The
precipitation of a pollutant begins at a particular pH. The
pollutant removal efficiency decreases by either
increasing or decreasing the pH of the solution for the
optimum pH.
3.3.3 Effect of Voltage
Voltage is related directly to the current density. So
increases in voltage increases the current flow. With an
increases in the voltage, the anode dissolution rate
increases. This leads to increases in the number of metal
hydroxide flocs results in the increase in pollutant removal
efficiency. An increase in voltage above the optimum
voltage does not result in an increase in pollutant removal
efficiency as sufficient number of metal hydroxide flocs is
available for the sedimentation of the pollutant.
3.3.4 Optimization using RSM
In the present study, CCD was applied to investigate and
validate the process parameters affecting the removal of
COD. pH (A), Voltage (B), and Time (C) are input variable
parameters. The interval of the allowed values for these
factors was deduced from the preliminary tests carried
out (Table 1). The factor levels were coded as -1.68 (low), 0
(central point or middle) and 1.68 (high). For this response
(Y), a polynomial model of the second degree is
established to quantify the influence of the variables.
4. Results and Discussions
The influence of process parameters such as pH, Voltage
and time on the COD reduction were studied on “one
parameter a time basis” i.e., by changing one
independent variable while fixing the others at a certain
constant level for the Al electrodes was studied.
4.1 Effect of Electrolysis Time
The effect of Electrolysis Time was studied by keeping
other two parameters constant at pH 7 and voltage 9 V.
The agitation speed was kept constant at 500 rpm and
spacing between the electrodes was nearly 20 mm. On
increasing the Electrolysis Time, the % of COD removal
increased up to 60 min and then slightly decreased as
shown in Figure 2. By increasing the Electrolysis Time
reduces the efficiency because metal hydroxide ions
formed by dissolution of anode. The maximum % COD
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 RESEARCH PAPERS
Figure 2. Effect of Electrolysis Time on COD Removal Percentage
removal is 84.8% which was achieved at the Electrolysis
Time (ET) of 60 min.
4.2 Effect of pH
The effect of pH was studied by keeping other two
parameters constant at voltage 9 V and 60 min
Electrolysis Time. The experiments were conducted at
different pH's 4 to 10 to study the effect of pH on the
electro-coagulation process. The agitation speed was
kept constant at 500 rpm and the spacing between the
electrodes was nearly 20 mm. On increasing pH, the % of
COD removal increased up to 8 and then a decline was
observed as shown in Figure 3.
% of Removal decreases due to the increase in H+ and
–
OH ions. The maximum % COD removal is 95.2% which
was achieved at the pH of 8.
4.3 Effect of Voltage
The effect of Electrolysis Time was studied by keeping
other two parameters constant (at Electrolysis Time 60 min
and pH 8). The analysis was done by varying the voltage
from 3-15 V using Al electrodes to study the effect of
Voltage on the EC process. The agitation speed was kept
constant at 500 rpm and the spacing between the
Figure 3. Effect of pH on COD Removal Percentage
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electrodes was 20 mm. The maximum % COD removal is
95.2% which was achieved at the voltage of 9 V and the
results are shown in Figure 4 respectively. Increase in
voltage results the reduction of electrode takes place in
less time and formation of hydroxide ions occurred and
also decreases the removal efficiency.
4.4 Optimization by RSM
The optimization of process parameters were carried out
for the Aluminium electrodes and the variation in response
was studied. Three parameters were selected for
optimization by CCD which showed significant influence
on COD removal percentage. They include pH, Voltage,
Electrolysis Time.
The optimum values obtained in preliminary studies have
been used as the basis for selecting the mid points (zero
level) in CCD (Table 1) for further optimization. The range of
parameters used in the experiment were listed in Table 1.
4.4.1 Experimental Design for Optimization
Experiments were performed according to the CCD at
different combination of parameters and the encoded
values and percentage of COD removal along with the
predicted values are given in Table 2.
Using the results of the experiments, the following second
order polynomial regression equation giving COD
removal percentage as a function of pH (A), voltage (B),
Electrolysis Time (C) was obtained.
Figure 4. Effect of Voltage on COD Removal Percentage
Parameters levels -1.68 -1 0 1 1.68
pH 6 7 8 9 10
Time (min) 30 45 60 75 90
Voltage (v) 3 6 9 12 15
Table 1. Coded and Real Values of Independent Parameters
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COD Exp (%) =95.22+2.38 A+0.96 B-1.76 C-1.13
AB+0.15 AC-2.53 BC-7.09 A2-8.11 B2-1.94 C2
The statistical significance of the ratio of mean square
variation due to regression and mean square residual
error was tested using ANOVA (Analysis of Variance). The
ANOVA for the second order equation is fit for COD removal
is resented in Tables 3.
The large value of F indicates that, most of the variation in
the response can be explained by the regression
equation. The associated p value is used to estimate
whether F is large enough to indicate statistical
significance of the high coefficient of R2 value means best
fit of the model. The R2 value provides a measure of how
much variability in the observed response values can be
explained by the experimental variables and their
interactions. The R2 value is always between 0 and 1. The
(1) closer the R2 value is to 1, the stronger the model is and the
better it predicts the response. In this case, the value of the
determination coefficient is R2 =0.998.
4.5 Optimization of Operating Conditions
The response surface contour plots of COD removal
efficiency over independent variables such as pH,
voltage and Electrolysis Time are shown in Figures 5, 6,
and 7. The contour plots given in Figures 5, 6, and 7 show
the relative effects of two variables when the volume of
solution is kept constant. It was proved that the aluminium

COD COD
Run pH Voltage(V) Time(min)
Expt (%) Pred (%)

1 6.32 9.00 60.00 71.36 71.16

2 8.00 14.05 60.00 74.13 73.9
3 9.00 6.00 75.00 81.4 81.53
4 8.00 9.00 60.00 95.2 95.21
5 7.00 12.00 75.00 73.4 73.35
Figure 5. The Combined Effect of Voltage and pH on COD Removal
6 8.00 9.00 60.00 95.2 95.21
7 9.00 12.00 75.00 76.39 76.14
8 7.00 12.00 45.00 81.9 82.22
9 8.00 9.00 60.00 95.2 95.21
10 8.00 9.00 60.00 95.2 95.21
11 8.00 9.00 60.00 95.2 95.21
12 8.00 9.00 34.77 93.8 92.68
13 9.00 6.00 45.00 79.2 79.7
14 8.00 3.95 60.00 71.1 70.67
15 7.00 6.00 45.00 72.3 72.99
16 8.00 9.00 60.00 95.2 95.21
17 7.00 6.00 75.00 74.5 74.23
18 8.00 9.00 85.23 86.3 86.76
19 9.68 9.00 60.00 79.6 79.15
20 9.00 12.00 45.00 83.7 84.42

Figure 6. The Combined Effect of pH and Electrolysis Time on

Table 2. Design of Experiments and Response for % COD Removal % COD Removal

Sum of Mean p-value

df F-Value
Squares Square Prob > F

A-pH 77.09 1 77.09 223.41 < 0.0001 Significant

B-Voltage 12.54 1 12.54 36.34 0.0001
C-Time 42.26 1 42.26 122.46 < 0.0001
AB 10.15 1 10.15 29.41 0.0003
AC 0.18 1 0.18 0.51 0.4902
BC 51.06 1 51.06 147.95 < 0.0001
A2 725.06 1 725.06 2101.11 < 0.0001
B2 946.93 1 946.93 2744.06 < 0.0001
C2 54.34 1 54.34 157.47 < 0.0001

Figure 7. The Combined Effect of Electrolysis Time and Voltage

Table 3. ANOVA for % COD Removal on % of COD Removal

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Electrode Electrolysis Voltage
pH
used time (min) (V)
Al 60 8 9
Table 4. Optimum Conditions for Al Electrode
works well for neutral pH and for slightly basic nature. As the
pH increased beyond that level does not shows significant
effect on COD removal due to the formation of soluble
metal hydroxide. The removal percentage of COD was
resulted as maximum at voltage-9 V, pH-8 for the fixed
Electrolysis Time of 60 min. As increase in voltage and time
also results decrease in COD efficiency due to formation
of hydroxide ions. The optimum conditions obtained from
present investigation is shown in Table 4.
Conclusion
The results of the present experiment carried by the
researchers provide the following conclusions. Coal
Gasifier effluent treatment by electro-coagulation using
Al electrode showed good reduction in COD compared
to other methods. The selection of process parameters
such as Electrolysis Time (ET), pH and Voltage were
important and they play a major role in removal of COD.
Central Composite Design was used to study the
interactive effects of Electrolysis Time, pH and Voltage for
Al electrode. The value of regression coefficient is R2
=0.998, which indicates 99.8% of the variability in the
response of COD could be explained by this model.
References
[1]. APHA, AWWA, WEF, (1995). Standard Methods for the
Examination of Water and Wastewater. 19th ed. APHA,
Washington, USA.
[2]. Balasubramanian N., and Madhavan., K. (2001).
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coagulation”. Chemical Engineering Technology, Vol. 24,
pp. 519-521.
[3]. Gursesa, A., Yalcina, M., and Dogar, C., (2002).
“Electro-Coagulation of some reactive dyes: A statistical
investigation of some electrochemical variables”. Waste
Management, Vol. 22, No. 5, pp. 491–494.
[4]. Guven, G., Perendeci, A., and Tanyolac, A., (2008).
“Electrochemical treatment of deproteinated whey
wastewater and optimization of treatment conditions with
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% of COD
response surface methodology”. Journal of Hazardous
removal Materials, Vol. 157, No. 1, pp. 69–78.
95.2
[5]. Guven, G., Perendeci, A., and Tanyolac, A., (2009).
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[6]. Kumarasinghe, D. L. Pettigrew, and L.D. Nghiem,
(2009). “Removal of heavy metals from mining impacted
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[7]. Manisankar, P., Viswanathan, S., and Rani, C., (2003).
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Gerardind, P.,Velasquez, J., Quintana, G., and Celzard,
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About the authors:

1. I, B.Uma Shankar, presently working as process engineer in Nicomet. I have completed my

M.Tech Industrial pollution Control Engineering in 2016 from Andhra University I have completed

my B.tech Chemical Engineering in 2013 from GMR IT, Rajam. I published one review article in AU

College of journal. My areas of interest include, design of industrial effluent and sewage treatment

plants.

2. Dr.M.V.V.Chandana Lakshmi currently working as Professor in the Department of Chemical Engg,

Andhra University. She did her Ph.D in the 2011 from Andhra University. She has significantly

contributed in the field of Biotechnology. She has published more than 70 research and review

articles in reputed National and International journals. She is author for more than three books. She

has attended more than 30 conferences and workshops. She Got a Certificate of Excellence by
nd
Education Expo TV (Research wing for Excellence in Professional Education & Industry) in the 2
th
Academic Brilliance Awards -14, Andhra Pradesh on 09 February, 2014.
 RESEARCH PAPERS

3. Dr.V.Sridevi currently working as Professor in the Department of Chemical Engg, Andhra

University. She did her Ph.D in the 2011 from JNTU, Ananatapur. She has significantly contributed

in the field of Industrial Pollution and Control Engineering. She has worked on Biodegradation, Bio

reactor design and Industrial Pollution & its control. She has published more than 90 research and

review articles in reputed National and International journals. She is author for more than three

books. She has attended more than 30 conferences and workshops and got a credit of “prestigious

author” from OMICS publications and got an award of ”Scientist of the year 2012” , “Eminent

Scientist of the year 2013” from National Environmental Science Academy.

Her ongoing projects are UGC for an amount of 16 lakhs and NTPC project

work order for an amount of 50 Lakhs.

4. L. Neelima Chandra Lekha currently working as Asst. Professor in the Department of Chemical

Engg, SVKR Engineering College.She obtained her M.Tech in Mineral Processing in 2016 from

Andhra University Visakhapatnam and B.Tech in Chemical Engineering in 2013 from Andhra

University. Her areas of interest include petroleum exploration and renewable energy resources.