Accepted Manuscript

Title: Treatment of Textile Dyeing Factory Wastewater by

Electrocoagulation with low sludge settling time: optimization
of operating parameters by RSM

Authors: Atousa Ghaffarian Khorram, Narges Fallah

PII: S2213-3437(17)30693-0
DOI: https://doi.org/10.1016/j.jece.2017.12.054
Reference: JECE 2101

To appear in:

Received date: 25-8-2017

Revised date: 12-12-2017
Accepted date: 22-12-2017

Please cite this article as: Atousa Ghaffarian Khorram, Narges Fallah, Treatment of
Textile Dyeing Factory Wastewater by Electrocoagulation with low sludge settling time:
optimization of operating parameters by RSM, Journal of Environmental Chemical
Engineering https://doi.org/10.1016/j.jece.2017.12.054

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Treatment of Textile Dyeing Factory Wastewater by Electrocoagulation with low

sludge settling time: optimization of operating parameters by RSM

Atousa Ghaffarian Khorrama, Narges Fallah*a

a
Department of Chemical Engineering, Amirkabir University of Technology, Tehran, Iran

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Correspondent Author * Email: [email protected]

Postal Address: Department of Chemical Engineering, Amirkabir University of Technology ,424 Hafez Ave,

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Tehran, Iran

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Highlights

 Studying of Industrial dyeing wastewater contains some additives, which are used for dyeing process

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such as sodium oxalate, starch, sodium chloride, sodium carbonate, sodium hydroxide, acetic acid,
except for color. These additives are effective on EC process performance as decolorization, COD


removal and sludge settling velocity. N
Discussing sludge settling velocity after EC process with Al electrodes and their difficulties.
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 Separating sludge after EC process with low sludge settling time (30 minutes).
 Determination of sludge settling volume kinetics to identify the best time of sludge settling.
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Abstract
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Dyeing wastewater differs from textile wastewater because industrial dyeing wastewater except of color
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contains some dissolved additives such as sodium oxalate and acetic acid. This article deals with the

treatment of industrial dyeing wastewater by electrocoagulation technique because the area needed for
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the treatment of industrial wastewater is a significant factor. In addition, effect of operational parameters

such as initial pH (4-9), current density (15-35 mA/Cm2) and EC time (20-60 minutes) was determined in
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low settling time of 30 minutes in comparison to other studies, which have settling time of 12 hours or
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more. Electrocoagulation includes three stages of oxidation reaction at the anode, break emulsion

particles and settling. In this study, Box–Behnken design as a response surface methodology (RSM) was

used to investigate the effects of major operating variables and optimization conditions of

electrocoagulation method on aluminum electrodes. Results showed that initial pH was important more
than other parameters, and initial pH and current density had interaction. Furthermore, operational

parameters are effective on settling velocity and low settling time is not appropriate for EC with Al

electrodes. Under optimized conditions, initial pH of 5.5, current density of 15 mA/cm2 and EC time of 23

min, the decolorization was predicted 98%. In the laboratory, decolorization under these conditions was

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obtained 97%. COD removal efficiency, sludge settling velocity (SSV), electrode consumption and energy

consumption under the optimum conditions were measured, which were 40%, 0.004 cm/min, 1.3 kg/m 3

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and 7.64 kWh/m3, respectively. Under optimal conditions, 40% of settled waste can be retrieval;

otherwise, more settling time is required. COD removal efficiency was low since wastewater contained

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dissolved additives such as sodium oxalate, polyvinyl alcohol, and acetic acid, which may be the cause of

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most COD of this wastewater.

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Keywords: Industrial dyeing wastewater; Electrocoagulation; Decolorization; COD removal; Sludge
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settling velocity; Low settling time.
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1. Introduction
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Textile wastewater is characterized by high-strength chemical oxygen demand (COD), color and
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suspended solids. Textile wastewater contains dyes, representing an important environmental problem

for many years. This wastewater includes many kinds of dyes such as reactive and disperse dyes. Reactive
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dyes such as azo dyes have been widely used owing to their chemical stability and versatility [1]. Industrial

dyeing wastewater except for color, which is the only compound in synthetic wastewater contains some
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additives, which are used for dyeing process in the textile industry. These compounds are effective in COD

removal, decolorization and sludge settling velocity (SSV). Therefore, further studies are needed on
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industrial dyeing wastewater.

In fact, most dyes are harmful even at very low concentration and need to be removed from wastewater

before discharging [2]. Several different treatment methods for decolorization have been reported in the
literature, such as photocatalytic process [3], adsorption [4], sedimentation [5], membrane processes [6]

and biological treatment [7]. Since most of dyes are hardly biodegradable at high concentration, biological

treatment cannot be applied to most kinds of textile wastewater without any pretreatment. Therefore,

they need a pretreatment method such as physical or chemical processes [8] in which EC process can be

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a good compact pretreatment method for biological methods due to its advantages.

The advantages of electrocoagulation (EC) process such as simplicity of design and operation, low

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electrolysis time (ET) and sludge production, cost-effective treatment system without the need for added

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chemicals have led it to be considered an excellent alternative process to overcome the drawbacks of

conventional technologies [9, 10]. Furthermore, biological system needs a large area for separating sludge

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due to their high settling time, therefore there is no area for pretreatment unit. EC due to lack of a large
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place is a good pretreatment method. There have been numerous studies on the practical usages of EC to
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treat wastewater containing arsenic [11], chromium [12], Ti/BDD (boron-dopeddiamond) [13], azo dye
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[14], dyeing wastewater [15], synthetic textile wastewater [16], olive oil mill wastewater [17] and landfill

leachate [18].
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The EC process is an electrochemical means of introducing coagulants and removing suspended solids,

colloidal material and metals as well as other dissolved solids from water and wastewater. In the EC
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process, the metal ions generation occurs at the anode when hydrogen gas is released from the cathode.

In most cases, during the EC operation, direct current is applied and anode electrode plates are sacrificed.
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Flocculated particles can be removed by sedimentation or floatation with H2 bubbles produced at the

cathode from water [19].

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pH is a crucial parameter in the EC process affecting the performance of the treatment efficiency. Types

of metal hydroxides formed in this process change depending on the initial pH. Aluminum ions (Al3+)

produced by dissolution of the anode (Eq. (1)) immediately undergoe spontaneous hydrolysis reactions
generating various monomeric species (Eq. (2)–(4)) over a wide pH range [20]. The dissolution of the

aluminum anode produces Al3+ and Al(OH)2+ at low pH, which, at appropriate pH values, are transformed

initially into Al(OH)3. However, depending on the pH of the aqueous medium, other ionic species such as

Al(OH)2+, Al2(OH)24+ and Al(OH)4-, as well as polymeric species such as Al6(OH)153+, Al7(OH)174+, Al8(OH)204+,

Al13O4(OH)247+ and Al13(OH)345+ may also be present in the system [21]. These intermediate species are

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finally converted into Al(OH)3(s); the overall process of flocs formation may be described as:

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Al → Al3+ + 3e- (1)

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Al3+ + H2O → Al(OH)2+ + H+ (2)

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Al(OH)2+ + H2O → Al(OH)2+ + H+ (3)

Al(OH)2+ + H2O → Al(OH)3 + H+

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These hydroxides (Al(OH)3) compounds (Eq. (4)) have large surface area as coagulant, being beneficial for
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rapid adsorption of soluble organic compounds and metal ions [10]. Since Al(OH)3 has higher weight and
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density, it settles faster, and it is easier to make the trapped colloidal separated from the aqueous medium
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by sedimentation or H2 flotation [22]. Dye precipitation process is primary responsible of the high

decolorization efficiency, and adsorption of the dye polymeric species colloidal by Al(OH)3 flocs has a more
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secondary effect. When the pH reaches 6.5, most of the aluminum hydroxides precipitate as Al-coagulant

and adsorb the colorant. Al(OH)4- is predominate in alkaline medium, and when the pH reaches 9, the
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formation of Al(OH)4- and dissolving some of the Al-coagulant will restore a portion of the adsorbed
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colorant into the solution. Moreover, it is clear that, especially at high pH values above 9, the quantity of

flocs diminishes according to equation (9); thus, the decolorization efficiency fall [23].

Precipitation process:
Dye + monomeric Al → [dye-monomeric Al] (s) (pH: 4-5) (5)

Dye + polymeric Al → [dye-polymeric Al] (s) (pH: 5-6) (6)

Adsorption process:

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Dye + Al(OH)3 → sludge (pH˃6.5) (7)

Dye-polymeric Al + Al(OH)3 → sludge (8)

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Al(OH)3 + OH- Al(OH)4 - (pH˃9) (9)

Until now, few studies have been conducted on industrial textile wastewater. Their results showed that

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EC method has high efficiency in decolorization [24, 25]. In most studies, settling time that has an
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important role in determining the size of unit was approximately 12 hours or more in comparison with 1
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hours of reaction time. Therefore, the size of settling part to the entire unit was very large, and the
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investment costs will be considerable. The aim of this study is to decolorize industrial dyeing wastewater
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with short settling time of 30 minutes. In the following, by applying Box–Behnken response surface design

(BBD) to optimize and investigate the influence of the three operational factors, including initial pH,
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current density and EC time on decolorization of industrial dyeing wastewater with the goal of 100%
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decolorization. Statistical experimental design method on batch scale was used to identify the most

important effective factor in electrocoagulation and decision on continuous EC process, which is used in
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industry. Furthermore, SSV was determined to survive the sludge separation after EC process.
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2. Material and Methods

2.1 Wastewater Characteristics

The wastewater was obtained from a textile dyeing factory located in Kordan Town, Iran, which is under

the supervision of the industrial towns of Alborz Province. Chemical composition of the wastewater varied
depending on the characteristics of the fiber material and the stage of the dyeing process (e.g. dying,

washing and drying). The industrial dye bath consisted of a mixture of dyes, including Reactive Black WNN,

Reactive Brown RNN, Reactive Orange 122, Reactive Red 4BL, Disperse Red B3, Disperse Yellow WR and

Disperse Navy Blue. The wastewater except for color, contains some additives, which are used for dyeing

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process such as sodium oxalate, starch, polyvinyl alcohol, sodium chloride, sodium carbonate, calcium

carbonate, carboxy methyl cellulose, sodium hydroxide, and acetic acid. The sample was maintained at

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fixed temperature of 4 °C. Table 1 shows the characteristics, which were gained from factory and analyzed

in laboratory.

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Table 1. Characteristics of industrial dyeing wastewater samples.

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2.2 Electrocoagulation Reactor and Operational Conditions
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In this work, a bench scale EC reactor was applied for the treatment of the industrial dyeing wastewater
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with a total volume of 1 L. The EC reactor was made from 5-mm Plexiglas with the dimension of 13 cm
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(length) * 8 cm (width) * 15 cm (height). Dimensions of electrodes were 2 mm (width), 14.1 cm (height)

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and 5.6 cm (length). Electrocoagulation cells consist of 5 pairs of parallel unalloyed Al plate electrodes,
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having higher efficiency than iron for decolorization [26], separated by 4 millimeters. A magnetic stirrer

was used to provide mixing of the solution. The mixing during EC tests was conducted well because
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wastewater’s pH at various points of reactor was measured during each run, and it was the same.
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A total of 500 cc of industrial dyeing wastewater with adjusted pH was used in each EC run and all runs

were conducted at room temperature. After each run, the electrodes were fully washed with acetone to
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take any solid residues on the surface, and the impurities on the aluminum electrode surfaces were

removed by dipping for 5 min in a solution freshly prepared by mixing 100 cm3 of HCl solution (35%) and

200 cm3 of hexamethylenetetramine aqueous solution (2.80%) [27], dried and weighted. The output of

each run was analyzed after settling for 30 minutes.

Fig. 1. Schematic set-up diagram: (1) cathodes, (2) anodes, (3) DC power supply, (4) reactor, (5) input

valve and (6) output valve.

2.3 Analytical Method

The natural pH of industrial dyeing wastewater was 8.5. Since, pH is one of the most important factors in

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decolorization, it is necessary to adjust it in a proper ranges. Adjustment of pH was conducted by NaOH

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and H2SO4 solutions and was measured by a Metrohm 744 pH meter. Conductivity was measured using a

WTW conductivity meter. Turbidity was determined using a Hatch spectrophotometer. COD and SSV were

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measured according to the standard method [28]. An ultraviolet-visible spectrophotometer (Model v-550)

was used to plot diagram of adsorption in the wavelength range 400-700 nm. Area under the adsorption

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curve is measured as color [29].
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2.4 Experimental Design
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The experimental runs were designed using Design Expert 7.0 software. Box-Behnken design and ANOVA
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analysis under RSM were chosen as a model of optimization. RSM is the most common technique used in

industrial research, particularly in situations where a large number of variables influencing the system’s
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features. RSM also identified the relationship between the controllable input parameters and the
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response variable. In this method, three factors were evaluated at three levels. The purpose of RSM is to

determine the optimum operating conditions or a region for the factors at certain operating
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specifications. Moreover, RSM is a powerful statistical-based technique to design experiments helping to

increase accuracy and reduce the number of experimental trials [30].

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This design includes 17 electrocoagulation experimental sets. The main operational variables were initial

pH, current density and EC time as independent variables, involving three levels; decolorization (Y) was

considered as response. The original factors of operational parameters were coded as given by Eq. (10):
 𝑥𝑖 − 𝑥𝑐𝑝
𝑋𝑖 = ∆𝑥𝑖
(10)

Where, 𝑋𝑖 is the coded level; 𝑥𝑖 is initial value; 𝑥𝑐𝑝 is the original value of the centered point; and ∆𝑥𝑖 is

the value of variable change step. Table 2 shows the levels of original and coded factors using Box-

Behnken design. The preliminary tests with different conditions according to previous studies were

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conducted for obtaining ranges of each operational variable.

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The experimental data (Table 3) were analyzed by the response surface procedure to fit the following

second-order polynomial model:

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𝑌 = β0 + ∑𝑘𝑖=1 β𝑖 𝑋𝑖 + ∑𝑘𝑖=1 β𝑖𝑖 𝑋𝑖2 + ∑𝑘𝑖=1 ∑𝑘𝑗=1 β𝑖𝑗 𝑋𝑖 𝑋𝑗 + 𝜀 (11)

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Where, Y is the response (decolorization, %); β0 , β𝑖 (i=1,2,3) and β𝑖𝑗 (i=1,2,3; j=1,2,3,) are the model
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coefficient and 𝑋𝑖 , 𝑋𝑗 are the coded independent variables.
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Table 2. Levels and ranges of variables in Box–Behnken statistical experimental design.

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3. Results and Discussions

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3.1 Statistical Analysis

Table 3 presents the Box-Behnken design for three factors of initial pH, current density and EC time with
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three levels for seventeen experiments. To develop a response surface method, a full quadratic model

was applied to experimental observations of the decolorization (Y). The significance of each coefficient of

response equation (Eq. (12)) was determined by applying p-values of each as listed in Table 4.
Table 3. Box–Behnken experiments with actual values of responses.

Table 4. Analysis of variance table (ANOVA) for response surface quadratic model (Y).

Values of “prob˃F” less than 0.05 indicates that model terms are significant. Values greater than 0.1

indicate that the model terms are not significant, which could be reduced from the model to improve it.

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In this case, p-values of x1x3 and x2x3 were 0.2911 and 0.6342, respectively, which were eliminated from

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the model. Eq. (12) gives the final equation in terms of actual factors.

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Decolorization = +92.16 + 4.84𝑥1 + 0.37𝑥2 − 0.66𝑥3 + 0.27𝑥1 𝑥2 − 0.96𝑥1 2 − 0.04𝑥2 2 + +8.85𝑥3 2

(12)

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The value of R2 for decolorization value is 0.99. The high R2 value indicates the suitability of the model and
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the success of the RSM [30]. Table 4 shows the ANOVA results for decolorization. Response function
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predictions agreed well with the experimental data.
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Since the p-values of pH and time coefficients are p<0.05, it implies that these are significant. In addition,
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R2 and Adj-R2 are very close, so the model has sufficient accuracy and 98.20% for Adj-R2 is suitable,
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showing that the model has covered 98.20% of the data. Furthermore, Fig. 2 shows the accuracy and

reliability of both values.

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Fig. 2. Regression plots of the actual data against the predicted values.
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3.2 Effects of Operational Parameters on Decolorization of Industrial Textile Dyeing Wastewater

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
Effect of Initial pH on Decolorization

pH has a significant influence on the performance of the EC process [27]. To verify the effect of pH of the

wastewater on decolorization, experiments were conducted by adjusting the initial pH in the interval from

4 to 9. Fig. 3 (a-c) shows the effect of the current density and pH on decolorization at three levels of the
EC time (20, 40 and 60 min). Fig. 3 shows that pH has a maximum value, being in acidic condition. In the

pH range of 4-6.5 depending on the current density and EC time, the maximum values of decolorization

were obtained. The study results agree very well with those presented in the previous literature [31, 32].

In acidic condition, Al3+ is altered into soluble monomeric kinds such as Al(OH)2+ and Al(OH)2+. These

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monomeric cations can transmute to hydroxypolymeric kinds such as Al2(OH)24+ and Al6(OH)153+ [21]. As

Fig. 3 shows, high efficiency obtained with initial pH value of 5.5, results from efficient precipitation of

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dye molecules, according to the mechanism outlined by equations 5 and 6. Furthermore, superior

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coagulant is Al(OH)3 in this pH, having a large area to absorb pollutants such as dyes molecules [33]. Thus,

maximum decolorization was more than 92% at initial pH of 5.5.

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
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Interaction between Initial pH and Current Density on Decolorization
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There is an obvious interaction between the initial pH (x1) and the current density (x2) on decolorization
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(x1x2 for p-value˂0.0001). It may be seen in Fig. 3, at a lower limit of current density, decolorization was

decreased by increasing the pH, but it has a reversed trend at a higher limit of current density.
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In acidic initial pH and a higher limit of current density, by increasing the initial pH, the decolorization
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efficiency was increased. At high constant current density, the coagulant dosage will be produced due to
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Faraday’s low (Eq. (13)) and in a pH range of 6.5-7, the decolorization of the solubility of Al(OH)3 is in its

minimum value and the adsorption process (Eq. (7,8)) is predominant [22, 23]. Therefore, efficiency
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increased, but at a lower limit of current density and acidic initial pH, the bubble generation will be also

increased, results in breaking flocs, thereby decreasing the removal efficiency.

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Faraday’s low is expressed as [34]:

I tEC M
C= ZFW
(13)
Where C is the metal concentration in the EC cell, M the molecular weight of anode (Al), Z the chemical

equivalence, F the Faraday’s constant and W the volume of the electrolytic cell.

As Fig. 3 shows, in alkaline pH and a lower limit of current density, by increasing the initial pH,

decolorization efficiency was decreased. In alkaline pH, the predominant reaction is given in Eq. (9). At

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constant current density of 15 mA/cm2, the amount of Al3+ and Al(OH)3 is released. As a result, the amount

of Al(OH)3 overcomes the amount of OH-, then more precipitation will be formed, causing more removal

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efficiency. Generally in a pH range of 6.5-7, the decolorization efficiency is almost constant at all current

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densities and is at its maximum value. The cause is that the solubility of Al(OH)3 is in its minimum value at

this pH range, and the adsorption process (Eq. (7,8)) is predominant [22, 23]. However, in alkaline pH and

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a higher limit of current density, by increasing the initial pH, decolorization is not significantly changed.

 Effect of Current Density on Decolorization

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Current density is another important parameter to control the reaction rate within the reactor. Current

density directly determines the dissolution rate of metal ions in the solution and size of bubble formation
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directly affecting the growth of flocs. This parameter affects the mixing solution and mass transfer in the
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electrodes [35].
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During electrocoagulation, metal hydroxides are formed. The metal dissolved or deposited depends on

the amount of electric current passing through the electrolyte solution. The monomeric and polymeric
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hydroxyl complexes can remove contaminants due to their high oxidative potentials. The polynuclear

hydrolytic species of Al, when produced in large numbers, are very good coagulants for forming flocs.
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Hydrolysis of Al ions leads to formation of large networks (e.g. Al–O–Al–OH) capable of absorbing

contaminants chemically. By increasing current density, degradation of anodized aluminum plates and

organic contamination removal increased [36]. The metal concentration in the EC cell was obtained from

Faraday’s low (Eq. (13)) [34].

In this study, the effect of current density to the EC cell was verified by varying the current density level

from 15 to 35 mA/cm2 at constant pH (6.5) and constant EC time (40 min). Fig. 3 shows the effect of current

density on decolorization of industrial textile dyeing wastewater. It was observed that current density had

the maximum value. When current density increases from 15 to 25 mA/cm2, decolorization increases and

after 25 mA/cm2 decreases. In this study, after 25 min, the efficiency of decolorization is reduced due to

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presence of particles in the samples, which is taken after settling due to short settling time of 30 minutes.

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 Effect of EC Time on Decolorization

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EC time affects the efficiency of electrocoagulation process. Electrolysis time determined the production

of Al3+ ions from Aluminum electrodes. It also affects the treatment efficiency of the electrochemical

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process as it may increase or decrease with current density or pH of the sample and the accumulation of
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hydroxide flocs. Fig. 3 (a-c) shows the influence of EC time on decolorization of industrial textile dyeing
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wastewater when it changed from 20 to 60 min at constant pH (6.5) and constant current density (25
M

mA/cm2). It was observed that EC time has the minimum value. When the EC time increased from 20 min

to 40 min, the amount of decolorization decreased, but decolorization efficiency faced a reverse trend
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after 40 min. This is due to differences in the amount and type of coagulant species produced during the
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EC at various times. However, these changes will have limited impact, unlike pH. Fig. 2 shows that the
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lowest removal efficiency of 96% is observed at 40 min. However at higher time range of 40 to 60 min,

the maximum of 97% decolorization is observed. The results of this study agree well with other studies,
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indicating that the optimum amount of decolorization occurred at around 20 min [37].
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Fig. 3. The effect of current density and pH on decolorization at three level of EC time (a) 20 min, b) 40

min and c) 60 min).

3.3 Performance of EC Process during Different Runs

The industrial dyeing wastewater used in this study contains two types of compounds. One type of

compounds is colored compound such as Reactive Black WNN, Reactive Brown RNN, Reactive Orange 122,

Reactive Red 4BL, Disperse Red B3, Disperse Yellow WR and Disperse Navy Blue. Another type of

compounds is non-colored compounds, being additives in the dyeing process in the textile industry such

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as sodium oxalate, starch, polyvinyl alcohol, sodium chloride, sodium carbonate, calcium carbonate,

carboxy methyl cellulose, sodium hydroxide and acetic acid. Both types of compounds are effective in

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creating wastewater’s COD. Therefore, part of COD is for dyes and another part is for other compounds.

Decolorization and COD removal of synthetic wastewater containing only dyes have high efficiency [15].

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In this study, as previously noted, decolorization of industrial dyeing wastewater was 97%, but COD

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removal efficiency was not high. Moreno-Casillas et al. discussed all effective wastewater compounds in

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COD and their removal after the EC process [38]. During EC tests, citric, salicylic, tartaric and oxalic acids
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which tend to react with Al(III) to form soluble compounds. For other compounds, the opposite may
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transpire in reacting with Al(III) to form insoluble compounds. All of these will be partially removed, and

COD removal efficiency will depend on the final pH. Since COD for industrial textile dyeing wastewater is
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usually a mixture of the compounds, COD will be only partially removed. Therefore, EC process is not alone
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an appropriate method for water recycling in the textile industry since it does not pass the COD’s standard

so that it should be integrated with other methods such as biological methods. As Table 5 shows, in
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optimum condition, pH of 5.5, current density of 15 mA/cm2 and EC time of 23 min, COD removal
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efficiency was found to be 40%.

Electrode consumption for all runs is calculated from the following equation [39]:
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kg i.tEC .Mw
ELC (m3 ) = z.F.v
(14)

Where Mw is molecular mass of electrode (Mw,Al = 26.98 g/mol), tEC is operating time (s), z is number of

electron transferred (zAl = 3), v is volume (m3) of the wastewater and F is Faraday’s constant (96500 C/mol).
Table 5 shows the electrode consumption for all runs. As Table 5 shows, electrode consumption is 1.3

kg/m3 under optimum condition, pH=5.5, current density=15 mA/cm2 and EC time=23 min.

Energy consumption for all runs is calculated from the following equation [39]:

V.I.t
EEC = VR
(15)

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Where V is cell voltage (in Volt), I is applied current (in Amp), t is electrolysis time (in h) and VR is the

volume of effluent (in liter).

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Table 5 shows the energy consumption for all runs. As Table 5 clearly shows, by increasing the EC time at

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constant current density, the energy consumption is increased. Additionally, by increasing current density

at constant EC time, the energy consumption is increased. Energy consumption is 7.64 kWh/m3 under

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optimum conditions, pH=5.5, current density=15 mA/cm2 and EC time=23 min.
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The sludge settling velocity is an important settle ability parameter of a sludge in designing a settling
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section of an EC plant [40]. As Table 5 shows, SSV was measured for all runs. As shown, the sludge settling

velocity is low. It may, however, be noted that the NaCl in industrial textile dyeing wastewater enhances
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the cell conductivity and anode dissolution, and deteriorates the sludge settling [38]. Therefore, settling
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is not a good method for separating sludge after EC process in the textile dyeing industry because size of

settling unit would be very large. Therefore, it is suggested that filtration be used instead of settling to
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separate the sludge after the EC process [41].

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Table 5: All Data during EC Process

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3.4 Optimization by Software

The statistical optimization of the software has been chosen to find the specific point maximizing

decolorization efficiency. The optimum operational conditions in the EC process to attain the maximum

decolorization were initial pH of 5.5, current density of 15 mA/cm2 and EC time of 23 min. In this condition,
decolorization was predicted 98%, being confirmed by the experimental results using the decolorization

percentage of 97%.

Although the purpose of the current study was not to optimize COD removal, analyzing COD acts as a

pretreatment for biological method. Therefore, in optimum conditions, COD removal efficiency was found

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to be 40%.

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Electrode consumption and energy consumption under optimum conditions were 1.3 kg/m3 and 7.64

kWh/m3, respectively.

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Additionally, the amount of SSV was obtained 0.004 cm/min.

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3.5 Settling Process
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Settling process determines for separation of sludge from treated wastewater. As Fig. 4 shows, settling
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velocity is very slow in some runs such as runs of 2, 8, 9, 14 and 16 in which lower than 10% of sludge was

settled after 150 minutes. While results of some experimental runs such as runs of 7, 10 and 15 showed
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high initial settling velocity and more than 40% of sludge was settled in early 50 minutes of settling
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process. Some runs (1, 3, 5, 6 and 11) which their data are not presented faced with phenomenon that

the treated wastewater formed as a gel liquid in the middle of cylinder and produced sludge stand at up
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and down of cylinder. The formation of jelly liquid was attributed to large concentrations of aluminum
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hydroxide, being hindered by high local viscosity and low density difference. Due to low volatility of

bubbles trapped in sludge, a portion of sludge stays at the top of gel liquid that consequently the
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measurement of sludge settling faced difficulty. Therefore, it seems that settling velocity is under the

influence of operational parameters such as initial pH, current density and EC time. Whereas settling is

not a good method for separating produced sludge after the EC process with Al electrodes, changing the

types of electrodes or using filtration instead of settling can be a good solution to this problem.
Fig. 4. Sludge settling velocity (SSV) for most runs.

3.5.1 Kinetics of Sludge Settling Volume in Optimum Run

As mentioned previously, the optimum condition is determined and the curve of SSV is shown in Fig. 5.

After that, the kinetics of this run was discussed.

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According to Fig. 5, settling data decrease linearly with the time in the first 75 minutes, which is described

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by Eq. (16) with R2= 0.9916. After 75 minutes, settling data remain nearly constant. Thus, the optimum

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settling time for this system is about 75 minutes.

𝑦 = −0.0051𝑥 + 1.0085

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(0 < x < 75 minutes) (16)

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Fig. 5. Sludge settling velocity (SSV) under optimum conditions.
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4. Conclusion
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Industrial units, including textile wastewater treatment unit are near large cities like Tehran in which the
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cost of land is very high. Therefore, the treatment units must be very compact. Biological wastewater

treatment methods are common in treating such wastewater, but unfortunately are not efficient in
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treating colored wastewater due to the toxicity of color to microorganism so that these units need a useful
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compact pretreatment unit. Therefore, the purpose of this study was to consider the EC unit with low

sludge settling time, needing a small area in comparison with another EC process. The experimental
A

results indicated that the EC process was an efficient and promising process for decolorization of textile

effluents. Therefore, biological methods performance must be increased. The effect of various parameters

such as initial pH, current density and EC time on the decolorization was specified. As the results indicated,

there was an interaction between the initial pH (x1) and the current density (x2) on decolorization. Under
optimized conditions, namely pH of 5.5, current density of 15 mA/Cm2 and EC time of 23 min,

decolorization was predicted to be 98%, being confirmed by the experimental results by the decolorization

percentage of 97%. Therefore, the experimental values had a good correlation with the predicted ones,

indicating suitability of the model and the success of the RSM in optimizing the EC process conditions in

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treating industrial textile dyeing wastewater with maximum decolorization under selected conditions of

independent variables. COD removal efficiency, sludge settling velocity, electrode consumption and

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energy consumption under optimum conditions were measured, which were 40%, 0.004 cm/min, 1.3

kg/m3 and 7.64 kWh/m3, respectively. Results showed that the EC process did not pass the COD’s standard

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since wastewater contained dissolved additives such as sodium oxalate, polyvinyl alcohol, and acetic acid,

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being the cause for most COD of the wastewater. Furthermore, it should be a good pretreatment method

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for biological methods because decolorization efficiency during the EC process is more than 97%. Whereas
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settling is not a good method to separate produced sludge after the EC process with Al electrodes,
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changing the types of electrodes or using filtration instead of settling can be a good solution to this

problem.
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Technology, vol. 56, pp. 204-211, 2007.
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 PT
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Fig. 1 Schematic set-up diagram: (1) cathodes, (2) anodes, (3) DC power supply, (4) reactor, (5) input
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valve and (6) output valve.

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 PT
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Fig. 2 Regression plots of the actual data against the predicted values.

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 PT
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(a) N
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Decolorization (%)
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 Current Density (mA/cm2)

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pH
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 Current Density (mA/cm2)

(b)
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pH
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Decolorization (%)

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 PT
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N
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(c)
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Decolorization (%)
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 PT
Current Density (mA/cm2)

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pH
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Fig. 3: The effect of current density and pH on decolorization at three level of EC time (a) 20 min, b) 40
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min and c) 60 min).

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 1.2

0.8

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h/h0 (Cm)

0.6

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0.4

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Run 10 Run 1 Run 2 Run 4 Run 7
run 8 Run 11 Run 12 Run 13 Run 14
Run 15 Run 9 Run 16 Run 17
0.2

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0
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0 50 100 150 200
Time (min)
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Fig. 4 Sludge settling velocity (SSV) for most of runs.

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 1.2

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0.8

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h/h0 (Cm)

0.6

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0.4

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0.2 N
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0
0 50 100 150 200
Time (min)
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Fig. 5 Sludge settling velocity (SSV) under the optimum condition.

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Table 1 Characteristics of industrial dyeing wastewater samples.

Value
Parameters
Experimental data Factory data

COD (mgL-1) 1125 -

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Turbidity (NTU) 37 -

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pH 8.5 -

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Conductivity (µS.cm-1) 1077 -

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Color (SU) 709 -

Sodium oxalate (mgL-1) - N 19

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Starch (mgL-1) - 4
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Polyvinyl alcohol (mgL-1) - 21

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Sodium coloride (gL-1) - 9

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Sodium carbonate (mgL-1) - 40

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Calcium carbonate (mgL-1) - 20

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Carboxy methyl cellulose (mgL-1) - 16

Sodium hydroxide (mgL-1) - 5

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Acetic acid (mgL-1) - 22

 PT
Table 2 The levels and ranges of variables in Box–Behnken statistical experimental design.

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Range and levels
Independent variables

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-1 0 1

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x1: initial pH 4 6.5 9

x2: Current Density (mA/Cm2) N 15 25 35

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x3: EC time (min) 20 40 60
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Table 3: Box–Behnken experiments with actual values of responses.
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Decolorization (%)
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Run pH Current Density (mA/cm2) Time (min)

Predicted Experimental
D

1 4.00 25.00 60.00

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97.38 97.12

2 6.50 35.00 60.00

96.23 96.53
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3 9.00 25.00 20.00

90.59 90.34
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4 6.50 25.00 40.00

96.43 96.69

5 6.50 25.00 40.00

96.43 96.17
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6 6.50 35.00 20.00

94.4 94.73

7 9.00 15.00 40.00

77.47 77.88
 8 4.00 25.00 20.00
96.43 95.99

9 9.00 35.00 40.00

89.93 89.7

10 9.00 25.00 60.00

92.41 92.48

11 6.50 15.00 20.00

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95.2 94.67

12 6.50 25.00 40.00

96.43 96.02

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13 4.00 15.00 40.00
95.7 95.92

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14 4.00 35.00 40.00
81.64 81.23

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15 6.50 15.00 60.00
97.02 96.91

16 6.50 25.00 N
40.00
96.43 96.75
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17 6.50 25.00 40.00
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96.43 96.54
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Table 4: Analysis of variance table (ANOVA) for response surface quadratic model (Y).
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Sum of Mean p-value

Source df F Value
Squares Square , Prob > F
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Model 493.19 7 70.46 125.45 < 0.0001

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x1-PH 46.66 1 46.66 83.08 < 0.0001

x2-Current Density 0.48 1 0.48 0.86 0.3793

 x3-time 5.81 1 5.81 10.35 0.0105

x1x2 168.61 1 168.61 300.23 < 0.0001

x12 150.73 1 150.73 268.40 < 0.0001

x22 71.93 1 71.93 128.08 < 0.0001

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x32 52.52 1 52.52 93.52 < 0.0001

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Residual 5.05 9 0.56

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Lack of Fit 4.64 5 0.93 8.88 0.0275

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Pure Error 0.42 4 0.10

Cor Total 498.24 16

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Table 5: All data during EC process.

 COD Electrode

Run Decolorization (%) removal consumption EEC (kWh/m3) SSV(*10-3)

(%) (kg/m3)

1 50.4 4.7618
97.12 30.17 5.7

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2 94.08 4.878
96.53 19.22 7.9

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3 16.64 4.783
90.34 36.57 1.88

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4 33.76 3.1746
96.69 25.89 3.76

5 33.76 3.33
96.17 26.44 3.76

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6
94.73 30.89 N
2.64
31.04 3.1921
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7 13.5 3.75
77.88 37 2.26
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8 16.64 1.626
95.99 38.9 1.88
D

9 63.04 4.8782
89.7 30.07 5.26
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10 50.4 7.5
92.48 37 5.64
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11 6.66 4.762
94.67 22.56 1.12

12 33.76 3.333
96.02 25.3 3.76
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13 13.5 1.67
95.92 38.67 2.26
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14 63.04 1.626
81.23 32.01 5.26

15 20.16 4
96.91 15.89 3.38

16 33.76 5
96.75 26.7 3.76
17 33.76 3.33
96.54 26.66 3.76

Optimum 97 40.01 7.64 4

1.3

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N
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D
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