Accepted Manuscript

Title: A comparative study of electrocoagulation,

electrochemical Fenton, electro-Fenton and
peroxi-coagulation for decolorization of real textile
wastewater: Electrical energy consumption and
biodegradability improvement

Author: Farshid Ghanbari Mahsa Moradi

PII: S2213-3437(14)00286-3
DOI: http://dx.doi.org/doi:10.1016/j.jece.2014.12.018
Reference: JECE 529

To appear in:

Received date: 24-9-2014

Accepted date: 21-12-2014

Please cite this article as: Farshid Ghanbari, Mahsa Moradi, A comparative study
of electrocoagulation, electrochemical Fenton, electro-Fenton and peroxi-coagulation
for decolorization of real textile wastewater: Electrical energy consumption and
biodegradability improvement, Journal of Environmental Chemical Engineering
http://dx.doi.org/10.1016/j.jece.2014.12.018

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1 A comparative study of electrocoagulation, electrochemical Fenton, electro-Fenton

2 and peroxi-coagulation for decolorization of real textile wastewater: Electrical

3 energy consumption and biodegradability improvement

5 Farshid Ghanbari a, Mahsa Moradi b,*

6 a. Department of Environmental Health Engineering, School of Public Health, Ahvaz

7 Jundishapur University of Medical Sciences, Ahvaz, Iran

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8 b. Department of Environmental Health Engineering, School of Public Health, Shahid

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9 Beheshti University of Medical Sciences (SBMU), Tehran, Iran

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11 The corresponding author: Mahsa Moradi, Tel. +989126907929,
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12 Email: Moradi.env@gmail.com
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13 Highlights
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14
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15  Iron as a dominant agent was utilized in four separate electrochemical processes.

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16  BOD5/COD ratio increased from 0.137 to 0.362 in electro-Fenton process.

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17  Color and COD removals were higher than 94% and 82% in electrochemical

18 Fenton.
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19  Combination effect of coagulation/oxidation mechanisms raised k value (10) in

20 ECF.

21

1
22 Abstract

23 The main problem of textile wastewater is strong color which must be removed before

24 discharge to the environment. Electrochemical processes have been separately studied for

25 decolorization of synthetic dyes and colored wastewater. In this study, iron-based

26 electrochemical processes including electrocoagulation (EC), electrochemical Fenton

27 (ECF), electro-Fenton (EF) and peroxi-coagulation (PC) were applied for real textile

28 wastewater decolorization in similar conditions. The effects of initial pH, electrical current

29 and electrolysis time on decolorization were evaluated. COD removal, electrical energy

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30 consumption, iron consumption and BOD5/COD ratio of each process were compared. All

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31 the processes sufficiently removed color from the wastewater in as much as between 77%

32 SC
to 94% decolorization efficiency was gained. The results indicated that decolorization

33 efficiency in EC and EF processes was strongly dependent on initial pH. At optimum

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34 conditions, the highest energy consumption and iron consumption were found in EF and
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35 PC respectively. Electrochemical processes based on Fenton reagent (ECF, EF and PC)

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36 enhanced BOD5/COD ratio from 0.137 to over 0.3 while EC process could not increase

37 BOD5/COD ratio significantly. All the processes followed the second order kinetic for
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38 COD parameter in optimum conditions. As a comparison from the obtained results, the

39 ECF process was more effective than the other processes with regard to color and COD
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40 removal.
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41
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42 Keywords: textile wastewater; electrocoagulation; electrochemical Fenton; electro-Fenton;

43 peroxi-coagulation

44

2
45 1. Introduction

46 Containing various kinds of dyes, wastewater of textile industry imposes environmental

47 concern for its intensive color and organic content. Due to toxicity and aesthetical

48 aspects, the presence of color in water is an important problem for disposal of colored

49 wastewater. BOD/COD ratio of textile wastewater is in the range of 0.1 to 0.25

50 indicating existence of non-biodegradable organic compounds such as dyes in textile

51 wastewater. Therefore, it is essential to find an efficient method of wastewater

52 treatment for color and toxic organic compounds removals from textile effluents [1, 2,

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53 3].

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54 Recently, electrochemical processes have attracted much attention for treatment of

55
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industrial wastewaters particularly textile and dyeing wastewaters. Electrochemical
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56 processes are versatile in treatment of different wastewaters having various qualities
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57 and are referred as benign technologies since the main reagent is electron. In fact, the
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58 most important advantage of the electrochemical processes is that the chemicals are not
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59 applied during treatment. In addition, these technologies can be automatically operated

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60 that decreases costs of operation and maintenance [4, 5]. However, there are also some
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61 disadvantages referred to the electrochemical processes such as formation of metal

62 hydroxide sludge as well as the need for electricity and electrode replacement
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63 expenses[1, 6].Iron as the fourth abundant element in the earth’s crust, is the most
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64 applicable element in water and wastewater treatment processes [7]. In addition tothe

65 application of iron in coagulation process, it has been used as a transition metal in

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66 catalytic oxidation processes specially in Fenton process for the generation of hydroxyl

67 radical (HO•) as a powerful oxidant with E0=2.8 V [1, 8]. In electrochemical processes,

68 iron as anode electrode can play both roles of coagulant and catalyst. However,

69 reduction and oxidation reactions in electrochemical cell influence formation of iron

3
70 species thereby determining the system function. Electrochemical processes based on

71 iron electrode and iron catalyst include electrocoagulation, electro-Fenton and

72 combination of both methods [9]. In electrocoagulation process, iron electrode is used

73 as anode for in situ generation of coagulant agents while in electro-Fenton process with

74 electrogenerated hydrogen peroxide; ferrous ion is chemically introduced to the

75 electrochemical cell for the formation of Fenton reagents [10]. In order to combine

76 coagulation and Fenton oxidation in electrocoagulation process, hydrogen peroxide can

77 be added to the electrochemical reactor as one of the Fenton reagents [11]. Actually, by

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78 addition of hydrogen peroxide, electrocoagulation process is converted to

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79 electrochemical Fenton process [12]. Also, in electro-Fenton process with electro-

80 generated hydrogen peroxide, iron anode can be used instead of platinum or DSA

81
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electrode that this process is known as the peroxi-coagulation process [13, 14]. The
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82 processes of electrocoagulation (EC), electrochemical Fenton (ECF), electro-Fenton
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83 (EF) and peroxi-coagulation (PC) use iron element as the coagulant agent and catalyst
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84 for the Fenton reaction. The main reactions of these processes are summarized as
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85 below:
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86

87 In electrocoagulation:
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Anode: 4Fe → 4Fe + 8e (1)

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Cathode: 2H O → 2OH + H (2)

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88 In electrochemical Fenton:

Anode: Fe → Fe + 2e (3)

Cathode: Fe + e → Fe (4)

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 Introduced H O + Fe → HO• + Fe + OH (5)

89 In electro-Fenton:

Anode: H O → Pt(HO• ) + H + e (6)

Cathode: O + 2H + 2e → H O (7)

Introduced Fe + H O + H → HO• + Fe + H O (8)

90 In peroxi-coagulation:

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91 Anode: The same as equation 3

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92 Cathode: The same as equation 7

93
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These electrochemical processes directly exert iron element for the production of HO•or
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94 flocs of Fe(OH)n for destruction or adsorption of organic compounds respectively.
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95 In literatures, various studies discussed the above-mentioned processes separately for

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96 removal of synthetic dyes [15, 16, 17]. It has not been studied related to comparison of

97 four electrochemical processes in treatment of real textile wastewater yet. In the present
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98 study, real textile wastewater was selected as a complex sample and decolorization
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99 efficiencies of iron-based electrochemical processes were investigated in several

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100 conditions. Finally, optimal conditions of each process were compared based on
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101 removal efficiencies of color and COD. Moreover, electrical energy consumptions of

102 electrochemical processes were calculated for the assessment of economic aspects. In
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103 this study, we have tried to keep the conditions of the four processes similar in case of

104 electrochemical cell, electrode type and size.

105

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106 2. Materials and methods

107 2.1. Materials

108 Textile wastewater used in the present study was collected from Mirinous Inc. in

109 Central province that is located in central part of Iran. The main characteristics of

110 textile wastewater are presented in Table 1. FeSO4.7H2O and H2O2 (30%) were

111 obtained from Merck company. Sulfuric acid (96%) was purchased from Sigma-

112 Aldrich. All solutions were prepared by deionized water. Graphite felt was purchased

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113 from Sazeh-Morakkab Inc. (Iran) with an average surface density of 290 g/m2. All iron

114 plates were supplied commercially for all conditions. Iron electrodes were thoroughly

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115 washed by acetone solution to degrease the electrode surface. After each run, the iron

116
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electrodes were washed with HCl (10%) and deionized water and dried in room
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117 temperature.
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118 2.2. Electrochemical cell

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119 The electrochemical cell in all the processes was a cylindrical glass reactor with a

120 diameter of 6cm and height of 14 cm containing 300 mL textile wastewater. A

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121 magnetic stirrer was used for mixing the solution during electrolysis. Electrolysis was

122 conducted in natural conductivity of the textile wastewater without addition of

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123 supporting electrolyte using a digital DC Power supply (Zhaoxin, china, 0-5 A, 0-60 V
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124 and 0-2 A, 0-20 V). Dimensions of iron electrodes in all electrochemical processes

125 were 30 mm × 1.2 mm × 100 mm that 7 cm of them was immersed in the solution.
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126 Graphite felt electrodes were used in electro-Fenton and peroxi-coagulation, having

127 dimensions of 70 mm × 120 mm × 3 mm with an effective surface area of 63 cm2. All

128 experiments were carried out in pH of 3 and 6.5. The pH of 3 is the ideal value for

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129 Fenton reaction and the pH of 6.5 is the natural pH of the studied real textile

130 wastewater.

131 Electrocoagulation process: a pair of iron electrode was used as anode and cathode

132 with distance of 2cm. The electrodes were installed within the electrochemical cells.

133 Electrochemical Fenton apparatus: this process was carried out in a condition similar

134 with that of the electrocoagulation which was merely different in adding H2O2 in

135 various concentrations before the electrolysis.

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136 Electro-Fenton process: The platinum sheet with dimensions of 10 mm × 25 mm was

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137 placed in the center of the cell as anode that was surrounded by graphite felt cathode

138

139
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covering the inner wall of cell. Before the electrolysis, 2 L/min compressed air was

bubbled for 12 min to saturate the aqueous solution with O2. Different concentrations
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140 of Fe2+ were added to the solution to investigate the effect of catalyst.
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141 Peroxi-coagulation (PC) process: PC was similar with the electro-Fenton process. An
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142 iron electrode was placed instead of platinum sheet as anode electrode. During the

143 electrolysis, the solution pH was regulated to 2.8-3.4 and 6.2-6.7 by either 0.1 M
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144 H2SO4 or 0.1 M NaOH every 12 min. The volume of acid and alkali for adjusting the

145 pH was less than 5 mL [17].

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146 2.3. Analytical method

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147 Within all the processes, chemical oxygen demand values were measured through the
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148 closed reflux colorimetric method (0-1500 mg/L) with a UV-visible spectrophotometer

149 (Hach-DR5000) [18]. ADMI unit was used for the color measurement using a

150 spectrophotometer (Hach-DR5000) by which the ADMI value can be easily determined

151 after the filtration. In spite of negligible difference between ADMI values in different

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152 pH levels, ADMI values were normalized. In electrochemical Fenton, as for the COD

153 analysis and prevention of interferences, the pH of taken sample was increased to about

154 9 and residual H2O2 was removed by heating of the sample in 45◦C water bath for 30

155 min[19]. The H2O2 concentration was determined by iodometric method [20].

156 BOD5values of the samples were determined in accordance with the standard methods

157 [18].

158

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159 3. Results and discussions

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160 3.1. Decolorization efficiency of electrocoagulation

161 SC
In electrocoagulation process, pH plays a great role in formation of iron species for the

162 generation of FeII and FeIIIhydroxides [21, 22]. Various pH values have been reported
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163 as optimal pH for the electrocoagulation process. Effect of pH on color removal was
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164 investigated at electrical current of 200 mA. Fig.1a shows decolorization of real textile
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165 wastewater at natural pH and pH of 3. As seen in Fig. 1a, high difference is evident in

166 case of color removal in the two conditions. For the reaction time of 40 min, the highest
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167 decolorization was 92.1% at pH of 6.5 while at the same reaction time but at pH of 3,

168 decolorization efficiency was 65.1%. According to these results, EC decolorization

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169 efficiency depends on the initial pH significantly. In acidic conditions, iron species are
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170 more soluble than in neutral pH. Thus, the coagulation of pollutants is well conducted

171 at natural pH of the wastewater which is close to neutral pH [23].

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172 Electrical current as the most important parameter in electrocoagulation process

173 determines the amount of coagulant dosage and size of bubbles and flocs[21]. The

174 effect of electrical current on color removal is illustrated in Fig 1b. As seen in Fig 1b,

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175 with increasing electrical current from 100 mA to 300 mA during 40 min,

176 decolorization efficiency increases from 44.5% to 93.2%. It might be regarded to the

177 fact that at higher electrical current, the quantity of iron oxidized expands which result

178 in the production of more Fe(OH)n flocs for removal of dyes from wastewater [22].

179 Although the highest color removal efficiency (93.2%) is gained in electrical current of

180 300 mA, 92.1% decolorization efficiency is achieved in condition of 200 mA that is the

181 optimal condition with less electrical energy consumption.

182

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183 3.2. Electrochemical Fenton decolorization efficiency

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184

185
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Fig. 2a depicts the effect of pH on decolorization of real textile wastewater by

electrochemical Fenton in condition of 500 mg/L H2O2 and 200 mA electrical current.
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186 Similar with the electrocoagulation, the effect of pH=3 and natural pH on
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187 decolorization were assessed. In contrast with the obtained results from
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188 electrocoagulation process, ECF decolorization efficiency during 40min reaction time
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189 at pH of 3 and 6.5 were 94.4% and 75.3% respectively. In other words, highest
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190 efficiency was achieved at pH of 3. The presence of H2O2 brings about the formation of
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191 Fenton reagent in electrochemical cell and consequently, the production of HO•which
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192 has better performance in acidic condition (pH=3) to attack to the organic compounds

193 [24]. Likewise, low pH aids to maintain Fe2+ and Fe3+ in the solution. These results
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194 were in agreement with other studies that investigated pH effect on ECF efficiency [9,
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195 25]. Regarding the results of EC and ECF, the pH determines performance of

196 electrochemical reactions. Effect of electrical current on ECF decolorization at pH of 3

197 and 500 mg/L H2O2 is displayed in Fig. 2b. The results showed that the decolorization

198 efficiency of real textile wastewater was found to increase with increasing the electrical

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199 current. Within 40 min electrolysis time, decolorization efficiencies in 100 mA, 150

200 mA, 200 mA and 300 mA conditions were 56.2%, 68.9%, 94.4% and 94.8%

201 respectively. In the ECF process, electrical current acts as the source of iron ions

202 catalyzing the decomposition of hydrogen peroxide which generates free radicals such

203 as hydroxyl radical and hydroperoxyl. Thus, by increasing the electrical current iron

204 ions increased and consequently more HO•was generated. Furthermore, electro-

205 generation of iron ions in electrochemical cell forms flocs which in turn, adsorb dye

206 molecules from wastewater [9]. Accordingly, color removal efficiency was improved

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207 by double performance of electro-generation of iron ions. In fact, iron species play a

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208 mutual role in electrochemical cell acting as the catalyst for Fenton reaction and

209 coagulant agent [26]. As the oxidizing agent, hydrogen peroxide is the main factor of

210
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the Fenton reaction. The effect of H2O2 concentration on decolorization efficiency was
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211 studied in different concentrations (250 to 1000 mg/L) at pH of 3 and 200 mA electrical
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212 current and the results are illustrated in Fig. 2c. As seen in Fig. 2c, with increasing the
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213 H2O2 concentration from 250 to 750 mg/L, decolorization efficiency increases
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214 dramatically in 20 min reaction time. It is clear that a higher concentration of hydrogen
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215 peroxide generates more HO•(equation 5) that induces destruction of the organic
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216 compounds and reduction of color. Nevertheless, decolorization decreased in 1000

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217 mg/L H2O2. This is due to the self-decomposition of hydrogen peroxide in high

218 concentrations based on equation 9 [1, 8]. Moreover, the excessive H2O2 can react with
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219 HO•and produces the hydroperoxyl which is a less reactive radical (equation 10) [27,
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220 28, 29]. It means that H2O2 concentration higher than an optimum concentration cannot

221 fulfill the expected results.

H O + H O → 2H O + O (9)

H O + HO• → HO• + H O (10)

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222 3.3. Electro-Fenton decolorization process

223 The influence of pH on the electro-Fenton decolorization of textile wastewater was

224 examined at pH of 3.0 and 6.5 with constant electrical current. The results are depicted

225 in Fig. 3a. The pH of solution governs the electro-generation of H2O2 and it is also an

226 important factor in production of free radicals and Fe2+ concentration. As shown in Fig.

227 3a, an interesting result can be observed. There is a high difference between

228 decolorization efficiencies in pH of 3 and pH of 6.5. As expected, the decolorization

229 rate decreased significantly when the pH of solution increased from 3 to 6.5. Due to the

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230 presence of high protons at pH of 3, dissolved oxygen should consume hydrogen ions

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231 to be converted to hydrogen peroxide (equation 7) [30]. Therefore, acidic condition is

232 SC
suitable for degradation of organic pollutants by electro-generation of Fenton reagent.

233 In addition, H2O2 decomposes to oxygen and H2O at neutral pH and the oxidation
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234 potential of HO•reduces at the neutral pH (from 2.8 to 1.9 V). Thus, HO•is a powerless
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235 oxidant around neutral pH [31, 32, 33]. At pH above 3, free Fe2+ concentration is
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236 abated and ferric oxyhydroxide complexes are formed which their reaction with

237 hydrogen peroxide is slow [32, 33].

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238 Fig. 3b shows color removal efficiency of EF under varying applied electrical current

239 in pH of 3 and ferrous ion concentration of 2 mM. Electrical current is a major factor
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240 for the production of HO• in the solution. According to Fig. 3b, for all applied
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241 electrical currents, decolorization rate is considerable during the first 160 min, and then

242 the color removal efficiency becomes constant. Color removals were 51.3%, 58.9%,
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243 77.2% and 71% for electrical current of 100, 200, 300 and 400 mA respectively. As can

244 be seen, more color was removed when electrical current was increased indicating the

245 higher hydrogen peroxide production in the wastewater and higher Fe2+concentration

246 regenerated at the cathode. Thus, it can be claimed that with increasing of the Fe2+ and

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247 H2O2, higher HO• is generated in the solution and Fenton chain reactions propagates.

248 As shown in Fig. 3b, when the electrical current is 400 mA, removal efficiency slightly

249 decreases. This reduction in efficiency is associated with the oxidation of H2O2 at the

250 anode electrode based on equation of 11and 12 at higher electrical currents [10, 16].

H O → HO• + H + e (11)

HO• → O + H + e (12)

251 The effect of ferrous dosage on electro-Fenton decolorization is presented in Fig. 3c

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252 under the following experimental conditions: pH of 3.0 and electrical current of 300

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253 mA. As can be seen in Fig. 3c, within 160 min of the electrolysis, the decolorization

254 efficiency of textile wastewater increased from 63% to 77.2% as Fe2+ concentrations
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255 was increased from 2mM (111.6 mg/L) to 3mM (167.5 mg/L). Regarding to Fenton
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256 chemistry, it is obvious that ferrous ion markedly affects the production of HO•and
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257 degradation of organic pollutants as a consequence. But at Fe2+ concentration of 4mM

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258 (223.3 mg/l), electro-Fenton efficiency decreases which is attributed to overdosing of

259 ferrous ion that scavenges HO•. These results are consistent with other studies that have
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260 so far been presented in the literature [26, 28, 34].

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Fe + HO• → Fe + OH (13)
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261
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262
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263 3.4. Peroxi-coagulation decolorization process

264 Among the electrochemical processes that have been used for degradation of

265 environmental pollutants in literature, peroxi-coagulation was used less frequently in

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266 comparison with the other processes. In this process, probability of reaction of H2O2

267 with Fe2+ is high since both reagents are produced simultaneously. High amounts of

268 Fe2+ induce complete consumption of H2O2. The excessive Fe2+ precipitated as

269 Fe(OH)2 and Fe(OH)3that remain suspended in the solution, are highly dependent on

270 the pH [9]. Fig. 4a shows pH effect on decolorization efficiency by PC process at 200

271 mA electrical current. As can be observed, at natural pH (pH=6.5), color removal

272 efficiency decreases slightly due to instability of hydrogen peroxide at neutral pH

273 which displays that oxidative reaction doesn’t occur due to the low probability of the

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274 presence of HO• in the solution so that the coagulation by Fe(OH)n is the major

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275 mechanism of color removal [9,25].

276 SC
In peroxi-cogulation process, production of both reagents of Fenton reaction is carried

277 out electrochemically. Accordingly, electrical current is the most important parameter
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278 for the treatment of textile wastewater by peroxi-coagulation. The effect of electrical
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279 current on the color removal efficiencies of PC was studied at pH of 3. It is clear in Fig.
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280 4b that increase of electrical current leads to greater decolorization efficiency. This is

281 due to simultaneous production of H2O2 and Fe2+ at the cathode and the anode
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respectively yielding higher generation of HO• and consequently, more decolorization

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282

283 efficiency. Meanwhile, at the higher electrical current, large amounts of Fe(OH)n
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284 precipitates that brings about adsorption of organic compounds [13, 17]. Small
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285 difference is there between the color removal obtained in electrical current of 300 mA

286 (79.9%) and 400 mA (80%). Hence, 300 mA electrical current can be selected as the
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287 optimum electrical current.

288

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289 Fig. 4 (a) effect of pH on peroxi-coagulation decolorization efficiency at electrical

290 current of 200mA. (b) effect of electrical current on peroxi-coagulation decolorization

291 efficiency at pH=3.

292

293 3.5. Comparison of COD removal of electrochemical processes

294 The COD parameter is used as an evaluating parameter for the process efficiency in

295 case of destruction and cleavage of organic compounds in chemical oxidation

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296 processes. Reduction of COD shows that organic compounds have been removed

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297 during the wastewater treatment [35]. Fig. 5 shows COD removal efficiency of the

298

299
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studied electrochemical processes in the optimal conditions. As shown in Fig. 5, ECF

provides the best efficiency for textile wastewater treatment while EF has the lowest
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300 efficiency. Regarding to the results, the maximum efficiency were 82.1%, 78.6%,
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301 71.1% and 64% for ECF, EC, PC and EF respectively. It should be notified that these
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302 results were achieved in different electrical currents and electrolysis times. In ECF and
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303 EC, maximum COD removal efficiencies were obtained in a short time (40 min) and
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304 electrical current of 200 mA while EF and PC required more time and electrical current
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305 to reach to the maximum efficiency. According to EC results, it can be stated that
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306 coagulation mechanism has better performance than oxidation mechanism with free

307 radicals produced in EF for removal of organic compounds. Also, the combination of
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308 coagulation and electro-oxidation processes in ECF and PC improves slightly higher
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309 COD removal efficiencies in comparison with EC and EF respectively. These results

310 revealed that COD and color removals of real textile wastewater follow the below

311 mentioned order: ECF ≥ EC > PC > EF.

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312 It should be mentioned that color of the wastewater in EF process changed from black

313 to yellow in all conditions. ECF and PC processes caused color change in some

314 experiments and wastewater color disappeared during electrocoagulation process with

315 generation of black sludge in which phase conversion of pollutants was occurred from

316 liquid phase to solid phase [36].

317 The kinetic study was considered as an organic matter index for COD parameter due to

318 the complexity of the wastewater [37].The rate of COD removal can be represented by

319 the following second-order kineticmodel which is based on integrated equations [1]:

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1 1

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− = (14)

320 whereC0 and Ctrepresent COD concentration (g/L) at the beginning and after
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321 electrolysis time, respectively. k (L/g.min) stands for rate constant and t is the
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322 electrolysis time (min). According to the equation 14, plotting 1/Ct versus t results in a
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323 straight line that its slope is k. The rate constant and R-squaredvalues obtained are
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324 summarized in table 2. As can be observed, all the processes follow second-order
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325 kinetic with regression coefficients more than 0.95. Regarding table 2, the highest k
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326 value is corresponded to ECF that is 10 times higher than that of the EF. This

327 difference is attributed to combination of coagulation and oxidation mechanisms in

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328 ECF and effectivenessof H2O2addition (in ECF) in comparison with electrogeneration
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329 of H2O2 (in EF). It is evident from these results that process of the electro-generation of

330 H2O2 in EF and PC processes has increased half-life value since long time is required
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331 for this process [36].

332

333

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334 3.6. Electrical energy consumption and iron consumption

335 The main operational cost of the electrochemical processes is related to the electrical

336 energy consumption that has been considered as an economical parameter. Electrical

337 energy consumption (EEC) per kg of the removed COD was calculated based on

338 equation 15[12, 21].

UIt
EEC = (15)
V × (Y × )

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339 where EEC, U, I, t and V are the electrical energy consumption (kWh/kg COD

340 removed), cell voltage (v), electrical current (A), electrolysis time (h) and volume of

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341 wastewater (L) respectively. Y is COD removal efficiency (COD0–CODt/ COD0) and

342 COD0 is initial COD concentration (g/L).The amount of ferrous ions released during
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343 the process is mainly dependent on electrical current and electrolysis time. The rate of
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344 ferrous ions released from the anode (w) follows the Faraday's law [36, 38]:
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itm
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w= (16)
zF
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345 where m is the molecular weight of the iron (g/mol), z is number of electrons involved
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346 in the redox reactions and F is the Faraday’s constant (F = 96487 C/mol). EEC and iron
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347 consumption of electrochemical processes at optimal condition are summarized in table

348 3. Regarding table 3, the highest energy consumption is attributed to EF process while
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349 it has the lowest iron consumption because catalyst of the ferrous ion in EF is not
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350 deactivated within system as a precipitated form. In addition to high efficiency, EC and

351 ECF processes are suitable from economical point of view since their electrical current

352 and required time are lower than those of the other processes. The high energy

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353 consumption in EF and PC can be related to anodic and cathodic reactions in the

354 solution for in situ electro-generation of Fenton reagents.

355

356 3.7. Biodegradability improvement

357 The BOD5/COD index is usually used for the assessment of physicochemical processes

358 as a pretreatment before the biological processes [39, 40]. Fig. 6 shows BOD5/COD

359 ratio after the treatment by different processes in conditions that are brought in table 2.

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360 As can be seen, the BOD5/COD of raw wastewater is 0.137; indicating that the

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361 biodegradability of this wastewater is very low. BOD5/COD value increased to 0.178,

362

363
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0.341, 0.362 and 0.317 for EC, ECF, EF and PC respectively. In contrast with the

results gained from the COD removal, EF revealed the highestefficiency in increase of
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364 BOD5/COD. Regarding to oxidation of organic matter in EF, it seems that non-
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365 biodegradable compounds have been transformed to more biodegradable matters. In

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366 other words, COD value decreased highly while BOD5 value slightly reduced from 180
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367 to 160 mg/L, so the ratio of BOD5 to COD increased. In EC, no considerable change
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368 was seen in the BOD5/COD ratio as decrease of COD was as much as that of the BOD5.
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369 The processes of ECF, EF and PC bring about enhancement of BOD5/COD over 0.3
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370 indicating substantial biodegradability [41]. This increase can be explained by

371 production of •OH by electrochemical assisted Fenton reagent that induces destruction
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372 and devastation of aromatic rings of real textile wastewater [42, 43].
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373 For the selection of process in industrial scale, many factors must be considered

374 including pollutant removal efficiency, energy and chemicals consumption,

375 mineralization efficiency, sludge production and target of process application as

376 pretreatment or post-treatment. In this way, regarding to the above mentioned result,

17
377 ECF has the high efficiency in color and COD removals, low energy consumption and

378 destructive potential of organic compounds for biodegradability augmentation.

379

380

381 4. Conclusion

382 In this study, electrochemical processes of EC, ECF, EF and PC were studied for the

PT
383 treatment of real textile wastewater. All the processes were able to decolorize textile

384 wastewater up to over 70%. Amongst these processes, although ECF generates sludge,

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385 it has the most efficiency in terms of COD and color removal. EC and EF processes

386 SC
were very dependent on pH because both processes have a single mechanism. The

387 coagulation mechanism in EC, ECF, and PC processes indicated more capability in
U
N

388 organic matter removal from wastewater. PC and EF processes require more time and
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389 electrical current for textile wastewater treatment that result in increase of electrical
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390 energy consumption extremely. Although, removal efficiency of EF was less than that

391 of the other processes, EF improved biodegradability due to the dominant mechanism
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392 of EF that is oxidation of refractory compounds to biodegradable compounds. All

393 processes followed second order kinetic for COD removal.

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394 Acknowledgment
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395 The authors would like to thank Dr. Mina Sayyadi for providing the platinum electrode.

396
A

397 References

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462 26. Wang X, Zeng G, Zhu J. Treatment of jean-wash wastewater by combined

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469 Water Res. 2005;39:3062-72.

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473 30. Wang C-T, Chou W-L, Chung M-H, Kuo Y-M. COD removal from real dyeing
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497 39. Hsu Y-C, Yang H-C, Chen J-H. The enhancement of the biodegradability of
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498 phenolic solution using preozonation based on high ozone utilization. Chemosphere.
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503 41. de Morais JL, Zamora PP. Use of advanced oxidation processes to improve the
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505 42. Kajitvichyanukul P, Suntronvipart N. Evaluation of biodegradability and

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511

512

513

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514

515
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Fig. 1 (a) Effect of pH on electrocoagulation decolorization efficiency at constant
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516 electrical current of 200mA (b) effect of electrical current on electrocoagulation
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517 decolorization efficiency at constant pH of 6.5

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518
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519
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520
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521
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522

523
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524

525

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526

527

528

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529

530
SC
Fig. 2 (a) Effect of pH on electrochemical Fenton decolorization efficiency at electrical
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531 current of 200mA and H2O2 of 500mg/L (b) effect of electrical current on
N

532 electrochemical Fenton decolorization efficiency at pH of 3 and H2O2 of 500mg/L (c)

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533 effect of H2O2 concentration on electrochemical Fenton decolorization efficiency at pH

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534 of 3 and electrical current of 200mA

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535
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536
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537
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538
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539

540

541

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543

544

545

546

547

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SC
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548
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549 Fig. 3 (a) effect of pH on electro-Fenton decolorization efficiency at electrical current

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550 of 200 mA and Fe2+ concentration of 2 mM. (b) effect of electrical current on electro-

551 Fenton decolorization at pH=3 and Fe2+ concentration of 2 mM (c) effect of

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Fe2+concentration on electro-Fenton decolorization efficiency at pH=3 and electrical

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552

553 current of 300 mA

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554
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555
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556

557

558

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560

561

562

563

564

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565

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566
SC
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A
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D
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567
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568 Fig. 4 (a) effect of pH on peroxi-coagulation decolorization efficiency at electrical

569 current of 200 mA. (b) effect of electrical current on peroxi-coagulation decolorization
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570 efficiency at pH=3.

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571

572

573

25
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575

576

577

578

579

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SC
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N
A
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D
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580
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581 Fig. 5 COD removal efficiency in iron-based electrochemical processes at optimum

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582 conditions
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583

584

585

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586

587

588

589

590

591

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592

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SC
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593

594 Fig. 6 BOD5/COD ratio after iron-based electrochemical processes treatment

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595
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596

597

598

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600

601

602

603

604

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605

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606 Table 1 Raw textile wastewater characteristics

Parameter Unit
SC Value
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COD mg/L 1310 ± 25
N
A

BOD5 mg/L 180 ± 20

M

Electrical conductivity mS/cm 1.26 ± 0.05

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pH - 6.50 ± 0.02

BOD5/COD - 0.137
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Color ADMI 2024 ± 50

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Appearance - Black
A

607 ∗ TSS value was negligible

608

609

28
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611

612

613

614

615

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616 Table 2 Second order constantsof electrochemical processes for COD removal of textile

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617 wastewater

Electrochemical process
SC
Rate constant (L. g-1 min-1) R2 t1/2 (min)
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Electrocoagulation 0.0702 0.978 10.87
N

Electrochemical Fenton 0.0931 0.967 8.2

A
M

Electro-Fenton 0.0086 0.991 88.93

Peroxi-coagulation 0.0155 0.958 49.33

D
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618
EP

619
CC

620

621
A

622

623

29
624

625

626 Table 3 Electrical energy consumption and iron consumption of various

627 electrochemical processes for textile treatment

Electrical current, mA Electrical energy Iron

Electrochemical Initial Electrolysis
(current density, consumption (kWh/kg consumption
process pH time (min)
mA/cm2) COD removed) (mg)

Electrocoagulation 6.5 40 200 (4.76) 2.73 139.3

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Electrochemical Fenton 3.0 40 200 (4.76) 3.38 139.3

Electro-Fenton 3.0 160 300 (4.76) 63.64 50.3a

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Peroxi-coagulation 3.0 120 300 (4.76b) (7.16c) 23.19 626.8

628 SC
a. This amount of iron is chemically introduced from out of reactor
629 b. Based on anode surface
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630 c. Based on cathode surface
N
A
M
D
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EP
CC
A

30